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American Chemical Society Division of Environmental Chemistry 239th ACS National Meeting & Exposition, San Francisco, CA, March 21-25, 2010 S. Al-Abed, Program Chair SUNDAY MORNING Antimicrobial Agents and Sustainability R. U. Halden, Organizer, Presiding. Papers 1-10 New Energy Technologies J. Marwan, Organizer, Presiding. Papers 11-21 Sustainable Water Production and Waste Treatment: Emerging Technologies for the Treatment and Utilization of Impaired Water Sources J. McCutcheon, Organizer; B. Li, Organizer, Presiding. Papers 22-29 Biochars for Environmental Sustainability: Green Fuels, Carbon Sequestration, and Long-Term Agricultural Production M. Chappell, Organizer; D. Laird, Organizer, Presiding. Papers 30-39 SUNDAY AFTERNOON Policies for Promoting Sustainable Chemistry R. U. Halden, Organizer, Presiding. Papers 40-48 New Energy Technologies J. Marwan, Organizer, Presiding. Papers 49-60 Sustainable Water Production and Waste Treatment: Emerging Technologies for the Treatment and Utilization of Impaired Water Sources B. Li, Organizer; J. McCutcheon, Organizer, Presiding. Papers 61-69 Nanoporous Materials for Environmental Applications B. Deng, Organizer, Presiding; R. Luthy, Organizer, Presiding. Papers 70-77 MONDAY MORNING Aquatic Redox Chemistry: Symposium in Honor of Donald L. Macalady T. Grundl, Organizer; S. B. Haderlein, Organizer; L. Katz, Organizer; P. G. Tratnyek, Organizer, Presiding. Papers 78-85 New Energy Technologies J. Marwan, Organizer, Presiding. Papers 86-96

Atmospheric Chemistry of Persistent Organic Pollutants R. R. Kommalapati, Organizer; K. Valsaraj, Organizer, Presiding. Papers 97-104 Nanoporous Materials for Environmental Applications R. Luthy, Organizer; E. Hoek, Presiding; B. Deng, Organizer, Presiding. Papers 105-112 MONDAY AFTERNOON Aquatic Redox Chemistry: Symposium in Honor of Donald L. Macalady S. B. Haderlein, Organizer; P. G. Tratnyek, Organizer; T. Grundl, Organizer, Presiding. Papers 113-120 New Energy Technologies J. Marwan, Organizer, Presiding. Papers 121-132 Fate and Transport of Pollutants in the Built Environment: Atmospheric Chemistry Moves Indoors H. Destaillats, Organizer; G. Morrison, Organizer; C. Weschler, Organizer, Presiding. Papers 133-140 Nanoporous Materials for Environmental Applications B. Deng, Organizer; J. Zheng, Presiding; R. Luthy, Organizer, Presiding. Papers 141-148 MONDAY EVENING Sci-Mix S. Al-Abed, Organizer, Presiding. Papers 61, 292-293, 304, 306-307, 312, 315, 332, 338, 353, 358, 367-368, 374, 389, 428, 467 TUESDAY MORNING Aquatic Redox Chemistry: Symposium in Honor of Donald L. Macalady T. Grundl, Organizer; S. B. Haderlein, Organizer; P. G. Tratnyek, Organizer; A. Stone, Presiding. Papers 149-156 Fate and Transport of Pollutants in the Built Environment: Atmospheric chemistry Moves Indoors G. Morrison, Organizer; C. Weschler, Organizer; H. Destaillats, Organizer, Presiding. Papers 157-165 Nanotechnology: Enabling Sustainable Solutions for Potable Water D. Dionysiou, Organizer, Presiding; N. Savage, Organizer, Presiding. Papers 166-176 Sustainable Waste Management: Issues and Challenges S. Al-Abed, Organizer; T. Tolaymat, Organizer, Presiding. Papers 177-185

TUESDAY AFTERNOON Aquatic Redox Chemistry: Symposium in Honor of Donald L. Macalady T. Grundl, Organizer; S. B. Haderlein, Organizer; P. G. Tratnyek, Organizer; M. Scherer, Presiding. Papers 186-193 Influence of Natural Organic Matter on the Fate and Transport of Metals, Colloids and Nanoparticles in the Aquatic Systems G. Aiken, Organizer, Presiding; H. Hsu-Kim, Organizer, Presiding; J. Ryan, Organizer, Presiding. Papers 194-202 Nanotechnology: Enabling Sustainable Solutions for Potable Water D. Dionysiou, Organizer, Presiding; N. Savage, Organizer, Presiding. Papers 203-214 Sustainable Waste Management: Issues and Challenges S. Al-Abed, Organizer; T. Tolaymat, Organizer, Presiding. Papers 215-223 WEDNESDAY MORNING Aquatic Redox Chemistry: Symposium in Honor of Donald L. Macalady T. Grundl, Organizer; P. G. Tratnyek, Organizer; S. B. Haderlein, Organizer, Presiding. Papers 224-231 Influence of Natural Organic Matter on the Fate and Transport of Metals, Colloids and Nanoparticles in the Aquatic Systems H. Hsu-Kim, Presiding; G. Aiken, Organizer, Presiding; J. Ryan, Organizer, Presiding. Papers 232-240 Energy Sustainability of the Water Infrastructure Using Microbial Fuel Cell Based Technologies B. Logan, Organizer; B. Rittmann, Organizer; J. Regan, Organizer, Presiding. Papers 241-249 Sustainable Processes for Drinking Water and Wastewater Treatment C. Clark, Organizer, Presiding; A. Cooper, Organizer, Presiding; A. Lindner, Organizer, Presiding. Papers 250-257 WEDNESDAY AFTERNOON Aquatic Redox Chemistry: Symposium in Honor of Donald L. Macalady T. Grundl, Organizer; S. B. Haderlein, Organizer; P. G. Tratnyek, Organizer; N. Blough, Presiding. Papers 258-265 Influence of Natural Organic Matter on the Fate and Transport of Metals, Colloids and Nanoparticles in the Aquatic Systems G. Aiken, Organizer, Presiding; H. Hsu-Kim, Organizer, Presiding; J. Ryan, Organizer, Presiding. Papers 266-274

Energy Sustainability of the Water Infrastructure Using Microbial Fuel Cell Based Technologies J. Regan, Organizer; B. Rittmann, Organizer; B. Logan, Organizer, Presiding. Papers 275-282 Sustainable Processes for Drinking Water and Wastewater Treatment C. Clark, Organizer; A. Cooper, Organizer; A. Lindner, Organizer, Presiding. Papers 283-290 WEDNESDAY EVENING General Posters S. Al-Abed, Organizer, Presiding. Papers 291-401 Aquatic Redox Chemistry: Symposium in Honor of Donald L. Macalady L. Katz, Organizer; T. Grundl, Organizer, Presiding; S. B. Haderlein, Organizer, Presiding; P. G. Tratnyek, Organizer, Presiding. Papers 402-437 Biochars for Environmental Sustainability: Green Fuels, Carbon Sequestration, and Long-Term Agricultural Production M. Chappell, Organizer, Presiding; D. Laird, Organizer, Presiding. Papers 438440 Energy Sustainability of the Water Infrastructure Using Microbial Fuel Cell Bases Technologies J. Regan, Organizer; B. Rittmann, Organizer; B. Logan, Organizer, Presiding. Papers 441-459 Fate and Transport of Pollutants in the Built Environment: Atmospheric Chemistry Moves Indoors G. Morrison, Organizer; C. Weschler, Organizer; H. Destaillats, Organizer, Presiding. Papers 460-462 Influence of Natural Organic Matter on the Fate and Transport of Metals, Colloids and Nanoparticles in the Aquatic Systems G. Morrison, Organizer; C. Weschler, Organizer; H. Destaillats, Organizer, Presiding. Papers 463-483 Nanoporous Materials for Environmental Sustainability R. Luthy, Organizer; B. Deng, Organizer, Presiding. Papers 484-489 New Energy Technologies J. Marwan, Organizer, Presiding. Papers 490-491 Sustainable Processes for Drinking Water and Wastewater Treatment C. Clark, Organizer, Presiding; A. Cooper, Organizer, Presiding; A. Lindner, Organizer, Presiding. Papers 492-494

Sustainable Water Production and Waste Treatment: Emerging Technologies for the Treatment and Utilization of Impaired Water Sources J. McCutcheon, Organizer; B. Li, Organizer, Presiding. Papers 495-501 THURSDAY MORNING Aquatic Redox Chemistry: Symposium in Honor of Donald L. Macalady T. Grundl, Organizer; S. B. Haderlein, Organizer; P. G. Tratnyek, Organizer; T. Waite, Presiding. Papers 502-509 Influence of Natural Organic Matter on the Fate and Transport of Metals, Colloids and Nanoparticles in the Aquatic Systems H. Hsu-Kim, Presiding; G. Aiken, Organizer, Presiding; J. Ryan, Organizer, Presiding. Papers 510-517 Energy Sustainability of the Water Infrastructure Using Microbial Fuel Cell Based Technologies B. Logan, Organizer; J. Regan, Organizer; B. Rittmann, Organizer, Presiding. Papers 518-526 Sustainable Processes for Drinking Water and Wastewater Treatment C. Clark, Organizer, Presiding; A. Cooper, Organizer, Presiding; A. Lindner, Organizer, Presiding. Papers 527-533 THURSDAY AFTERNOON Aquatic Redox Chemistry: Symposium in Honor of Donald L. Macalady T. Grundl, Organizer; S. B. Haderlein, Organizer; P. G. Tratnyek, Organizer; S. Fendorf, Presiding. Papers 534-541 Influence of Natural Organic Matter on the Fate and Transport of Metals, Colloids and Nanoparticles in the Aquatic Systems G. Aiken, Organizer, Presiding; H. Hsu-Kim, Presiding; J. Ryan, Organizer, Presiding. Papers 542-550 Energy Sustainability of the Water Infrastructure Using Microbial Fuel Cell Based Technologies B. Logan, Organizer; B. Rittmann, Organizer; J. Regan, Organizer, Presiding. Papers 551-558

ENVR 1 Examining the sustainability of persistent antimicrobial compounds R. U. Halden, [email protected] School of Sustainable Engineering and the Built Environment, The Biodesign Institute at Arizona State University, Tempe, AZ, United States Antimicrobial agents are recognized as lifesaving products of applied chemistry. Yet, their extensive use in disposable household products also is known to cause widespread environmental contamination of aquatic and terrestrial environments. This literature review seeks to define sustainable uses of antimicrobials. It examines opportunities to meet public health objectives without causing unwanted environmental contamination. ENVR 2 From antimicrobial to anti-inflammation: Application of triclocarban as a potent inhibitor of soluble epoxide hydrolase in a murine model J. Liu1, [email protected], H. Qiu2, C. Morisseau1, S. H. Hwang1, H.-J. Tsai1, A. Ulu1, N. Chiamvimonvat2, and B. D. Hammock1. 1Department of Entomology, University of California, Davis, CA, United States, 2Division of Cardiovascular Medicine, University of California, Davis, CA, United States An increasing use of the anti-microbial triclocarban (TCC) in personal care products (PCP) has generated serious environmental pollution, which calls for more concerns on the biological effects of TCC. TCC has been reported as an inhibitor of soluble epoxide hydrolase (sEHI) in vitro. Here we demonstrated the anti-inflammatory effect of TCC as a sEHI in a LPS-challenged murine model. TCC is effectively anti-inflammatory evidenced by the observations that it significantly reversed LPS-induced hypotension and repressed the increased release of inflammation-related cytokines from LPS challenge, as well as shifted the oxylipin profile in vivo as expected as a sEHI. It is likely that inhibition of sEH contributed in a substantial portion to the anti-inflammatory effects of TCC in vivo. This causes more cautious in use of the TCC-containing PCPs. It may be a promising starting point for developing the new usages of TCC and re-evaluation of the biological effects of TCC. ENVR 3 Role of soil natural organic matter on natural transformation of Azotobacter vinelandii N. Lv1,2, [email protected], J. L. Zilles1, [email protected], and T. H. Nguyen1,2, [email protected] 1Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, 205 N.Mathews Ave., Illinois, United

States, 2Center of Advanced Materials for the Purification of Water with Systems (waterCAMPWS), Urbana, Illinois, United States Both antibiotics and antibiotic resistance genes are introduced into agricultural soil by land application of manure. The fate of the resistance genes is complex because they can spread into different microorganisms through horizontal gene transfer and increase in concentration as their host cells grow. The objective of our study is to investigate one type of horizontal gene transfer, natural transformation, with dissolved and adsorbed DNA and under different environmental conditions. Quartz crystal microbalance with dissipation (QCM-D) was used to study the conformation of adsorbed DNA on silica or natural organic matter (NOM) surfaces. Transformation efficiency was quantified with the soil bacterium Azotobacter vinelandii. Results from QCM-D experiments showed that chromosomal DNA adsorbed to silica surfaces has a more compact and rigid conformation in the presence of Ca2+ compared to Na+ and the reverse when adsorbed to NOM surfaces. However, extracellular chromosomal DNA transformed A. vinelandii with efficiencies in the same range (10-5 to 10-3 per cell), whether the DNA was in dissolved form or adsorbed on silica and NOM surfaces. Current work investigates natural transformation with an ampicillinresistant plasmid and in the presence of dissolved NOM. We hypothesize that the presence of dissolved NOM will influence plasmid DNA adsorption and decrease its transformation frequency. This study is identifying factors that influence gene transfer and therefore should be considered in the study of DNA fate and transport in the soil environment. ENVR 4 Use of sustainable polyphenols as antimicrobial and antibiofouling agents against Streptococcus mutans V. R. Sendamangalam1, [email protected], D. S. Kim2, [email protected], and Y. Seo2,3, [email protected] 1 Department of Bioengineering, University of Toledo, Toledo, Ohio, United States, 2Department of Chemical & Environmental Engineering, University of Toledo, Toledo, Ohio, United States, 3Department of Civil Engineering, Department of Chemical & Environmental Engineering, University of Toledo, Toledo, Ohio, United States Bacterial biofilm formation on various medical devices (e.g., catheters and prosthetic devices) has been of great concern due to their inherent resistance to antimicrobial agents. To control biofilm formation on medical devices, natural polyphenols found in plants, fruits, and vegetables, have recently received much attention as sustainable antimicrobial/ antifouling agents. In this study, Cardanol obtained from cashew nut shell liquid was selected as a model natural polyphenol and its antimicrobial/antifouling activities on Streptococcus mutans were observed and compared to those of commercially available polyphenols (Ascorbic acid, Gallic acid, Quercetin, Salicylic acid and Tannic acid).

Commercially available polyphenols with distinct structure differences (numbers of phenol rings, OH groups, and carboxyl groups) were selected to monitor the effect of the molecular structures of the polyphenols on antimicrobial and antifouling activities. For antibiofouling tests, all tested polyphenols were applied to surface to form coating on microtiter plates and then biofilm formation of Streptococcus mutans was observed. For monitoring the antimicrobial activities of polyphenols, minimum inhibitory concentration (MIC) and sucrosyl transferase enzyme activity of Streptococcus mutans were elucidated. Key Words: Polyphenols, Antimicrobial activity, Antibiofouling activity, Minimum Inhibitory Concentration ENVR 5 Development of an online solid-phase extraction liquid chromatography tandem-mass spectrometry (LC-MS/MS) method for the determination of the antibacterial triclocarban and its analogs in biological samples N. H. Schebb, [email protected], K. C. Ahn, [email protected], H.-J. Tsai, [email protected], S. J. Gee, [email protected], and B. D. Hammock, [email protected] Department of Entomology, University of California, Davis, Davis, CA, United States The antibacterial compound triclocarban (TCC) is widely used in personal care products up to a concentration of 1.5%. Recent studies of our group have shown that TCC exhibits an unintended high biological activity. In particular, the enzyme, soluble epoxide hydrolase (sEH), is inhibited by TCC at nanomolar concentrations. The sEH is involved in regulation of inflammatory mediators in the arachidonate cascade. sEH inhibition reduces inflammation in several mammalian species It also has been reported that TCC may act as an endocrine disruptor by enhancing the activity of sex steroid hormones such as testosterone and estradiol. In order to investigate the biological levels of TCC and its metabolites/analogs occurring after TCC exposure, we developed a new liquid chromatography-tandem electrospray mass spectrometry (LC-ESI-MS/MS) method applying turbulent-flow chromatography as online solid phase extraction. While the matrix proteins and salts were washed to waste with the online column, the target analytes were effectively trapped. Furthermore, in combination to a fast separation on 1.7 µm particle filled RP-18 column, TCC and its six metabolites/analogs were separated within 7 minutes. Together with the sensitive negative ESI-MS detection in multi-reaction monitoring mode, the observed lowest limits of detection of TCC and its metabolites/analogs were around 0.1 nM (2 fmol on column). The method was successfully applied to biological samples such as urine and blood. The resulting analytical platform allows the direct injection of these crude biological mixtures into the instrument after centrifugation without any further sample preparation. Furthermore the method was used to investigate biological levels of TCC arising after human exposure by showering. The resulting preliminary data regarding the pharmacokinetic of TCC in humans will be presented.

ENVR 6 Triclosan and methyl-triclosan dissipation in soils after biosolid application N. Lozano1,2, [email protected], A. Torrents1, C. P. Rice2, and M. Ramirez3. 1Department of Civil and Environmental Engineering, University of Maryland, College Park, MD, United States, 2Environmental Quality Laboratory, Agriculture Research Services - United States Department of Agriculture, Beltsville, MD, United States, 3DC Water and Sewer Authority, Washington, DC, United States TCS is removed in wastewater treatment plants (WWTP) primarily as biosolids (approx. 66%); therefore, biosolids disposal as land applications represents a significant path for release to the environment. Biosolids collected over three years from a large WWTP had concentrations of TCS and MeTCS ranging from 14.4 to 18.3 and 0.11 to 0.19 ppm, respectively. Multiple, single and zero applications of biosolids were distributed over 26 different commercial farms located in northern Virginia. The earliest applications occurred in 1992 and soils samples were collected within 7 months after application and as long as 14 years after treatment. Data showed that TCS was clearly dissipated from the soils and concentrations were reduced to near-background levels after 16 months. There was evidence of MeTCS formation in these soils. These results were validated in a small control-plot study carried out on farmland near Beltsville Maryland. ENVR 7 Comparative proteomic study to assess triclosan toxicity to green microalgae Chlamydomonas reinhardtii H. U. Deepthike, [email protected], and J. O. Boles. Department of Chemistry, Tennessee Technological University, Cookeville, TN, United States The toxicity of triclosan, a common antimicrobial compound present in consumer products, to green microalgae is well-documented. However, the toxicity assessments in those studies are based on measurement of biomass or study of the effects on the growth curves of microalgae species even though those parameters may not explicitly represent the healthiness of the population. This study purposes an alternative proteomic approach to asses the effects of triclosan in the growth medium to microalgae. Two dimensional electrophoresis maps of extractable proteins from triclosan-treated and control Chlamydomonas reinhardtii cultures showed significant differences in extractable proteome. Emphasis is focused on mass spectral identification of those differentially expressed proteins to facilitate the investigation of the largely unknown mechanisms of toxic effects of triclosan on algae. ENVR 8

Abundance and distribution of tetracycline resistance genes in freshwater aquaculture facilities J. A. Pedersen1,2, [email protected], E. E. Seyfried1,3, K. F. Rubert IV2, R. J. Newton5, and K. D. McMahon1,4. 1Department of Civil and Environmental Engineering, University of Wisconsin - Madison, Madison, Wisconsin, United States, 2Department of Soil Science, University of Wisconsin - Madison, Madison, Wisconsin, United States, 3United States Environmental Protection Agency, Seattle, Washington, United States, 4Department of Bacteriology, University of Wisconsin - Madison, Madison, Wisconsin, United States, 5 Department of Marine Sciences, University of Georgia, Athens, Georgia, United States We investigated the occurrence and abundance of tetracycline resistance genes (tetR) in four aquaculture facilities with contrasting OTC treatment histories. Endpoint and real-time polymerase chain reaction methods were used to detect and quantify tetR genes in water, sediment and feed samples collected from the four aquaculture facilities. Effluent water samples had markedly higher tetR gene concentrations than did corresponding influent samples (3- to 50-fold higher). TetR concentrations in sedimentation pond samples were higher in control facilities than in treatment facilities (5- to 600-fold higher). Surprisingly, unmedicated feed contained substantial concentrations of all genes, but medicated feed had significantly higher tetR levels than unmedicated feed (1- to 40-fold higher). OTC concentrations were quantified for each of these matrices and were compared to the corresponding tetR concentrations. This study has important implications for the management of aquaculture activities and underscores the need to further evaluate potential environmental reservoirs of antibiotic resistance. ENVR 9 Natural transformation of Azotobacter vinelandii in soil with and without antimicrobials H. E. Goetsch1,2, [email protected], T. H. Nguyen1,2, [email protected], and J. L. Zilles1, [email protected] 1Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana-Champaign, IL, United States, 2The Center of Advanced Materials for Purification of Water Systems, Urbana-Champaign, IL, United States Antibiotic resistance genes are introduced into agricultural soil through land application of manure and can persist if adsorbed to soil grains. The presence of adsorbed DNA allows the possibility of transfer of antibiotic resistance genes into native soil bacteria. In this study, natural transformation is considered in the presence of soil. Non-sterile soil is spiked with competent Azotobacter vinelandii and DNA adsorbed to soil grains. In order to quantify transformation frequencies, bacteria must be recovered from the soil. A soil wash protocol has been developed that recovers 66% of spiked A. vinelandii cells, as assessed by plate

counts, and about 3x108 cells of native soil bacteria per gram of soil as quantified by microscopy. Background levels of resistance to antibiotics in native soil bacteria and fungal contamination have typically prevented quantification of natural transformation in soil. Through the use of nitrogen-free Burk medium and cycloheximide as an antifungal, we have reduced the background and obtained a detection limit of 2x10-6 transformants per A. vinelandii cells. Current experiments are investigating the influence of tetracycline antibiotics on natural transformation by plasmid DNA in non-sterile soil. We hypothesize that plasmids containing homology with the A. vinelandii chromosome will transform more efficiently and that the presence of tetracycline will result in higher transformation rates for plasmids encoding tetracycline resistance. These hypotheses will be tested by conducting natural transformation experiments with non-sterile soil spiked with competent A. vinelandii and different plasmid DNA in the presence and absence of tetracyclines. ENVR 10 Life cycle assessment of tylosin and chlortetracycline antimicrobial use at swine production facilities J. Stone1, [email protected], K. Aurand1, S. Clay2, and R. Thaler3. 1 Department of Civil and Environmental Engineering, South Dakota School of Mines and Technology, Rapid City, SD, United States, 2Department of Plant Sciences, South Dakota State University, Brookings, SD, United States, 3 Department of Animal and Range Science, South Dakota State University, Brookings, SD, United States This study investigates the environmental effects associated with tylosin and chlortetracycline (CTC) antimicrobial sub-therapeutic use within Midwestern US swine production facilities following life cycle assessment (LCA) methodology. Environmental LCA-associated impacts were modeled using SimaPro and assessed using EcoIndicator 99 for antimicrobial manufacturing, feed blending and transport, metabolic and manure emissions, and facility operations for starter, grower, and finishing swine operations. LCA results suggest current high energy demands associated with manufacturing fermentation processes and large transport distances to producers of CTC and tylosin increased disability adjusted life year (DALY) climate change impacts compared to no antimicrobial use. Feeding CTC resulted in several local positive changes including increased feed utilization and reduced manure greenhouse gas emissions. However, these positive changes in the local environment did not offset negative global impacts associated with material manufacturing and transport. Using renewable energy sources for production and transport would result in net environmental enhancement. ENVR 11 Bose-Einstein condensation nuclear fusion: Applications

Y. E. Kim, [email protected] Purdue University, Department of Physics, West Lafayette, Indiana, United States Applications of recently developed theory of Bose-Einstein condensation nuclear fusion (BECNF) [1] are described. The experimental results of deuteron-induced nuclear reactions in metal observed in electrolysis and gas loading experiments show many different signatures of nuclear fusion (excess heat including "heatafter-death", nuclear ashes, radiations, formation of micro-scale craters, etc.). The theory is capable of explaining most of these diverse experimental results. Theoretical explanations of the experimental observations will be described. Key experimental tests of theoretical predictions will be discussed. [1] Y. E. Kim, "Theory of Bose-Einstein Condensation Mechanism for DeuteronInduced Nuclear Reactions in Micro/Nano-Scale Metal Grains and Particles", Naturwissenschaften (2009) 96:803-811 (published online 14 May 2009) and references therein. ENVR 12 Bose-Einstein condensation nuclear fusion: Theory Y. E. Kim, [email protected] Purdue University, Department of Physics, West Lafayette, Indiana, United States Theory of Bose-Einstein condensation nuclear fusion (BECNF) [1] has been developed to explain many diverse experimental results of deuteron-induced nuclear reactions in metals observed in electrolysis and gas loading experiments. The theory is based on a single conventional physical concept of Bose-Einstein condensation of deuterons in metal and provides a consistent theoretical description of many of the diverse experimental results. It also has predictive powers as expected for a quantitatively predictive physical theory. The basic concept and important features of the BECNF theory will be presented. [1] Y. E. Kim, "Theory of Bose-Einstein Condensation Mechanism for Deuteron-Induced Nuclear Reactions in Micro/Nano-Scale Metal Grains and Particles", Naturwissenschaften (2009) 96:803-811 (published on line 14 May 2009) and references therein. ENVR 13 Wave model and its implication to an environmental safe nuclear reactor X. Z. Li, [email protected] Department of Physics, Tsinghua University, Beijing, China Enrico Fermi built the first fission reactor successfully just three years after the discovery of nuclear fission because he developed an age theory to describe the neutron slowing-down process in time. The fast neutron was treated as a granular particle until its energy approaches thermal energy; then, the resonance

of neutron wave enhances the fission cross-section greatly. The deuterium/palladium system has shown its prospect as an environmental safe nuclear reactor. We have to deal with deuteron wave inside palladium lattice from the beginning. The key parameter is the ratio of absorption to transmission. A wave model is established to optimize this key parameter based on the correlation between deuterium flux and the heat effect (Tsinghua University). An identity has been derived to explain the experimental results. It is qualitatively consistent with super wave phenomena (Israel Energetics), ultrasonic stimulation (Stringham, Arata), super lattice effect (Iwamura, Kobe group), etc. The implication of an environmental safe nuclear reactor will be discussed. ENVR 14 Tunneling beneath the 4He* fragmentation energy A. Meulenberg1, and K. P. Sinha2, [email protected] 1HiPi Consulting, Frederick, MD, United States, 2Department of Physics, Indian Institute of Science, Bangalore, Karnataka, India A mechanism, involving optical phonons and electric fields (internally or externally generated) in a lattice forms D- D+ pairs, reduces the repulsive d-d Coulomb barrier (length and height), and increases the tunneling probability by > 100 orders of magnitude. The energy required to overcome the d-d potential barrier, comes from the electron pair in the potential well of one of the deuterons. With this greatly enhanced barrier-penetration probability, the energy level of nuclei with reasonable tunneling probability drops from the multi-100 keV range down into the eV range. Normal tunneling is into resonant states above the fragmentation energy. In the lattice, with tightly-bound electrons sharing the deuterons' energy, the possibility of a lower-energy excited nucleus becomes real. If the excited nucleus, 4He*, cannot fragment, and 0-0 gamma decay is highly forbidden, this model accounts for all the unusual experimental observations of CMNS (i.e., tritium, 3He, neutrons, 4He, and transmutation). ENVR 15 Theoretical aspects on deuterons-to-4He channels A. Takahashi, [email protected] Research Department 1, Technova Inc., Suita, Osaka, Japan The two body d + d fusion cannot give 4He as major product. If there happens the 4 He* (Ex) state with Ex < 19.8 MeV, the final product becomes 4He with ground state, after electromagnetic transition. To realize this process by a d+d reaction, there should exist the third coupling field which must take more than the 4 MeV difference energy (23.8 MeV ­ 19.8 MeV; here 23.8 MeV is Q-value of a d+d fusion) of the d-d system in the initial state interaction. The many-body interaction process between the d+d pairing and the third field of photon-phonon coupling in the lattice of condensed matter may be considered. Due to the very short range

force of d+d strong interaction and its very short life time of virtual intermediate compound state, no processes have ever been proved to remove the 4 MeV gap energy. Deuteron-cluster fusion, i.e,. 4D fusion, can produce 4He-atoms as major ash of reactions, and tritons, protons, and deuterons as minor products. To realize the conditions of 4D fusion, the microscopic ordering/constraint process for the dynamic Platonic symmetry should be satisfied. The 4D/TSC model by the author is one of theoretical models which can give rational explanations to the key CMNS/LENR experimental results, such as heat emission with 4He ash and without neutrons. The paper discusses also on explanation of the SPAWAR result of high energy neutrons and the Kobe result of 2-6 MeV charged particle spectra observed in the nano-Pd/ZrO2 D-charging condition. ENVR 16 Final products of 4D-fusion by tetrahedral symmetric condensate A. Takahashi, [email protected] Technova Inc., Suita, Osaka, Japan Our TSC theory papers have been published in LENR-Sourcebook Vols.1 and 2 by ACS in 2008 and 2009. In this paper we further discuss and predict possible final products by 4D-fusion via intermediate compound nucleus 8 Be*(Ex=47.6MeV). For the cases of even spin-parity transitions through the initial state, intermediate compound state (8Be*) and final out-going channels, we predict final products, which will be mostly charged particles of -particles, tritons, deuterons and protons with various energies discretely distributing in the region from 0.2 to 23.8MeV. Especially, -particles with lower energies in 2-5 MeV region will be dominantly produced through fragmentations of 8Be* via excited states of fragmented nuclei as 4He* and 6Li*. The 23.8 MeV -particle peak will not be major channel. Significant emission of tritons (1-5 MeV in kinetic energy) is predicted through symmetric and asymmetric fragmentations of 8Be*. These tritons will induce secondary t-d reactions in its slowing down process in PdDx matter to emit weak amount of 10-17 MeV high energy neutrons which would have been observed by SPAWAR experiments and in our past experiments in 1990s. ENVR 17 Modeling excess heat in the Fleischmann-Pons experiment P. L. Hagelstein1, [email protected], and I. U. Chaudhary2. 1Department of Electrical Engineering and Computer Science, Massachusetts Institute of Technology, Cambridge, MA, United States, 2Department of Computer Science and Engineering, University of Engineering and Technology, Lahore, Pakistan We review results obtained in modeling the surface electrochemistry, deuterium diffusion, phonon excitation, coherent dynamics, and helium diffusion relevant to excess heat production in the Fleischmann-Pons experiment.

ENVR 18 Underlying mechanism of the nuclear CF implied by the energy-momentum consevation T. Sawada, [email protected] Institute of Quantum Science, Nihon University, Chiyoda-ku, Tokyo, Japan The final states of the d-d reactions in vacuum at low energy are t+p and He(3)+n with 50% each. On the other hand in the nuclear CF, the reaction changes to d+d ->He(4). However the two conservations are not compatible in the latter reaction. Namely from the momentum conservation the momentum q of He(4) must be zero, whereas the energy conservation requires q=422MeV. To recover the consistency, it must proceed under the influence of the localized external field, whose spread is r=0.47 fm. from the uncertainty relation. There is only one candidate which satifies all the requirements. It is magnetic field produced by the magnetic monopole. ENVR 19 Ultra high density deuterium clusters for low energy nuclear reactions G. H. Miley1, [email protected], X. Yang1, and H. Hora2. 1Department of Nuclear, Plasma and Radiological Engineering, University of Illinois, Urbana, IL, United States, 2Department of Theoretical Physics, University of New South Wales, Sydney, Australia Our low energy nuclear reaction research (LENR) has embedded ultra high density deuterium "clusters" (D cluster) in Palladium (Pd) thin films. These clusters approach metallic conditions, exhibiting super conducting properties. [1] They represent "nuclear reactive sites" needed for LENR. The resulting reactions are vigorous, giving the potential for a high power density cell. Clusters are achieved through electrochemically loading-unloading deuterium into a thin metal palladium film creating local defects which form a strong potential trap where deuterium condenses into "clusters" of ;100 atoms. Research now focuses on nano-manufactured structures to achieve a high volumetric density of these trap sites. Alternately condensed deuterium inverted Rydberg 2.3-pm deuteron spacing is being studied. [2] To initiate reactions in these ultra high density deuterium clusters, efficient ways are needed to excite the deuterium via a momentum pulse. One is through pulsed electrolysis to achieve high fluxes of deuterons hitting the clusters. [3] Another method uses ion bombardment from a pulsed plasma glow discharge. [4] Electron beam and laser irradiation represent other approaches to be explored. [1] AG Lipson, BJ Heuser, CH Castano, A Celik-Aktas, Physics Letters A. 339 (2005) 414-423. [2] Holmlid, Hora, Miley Yang, Laser and Part. Beams 27, 529 (2009)

[3] X. Yang, G. H. Miley, H. Hora, 2009, SPESIF-2009, AIP Conf. Proceeding, 1103, pp. 450-458 [4] A.G. Lipson, A.S. Rusetskii, A.B. Karabut, and G. Miley, J. of Experimental and Theoretical Physics, Vol. 100, No.6, pp. 1334-1349, (2005) ENVR 20 Heavy electrons in nano-structure clusters in solid surfaces and their interactions with positive nuclei (protons and deuterons) D. Alexandrov, [email protected] Department of Electrical Engineering, Lakehead University, Thunder Bay, Ontario, Canada The existence of heavy electrons is found theoretically in nano-structure clusters that are in the solid surfaces. Basis of the investigation is the electron band structures of nano-structure clusters in these surfaces. The existence of electron energy pockets is found for the electrons in the conduction bands of these clusters that can be considered to be nano-confining potential valleys of dimensions in the range of the primitive cell. The Schroedinger equation is solved and the following conclusions are found based on the solution: i) the electron effective mass changes when the confined electron interacts with both positive nuclei and external electro-dynamic field and it can increase significantly determining the electron as heavy (meff > 400 m0); ii) the critical electron effective mass is determined as value for which the distance between the electron and the deuteron (proton) becomes 1.5fm, and the corresponding parameters of the electro-dynamic field such as magnitude and frequency are found. It is found that a stable electron-deuteron (proton) domain appears. ENVR 21 Only conventionally viable cold nuclear fusion theory? R. W. Bass, [email protected] 5208 Bryant Irvin Road (#3144, Fort Worth, TX, United States Bass June 1991 gave only known Cold Fusion theory based upon accepted Quantum Mechanics which corrects Princeton "Einstein Prof. of Science" James Peebles' QM book's mistakenly localized "disproof of CF possibility" that ignored global nature of problem, such as Bloch's Theorem re periodic lattices, & passes the "Rabinowitz Acid Test" by correctly predicting CF in heavy water but not in ordinary water with a Pd cathode but vice versa with Ni cathode & also predicts with 97% accuracy the empirically measured Schwinger Ratio & shows in Bass's MIT Cold Fusion Colloquium lecture "Do Conjectures/Concepts of Schwinger, Turner, Chubb, R. Bush, Lamb & Parmenter, et al Resolve the Chief Challenge to Cold Fusion Theory?" how to develop a more elaborate algorithm that would be usefully predictive re external stimuli triggering "resonant transparency of Coulomb Barrier" when Schwinger Ratio is closer to an odd than an even integer.

ENVR 22 Sulfate radical remediation of contaminant antibiotics in water K. A. Rickman1, [email protected], S. P. Mezyk1, J. R. Peller2, and D. D. Dionysiou3. 1Department of Chemistry and Biochemistry, California State University at Long Beach, Long Beach, California, United States, 2Department of Chemistry, Indiana University Northwest, Gary, Indiana, United States, 3 Department of Civil and Environmental Engineering, University of Cincinnati, Cincinnati, Ohio, United States The removal of trace amounts of pharmaceuticals such as antibiotics from reclaimed waters is one of the largest problems currently facing water utilities. The use of advanced oxidation processes (AOPs), which generate radicals to non-selectively destroy such chemical contaminants in waters, is therefore being considered. AOPs typically produce oxidizing hydroxyl radicals, but another approach is to use sulfate radicals which are also highly oxidizing species. In this study, we have determined the absolute rate constants for sulfate radical reactions with a large library of beta-lactam antibiotics in waters, by means of the hydrated electron reduction of persulfate (S2O82-) by electron pulse radiolysis. These kinetic data has been combined with efficiency measurements, determined through steady-state radiolysis and HPLC techniques, to allow an overall evaluation of the feasibility of using these processes. ENVR 23 Antibiotic oxidation and deactivation in water by treatment with KMnO4 L. Hu1, [email protected], H. Martin1, K. Wammer2, A. Stemig2, and T. Strathmann1. 1Department of Civil & Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 2Department of Chemistry, University of St. Thomas, St. Paul, MN, United States There is growing interest in the fate of antibiotics in drinking water treatment facilities due to their widespread detection in source waters. Potassium permanganate (KMnO4), a chemical widely used by water utilities (e.g., for Mn control), shows promise as an alternative oxidant for treating waters contaminated with antibiotics. This contribution reports on oxidation of commonly detected antibiotics (e.g., lincomysin, trimethoprim, ciprofloxacin) with KMnO4. Experiments demonstrate that KMnO4 is a selective oxidant, with apparent second-order rate constants at pH 7 for the target antibiotics ranging from <0.03 to 72 M-1 s-1. Reaction rates are highly dependent upon pH due to changes in antibiotic speciation. LC-MS/MS analysis of reaction products indicates that amino and heterocyclic N groups are the primary sites of KMnO4 reaction in several antibiotics. Microbial growth inhibition bioassays demonstrate that treatment of antibiotic solutions with KMnO4 yields products that possess negligible antibacterial activity in comparison with the parent drugs.

ENVR 24 Photocatalytic antifungal effect of TiO2 on Candida albicans under white light and different buffer systems A. Stoddard, [email protected], E. Mintz, [email protected], S. Mehrabi, [email protected], and D. Low, [email protected] Chemistry, Clark Atlanta University, Atlanta, GA, United States Candida albicans is an important pathogenic species of the genus Candida, a collection of yeast form fungi. It is normally present in the normal flora in and on the human body. Under certain circumstances, it may cause superficial infections of the skin, mouth, or vagina and severe invasive systemic infections. The photocatalytic inactivation of microorganisms in water with TiO2 is currently of great interest. In this study the photocatalytic inactivation of Candida albicans H137 (a clinical isolate from the CDC, Atlanta, GA) by TiO2 under warm whitelight and buffers was investigated. Our data revealed no inactivation of Candida albicans by TiO2 in plain water, 10 mM phosphate buffer in the pH range from 4.2 to 8.5, or 150 mM sodium chloride solution. However, significant photocatalytic antifungal activity was observed in 100 mM bicarbonate buffer at pH 6, 8, and 10. The rate of fungal inactivation increased as the pH of the bicarbonate buffer was decreased. The formation of oxidized bio molecules was studied by following the reaction of the reaction supernate with 2,4-dinitrophenylehyrazine. ENVR 25 Removing steroids from drinking water using advanced oxidative and reductive chemistry E. M. Abud1, [email protected], K. L. Swancutt1, D. D. Dionysiou2, and S. P. Mezyk1. 1Department of Chemistry and Biochemistry, California State University at Long Beach, Long Beach, California, United States, 2Department of Civil and Environmental Engineering, University of Cincinnati, Cincinnati, Ohio, United States One of the biggest challenges in reusing wastewater is removing anthropomorphic chemical pollutants. Even at trace levels, many contaminants in our water have major impacts on the biosphere and human health. Unfortunately, classical methods of wastewater treatment are incapable of quantitatively removing steroids from water. Therefore, for the active removal of steroids from various quality waters, radical-based advanced oxidation/ reduction processes continue to gain interest as the technology of choice. These AO/RPs generate oxidizing and/or reducing radicals directly in water which then react with, and destroy, trace levels of chemicals. In this work we have investigated the use of oxidizing hydroxyl (·OH) and sulfate (SO4-·) radicals to quantitatively destroy estrogenic steroids in water. We have determined absolute reaction rate constants for these two oxidizing radicals, as well as investigated the efficiencies

of these reactions. This research was supported in part by the National Institute of General Medical Science Grant 5 T34 GM008074-23. ENVR 26 Optimizing energy generation in wastewater treatment by coupling hydrogen producing biofermentor and microbial fuel cell in continuous scale operation Y. Sharma, [email protected], and B. Li, [email protected] Civil and Environmental Engineering, University of Connecticut, Storrs, CT, United States In this study, the clean energy was generated from organic wastewater using two technologies of anaerobic hydrogen production and microbial fuel cells (MFC). To optimize hydrogen production, operational parameters of contaminant concentration, pH and temperature were studied extensively in batch and continuous reactors. Using a batch design (volume: 100 mL), 224 L of H2 was recovered from 1 m3 of wastewater with an initial COD of 1 g/L. In a continuous scale operation (volume: 2L), the hydrogen production increased to 298 L. The hydrogen production increased with decreasing contaminant concentration and increasing temperature (within mesophilic range) with an optimal pH range of 5.5-6. During hydrogen production, acetic and butyric acid were produced. To treat these liquid products, a single chamber MFC using oxygen as electron acceptor was operated on a continuous scale. The power output was 4.2 Watt/m3 of effluent. The complete removal of organic contaminants was achieved. ENVR 27 Manganese dioxide as the new cathode catalyst to degrade contaminants in microbial fuel cell (MFC) X. Li, [email protected], and B. Li, [email protected] Civil and Environmental Engineering, University of Connecticut, Storrs, CT, United States This study focused on manganese oxide with the structure of octahedral molecular sieves 2 (OMS-2) to replace platinum as the cathode catalyst in microbial fuel cells (MFCs). The undoped (ud-OSM-2) and three doped with cobalt (Co-OMS-2), copper (Cu-OMS-2), cerium (Ce-OMS-2) were investigated. The novel OMS-2 cathodes were examined in granular activated carbon MFC (GACMFC). The results showed that the Co-OMS-2 and Cu-OMS-2 exhibited the good catalytic property of oxygen reduction reaction (ORR). The voltage of the Co-OMS-2 GACMFC was 217mV and the power density was 180mW/m2, and the voltage of the Cu-OMS-2 GACMFC was 214mV and the power density was 165mW/m2. Furthermore, the degradation rates of organic substrates in the OMS-2 GACMFCs were twice as that in the platinum GACMFCs, which expedites wastewater treatment. This study indicated that using OMS-2 manganese oxides to replace platinum as the cathodic catalyst could enhance

power generation, increase contaminant removal and substantially reduce the cost of MFCs. ENVR 28 Development of chemically engineered porous metal oxides for phosphate removal C. McManamon, [email protected] Chemistry, University College Cork, Cork, Ireland Phosphorus is an important element that is widely used in agriculture as a fertilizer and in industry as a detergent. However, the use of phosphorus poses many problems, notably eutrophication, when it is released into aquatic environments. Ordered mesoporous silica has proven to be a good adsorbent of materials such as metal ions due to their high specific surface area, controlled pore diameters and controlled morphology. Mesoporous silica doped with various transition metal oxides (Zr, Ti and Fe) were studied for their ability to remove orthophosphate ions from waste water by adsorption. The materials were characterized by means of N2 physisorption, x-ray diffraction (XRD) [Table1]and transmission electron microscopy (TEM). d Spacing Surface (Å) area (m2/g) 81 87 85 80 83 88 85 83 85 85 587 667 694 718 610 683 660 630 717 660 Pore Volume (cm3/g) 0.20 0.11 0.13 0.15 0.08 0.16 0.18 0.11 0.12 0.18 Pore Diameter (Å) 60 48 54 64 42 62 63 44 52 63

Sample Un-doped silica Zr 20:1 Ratio 40:1 Ratio 80:1 Ratio Ti 20:1 Ratio 40:1 Ratio 80:1 Ratio Fe 20:1 Ratio 40:1 Ratio 80:1 Ratio

Adsorption was determined by Uv-Vis spectroscopy before and after extraction. The mesoporous materials demonstrated a high level of adsorption affinity for orthophosphate and up to 100% removal was observed. ENVR 29 Preparation of modified layered double hydroxide catalysts using electrocoagulation and its use for nitrate removal J. A. Gomes1, [email protected], S. Afrin3, I. Haider1, K. Das3, P. Bernazzani2, G. M. Irwin2, and D. Cocke3. 1Dan F. Smith Dept. of Chem. Engineering, Lamar University, Beaumont, TX, United States, 2Department of Chemistry and Physics, Lamar University, Beaumont, P.O. Box 10022, TX, United States, 3Gill Chair of Chemical Engineering, Lamar University, Beaumont, P.O. Box 10053, TX, United States Layered Double Hydroxides (LDHs), such as green rust (pyroaurite-type structure) and hydrotalcites (brucite-type), are a group of anion-exchangeable materials containing mixed metal hydroxides. They have relatively weak interlayer bonding compared to cationic clays resulting excellent ability to capture inorganic anionic contaminants, such as nitrates. With the increasing sources of nitrogen and nitrates from natural, agricultural, and man-made activities, nitrate contamination of groundwater is a common problem. Existing nitrate treatment processes such as distillation, reverse osmosis, and ion exchange, are expensive and have inherent disadvantages. In this study, we present results of our exploratory investigation on preparation of modified LDHs impregnated by transition metals, and their feasibility for catalytic removal of nitrate. The study also included the characterization of modified LDHs using XRD, FTIR, SEM, TG/DSC, and Mössbauer spectroscopy. The removal efficiency of nitrate as measured by ion selective electrode for some real water samples will also be presented. ENVR 30

Hydrothermal carbonization of animal wastes for carbon sequestration and energy generation J. R. V. Flora1, [email protected], K. S. Ro2, S. Bae3, and N. D. Berge1. 1 Department of Civil and Environmental Engineering, University of South Carolina, Columbia, SC, United States, 2Soil, Water & Plant Research Center, USDA-ARS Coastal Plains, Florence, SC, United States, 3Department of Chemistry and Energy and Environmental Studies Program, North Carolina A&T State University, Greensboro, NC, United States Hydrothermal carbonization of swine manure and poultry litter was conducted at 200 oC for 20 hours at a 4:1 water:feedstock ratio. Carbon content of the solid, liquid and gas-phases was measured to determine the mass of carbon sequestered within the biochar. Carbon mass recoveries ranged from 95-100%. Results indicate the solid phase retains the majority of the carbon (approximately 70% of the carbon), suggesting that HTC may be effective for biochar production and carbon sequestration. The final gas was composed primarily of CO2 with trace amounts of H2 and CH4 and accounted for approximately 2% of the initial carbon mass. The energy content of the carbonized swine solids was 22703 KJ/kg (feedstock is 17068 kJ/kg), while the energy content of carbonized poultry litter was 11729 kJ/kg (equivalent to feedstock). These results suggest HTC of animal wastes is a means to effectively sequester carbon, while producing a feedstock for subsequent energy generation. ENVR 31 Changes in physicochemical characteristics of biochars by hydrothermal and dry carbonization of swine solids and poultry litter S. Bae1, [email protected], K. S. Ro2, J. R. V. Flora3, J. Novak2, and N. D. Berge3. 1 Department of Chemistry and Energy and Environmental Systems Program, North Carolina A&T State University, Greensboro, NC, United States, 2Coastal Plains, Soil, Water & Plant Research Center, USDA-ARS, Florence, SC, United States, 3Department of Civil and Environmental Engineering, University of South Carolina, Columbia, SC, United States Biomass conversion from agricultural residues is an important resource for renewable energy production. Biochar, the carbonaceous materials derived from biomass conversion, has received a great attention due to its useful applications. Combination of feedstock and thermal processing conditions produces a distinctive physical and chemical property of biochar. In this study, two different carbonization processes were performed to investigate their impact on the composition, especially exhibited by functional groups. Various biochars were produced by the hydrothermal and dry carbonization techniques with swine solid and poultry litter. The effects of reaction temperature, the reaction time, and water content on changes in surface chemistry have been investigated. Hydrothermal carbonization was performed in a tubular reactor at different temperatures (200 oC, 250 oC) for different reaction times (4 hrs, 20 hrs). The

physicochemical characteristics of biochars have been investigated by FT-IR spectroscopy, an optical contact angle measuring system and 13C-NMR spectroscopy. ENVR 32 Biochars from agricultural residuals as adsorbents for environmental remediation I. M. Lima1, [email protected], K. S. Ro3, [email protected], A. A. Boateng2, [email protected], and K. T. Klasson1, [email protected] 1U.S. Department of Agriculture, Southern Regional Reseach Center, Agricultural Research Service, New Orleans, LA, United States, 2U.S. Department of Agriculture, Eastern Regional Research Center, Agricultural Research Service, Wyndmoor, PA, United States, 3U.S. Department of Agriculture, Coastal Plains Soil, Water, and Plant Research Center, Agricultural Research Service, Florence, SC, United States Water and air quality as well as public health impacts of agricultural residuals prompted the need for viable solutions for their conversion and reuse. Researchers with the Agriculture Research Service (ARS) of the USDA have been converting plant and animal residuals into biochars via slow pyrolysis. The biochars possess good adsorption properties, particularly with respect to the uptake of metal ions. These low surface area materials can be further activated and the resulting activated biochars also displayed good adsorption towards ammonia gas removal as well as increased porosity. Several chars were produced by slow pyrolysis under nitrogen at either 700°C or 800°C for 1 hour and their physical, chemical and adsorptive properties were determined and compared to coal based chars. Best performing chars were those made from broiler manure with an adsorption efficiency of 0.96 g/mmole of Cu2+ adsorbed. ENVR 33 Advanced solid-state NMR spectroscopy for investigating charcoal J. Mao1, [email protected], and K. Schmidt-Rohr2, [email protected] 1Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, United States, 2Department of Chemistry, Iowa State University, Ames, IA, United States The characteristics of biochar samples and aromatic rings in humic acids (HAs) were investigated in detail by advanced NMR techniques. They included direct polarization/magic angle spinning (DP/MAS), C-H recoupled dipolar dephasing, and two-dimensional 1H-13C heteronuclear correlation. The samples were two biochar samples and several soil HAs. Compared with cross polarization/magic angle spinning, DP/MAS gave quantitative structural information. In HAs, charcoal is distinguished from other aromatic rings, such as those of lignin, based on the chemical shift, fraction of nonprotonated C, and large average H-toC distance in the fused aromatic rings of charcoal. The aromatic cluster sizes in

these samples have been estimated from the fraction of aromatic carbons along the edge of clusters (bonded to H, O, or alkyl C) combined with analysis of the long-range C-H dephasing data. The average aromatic clusters in charcoal consist of fewer than 40 carbons and significantly less in the HAs. ENVR 34 Sorption of water by biochars D. W. Rutherford, [email protected], C. E. Rostad, and R. L. Wershaw. US Geological Survey, Denver, Colorado, United States Even though chars are frequently referred to as hydrophobic, several studies suggest that the presence of these pyrogenic materials in soils increases the soil's water holding capacity. Biochars were produced under controlled conditions (temperature and duration) in the laboratory from plant materials (wood and switchgrass) as well as purified biomass components (cellulose and lignin). Water uptake isotherms were measured by vapor sorption for these biochars. The water uptake isotherm was used to evaluate water uptake properties of each char, independent of the effects of particle size, state of soil aggregation, or mineral contributions. These isotherms showed that water uptake by biochar involved a combination of absorption and adsorption processes, which vary in the contribution to total uptake, based on the formation conditions of the chars. In most cases, the water uptake of the chars equaled or exceeded the water uptake of the uncharred parent material. ENVR 35 Greenhouse gas emission from soil amended with biochar made from hydrothermally carbonizing swine solids K. S. Ro1, [email protected], J. Novak1, S. Bae3, J. R. V. Flora2, and N. D. Berge2. 1USDA-ARS, Florence, South Carolina, United States, 2Department of Civil and Environmental Engineering, University of South Carolina, Columbia, SC, United States, 3Department of Chemistry and Energy Environ. Studies Program, North Carolina A&T State University, Greensboro, NC, United States Biochar made from hydrothermally carbonizing swine solids was mixed with a 50/50 mixture of Norfolk Ap and E horizon at a rate of 20 g kg-1. During the incubation period of 54 days, greenhouse gas (CO2 and N2O) emission fluxes were calculated by nonlinearly regressing time-series headspace gas concentrations measured by a photoacoustic multi-gas analyzer. Throughout the incubation period, the control soils did not produce any significant CO2 nor N2O fluxes. Biochar-amended soil, however, emitted CO2 fluxes as high as 7.1 g CO2 m-2d-1 in the beginning of incubation. Based on 13C-NMR spectra of the biochar, we speculate that the high CO2 fluxes were attributable to aliphatic compounds in the biochar. The biochar-amended soil produced a small N2O flux of 0.13 mg N2O m-2d-1 only on day 20 (2 days after leaching test). Similarly on that day,

control soils produced about 0.06 mg N2O m-2d-1, suggesting that anaerobic condition may be the driving force for N2O emission. These N2O fluxes are about two orders of magnitude smaller than that measured from Australian unfertilized soils. Addition of swine solid biochar dramatically increased soil CO2 emission; however, N2O emission was not significantly affected. ENVR 36 Biochar, manure, or sawdust additions to calcareous subsoils: Effects on nutrient availability and carbon storage R. D. Lentz, [email protected], and J. Ippolito. USDA-ARS-NWISRL, Kimberly, ID, United States Additions of organic materials to eroded calcareous soils have been suggested as a means of increasing nutrient availability to crops and a way to increase soil carbon storage. We hypothesized that the addition of biochar (hardwood derived, 73% C, 15% ash) would more beneficial on both fronts, due primarily to its more recalcitrant nature. A pot study compared the effect of four amendments, biochar, dairy manure, sawdust, and acidified sawdust, all applied at three rates of 0, 1, and 2% to a highly calcareous, silt loam subsoil. Treatment effects on soil total C and N, organic C, inorganic N, bicarbonate extractible (Olsen) P, and DTPAextractible Cu, Fe, Mn, Zn were measured and nutrient uptake by two bean varieties growing in the amended soils were determined. Leachate from treated soils was collected to evaluate nutrient losses. This report will discuss results from the first year of this long-term experiment. ENVR 37 Sorption of the antimicrobial sulfamethazine to biochar M. Teixido1,2,3, [email protected], J. J. Pignatello2,3, [email protected], and J. Peccia2, [email protected] 1Department of Química Analítica, Universitat de Barcelona, Barcelona, Barcelona, Spain, 2 Department of Chemical Engineering, Yale University, New Haven, Connecticut, United States, 3Department of Environmental Sciences, The Connecticut Agricultural Experiment Station, New Haven, Connecticut, United States Sulfonamides are among the most widely used veterinary antimicrobials. Due to the potential for transmitting antibiotic resistance, there is increasing concern regarding the land application of manure from sulfonamide medicated animals. Biochar, a product of emerging biomass pyrolysis technologies, has shown promise as an agricultural soil amendment. In view of the strong sorptive properties of black carbon, we hypothesized that biochars may enhance sorption of sulfonamides and reduce their bioavailability. Sorption experiments under controlled pH and ionic strength were conducted for sulfamethazine, 4-amino-N(4,6-dimethylpyrimidin-2-yl)benzenesulfonamide, on different well-characterized biochars. The biochar distribution coefficient KBC was strongly pH-dependent, but

did not vary much over the pH range typical of most soils. The neutral form sorbs more strongly than the cationic and anionic forms. Depending on biochar, the KBC (neutral form) varied by about five orders of magnitude, and was as much as 103 times greater than KOC values reported for humic acid. ENVR 38 Survey of the chemical properties of a suite of biochars J. E. Amonette1, [email protected], Y. Hu1, N. J. Schlekewey1, D. R. Humphrys1, S. S. Dai1, Z. W. Shaff1, C. K. Russell1, S. D. Burton2, J. Z. Hu2, and B. W. Arey2. 1Division of Fundamental and Computational Sciences, Pacific Northwest National Laboratory, Richland, WA, United States, 2Environmental and Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, United States We collected fifteen biochars representing a wide range of feedstocks and pyrolysis conditions and analyzed them for their chemical properties. The biochars included one prepared by a hydrothermal process, four prepared by slow pyrolysis, five prepared by fast pyrolysis, and five prepared by a gasification process. Heat treatment temperatures (HTT) ranged from 180° C for the hydrothermal biochar to about 475-500° C for the slow- and fast-pyrolysis biochars and 600-900° C for the gasifier biochars. Feedstocks included glucose, pine, maple, and oak wood, pine bark, wheat straw, corn cob, corn stover, and switchgrass. Significant differences in bulk elemental composition, functionalgroup chemistry, and surface-chemical properties were measured. Correlation with process and feedstock suggests that the dominant factor controlling biochar chemical properties is the process (HTT and residence time); the feedstock contributes to a lesser extent. Matching biochar and soil chemical properties is recommended before soil application; post-process modifications may be needed in some instances. ENVR 39 Water extracts of biochars: Effects of formation conditions on pH and dissolved organic carbon C. E. Rostad, [email protected], D. W. Rutherford, and R. L. Wershaw. Branch of Regional Research, US Geological Survey, Denver, Colorado, United States Application of biochar to soil has been proposed as a long-term sink for atmospheric carbon while improving soil fertility and increasing crop production. However, the effect of adding large amounts of biochar to soil on nearby surface waters is unknown. We have found that formation conditions have a substantial effect on surface area, acid functional groups, and water sorption of the resulting char, independent of source material. As an indication of the effects of largescale biochar incorporation into agricultural soils to surface waters downstream

(without soil interaction), chars from cellulose, lignin, pine, and switchgrass from various formation conditions were extracted with water. Dissolved organic carbon of the water extract from chars decreased rapidly with longer charring times and greater charring temperature. As dissolved organic carbon decreased, the dissolved inorganic carbon, from carbonates or oxides, increased. The pH of the water extracts varied from 3 to 10. The range of heating times and temperatures produce very complex changes in biochar, and have dramatic effects on water extracts from the biochar as well. ENVR 40 Do flame retardants save lives? How peer-reviewed science can impact regulatory decision-making A. Blum1,2, [email protected] 1Department of Chemistry, University of California, Berkeley, Berkeley, CA, United States, 2Green Science Policy Institute, Berkeley, CA, United States Scientific papers about health and environmental impacts of flame retardant chemicals often state, "Fire retardant chemicals save lives," but this is not well documented. Reducing sources of ignition is more effective in preventing fires than adding potentially toxic chemicals to consumer products. The over 50% decrease in fire deaths nationwide since 1980 has been explained by a similar decrease in smoking, improved fire safety codes, and increased use of smoke detectors and sprinklers. The introduction of fire safe candles and cigarettes should bring further reductions in fire deaths. Chemical industry proposals to expand the usage of fire retardant chemicals in consumer products failed recently after peer-reviewed scientific information was brought into regulatory decision-making: This presentation discusses the origins of fire safety standards, how they influence the use of chemicals, and how green chemistry research and alternative strategies and technologies can increase fire safety and reduce potential toxicity and environmental harm. ENVR 41 Toward sustainable use of organohalogens R. U. Halden, [email protected] School of Sustainable Engineering and the Built Environment, The Biodesign Institute at Arizona State University, Tempe, AZ, United States Halogenated organic compounds (organohalogens) are key ingredients in a variety of commercial products including agrochemicals, paints, solvents, surfactants, textiles, pharmaceuticals and personal care products. With increasing halogen content, organic compounds become more durable and inert but also more environmentally persistent and toxic. This literature review showcases the importance of organohalogens for modern society and explores

regulatory mechanisms aimed at striking a balance between the benefits and risks of this widely used group of organic compounds. ENVR 42 Fate and transport of triclocarban and triclosan in biosolid processes and soils amended with biosolids T. A. Ogunyoku, [email protected], B. D. Giudice, and T. M. Young. Department of Civil and Environmental Engineering, University of California, Davis, Davis, CA, United States Triclocarban (TCC) and triclosan (TCS) are antimicrobial active ingredients found in common household and personal care products. TCC and TCS end up in wastewater treatment plants (WWTPs) after consumer use, and are found in sludge after primary and secondary treatment. One objective of this study was to asses the degree of treatment of TCC and TCS for different biosolid processing systems. Sludge and biosolid (i.e. treated sludge) samples were collected from nine anonymous California WWTPs. Biosolids are commonly land-applied as a form of beneficial reuse of the organic matter as fertilizer. Another objective of this study was to qualitatively and quantitatively demonstrate whether or not these chemicals are mobilized via runoff. Several microplots containing soil were amended with biosolids at typical agricultural rates and subjected to successive simulated rainfall events. Runoff from the plots was collected. All samples were extracted and analyzed by liquid chromatography electrospray ionization mass spectrometry. ENVR 43 Is biodegradability a desirable attribute in material design? M. A. Barlaz, [email protected] Civil, Construction, and Environmental Engineering, North Carolina State University, Raleigh, NC, United States End-of-life material management can be an important component of the environmental performance of a material or consumer product. While composting is a viable alternative for biodegradable materials, only limited types of products are typically collected for composting. The majority of municipal waste in the U.S. is buried in landfills, where the desirability of biodegradability is less certain. Anaerobic biodegradation in landfills leads to methane production. While methane is recovered for beneficial use at about 500 U.S. landfills, the carbon footprint of a material in a landfill will be governed by its decay rate, the methane collection efficiency and the fraction of the organic carbon that is converted to biogas. The issue is further complicated by the range of landfill performance with respect to gas collection in the U.S. and globally. This presentation will quantitatively address the carbon footprint for a hypothetical biodegradable material during the disposal phase.

ENVR 44 Quarternary ammonium compounds (QACs): When are greener surfactants always less persistent? B. Brownawell, [email protected], X. Li, and P. A. Lara-Martin. School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, NY, United States QACs are an important class of cationic surfactants. However, many are superhydrophobic cation exchangers, and strong particle sorption limits bioavailability and biodegradation in the environment. As a result, QACs are among the most prevalent contaminants in sewage sludges, biosolids and sediments. Lack of degradation of fabric softener ingredient ditallowdimethylammonium compounds (DTDMAC) led to their phase-out in Europe and replacement with highly biodegradable esterquats. Esterquats are a successful example of structural modifications designed to impart biodegradability to molecules with similar function. On the other hand, vegetablebased oleophilic feedstocks have become increasingly relied upon in recent years. Unfortunately, for some QACs, these "greener" replacements are still very persistent in sewage sludges and sediments. For example, there has been some replacement of C16-18 alkyl-chain enriched DTDMAC with environmentally persistent palm- and coco-based dialkyldimethyl ammoniums enriched with C1214 alkyl chains. There has been some replacement of relatively biodegradable alkyltrimethylammonium compounds with C14-C18 alkyl chain lengths (e.g., cetrimonium and stearalkonium) with much less biodegradable behentrimonium (C20-22) derived from rapeseed oil. Behentrimonium has been found to be one of the most abundant wastewater contaminants in the environment. It is argued that some surfactant replacements with "greener" vegetable feedstocks ignore simple chemical design considerations and rely on flawed biodegradability screening tests, both resulting in unintended environmental exposures. ENVR 45 Who is responsible for MTBE contamination in Indiana and do state restrictions work? R. D. Barreto, [email protected] Department of Biology and Chemistry, Purdue University North Central, Westville, IN, United States MTBE has become a common groundwater contaminant, even in areas where reformulated gasoline (RFG) was not used. In the Midwest (IN, MI, IL), where the reformulating agent of choice is ethanol, previous work has shown that MTBE was present in 60-80% of the gasoline sold, resulting in numerous cases of groundwater contamination. To address these concerns, the Indiana State legislature adopted a partial ban on the use of MTBE. This ban, effective July 23, 2004, limits the amount of MTBE in gasoline to 0.5% by volume (less than 5000 ppm). To test the effectiveness of this ban, gasoline samples were collected from

sites throughout Indiana immediately prior to and after the initiation date and one year after initiation. The results showed that MTBE concentrations did fall below the 0.5% level mandated. (In 2000, 11.5% exceeded this level.) Yet, more than 50% of the gasoline still contained MTBE levels of greater than 100 ppm. MTBE concentration remained essentially constant immediately prior to and after the ban and remained so one year after its implementation, with levels kept just below those required. The petroleum industry has far greater control on the "residual" amounts of MTBE present in gasoline than was previously thought. This control is easily exercised when the industry is legally compelled. The petroleum industry should have exercised this control and restricted or removed MTBE from the gasoline in states where it was not used as a reformulating agent and could have done so at any point in the past. They are therefore responsible for groundwater contamination by MTBE in areas where MTBE is not mandated or used. MTBE still remained a threat to ground water throughout Indiana. In the five years since the ban went into effect, MTBE appeared as contaminant in 1225% of groundwater contamination sites. ENVR 46 Persistent organic pollutants in building insulation: A dilemma for sustainability A. Madonik, [email protected] Green Science Policy Institute, Berkeley, CA, United States Green builders seek to improve energy efficiency using high R-value insulation, and adding insulation to existing buildings can reduce energy consumption as well. Polystyrene and rigid polyurethane are lightweight, high R-value insulation materials, but they are easily ignited, and code requirements effectively mandate the use of flame retardants (FRs) in their formulation. All polystyrene insulation contains approximately 1% by weight hexabromocyclododecane (HBCD), currently one of the highest priority persistent organic pollutants (POPs) targeted for regulation in Europe. Rigid polyisocyanurate foam can meet flammability requirements without added FRs, but all spray-on polyurethane formulations contain FRs, often including both brominated and chlorinated organics at levels typically exceeding 10% of the foam weight. These FRs are generally not chemically bound to the foam and have become pervasive POPs. This paper compares the toxicity and performance of petroleum-based foams with that of other insulation products derived from renewable or inherently non-flammable materials. ENVR 47 Development of a simple sustainability index for the chemical industry M. L. Cohen, [email protected] Cytec Industries Inc., Stamford, Connecticut, United States

A number of methodologies for providing quantification of sustainability for chemical processes have been developed over the last decade. None seem to have gained broad adoption, however, perhaps due to complexity and/or lack of availably of required information. In the current absence of full life cycle data for the bulk of raw materials used in the chemical industry, we propose a scoring system based on readily available information. Using this we present a straightforward set of metrics, based on the Twelve Principles of Green Chemistry, that may be used to develop a sustainability index for production of a given chemical product. ENVR 48 Green chemistry policy: A comparison of China, India, and the United States K. Matus, [email protected] Center for Green Chemistry and Green Engineering, Yale University, New Haven, CT, United States What is the role of policy in promoting green chemistry? What are some of the different models that have been used, and how effective have they been? This presentation will explore the different policy approaches that have been developed in the United States (at the state and national level), China and India. One important conclusion is that strategies for success vary greatly according to the industrial and institutional contexts of each country. In each country, there have been unique barriers to green chemistry. However, despite the very different situations in these three countries, there are also barriers, as well as potential policy approaches, that are held in common. Policy issues that need to be addressed include education and training, instigating collaborative arrangements between government, industry and academia for both research and implementation, and a greater understanding of the impact of other environmental and economic policies on green chemistry. ENVR 49 Possible d/d enhancement reaction rates by using 0.5 to 1 keV deuterons on metallic lattices J. Dufour, [email protected] Department of Nuclear Sciences, CNAM, Paris, Ile de France, France Recently, experimental observations were made, showing an enhancement of d/d reaction rates, for energies of the deuteron between 3000 and 10000 eV on the one hand [1] and at very low energy of the deuteron on the other hand [2]. For both experiments, this enhancement was ascribed to the screening effect of the electrons of the metallic lattice where the reactions take place. In [3], it was suggested that a coupling between the deuterons in the target with the incident deuterons could explain this enhancement (fusion reactions taking place between the deuterons already trapped in the target). This possible effect was

evaluated and a potentially interesting window for the energy of the incident deuterons was identified (0.5 to 1 keV). A prototype has been built to generate deuterons in the required window. It will be described and the first results will be presented. Some indications will be given on the (existing) means to upscale the process in case of success with the prototype. References: [1] A. Huke et al. Enhancement of deuterons fusion reactions in metals and experimental implications. Physical Review C, 78:015803, 2008. [2] P.A Mossier Boss et al. Use of CR-39 in Pd/D co-deposition experiments. Eur. Phys. J.appli. Phys. 40, 293-303 (2007). [3] J. Dufour. Possible existence of an attractive Yukawa type of potential and consequences on the understanding of alpha disintegration constants and d/d reactions at low energy of the deuteron. Submitted 18-02-2009 to Physical Review C. J. Dufour Laboratoire des Sciences Nucléaires CNAM, 2 rue Conté 75003 Paris France ENVR 50 Light water electrolysis with pulsed current between two cathode connections: Search for excess heat W. Williams1, [email protected], and R. Godes2. 1Department of Electrical Engineering, University of California at Berkeley, Berkeley, CA, United States, 2 Brillouin Energy Corp., Berkeley, CA, United States Sodium hydroxide solution is electrolyzed between nickel wire cathode and anode, and evolved gases recombined to water within the cell. Cathode wire ends are connected to a high-current alternating pulse generator. A control cell, operated simultaneously, has ohmic heater in place of electrolysis. Temperatures are compared to detect excess heat. ENVR 51 Does gas loading produce anomalous heat? D. A. Kidwell1, [email protected], D. L. Knies2, and K. S. Grabowski2. 1 Chemistry Division, Naval Research Laboratory, Washington, DC, United States, 2Materials Science and Technology Division, Naval Research Laboratory, Washington, DC, United States Pressurization of nanosized palladium with deuterium appears to be a simpler and more rapid method to generate anomalous heat compared to electrolytic systems. In hundreds of reactions, we have routinely prepared palladium nanoparticles inside an aluminosilicate matrix and have found that these systems produce up to 8 fold more heat with deuterium compared to hydrogen. Furthermore, a characteristic signature of a pressurization reaction is its reversibility - the heat released upon pressurization should be absorbed upon

evacuation. This reversibility is observed with hydrogen but not deuterium where heat in > heat out. Although we are still seeking conventional explanations for this excess heat, it does not appear to be explained by impurities in the deuterium gas nor other simple chemical or physical sources. The selection and preparation of the particles, the experimental set-up, and results will be discussed. ENVR 52 Chemical and electrochemical studies of co-deposition systems in H2O and D2O M. H. Miles, [email protected] Dixie State College, St. George, UT, United States Experimental studies including cyclic voltammetry (CVA) and electrochemical impedance spectroscopy (EIS) were performed on several co-deposition systems. The palladium deposited onto a copper substrate for both the PdCl2 + LiCl and the PdCl2 + NH4Cl + NH4OH solutions produced high capacitance values (100 Farads per gram of Pd) equal to those of supercapitor materials. These high capacitance values for the deposited palladium produced a collapsing and tilting of the cyclic voltammograms that approached Ohm's Law behavior. This behavior is predicted for large capacitance electrodes when using faster voltage scans. The main focus in these experiments was on the 0.025 M PdCl2 + 0.15 M NH4Cl + 0.15 M NH4OH system because the deuterium analog produced excess power in three out of three prior experiments. Each Pd++ ion deposited is replaced by two H+ ions to maintain electroneutrality, and the electrolysis gases (H2, O2) drive off the NH3, thus large pH changes occur (pH = 8.87 to pH = 1.25). Chlorine evolution and the formation of nitrogen trichloride (NCl3) occur under acidic conditions, but this unwanted chemistry can be avoided by the simple addition of LiOH following the co-deposition step. Calorimetric results giving large excess heat effects were found for the deuterated codeposition systems. ENVR 53 Measurements of excess power effects in Pd/D2O systems using a new isoperibolic calorimeter M. H. Miles1, [email protected], and M. Fleischmann2, [email protected] 1 Dixie State College, St. George, UT, United States, 2Chemistry, University of Southampton, Southampton, United Kingdom Relative inexpensive isoperibolic calorimeters have been designed and constructed with the goal of obtaining a constant heat transfer coefficient that is insensitive to normal changes in the electrolyte level. The first four prototypes were constructed from copper tubing and used different insulating materials. The outer copper cylinder has a 5.1 cm (2.0 inch) diameter and a 28 cm length. The

inner copper cylinder (3.2 cm x 20 cm) is completely separated from the outer cylinder by the insulating material. The glass electrochemical cell (2.5 cm x 20 cm) positioned inside the inner copper cylinder contains 50 mL of electrolyte and has two thermistors positioned on opposite sides of the outer wall of the glass cell. Thermal contact between the glass cell and the inner copper tube is provided by Mobil 1 (5W-30W) motor oil (50 mL) as a heat conducting fluid. This calorimetric design provides for high cell operating temperatures. The heat transfer coefficient (kC) for Cell B is 0.1334 W/K, the heat capacity (CpM) is 456 J/K and the time constant is 40 minutes. Measurements of excess power effects using this new calorimeter will be reported. Financial help is acknowledged by M.H.M. from an anonymous fund at the Denver Foundation via Dixie State College. ENVR 54 Heat and radiation generation during hydrogenation of CH compound T. Mizuno, [email protected] Hydrogen Engineering Application and Development Company, Sapporo, Japan Securing new sources of energy has become a major concern, because fossil fuels are expected to be depleted within several decades. In some of the major wars of the 20th century, control of oil was either a proximate cause or a decisive factor in the outcome. Especially in Japan and Germany, a great deal of research was devoted to making liquid fuels from coal. In one such experiment, a large amount of excess heat was observed. The present study was devoted to replicating and controlling that excess heat effect. The reactant is phenanthrene, a heavy oil fraction, which is subjected to high pressure and high heat in the presence of a metal catalyst. This results in the production of excess heat and strong penetrating electromagnetic radiation. After the reaction, an analysis of residual gas reveals a variety of hydrocarbons, but it seems unlikely that these products can explain the excess heat. Most of them form endothermically, and furthermore heat production reached 60 W. Overall heat production exceeded any conceivable chemical reaction by two orders of magnitude. ENVR 55 Hybrid, high temperature CMNS reactor: Progress report of experiments performed at INFN-LNF (Italy) F. Celani1, [email protected], P. Marini2, V. di Stefano2, V. di Stefano2, M. Nakamura2, O. M. Calamai2, A. Spallone1, E. Purchi2, V. Andreassi1, B. Ortenzi1, E. Righi1, G. Trenta1, G. Cappuccio1, D. Hampai1, F. Piastra1, and A. Nuvoli1. 1Laboratori Nazionali di Frascati, (1) Istituto Nazionale di Fisica Nucleare, Frascati (Rome)-, Italy, 2ISCMNS_Group, International Society of Condensed Matter Nuclear Science, Rome, Italy

Since ICCF14 Conference (2008), our Group presented experimental data on procedures to generate anomalous excess power (up to 5W) at high temperature (400- 500° C). The device was based on innovative hybrid system: long (65 cm) and thin (F=50 mm) Pd wire was multi-coated by a "mixture" of nanomaterials (including Pd) and applied large electromigration currents (to 45000 A/cm2). Such Pd nano-coated wire was inserted into a SS chamber (walls at 30° C) and applied: pressurized Deuterium gas (to 8 bar), high temperature (to 500° C, due to electromigration). A similar Pt wire, used as blank, was put in close contact with the Pd wire and both electrically insulated by fibre-glass sheaths. No anomalous effects were found using 4He gas. In order to further improve, and increase, the anomalous excess power (and, overall, transfer the anomalous high temperature from the Pd wire to the SS wall) was build a compact new reactor. Several deleterious problems arose because S emission from the SS wall: S poisoned the catalytic proprieties of nanocoated wire. Now is under test a new SS reactor with internal walls covered by a further Cu (3N) tube. In principle, such improved new reactor can operate up to: 800° C, 50 bar. We will report the latest experimental results. ENVR 56 Improvement of thermal irradiation by nanocoating of thin wires F. Celani1, [email protected], P. Marini2, V. di Stefano2, M. Nakamura2, O. M. Calamai1, A. Spallone1, E. Purchi2, V. Andreassi1, B. Ortenzi1, E. Righi1, G. Trenta1, G. Cappuccio1, D. Hampai1, F. Piastra1, and A. Nuvoli1. 1Laboratori Nazionali di Frascati, Istituto Nazionale di Fisica Nucleare, Frascati, Rome, Italy, 2 ISCMNS_Group, International Society of Condensed Matter Nuclear Science, Rome, Italy During experiments on CMNS (ICCF14 Conference, 2008), we observed that the apparent self-temperature (by Joule heating) of a long (l=65cm) and thin (F=50mm) Pd wire with the surface slightly nano-coated (under 4He gas), was lower than a similar one of Pt with regular surface. A second Pt wire, close to the Pd or Pt, was used as an independent test of the temperatures. In order to elucidate the phenomenon, we built a dedicated apparatus: to maximize the effect, the reaction chamber was kept under mild vacuum (10-4Atm) and a second wire, of Pt, was kept close to the Pd under test in order to cross-check the results. Experiments were made, without opening the reactor, with "virgin" Pd wire with surface oxidized à virgin à after H2 absorption and proper degassing of virgin wire. The results showed that the surface modified wires have a temperature as low as 90° C (specially that after H2 treatments), in the temperature range of 400-600° C, in respect to the virgin one. A more sophisticated apparatus is under construction and we will test also the nanocoated Pd wires. Such effects can be applied in devices that need large heat dissipation under vacuum conditions (like satellites). The phenomenon was predicted by Max Plank but never observed at macroscopic levels.

ENVR 57 Material characterization of Pd foils employed in calorimetric electrochemical experiments F. Sarto, [email protected], E. Castagna, S. Lecci, and V. Violante. ENEA, Frascati, Rome, Italy A research activity has been carried out during the last years, focused on the investigation of the effect of the metallurgy and surface characteristics of the Pd cathodes on the reproducibility of excess heat production in electrochemical experiments. A systematic approach has been followed in the characterization of the material status of the Pd foils used as cathodes, resulting in the development of a database including all the information collected for each sample. The employed characterization techniques included scanning electron microscopy, energy dispersive x ray micro-analysis, secondary ion mass spectroscopy, atomic force microscopy, electron backscatter diffraction spectroscopy, atomic force microscopy, light scattering, nano-indentation. A critical analysis of the experimental results will be presented, aimed to identify correlations of the investigated properties with the excess heat reproducibility and to outline the limits and potentialities of the characterization techniques. ENVR 58 Role of surface properties in the electromagnetic field interaction with the Pd/electrolyte interface F. Sarto, [email protected], E. Castagna, S. Lecci, and V. Violante. ENEA, Frascati, Rome, Italy The evolution of the electromagnetic field at the Pd cathode/electrolyte interface during hydrogen (deuterium) loading is a complex mechanism that involves the modifications of the surface properties of the metallic electrode. In particular, the variation of the dielectric constant of the metal due to hydrogen (deuterium) permeation and charge polarization and the roughening of the surface morphology can affect the electromagnetic field spatial distribution in the region close to the metal/electrolyte interface. A tentative model to describe such effects will be presented, with the aim to get a qualitative estimate of the relevance of these mechanisms to the excess heat production, and to give insight into the experimentally observed correlations between excess heat occurrence and cathode surface properties. ENVR 59 Impact of an applied magnetic field on a high electrical impedance LANR device M. Swartz, [email protected] JET Energy Inc., United States

We report on the solution electrical conductance of a lattice assisted nuclear reaction device in a static magnetic field. Dual anode PhusonÒ - type Pd/D2OPd(OH)2/Au (DAP) LANR devices were driven at their optimal operating point. Two current sources drove the loading and the 4 terminal electrical conductance examination of the loading PdDx cathode. The applied magnetic field intensity was ­0.1 Tesla. The magnetic field decreased the solution electrical conductance of the operational DAP LANR system from 196.5 to 166.5 microsiemens (15.2 % decrease). The decrease was greatest for lower electrical driving current (1ma vs. 10 mA input current yielded 13.1+(-2.9)% vs 7.87+(-7.4)% incremental conductance decrease). The decrease was greatest when the applied magnetic field was parallel to the driving electrical field intensity (parallel vs perpendicular 15.2% vs 0-9.8%). A larger impact resulted from increasing applied current (1 to 10 mA) which yielded a 76 % increase in solution electrical conductance, irrespective of any applied H-field. ENVR 60 Anomalous heat evolution in charging of Pd nano-powders with hydrogen isotopes A. Kitamura1, [email protected], Y. Sasaki1, Y. Miyoshi1, A. Taniike1, A. Takahashi2, R. Seto2, and Y. Fujita2. 1Division of Marine Engineering, Kobe University, Graduate School of Maritime Sciences, Kobe, Japan, 2 Technova Inc., Tokyo, Japan Using a revised twin system capable of calorimetry for Arata-Zhang-type gas loading experiments, we have found that hydrogen isotope gas charging of Pd nano-powders can produce anomalously large energy, and that the effect is a strong function of the particle size [Phys. Lett. A, 373 (2009) 3109­3112]. The 10-nmø nano-composite of Pd·ZrO2 produced energy of 2.4±0.2 (1.8±0.4) eV/D(H)-atom, as well as large loading ratio of D(H)/Pd = 1.1 ± 0.0 (1.1 ± 0.3), respectively. These values are significantly larger than those of 0.1-ø Pd powders, 0.26 (0.20) eV/D(H)-atom with D(H)/Pd = 0.44 (0.44), and those of Pdblack, 0.66 (0.62) eV/D(H)-atom with D(H)/Pd = 0.84 (0.79). Multilateral diagnostics for the sample are performed to clarify the underlying physics; in situ monitoring of neutron and gamma-ray, a Si surface-barrier detector (SSBD) or an ion-implanted Si detector (IISD) for charged particles, an imaging plate (IP) for sample radioactivity, PIXE for elemental analysis, and QMS for 4He detection. ENVR 61 Sulfonated pentablock copolymers for water permeable dense membranes J. E. Flood, [email protected], C. L. Willis, D. A. DuBois, R. C. Bening, and B. Krutzer. Kraton Innovation Center, Houston, Kraton Polymers, LLC, Houston, TX, United States

In the past year, several papers have been published on sulfonated pentablock copolymers from Kraton Polymers. Very high water transport rates and good salt rejection were reported, indicating that these new polymers could be useful for water purification. The present paper will expand on the previous work and report on the effect of relative humidity and temperature on water transport rates, and how blends of different ion exchange capacity (IEC) polymers perform. In addition, preliminary studies indicate that these polymer offer good chemical resistance to chlorine, and strong bases and acids. ENVR 62 Elimination of phenyl-urea herbicides in water matrices by combined chemical oxidation-membrane filtration treatments F. J. Benitez, [email protected], J. L. Acero, [email protected], F. J. Real, [email protected], and C. Garcia, [email protected] Chemical Engineering Dept., University of Extremadura, Badajoz, Spain Phenyl-urea herbicides are largely found in surface waters and wastewaters as a consequence of their extensive use in agriculture today. Due to their pollutant power, the removal of phenyl-ureas constitutes a prioriry objective in water treatment technologies. Four selected phenyl-ureas herbicides (linuron, diuron, chlortoluron and isoproturon), dissolved in two water matrices (a groundwater and and a reservoir water), were subjected to sequential combinations of chemical treatments and membrane filtration processes. Two specific sequences were conducted: firstly, a chemical oxidation stage (where UV radiation, ozone and ozone plus hydrogen peroxide were used) followed by a nanofiltration process; and secondly, a membrane filtration stage (by using UF and NF membranes) followed by an ozonation stage.Values for the herbicide removals in the oxidation stages and for the rejection coefficients in the filtration stages are provided, and the partial contribution of the different stages is established for each combined treatment. High values (over 80%) were reached for the global phenyl-ureas elimination by most of the combined processes tested. Specifically, the sequence constituted by a NF stage followed by the ozonation of the permeate stream was the most effective, and produced an effluent of a higher quality than any other treatment. ENVR 63 Leveraging a global source of agroindustrial wastewater: Water reuse and energy production from cassava waste using hybrid adsorption anaerobic membrane bioreactors M. L. Somers1,2, [email protected], and L. Schideman1,2. 1Department of Agricultural and Biological Engineering, University of Illinois at UrbanaChampaign, Urbana, Illinois, United States, 2Center of Advanced Materials for the Purification of Water with Systems, Urbana, Illinois, United States

Cassava, Manihot esculenta Crantz, is a staple food for over 700 million people in tropical countries across the globe. Processing of the tuber requires large volumes of water, yielding wastewater high in organics and cyanide. The wastewater is often released without treatment, causing pollution of water bodies to the detriment of human health and aquatic habitats. Energy production through aneorobic processsing can act as a useful incentive for treatment. However, cyanotoxicity of the wastewater is an impediment for production of energy through methanogenesis. This study focuses on the efforts to use hybrid adsorption anaerobic membrane bioreactors (AnMBRs) to attenuate cyanotoxicity and hence, open a pathway to treat water while producing energy. Addition of a sorbent to the AnMBR is investigated for effectiveness in moderating variable cyanide concentrations in the influent and decreasing cyanide levels in the final effluent. The extent of in-situ sorbent regeneration is also elucidated. ENVR 64 Treatment of brackish water reverse osmosis (BWRO) concentrates: Ionic separation performance of electrodialysis W. S. Walker, [email protected], Y. Kim, and D. F. Lawler. Department of Civil, Architectural and Environmental Engineering, University of Texas, Austin, TX, United States The objective of this research was to evaluate electrodialysis (ED) for treating RO desalination concentrate waste to increase water recovery and decrease the volume requiring disposal. Experiments involved synthetic supersaturated RO wastes (7-18 g/L TDS) representing waters from Arizona, Texas, and Florida in a laboratory batch-recycle ED system that was monitored continuously for flow, pressure, conductivity, temperature, and pH and intermittently for anion (ion chromatography) and cation (ICP) concentrations. The solutions were separated successfully at 50% single-stage ED recovery with TDS removal up to 99.5%. The rate limitation on ED performance was proportional to the square root of the bulk velocity (1-5 cm/s). The specific energy consumption (kW/m3) of ED treatment was proportional to the applied voltage (0.7-1.8 volts/cell-pair). The separation rates for individual ions vary with voltage and velocity. ED treatment of RO concentrate waste was found to be technically feasible and (especially in zero-liquid discharge scenarios) economically reasonable. ENVR 65 Water and ion transport of NexarTM: A novel sulfonated pentablock copolymer membrane for desalination applications G. M. Geise, [email protected], B. D. Freeman, and D. R. Paul. Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas, United States

One approach to increasing the sustainability of desalination is to decrease the energy requirement by developing high flux membranes. NexarTM is a sulfonated styrenic pentablock copolymer that has been shown to have high water permeability. The block copolymer architecture allows for preparation of a membrane with high levels of sulfonation and favorable mechanical properties. Transport properties of NexarTM can be tailored by varying the hydrophobic character of the material by adjusting the molecular weights of the blocks of the copolymer. Also, transport properties can be tailored by varying the hydrophilic character of the material by adjusting the degree of sulfonation. The highly charged nature of sulfonated polymers results in unique ion sorption and transport behavior. Understanding ion sorption and transport in these materials is critical to the development of highly selective membrane materials. Favorable permeability selectivity can be achieved by tuning the hydrophobic character and hydrophilic character of the material. ENVR 66 Thin film nanocomposite membranes with seawater reverse osmosis performance M. L. Lind, [email protected], and E. M. V. Hoek. Civil & Environmental Engineering, University of California Los Angeles, Los Angeles, CA, United States Previously, we have explored the role of support membrane material, interfacial polymerization conditions, and post-formation treatment processes on polyamide thin film composite RO membrane properties.1 Also, we demonstrated zeolitepolyamide nanocomposite thin films had dramatically improved permeability and interfacial properties when compared to similarly formed pure polyamide brackish water reverse osmosis (RO) membranes.2,3 More recently, we are exploring methods for fabricating nanocomposite thin films with seawater RO separation performance. We will discuss the role that various interfacial polymerization posttreatment processes play in the performance and properties of nanocomposite seawater RO membranes. We show that a complex interplay exists between nanocomposite formation conditions and resulting membrane properties and performance. We will discuss the unique mechanisms of water and salt transport through nanocomposite RO membranes through our interpretation of characterization results including water and solute transport as well as thin film pore structure, chemistry, and morphology. 1. doi:10.1016/j.memsci.2007.11.038 2. doi:10.1016/j.memsci.2007.02.025 3. doi: 10.1557/jmr.2009.0189 ENVR 67

Engineering osmosis for sustainable desalination: A high recovery and affordable alternative to reverse osmosis J. R. McCutcheon, [email protected] Chemical, Materials, and Biomolecular Engineering, University of Connecticut, Storrs, Connecticut, United States Engineered osmosis (EO) is a platform technology for capturing waste heat and monetizing it in high-value resources. EO technologies work by harnessing the osmotic potential energy (salinity gradient) between a dilute feed solution and a highly concentrated draw solution. The natural tendency of fluids to flow from low solute concentration to high solute concentration (osmosis) drives pure water across a selective membrane barrier into the concentrated draw solution. In water and separation applications (ie. forward osmosis), the membrane prevents the passage of contaminants and salts and has been considered a high recovery desalination alternative to reverse osmosis. One particular technology, known as the ammonia-carbon dioxide forward osmosis desalination process, employs a regenerable draw solution consisting entirely of ammonia-carbon dioxide salts. These salts generate large osmotic pressures and enable high productivity and recovery desalination. Appropriate membrane design is the last technical challenge preventing EO from further development. ENVR 68 Reverse draw solute flux in forward osmosis modules: Modeling and experiments W. Phillip, [email protected], J. S. Yong, [email protected], and M. Elimelech, [email protected] Department of Chemical Engineering, Yale University, New Haven, CT, United States Forward osmosis (FO) is a membrane technology which is increasingly being studied after recent reports have demonstrated its potential use for sea and brackish water desalination, wastewater reclamation, and energy generation. These reports have also identified shortcomings which must be overcome before the technology is widely adopted. One of these drawbacks, which is the focus of this paper, is the reverse permeation of draw solutes. The high concentration of draw solutions used in FO results in some of the dissolved solutes permeating the membrane into the feed solution. Minimizing this reverse permeation is crucial for the efficient operation of FO systems. A model describing the reverse permeation of both electrolytes and non-electrolytes is developed, and then experimentally tested. This model serves as a basis for FO process design. ENVR 69 Inorganic draw solutions for forward osmosis processes A. Achilli1, [email protected], T. Y. Cath2, and A. E. Childress1. 1Department of Civil and Environmental Engineering, University of Nevada, Reno, Reno, NV,

United States, 2Division of Environmental Science and Engineering, Colorado School of Mines, Golden, CO, United States Forward osmosis (FO) processes use a hypertonic draw solution to induce mass transport of a solvent (i.e., water) through a selectively permeable membrane. In this investigation, a protocol for the selection of optimal draw solutions was developed and used to determine the most appropriate draw solutions for treatment of impaired water sources. More than 500 inorganic compounds were screened as draw solute candidates by taking into consideration water solubility, phase, hazard, osmotic pressure, and cost. The screening process resulted in 14 draw solutions suitable for FO applications. They were then tested in the laboratory to evaluate water flux and reverse salt diffusion through the FO membrane. Reverse osmosis (RO) reconcentration and rejection were evaluated using RO system design software. Analysis of experimental data and model results found a small group of appropriate draw solutes for FO processes with currently available FO membranes; the most suitable draw solution for a specific application will depend on feed solution composition and operating conditions. ENVR 70 Self-assembly synthesis and functionalization of mesoporous carbon materials for separation applications S. Dai, [email protected] Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, United States Porous carbon materials are ubiquitous in separation, catalysis, and energy storage/conversion. Well-defined mesoporous carbon materials are essential for a number of the aforementioned applications. Ordered porous carbon materials have previously been synthesized using colloidal crystals and presynthesized mesoporous silicas as hard templates. The mesostructures of these carbon materials are connected via ultrathin carbon filaments and can readily collapse under high-temperature conditions. Furthermore, these hard-template methodologies are extremely difficult to adapt to the fabrication of large-scale ordered nanoporous films or monoliths with controlled pore orientations. More recently, my research group at the Oak Ridge National Laboratory and several others around the world have developed alternative methods for synthesis of highly ordered mesoporous carbons via self-assembly. Unlike the mesoporous carbons synthesized via hard-template methods, these mesoporous carbons are highly stable and can be graphitized at high temperature (>2800° C) without significant loss of mesopores. The surface properties of these materials can be further tailored via surface functionalization. This seminar will provide an overview and perspective of the mesoporous carbon materials derived from softtemplate synthesis and surface functionalization and their fascinating applications in separation.

Acknowledgment: This work is supported by Office of Basic Energy Sciences, U.S. Department of Energy under contract DE-AC05-00OR22725 with Oak Ridge National Laboratory, managed and operated by UT-Battelle, LLC. ENVR 71 "Nonporous" sorbents for gas storage J. L. Atwood, [email protected] Department of Chemistry, University of Missouri-Columbia, Columbia, MO, United States In 2002, we discovered that the well-known macrocycle p-tert-butylcalix[4]arene undergoes single-crystal-to-single-crystal phase transitions upon guest uptake and release. The calixarene does not possess pores or channels in the solid state. However, despite a lack of porosity of the material, guest transport through the solid occurs readily until a thermodynamically stable structure is achieved. In order to actively facilitate this dynamic process, the host molecules undergo significant positional and/or orientational rearrangement. This transformation of the host lattice is triggered by weak van der Waals interaction between the molecular components. In order for the material to maintain its macroscopic integrity, extensive cooperativity must exist between molecules throughout the crystal, such that rearrangement can occur in a well-orchestrated fashion. Recently, several new, non-porous organic solids have also been found to exhibit remarkable sorption behavior. This has led us to the so-called `frustrated organic solids'. In this discussion, the focus will be on the use of the organic solid state for the capture of environmentally troublesome gas molecules. ENVR 72 Efficient screening of metal organic framework materials for kinetic separations of adsorbing molecules D. S. Sholl, [email protected], E. Haldoupis, T. Watanabe, S. Keskin, and S. Nair. School of Chemical & Biomolecular Engineering, Georgia Institute of Technology, United States Metal-organic frameworks (MOFs) are an interesting class of crystalline nanoporous materials because their structure and chemical functionality can be controlled to a far greater degree than other nanoporous materials such as zeolites. A crucial challenge in using MOFs for any desired application is to select the MOFs with the greatest promise among the thousands of distinct structures that are known. We will describe a modeling framework that efficiently characterizes large numbers of MOFs in a way that gives useful information for considering MOFs for kinetic separations, that is, applications in which separation is achieved using both adsorption affinity and diffusion selectivity. We have demonstrated this approach to identify high performance materials for use in gas separation membranes, but our methods will also be useful in other

chemical separations. We will also discuss how spatially periodic quantum chemistry calculations can be used to examine the bonding of water, nitrous oxide, hydrogen sulfide and related species to open metal sites in MOFs. This bonding can be used either as a means to capture molecules within a MOF or to reversibly functionalize MOFs to alter their pore geometry and functionality. ENVR 73 Functionalization of nanocrystalline zeolites for environmental applications S. C. Larsen, [email protected], A. Petushkov, [email protected], and K. Barquist, [email protected] Chemistry, University of Iowa, Iowa City, IA, United States Nanocrystalline zeolites were functionalized with various organic functional groups by the reaction of surface silanol groups with organosilane reactants. For example, aminopropyltriethoxysilane (APTES) was used to functionalize the zeolite surface with amine groups to facilitate environmental applications. The increased external surface area of nanocrystalline zeolites relative to micronsized zeolites facilitates the functionalization and subsequent development of these materials for applications in environmental remediation and biomedicine. The stability of nanocrystalline zeolites is a critical issue that was investigated with dissolution experiments of nanocrystalline NaY and functionalized nanocrystalline NaY. The resulting solids and solutions were analyzed with several different analytical techniques, such as powder X-ray diffraction, transmission electron microscopy, inductively coupled plasma/optical emission spectroscopy, and aluminum solid state magic angle spinning NMR. The results suggest that functionalized zeolites are more resistant to dissolution in aqueous solution relative to unfunctionalized zeolites with similar crystal sizes. ENVR 74 Transformation and toxicity of CdSe/ZnS core-shell quantum dots after simulated environmental weathering J. A. Pedersen1,2,3, [email protected], K. M. Metz4, [email protected], T. C. King Heiden5, [email protected], P. N. Wiecinski2, [email protected], A. D. Mangham6, [email protected], R. E. Peterson2,7, [email protected], W. Heideman2,7, [email protected], and R. J. Hamers8, [email protected] 1Environmental Chemistry and Technology Program, University of Wisconsin - Madison, Madison, Wisconsin, United States, 2Molecular and Environmental Toxicology Program, University of Wisconsin - Madison, Madison, Wisconsin, United States, 3Department of Soil Science, University of Wisconsin - Madison, Madison, Wisconsin, United States, 4 Department of Chemistry, Albion College, Albion, Michigan, United States, 5 Department of Biology, University of Wisconsin - La Crosse, La Crosse, Wisconsin, United States, 6Division of Chemical & Materials Sciences, Pacific

Northwest National Laboratory, Richland, Washington, United States, 7School of Pharmacy, University of Wisconsin - Madison, Madison, Wisconsin, United States, 8Department of Chemistry, University of Wisconsin - Madison, Madison, Wisconsin, United States Once released into the environment, engineered nanomaterials may be transformed by microbially mediated redox processes altering their toxicity and fate. Little information is currently available on engineered nanomaterial transformation under environmentally relevant conditions. We have developed chemical models of important environmental redox processes to investigate nanomaterial transformation ("weathering") under simulated environmental conditions. One such system is based on the extracellular hydroquinone-driven Fenton chemistry produced by lignolytic fungi. We demonstrate the utility of the assay using functionalized CdSe/ZnS core-shell quantum dots as prototypical nanoparticles. Quantum dot transformation was assessed by UV-Visible spectroscopy, infrared spectroscopy, inductively- coupled plasma-optical emission spectroscopy, dynamic light scattering, transmission electron microscopy, and energy dispersive x-ray spectroscopy. We examined the toxicity to zebrafish embryos of quantum dots before and after simulated environmental "weathering". Quantum dot transformation under oxidative environmental conditions and concomitant changes in toxicity will be discussed. ENVR 75 Nanostructured titanium oxide photocatalytic particles, films, and membranes for environmental applications H. Choi1, [email protected], and D. D. Dionysiou2. 1Department of Civil Engineering, University of Texas at Arlington, Arlington, Texas, United States, 2 Department of Civil and Environmental Engineering, University of Cincinnati, Cincinnati, Ohio, United States TiO2 photocatalysis, one of the most powerful advanced oxidation technologies (AOTs), has a great potential to completely destroy harmful and nonbiodegradable organic contaminants in water. The technology has received great attention for environmental remediation due to its effectiveness to generate hydroxyl radicals under UV light irradiation without addition of other chemicals. We have been pioneering so-called TiO2-based advanced oxidation nanotechnologies, including the systematic self-assembling-based synthesis of highly efficient porous TiO2 photocatalysts in the form of particles, films, and membranes. The materials can be also activated under visible light irradiation to utilize sustainable solar energy for environmental remediation. Especially, TiO2 photocatalytic membranes exhibit multifunctional capability such as decomposition of organic chemicals, destruction of biological toxins, disinfection of pathogenic microorganisms, physical separation of contaminants, and antibiofouling action. In the presentation, we will share our experience on the development of innovative TiO2 materials and their applications to AOTs for water and wastewater treatment.

ENVR 76 Activation of H2O2 at neutral pH values by iron- and alumina-containing SBA-15 mesoporous silica A. L. Pham1, [email protected], F. M. Doyle2, and D. L. Sedlak1. 1 Department of Civil and Environmental Engineering, University of California at Berkeley, Berkeley, CA, United States, 2Department of Materials Science and Engineering, University of California at Berkeley, Berkeley, CA, United States Iron oxides can catalyze the conversion of H2O2 into strong oxidants (e.g., hydroxyl radical) capable of transforming recalcitrant contaminants. This process, often called the heterogeneous Fenton's reaction, is very inefficient at neutral pH values because most H2O2 is decomposed by side reactions that produce H2O and O2, resulting in H2O2 loss. To test the hypothesis that inefficient H2O2 decomposition reactions can be minimized by changing the physico-chemical properties of iron reactive sites, modified iron-containing catalysts were synthesized and tested. The catalysts contained iron in the matrix of alumina and silica and were produced by impregnation of iron and alumina on mesoporous SBA-15 silica. At neutral pH values these catalysts were better than iron oxides at decomposing H2O2 to strong oxidants that degraded model contaminants. Factors affecting the efficacy of the catalysts, such as iron and alumina loading, catalyst morphology and crystallinity were investigated. The roles of silica and alumina, the nature of the oxidant produced as well as the reaction mechanism are discussed along with approaches for further improving the efficacy of heterogeneous mesoporous catalysts. ENVR 77 Debromination of polybrominated diphenyl ethers by nano-iron particles and carbon-supported nano-iron particles Y. Zhuang, [email protected], S. Ahn, and R. G. Luthy. Civil & Environmental Engr., Stanford University, Stanford, CA, United States Polybrominated diphenyl ethers (PBDEs) are widely used as flame-retardants in many consumer products. There is increasing evidence that PBDEs may persist in the environment, accumulate in organisms and present risks to human health. Nanoscale zerovalent iron particles, catalyzed bimetallic nano-iron particles, and carbon substrate support materials with embedded nano-iron were synthesized and investigated for their effectiveness to degrade PBDEs. Dehalogenation kinetics for selected PBDEs and the identification of reaction intermediates and products are compared for different materials in batch reactor experiments. The effects on reaction kinetics will be presented for a palladium catalyst and for PBDE sorption into carbon substrate support material with embedded nano-iron. These findings are augmented by microtomography, micro-XAS, XRD, SEM and TEM to better understand the interactions among the reactant, nano-iron particles and the carbon support material. While sorption on carbon substrates

concentrates PBDEs from solution, sorption slows the overall reaction with embedded nano-iron. ENVR 78 Natural organic matter - what else? R. P. Schwarzenbach1, [email protected], M. Aeschbacher1, [email protected], K.-U. Goss2, and M. Sander1, [email protected] 1Department of Environmental Sciences, ETH Zurich, Zurich, Zurich, Switzerland, 2Analytical Environmental Chemistry, Helmholtz Centre for Environmental Research UFZ, Leipzig, Germany Many environmental chemists devote or have devoted a significant part of their scientific life to unravel the numerous secrets of natural organic matter (NOM). Professor Don Macalady is undoubtedly one of them. He has not only influenced the field by his own scientific contributions, but also by educating students that continue to contribute to all kinds of aspects of NOM research. In this talk, in honor of him, we review some of our old and recent work on the assessment of the variability of those NOM properties and characteristics that are pertinent for the quantification of sorption and electron transfer reactions of organic pollutants involving NOM. Among other things, we address the question of which structural NOM moieties govern organic pollutant sorption and transformation processes, and to what extent these processes are influenced by the redox state of NOM. ENVR 79 Organic sulfur associated with aquatic humic substances G. Aiken, [email protected] US Geological Survey, Boulder, Colorado, United States The speciation of sulfur associated with dissolved organic matter isolated from a variety of oxic, freshwater environments and the Pacific Ocean was investigated using X-ray adsorption near edge spectroscopy (XANES). Organic sulfur contents for the samples ranged from 0.4% to 1.9% of the atomic composition and were strongly dependent on the redox chemistry of the environments whence the samples originated, especially with regard to potential interactions with sulfide in sulfate reducing environments. Reduced sulfur content (thiophene, organic sulfides and thiols) ranged from 22-70% of total sulfur. In general, humic acid fractions were found to have the largest percentage of reduced sulfur, followed by the fulvic acid and hydrophobic acid fractions. Hydrophilic fractions of the DOC contained a large percentage of oxidized organic sulfur (sulfonate and sulfate moieties). The binding of reduced sulfur groups with soft metals, such as mercury, may inhibit the oxidation of these groups and control metal biogeochemistry.

ENVR 80 Equilibrium and kinetic isotope effects as probes of redox states and processes C. J. Cramer, [email protected] Department of Chemistry and Supercomputing Institute, University of Minnesota, Minneapolis, MN, United States Electronic structure calculations from first principles provide powerful tools for the prediction of aqueous oxidation and reduction potentials and for interpreting equilibrium and kinetic isotope effects associated with redox states and processes. Combinations of density functional theory and explicit or continuum solvation modeling can offer excellent quantitative accuracy with respect to computing the free energy changes associated with electron-transfer processes, and coupling these models with elementary Marcus theory can extend beyond their reach to the prediction/interpretation of kinetic isotope effects associated with electron transfer processes. When very heavy elements are of interest, like mercury, nuclear volume effects can play a role in isotopic fractionation that is related to redox state, and the inclusion of relativistic effects in the computational protocol is required. Methods and some recent applications will be discussed. ENVR 81 Influence of strongly reducing conditions on spectroscopic properties and proton binding of natural organic matter F. Maurer, [email protected], I. Christl, and R. Kretzschmar. Department of Environmental Sciences, ETH Zurich, Zurich, Switzerland Proton and metal cation binding to natural organic matter (NOM) may be enhanced under anoxic conditions due to the formation of reactive binding sites resulting from reductive alteration of NOM. We reduced a purified humic acid using an electrochemical cell that allowed us to determine the amounts of electrons and protons involved in reduction reactions. We then investigated the effects of reduction on spectroscopic properties (UV-vis, IR, C-1s NEXAFS, fluorescence) and proton binding of the humic acid in the pH range of 4­10. During reduction, ;0.5 mol/kg of protons and electrons were transferred to the humic acid. Spectroscopic differences between the untreated and reduced humic acid were minor. The amount of protons consumed during reduction was quantitatively recovered as proton-reactive sites in the pH range of 7­10. Our findings support the concept of quinoid moieties playing a major role in the redox activity of humic substances. ENVR 82 Novel electrochemical approach to quantify the redox state of humic substances: Advantages and applications

M. Aeschbacher, [email protected], R. P. Schwarzenbach, [email protected], and M. Sander, [email protected] Department of Environmental Sciences, ETH Zurich, Zurich, Zurich, Switzerland Redox reactions involving humic substances (HS) play a key role in biogeochemical processes and in pollutant dynamics. In this work, we present mediated electrochemical reduction and oxidation (MER/MEO) in which redoxactive organic radicals facilitate the electron transfer between the working electrode and the redox-active moieties in HS. MER/MEO quantitatively recovered electrons on HS samples pre-reduced to different extents by direct electrochemical reduction. Compared to previous methods that relied on chemical bulk reductants and oxidants, MER/MEO have several advantages, including (i) the direct, chronocoulometric quantification of electron transfer to/from HS, with low detection limit, (ii) fast electron-transfer kinetics, and (iii) electrochemical potential control independent of pH. MER/MEO were used to confirm redox-buffer properties of HS in cyclic reduction and O2 re-oxidation experiments. MER-quantified electron acceptor capacities of a variety of humic and fulvic acids showed a high linear correlation with the aromaticities and the C/H ratios, indicating aromatic redox-active moieties, likely quinones. ENVR 83 Stable isotope fractionation associated with redox chemistry J. R. Black1, [email protected], S. G. John2, and A. Kavner1,3. 1Institute for Geophysics and Planetary Physics, University of California, Los Angeles, Los Angeles, CA, United States, 2Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA, United States, 3Earth and Space Sciences, University of California, Los Angeles, Los Angeles, CA, United States The aqueous redox chemistry of transition metals is an important control over their transport and distribution in the environment. Many transition metal species also have a rich stable isotope geochemistry, which can now be examined in more detail given advances in high-resolution mass-spectrometry. Stable isotope fractionation is governed by a number of processes, such as mass-transport, equilibrium and reaction kinetics. Here we present mass-dependent mechanistic models to explain the currents and isotopic fractionation observed in metals electroplated on rotating disc electrodes. In all cases studied (e.g., Fe, Cu and Zn) the lighter isotopes are preferentially partitioned into the metallic phase. The magnitude of these fractionations are much larger than that predicted by equilibrium stable isotope theory and models show that a balance of the equilibrium fractionation between the aqueous species, surface species and final metal product and the diffusive supply of reactant to the electrode surface can explain these trends. ENVR 84

Nitrogen isotope fractionation during the oxidation of substituted anilines at manganese oxide surfaces M. Skarpeli-Liati1, [email protected], M. Jiskra1, A. J. Turgeon2, W. A. Arnold3, C. J. Cramer2, R. P. Schwarzenbach1, and T. B. Hofstetter1. 1 Department of Environmental Sciences, IBP/ETH Zurich, Zurich, Zurich, Switzerland, 2Department of Chemistry and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota, United States, 3Department of Civil Engineering, University of Minnesota, Minneapolis, Minnesota, United States Oxidative transformation of aromatic amino groups is an important initial degradation step of many organic water contaminants including pesticides, antibacterial agents, or dyes. We studied the 15N-kinetic isotope effects (15NKIEs) as a diagnostic tool for identifying and quantifying aromatic N atom oxidation, which occurs in aquatic environments at manganese oxide surfaces (MnO2). Compound-specific isotope analysis of a series of Cl-, OCH3-, and CH3subsituted anilines revealed that the oxidation of aromatic NH2-groups is accompanied by characteristic inverse 15N-KIEs between 0.9917-0.9987. The magnitude of the 15N-KIEs agreed with density-functional theory calculations of isotope effects pertinent to the oxidation of substituted anilines to the corresponding radical cations as well as with electrochemical oxidation experiments. Effects of type and position of aromatic substituents on the magnitude of the inverse 15N-KIE suggest that N isotope fractionation originates from the degree of imine-type bonding at the N atom during formation of the radical cation intermediates. Distinctly different normal 15N-KIEs up to 1.0066 were found for the faster oxidation of anilinium cations at pH 4 pointing towards a different oxidation mechanism for protonated aromatic amines. ENVR 85 Reduction of nitrogen containing energetic compounds: Computational chemistry perspective O. Isayev1, [email protected], L. Sviatenko2,3, L. Gorb4, F. Hill5, and J. Leszczynski3,5. 1Department of Chemistry, Case Western Reserve University, Cleveland, OH, United States, 2Department of Chemistry, Kirovograd State Pedagogical University, Kirovograd, Ukraine, 3Interdisciplinary Center for Nanotoxicity, Department of Chemistry and Biochemistry, Jackson State University, Jackson, MS, United States, 4SpecPro, Inc, Huntsville, AL, United States, 5Environmental Laboratory, US Army ERDC, Vicksburg, MS, United States Present study focuses on a computational simulation of a one electron reduction of nitroaromatic compounds (NACs) by iron(II) containing species in water and at the surface of minerals. The first step of the simulation consists of the accurate computational prediction of the probability of the electron transfer (reduction) between the nitrogen-containing compounds and for iron-containing moiety using a state-of-the-art Density Functional Theory (DFT) approaches. The careful

selection of more than thirty combinations of DFT functionals and basis sets has resulted in two computational protocols which provide experimental accuracy for the nitrocompounds, quinones, and diazocyclic compounds. The second step includes ab initio Car-Parinello molecular dynamics simulations of electron transfer in solvent (bulk water) between nitrobenzene (NB) and Fe2+, FeOH+, Fe(OH)2, Fe(OH)3- species. Similar results are expected from the adsorption of NB onto an iron(II)oxide surface. These simulations are currently in progress. ENVR 86 Characterization of nuclear emissions resulting from Pd/D co-deposition P. A. Mosier-Boss1, [email protected], F. E. Gordon2, and L. P. G. Forsley3. 1 Code 71730, SPAWAR Systems Center Pacific, San Diego, CA, United States, 2 retired, retired, San Diego, CA, United States, 3S&T, JWK International, Annandale, VA, United States Evidence of heat from Pd/D co-deposition includes SEMs showing molten-like features and infrared imaging showing that the cathode is the heat source and not the Joule effect. However, heat does not, by itself, prove that nuclear processes are occurring inside the deuterium-loaded palladium lattice. This requires the detection of some nuclear ash. The results of new CR-39 results will be discussed as well as neutron and gamma ray emissions resulting from the application of the Superwave, and other, charging protocols to the Pd/D codeposition process. ENVR 87 Hot spots, chain events and micro-nuclear explosions M. Srinivasan, [email protected] Physics Group, Bhabha Atomic Research Centre Mumbai, Trombay, Mumbai, India During 1990, we presented results that suggested the occurrence of micronuclear explosions at localized hot spots in which both Tritium and neutrons are generated in deuterated Pd and Ti samples, based on the measurement of the multiplicity distribution of neutron counts, It was estimated that 1012 to 1014 LENR reactions take place in these hot spots. The rationale for arriving at the micro nuclear explosion hypothesis is examined in a comprehensive review paper included in the ACS LENR Source Book Vol 2 (2009). Recently other researchers have reported observing hot spots in their excess heat producing cathodes. It is speculated that the concept of micro nuclear explosions can be extended to heat generating helium producing reactions also. Theoretical models which depend on the catalyzing role of intermediary agents such as BoseEinstein condensates, Erzions, poly neutrons, trapped neutrons, etc. support the possibility of occurrence of such chain events.

ENVR 88 Charged particle emissions from the surface of the Pd and Ti deuterides upon their excitation with electron and X-ray beams A. Lipson1, [email protected], I. Chernov2, [email protected], A. Roussetski3, [email protected], M. E. Melich4, [email protected], B. Lyakhov1, [email protected], A. Tsivadze1, [email protected], and A. Lider2, [email protected] 1A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russian Federation, 2 Tomsk Polytechnic University, Tomsk, Russian Federation, 3P.N. Lebedev Physics Institute, Russian Academy of Sciences, Moscow, Russian Federation, 4 Naval Postgraduate School, Monterey, CA, United States [Presented posthumously by Jan Marwan and George Miley] Electron beam stimulated emission of energetic charged particles accompanying deuterium desorption from a metal deuteride target has been detected. The targets represented deuterium loaded Pd/PdO and Ti foils of 50 micron thick. The charged particles energies and identities were determined using a set of accelerator calibrated CR-39 detectors covered with various metal foils. We observed statistically significant emission of DD-reaction product (3 MeV protons) and energetic charged particles (11-20 MeV) in experiments with the Pd/PdO:Dx and the TiDx targets in vacuum, stimulated by a weak electron beam (J ; 0.6 mA/cm2, U = 30 keV). We also obtained similar, but more intensive emissions during irradiation of the TiDx target with X-ray tube ((U =100 kV, I =5.0 mA) at ambient conditions in air atmosphere. Our data support the theoretical prediction that electron excitation of a D- subsystem in metal deuterides can result in significant changes in the associated dynamics. ENVR 89 Anomalous hydrogen evolution subject to pulsed electric explosion of thin titanium foils in water L. I. Urutskoev1,2, [email protected], D. V. Filippov1,2, [email protected], A. A. Rukhadze3, and L. A. Lebedev4. 1Moscow State University of Printing Arts, Moscow, Russian Federation, 2RECOM, National Research Center [ldquot]Kurchatov Institute[rdquot], Moscow, Russian Federation, 3General Physics Institute (Russian Academy Of Sciences), Moscow, Russian Federation, 4 State Research and Development Center for Expertise of Projects and, Moscow, Russian Federation Experimental studies of pulsed electric explosion of thin titanium foils in deionized bi-distillate (H2O), with discharge power of ; 0.2 GW, are described. We have reliably established that an electric explosion of titanium foil in water induces production of a considerable amount of molecular hydrogen (NH2 ; 2×1022 molecules). The quantity of formed hydrogen was carefully measured by means of the diversified techniques. It was shown that the origin of about half of

this amount (0.5 litre) cannot be explained by water decomposition. Careful search of the "impurity" hydrogen source was not crowned with success. The authors advanced a hypothesis on the nuclear mechanism of the origin of observed molecular hydrogen. Test experiments was made and obtained a number of the results to back up the hypothesis. ENVR 90 Nuclear transmutation in a gas-loading D/Pd system B. Liu1,2, X. Li1, [email protected], Q. Wei1, C. Liang1, and J. Yu1. 1 Department of Physics, Tsinghua University, Beijing, China, 2China ShenHua Energy Company Limited, ShenHua Group Corporation, Beijing, China When deuterium gas permeates through a thin palladium film, it was thought as a diffusion process only. However, after ;80 times absorption and desorption processes accompanied with permeations, nuclear transmutation was discovered on the surface of palladium film using SEM (scanning electron microscopy). At first glance, it was noticed that the macroscopic deformation of palladium was so large that the palladium film might increase its thickness while decrease its diameter of a rounded palladium film. The stress at the rounded sealing line might even cut the palladium film into two pieces: the central rounded piece and the ring-shape edge piece. SEM analysis revealed that new elements (Cu, Zn, Si, etc.) were detected in the permeation area, but there were no such elements in the original palladium film or in the ring-shape area where no permeation happened. The temperature of palladium film was much higher than that of Iwamura experiments in Advanced Technology Research Center, Mitsubishi Heavy Industries. Besides, there was no super lattice on the surface of our palladium films. Metallography analysis will be shown as well. ENVR 91 On the production of energy and helium in low energy nuclear reactions J. C. Fisher, [email protected] Neutronics Corporation, United States Competing theories of low energy nuclear reactions lead to distinct predictions for the energy to helium production ratio. For deuterium fuel many theories predict a ratio of 24 MeV per 4He corresponding to the fusion reaction 2H + 2H 4 He. Polyneutron theory predicts 20 MeV per 4He corresponding to the overall reaction 4(2H) 4(1H) + 4He. Both predictions are lower limits that neglect the energy that may be generated in helium-free side reactions such as transmutations. Both lie within the experimental uncertainty of current measurements. It may be possible to distinguish among theories by measuring the energy to helium ratio in experiments using lithium as fuel. Polyneutron theory predicts a ratio in the range 2.7-5.5 MeV per 4He for lithium fuels

depending on the mix of Li isotopes. Experimental confirmation of this ratio would strongly favor polyneutron theory. ENVR 92 Low energy nuclear transmutation reactions induced by deuterium permeation through multilayer Pd and CaO thin film Y. Iwamura1, [email protected], T. Itoh1, N. Yamazaki1, N. Watari1, J. Kasagi2, Y. Terada3, and T. Ishikawa4. 1Advanced Technology Research Center, Mitsubishi Heavy Industries, ltd, Yokohama, Kanagawa, Japan, 2 Laboratory of Nuclear Science, Tohoku University, Sendai, Miyagi, Japan, 3 Japan Synchrotron Radiation Research Institute, Sayo-gun, Hyogo, Japan, 4 SPring-8 Center, RIKEN, Sayo-gun, Hyogo, Japan Low energy nuclear transmutations in condensed matter have been observed in the Pd complexes, which are composed of Pd and CaO thin film and Pd substrate, induced by D2 gas permeation through Pd multilayer complexes[1]. Permeation of deuterium is attained by exposing one side of the Pd complex to D2 gas while maintaining the other side under vacuum conditions. Transmutation reactions of Cs into Pr, Ba into Sm and Sr into Mo were observed. Especially, transmutation of Cs into Pr has been confirmed by in situ measurement using xray fluorescence spectrometry (XRF) at SPring-8 in Japan. Similar experiments have been performed by some researchers and positive results have been obtained in some cases. However, more systematic experiments and theoretical approaches are required for making clear the nature of this phenomenon. [1] Y. Iwamura, Jpn. J. Appl. Phys. 41 (2002) 4642-4648. ENVR 93 Anomalous elements on the cathode surface after aqueous electrolysis J. Dash, [email protected] Portland State University, Portland, OR, United States The presence of localized concentrations of an anomalous element ( silver) on the surfaces of palladium cathodes after electrolysis in either light water or heavy water electrolyte was first reported in 1994 [1]. Similar results were reported for titanium cathodes after electrolysis in heavy water electrolyte [2]. More recently, off-the-shelf battery fluid (Sp.G. 1.26) was substituted for analytical-grade H2SO4 (Sp.G. 1.84) in the electrolyte. Silver was found in localized concentrations on palladium cathodes after electrolysis. These results are consistent with a mechanism proposed previously [1]. REFERENCES [1] J. Dash, G. Noble, and D. Diman, "Surface Morphology and Microcomposition of Palladium Cathodes after Electrolysis in Acidified Light and Heavy Water: Correlation with Excess Heat" Trans. Fusion Technology, 26, 299(1994).

[2]. J. Warner and J. Dash, ` Heat Produced during the Electrolysis of D2O with Titanium Cathodes', ICCF8 Conference Proceedings 70, 161, Societa Italiana Physica, Bologna, 2000, F. Scaramuzzi, editor. ENVR 94 Anomalous transmutation in an emission-free exhaust gas handling system X. Jiang1, [email protected] 1Environmental Tech. Co. Ltd, Yixing, Jiangsu, China, 2Department of Aeronaustics and Astronautics, Beijing University, Beijing, China The experimental results of anomalous nuclear reaction reported by Jiang, Borkris, Miley and Patterson plus similar results reported by Mizuno, et al. challenge the current atomic model.. The phenomenon seems highly reproducible. It appears that there are situations in which nuclei split open at the stimulus only chemical energies. Ronald J. Kovac reported that elemental transmutation appears to have occurred when a vacuum tube containing only nitrogen(14N) was exposed to electromagnetic force field. Gas spectrometer analysis revealed that the contents in the tube after electromagnetic shaping included substantial amounts of helium 4He and lithium Li. A system for gas handling as an anomalous transmutation reaction discovered by Yuguang Zhang is described in this paper. The emission-free exhaust gas handling device (publication number WO 2008 083530) is provided, which is a container only having inlets. At least two stages of exchangers are provided in series in the container from an exhaust gas inlet and a mixing gas chamber arranged at the communicating location between two stages of exchangers. An exchanging gas chamber in the first stage of the exchanger is provided with an orifice communicating with air and each of the mixing gas chambers from the second to the last stage of exchangers is disposed with a return pipe communicating with the inlet of the first stage of the exchanger. ENVR 95 Observation of radiation and transmutation processes of bubble cavitation in free water jet V. Vysotskii1, [email protected], and A. A. Kornilova2. 1Radiophysical Dept, Kiev National Shevchenko Univ., Kiev, Ukraine, 2Department of Physics, Moscow State University, Moscow, Russian Federation In this work we present our results on intensive cavitation-induced X-Ray radiation in supersonic water jet obtained either in free space or near the end of the water output channel. We deeply investigated the X-Ray generation during bubble cavitation at super-high pressures of water (from 200 atm up to 3000 atm). The minor part of this X-Ray radiation (Ex1 keV) was generated at the surface of the supersonic free water jet within the area of cavitation at any

pressure. The energy of radiation released at the surface of the water output channel (made of stainless steel) was estimated to be Ex2 keV. In case lead covered the surface, the energy was found to be higher Ex"4.5-5 keV. The total activity of X-Ray generation was about 0.1 Ci. The different radiation phenomena were analysed and specifically detected by X-Ray photo-plates. Further experiments were combined with the cavitation-driven nuclear synthesis. The transmutation phenomena in the area of interaction of cavitating water jet at pure surfaces (e.g. made of Ag with purity 99.99%) will be presented and discussed. ENVR 96 Model for sonofusion R. S. Stringham, [email protected] First Gate Energies, United States Experimental sonofusion results needed a mechanism to explain the measured 4 He, T, and heat produced. A model is introduced based on high-density low energy transient astrophysical behavior and it creates an environment for fusion events. The charged particles, deuterons and electrons, cavitationally implanted into a lattice where electrons are stripped from deuterons, charge separation, exist as accelerating electrons rushing back toward the deuteron cluster. The transient cluster is surrounded and stabilized by an accelerating shell of free electrons. Their EM forces squeeze and cool the deuteron contents into a BEC phase. The high Tc of the BEC deuteron cluster (no electrons are present) is due to the Mev differences between ground state and the next available energy state of the nuclear shell model. The fusion environment is essential to the cluster's low temperature and high density. Fusion events of this model are similar to those in muon fusion. ENVR 97 Harmonic fitting of atmospheric POPs' concentrations measured near the Great Lakes over the last 17 years R. A. Hites, [email protected], and M. Venier, [email protected] School of Public & Environmental Affairs, Indiana University, Bloomington, IN, United States One of the challenges in tracking the atmospheric concentrations of POPs is accounting for all of the sources of variation such that changes in these concentrations resulting from the elimination of sources can be teased out from other variations. We have previously identified time (as Julian Days, JD), local human population (POP), and seasonality (expressed as atmospheric temperature) as the most important factors in determining the atmospheric concentrations of POPs. Most recently, we have combined these parameters into a single harmonic equation of the form: ln(C) = a0 + a1JD + a2sin(z JD) + a3cos(z JD) + a4log2(POP), where z = 2p/365.25. Each parameter is associated with a

partial sum of squares that indicates the importance of that parameter in the overall regression. The regression was applied to vapor, particle, and precipitation concentrations of several POPs measured by the Great Lakes' Integrated Atmospheric Deposition Network every 12 days since 1992. ENVR 98 Theoretical mechanism for the production of HONO and NH4NO3 from gas phase homogeneous reaction of nitrogen dioxide B. Zhang, [email protected], and F.-M. Tao. Department of Chemistry and Biochemistry, California State University, Fullerton, Fullerton, CA, United States Reaction mechanisms for the production of nitrous acid (HONO) from the homogeneous gas-phase hydrolysis of nitrogen dioxide (NO2) are explored by density functional theory and ab initio calculations. Molecular structures, energetics, and vibrational spectra of the intermolecular complexes and reaction intermediates of nitrogen dioxide with water and ammonia were calculated using MP2 and B3LYP methods with the aug-cc-pvdz basis set. It was found that water, ammonia, and temperature are critical parameters in the eventual conversion of nitrogen dioxide into HONO and ammonium nitrate (NH4NO3). ENVR 99 Passive sampling of atmospheric POPs using polyethylene samplers R. Lohmann1, [email protected], E. Morgan1,2, and K. Bollinger1,3. 1 Graduate School of Oceanography, University of Rhode Island, Narragansett, RI, United States, 2Chemistry, Simmons College, Boston, MA, United States, 3 Ocean Engineering, University of Rhode Island, Narragansett, RI, United States Passive polyethylene (PE) samplers were deployed in the atmosphere concurrently with one traditional high-volume sampler using polyurethane foam (PUF) plugs and a glass fiber filter. Deployment times were on the order of two weeks per PE sampler, and about one week for the hi-vol sampler. Samplers were analyzed for polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs). Results from passive samplers were converted to truly gasphase concentrations using equilibrium partitioning constants. These were predicted from the compounds PE-water partitioning coefficients divided by their respective air-water equilibrium partitioning constants. ENVR 100 Endocrine disruptors in the Puget Sound

S. Iverson1,2, [email protected], J. Bell1,3, and R. Barsh1,3. 1Friday Harbor Marine Laboratories, University of Washington, Friday Harbor, WA, United States, 2The Evergreen State College, Olympia, WA, United States, 3 Kwiaht Center for the Historical Ecology of the Salish Sea, Lopez Village, Washington, United States Endocrine disrupting compounds are a current subject of toxicology and environmental research. Their widespread use since WWII has made them detectable almost everywhere. Understanding their fates and effects is critical to our own health and a healthy environment. We used LCMS to study pyrethroid pesticides, flame retardants, and nonionic surfactants in the San Juan Islands north of Seattle. Our results show detectable levels of endocrine disruptors in this relatively pristine environment. In sediments and filter feeders we found levels that were unsafe, especially around populated areas. ENVR 101 Atmospheric precursors and pathways to highly persistent perfluorinated acids S. A. Mabury, [email protected] Chemistry, University of Toronto, Toronto, ON, Canada Perfluorinated acids (PFAs) are widely disseminated in the global environment, are exceptionally persistent, and the larger of which are bioaccumulative reaching significant concentrations in Arctic mammals. A number of volatile polyfluorinated precursors (alcohols, olefins, acrylates) are commonly detected in the atmosphere and have been shown to undergo atmospheric transport and OH driven transformation reactions to yield the perfluorinated acids. Two primary mechanistic pathways contribute to the production of carboxylic PFAs or PFCAs. The gas phase route involves loss of ozone from a proposed tetroxide intermediate to directly form the PFCA. A second route involves production of a perfluorinated alcohol from reaction of an perfluorinated peroxy radical with an alpha hydrogen containing peroxy radical with subsequent condensed phase loss of HF to form the acid fluoride and hydrolysis to form the PFCA. This talk will highlight the known precursors that can proceed via these mechanisms and suggest likely further candidates as likely to yield PFAs under typical environmental conditions. ENVR 102 Atmospheric lifetime and global distribution and fate of DDT G. Lammel1,2, [email protected], I. Stemmler2, A. Dvorská1, I. Holoubek1, J. Jarkovský1, J. Klánová1, and A. Stohl3. 1Research Centre for Environmental Chemistry and Ecotoxicology, Masaryk University, Brno, Czech Republic, 2Max Planck Institute for Chemistry, Mainz, Germany, 3Norwegian Institute for Air Research (NILU), Kjeller, Norway

Dichlorodiphenyltrichloroethane and its major metabolites, DDE and DDD, are persistent, accumulate along food chains, cause detrimental effects in marine and terrestrial wild life, and pose a hazard for human health. From old stocks, due to illegal use, as impurity of another pesticide (dicofol), and for vector control purposes DDT is currently at least regionally increasingly introduced into the environment. The degradation rates, however, are insufficiently known and the total global `life cycle' had not been described comprehensively so far. DDT sources in central, western and northern Europe are localized using monitoring data. Lifetimes at a high mountain site correspond to kOH < 1.5x10-12 cm3 molec-1 s-1 for p,p'-DDT, -DDE and -DDD, i.e. partly significantly lower than estimated. By global multicompartmental modelling of the atmospheric and oceanic transports the total global `life cycle', 1950-2000, geographic and multicompartmental distributions and the significance of re-volatilisation for long-range transport (`grasshopping') are assessed. ENVR 103 Correlation study between airborne polycyclic aromatic hydrocarbons (PAHs) and soil borne PAHs in El Paso, TX C. Yamaguchi1, [email protected], C. M. Tilley2, A. M. Lopez2, and W.-Y. Lee1,2, [email protected] 1Environmental Science and Engieering Ph.D. Program, The University of Texas at El Paso, El Paso, TX, United States, 2 Department of Chemistry, The University of Texas at El Paso, El Paso, TX, United States Soil borne Polycyclic Aromatic Hydrocarbons (PAHs) and organic carbon in soil were studied to project the pollution level of PAHs in ambient air. Three soil samples at six sampling sites in El Paso, TX were collected during winter 2008 and summer 2009 along with three air samples collected at each site in threeweek periods. PAHs in samples were extracted and analyzed by Gas chromatography-Mass spectrometry. The results showed that: 1) levels of total organic carbon (TOC) in soil was positively associated with the concentrations of PAHs; 2) greater correlation between TOC and PAH concentrations was observed in winter soils; 3) soil samples collected during winter exhibited higher concentrations of PAHs than samples collected during summer; 4) concentrations of PAHs in air samples were found to be higher in summer than in winter. Further data analysis seeking an empirical regression correlation of airborne and soil borne PAHs will be presented. ENVR 104 Organochlorine pesticides and PAHs in the atmosphere and surface water of the North Atlantic and Arctic Ocean R. Lohmann1, [email protected], R. Gioia2, K. C. Jones2, L. Nizzetto2,3, C. Temme4,5, Z. Xie4, D. Schulz-Bull6, I. Hand6, E. Morgan1, and L. Jantunen7.


Graduate School of Oceanography, University of Rhode Island, Narragansett, RI, United States, 2Lancaster Environment Centre, Lancaster University, Lancaster, United Kingdom, 3Department of Structural and Functional Biology, University of Insubria, Varese, Italy, 4Institute for Coastal Research, GKSS Research Centre Geesthacht, Geesthacht, Germany, 5Eurofins GfA GmbH, Hamburg, Germany, 6Institute for Baltic Sea Research (IOW), RostockWarnemuende, Germany, 7Environment Canada, Egbert, Ontario, Canada Surface seawater and boundary layer atmospheric samples were collected on the FS Polarstern during cruise ARKXX in the North Atlantic and Arctic Ocean in 2004. Samples were analyzed for persistent organic pollutants (POPs), with a focus on organochlorine pesticides, including hexachlorocyclohexanes (HCHs), chlordanes, DDTs, hexachlorobenzene (HCB) and polycyclic aromatic hydrocarbons. In addition, the enantiomer fractions (EFs) of pesticides, notably a-HCH and cis-chlordane (CC), were determined. In contrast to dissolved compounds, atmospheric POPs did not display trends with temperature. Airwater exchange gradients suggested net deposition for all compounds, though HCB was closest to air-water equilibrium. EFs of a-HCH in the atmosphere ranged from 0.42 to 0.48, somewhat lower than previous observations. ENVR 105 Using nanotechnology to tailor reverse osmosis membrane transport, mechanical, and interfacial properties E. M. V. Hoek, [email protected] Department of Civil & Environmental Engineering, University of California, Los Angeles, Los Angeles, CA, United States ENVR 106 Fabrication and characterization of thin-film nano-composite membrane with hydrophilized ordered mesoporous carbon E.-S. Kim, [email protected], and B. Deng, [email protected] Department of Civil and Environmental Engineering, University of Missouri, Columbia, MO, United States To enhance the performance of thin-film composite membrane, nano-fillers are often used as additives in the polymerization process. Nano-fillers have to be hydrophilic to be dispersed in the aqueous phase to make thin-film nanocomposite membrane (TFN) by interfacial polymerization. In this study, hydrophilized ordered mesoporous carbons (H-OMCs) were explored for TFN preparation. H-OMC was prepared from silica template, and atmospheric argon plasma was applied to enhance surface hydrophilicity. m-phenylinediamine with trimesoyl chloride were polymerized to make polyamide thin film layer. The results indicated that 5% loading of H-OMCs increased membrane surface

hydrophilicity, wettability and pure water permeability. Rejection of bovine serum albumin was also slightly increased. ENVR 107 Integrated nano composite membranes for biological and organic fouling prevention F. Diagne, [email protected], R. Malaisamy, [email protected], and K. L. Jones. Civil Engineering, Howard University, Washington, DC, United States Commercial PES microfiltration membranes (0.1µM) were modified by the polyelectrolyte multilayer modification method using polystyrenesulfonate (PSS), poly(diallyldimethylammonium chloride) (PDADMAC) and silver nanoparticles embedded in PSS. Films were kept thin (1.5 bi-layers of polyelectrolyte) in order to minimize the flux decline resulting from the increased thickness after modification. Aqueouss olutions of humic acid (20 mg/L) and of Escherichia coli (E.coli suspension (106 CFU/mL) were filtered separately through both the unmodified and modified PES membranes under stirred, batch conditions. Filtration and cleaning studies confirm that the modification reduces the organic fouling and increases the flux recovery by 6.4 and 16.5 percent, and after biological fouling and cleaning, the flux recovery increased by 8.5 and 11.8 percent respectively for the membranes modified with and without nanoparticles. Membrane characterizations confirm the increased surface charge, the even distribution of nanoparticles, integrity (SEM) and the chemical modification (FTIR) of the modified membranes. ENVR 108 Investigating gas transport in membrane proteins using block co-polymer membrane vesicles M. Kumar1, [email protected], F. Itel2, W. P. Meier2, and J. L. Zilles1. 1 Department of Civil and Environmental Engineering, University of Illinois at Urbana Champaign, Urbana, Il, United States, 2Department of Chemistry, University of Basel, Basel, Basel, Switzerland Protein-polymer hybrid membranes created by inserting membrane proteins in block copolymers can be designed to have unique properties, such as selective and controlled gas permeability. CO2 transport across water channel proteins, aquaporins (AQPs), has been a controversial topic. The high permeability of cell lipid membranes precludes the need for specialized membrane proteins and leads to a high background permeability in lipid-based reconstitutions. We show that Polymethyloxazoline ­ Polydimethylsiloxane (PMOXA-PDMS) based block copolymers with incorporated aquaporins are an excellent system to study CO2 transport and emulate as bioinspired gas separation membranes. The CO2 permeabilities of membranes, without incorporation, are three orders of

magnitude lower than lipid bilayers (10-6 cm/s vs 10-3 cm/s) in stopped flow studies, making this a sensitive system. Using this system, we show that the previously untested E.coli aquaporin Aquaporin Z (AqpZ) does not transport CO2, while the known CO2 transporter NtAqp1 (from tobacco leaves) shows the expected permeability. ENVR 109 Transport of engineered nanoporous silicate particles and its effect on uranium fate and transport in porous media C. Liu, [email protected], J. Shang, Z. Wang, J. Li, and J. Liu. Pacific Northwest National Laboratory, Richland, WA, United States An engineered material of nanoporous silicate particles (NSP) has been synthesized and functionalized for environmental remediation application. The material has high ion selectivity, dense population of absorbing sites, fast adsorption kinetics, and stable silicate structure, which yield a potentially efficient material for capturing contaminants from groundwater and wastewater. A scanning optical fiber-laser excitation fluorescence profiler was developed to insitu track particle transport in a column system. This presentation will show our recent results in: 1) characterization of particle surface property and particle interaction force with uranium-contaminated sediment that was collected from Hanford site; 2) the retention/release of NSP in saturated porous media under dynamic flow conditions; and 3) the effect of NSP transport on the reactive transport of uranium in the contaminated sediment. Microscopic measurements and numerical simulations were performed to provide mechanistic insights on the transport of NSP and its effects on the fate and transport of uranium. ENVR 110 Fate and transport of silica nanoparticles in a fixed bed adsorber and its impact on removal of organic contaminants G. A. Sorial1, [email protected], H. Salih1, R. Sinha2, R. Krishnan2, and C. Patterson3. 1Civil and Environmental Engineering, University of Cincinnati, Cincinnati, OH, United States, 2Shaw Environmental Inc, Cincinnati, OH, United States, 3US EPA, Cincinnati, OH, United States Adsorption isotherm, kinetics and column breakthrough experiments evaluating trichloroethylene (TCE) adsorption onto granular activated carbon (GAC) were conducted in the presence and absence of SiO2 nanoparticles (NPs). Zeta potential and pH of point of zero charge of the NPs and the GAC were measured. Particle size distribution (PSD) of the NPs dispersions were also obtained as a function of time. The surface area and the pore size distribution of the virgin and the exhausted GAC were obtained along with (Transmission Electron Microscopy (TEM), High Resolution Scanning Electron Microscopy (HRSEM), and Fourier Transform Infra Red Microscopy (FTIR) analysis. The effect of SiO2 on the TCE

adsorption and their fate and transport in the GAC column was found to be a function of zeta potential, concentration, and PSD. A direct electrostatic attraction was observed between the SiO2 and GAC. The isotherms, breakthrough and the kinetic data showed a noticeable increase in the amount of TCE adsorbed in the presence of SiO2, suggesting that the SiO2 particles are providing additional surface area. ENVR 111 Immobilization of zero-valent iron nanoparticles into polymer/carbon nanotube composite nanofibers for environmental applications S. Xiao1, [email protected], M. Shen2, [email protected], R. Guo2, [email protected], S. Wang1, [email protected], and X. Shi2, [email protected] 1College of Textiles, Donghua University, Shanghai, China, 2 College of Chemistry, Chemical Engineering and Biotechnology, Donghua University, Shanghai, China We present a facile approach to immobilizing zero-valent iron nanoparticles (ZVI NPs) into electrospun polymer/carbon nanotube composite nanofibrous mats. Electrospun poly(acrylic acid)/poly(vinyl alcohol)/multiwalled carbon nanotube (MWCNT) composite nanofibrous mats were first heated to render them water stable, and were then used as nanoreactors to complex ferric iron for subsequent formation and immobilization of ZVI NPs. We show that the formed ZVI NPs (mean diameter = 1.6 nm) are uniformly distributed into the nanofibers and the incorporation of MWCNTs significantly improves the mechanical property of the fiber materials. The produced ZVI NP-containing composite nanofibrous mats exhibit a superior capability to decolorize the dyes of acid fuchsine, acridine orange, and methyl blue, which are model dyes in wastewater of the printing and dyeing industry. Findings from this study suggest a significant potential of using the electrospun nanofibers as nanoreactors to synthesize reactive iron NPs for a broad range of environmental remediation applications. ENVR 112 Kinetics of transport, dispersion and deposition of nano-particles in porous media E. Sahle-Demessie1, [email protected], G. Sorial2, Z. Li2, and A. Aly Hassan2. 1Office of Research and Development/NRMRL, U.S. Environmental Protection Agency, Cincicinnati, OH, United States, 2Department of Civil and Environmental Engineering, University of Cincinnati, Cincinnati, OH, United States The potential impact of the transport of nanoparticles is an essential part in the risk assessment of fate and disposal of nanoparticles and associated contaminants. Experimental studies are being conducted to better understand the kinetics of aggregation and transport of nano-particles in porous media and

their deposition from flowing suspensions onto solid surfaces or collectors. Transport and deposition of nano-particles (CeO2, TiO2, ZnO) are influenced by the surface chemical characteristics of the porous media and nano-particles, size and morphology of nanoparticles and porous media, the chemistry of the solution, and the fluid flow regime. Non-sorbing tracer was used to predict the movement of well dispersed nano-particles through a sand packed column, operating under upflow condition and the Peclet numbers were determined to estimate hydrodynamic dispersion coefficient. From rate of particle deposition the experimental attachment efficiencies were calculated and compared with theoretical mathematical model predictions. ENVR 113 Electron shuttling by natural organic matter: Twenty years after G. Sposito, [email protected] Department of Environmental Science, Policy & Management, University of California at Berkeley, Berkeley, California, United States Two decades ago, Donald Macalady and his coworkers proposed that "natural organic matter can effectively mediate the reduction of [pollutant] compounds in reducing environments". They provided a now-famous graphic representing this process, terming natural organic matter (NOM) an "electron-transfer mediator" that could be "replenished through microbial processes". This prescient hypothesis has engendered a body of chemical research directed toward answering several fundamental questions about electron shuttling, as it is now termed: Is electron shuttling by NOM ubiquitous? What constituents of NOM are involved? How can these constituents be quantitated? What are the mechanisms of electron shuttling? This presentation will review the current status of answers to these questions. ENVR 114 Activated benzoquinones, generated by manganese(III,IV) (hydr)oxides, rapidly form adducts with oxygen- and nitrogen-donor nucleophiles P. M. Flanders, [email protected], Z. Shi, and A. T. Stone. Department of Geography and Environmental Engineering, Johns Hopkins University, Baltimore, MD, United States Benzoquinones stable in water such as p-benzoquinone and juglone are sufficiently electrophilic to form Michael-Type adducts with strong, sulfur-donor nucleophiles (e.g. bisulfide ion) but not with environmentally-relevant oxygenand nitrogen-donor nucleophiles. In our work, dihydroxybenzenes bearing electron-withdrawing acetyl and carboxylic acid groups are oxidized by manganese(III,IV) (hydr)oxides typical of those found at oxic/anoxic interfaces into novel benzoquinones. The novel benzoquinones form adducts with OH-/H2O,

anilines, imidazoles, and phenols on timescales of minutes, rather than hours. Mono- and di-adducts have been confirmed using LC-ESI-MS. Reactions of this kind may contribute to the incorporation of oxygen- and nitrogen-containing chemicals, both natural and synthetic, into natural organic matter. ENVR 115 Structural and functional analysis of flavins used during microbial iron reduction B. W. Puls1, [email protected], J. D. Kubicki1, and M. Tien2. 1Geosciences, The Pennsylvania State University, University Park, PA, United States, 2Biochemistry and Molecular Biology, The Pennsylvania State University, United States We use quantum chemical calculations and UV-Vis spectroscopy to analyze the structures and functions of flavins used in extracellular electron transfer by the dissimilatory iron-reducing bacterium Shewanella oneidensis. Flavins increase the rate of electron transfer by chelating reducible iron and/or shuttling electrons between outer-membrane cytochromes and iron-oxide minerals (Canstein et al., 2008; Marsili et al., 2008). Our goals are to 1) determine the potential for flavins to chelate reducible iron and 2) determine the potential for each mediator to shuttle electrons. We use UV-Vis spectroscopy to measure the electronic spectra and quantum chemistry to calculate the minimum energies and expected UV-Vis peaks for several structural configurations of each flavin in four states: 1) oxidized, 2) reduced, 3) bound to reducible iron (Fe3+), and 4) bound to reduced iron (Fe2+). We determine the potential for flavins to chelate reducible iron and shuttle electrons by analyzing the measured spectra and the calculated minimum energies and peaks. We also measure binding constants for flavins with reducible iron (Fe3+) and reduced iron (Fe2+) by monitoring absorbance changes during UV/Vis titrations. This study is the first step towards describing the role of flavins used in extracellular electron transfer on a molecular level. Canstein H. et al. (2008) Secretion of flavins by Shewanella species and their role in extracellular electron transfer. Appl. Environ. Microbiol. 74, 615-623. Marsili E. et al. (2008) Shewanella secretes flavins that mediate extracellular electron transfer. PNAS 105, 3968ENVR 116 Reactions of aqueous iron-DFOB (desferrioxamine B) complexes with flavin mononucleotide in the absence of strong iron(II) chelators D. Kim1, O. W. Duckworth3, and T. J. Strathmann1,2, [email protected] 1 Department of Civil & Environmental Engineering, University of Illinois at Urbana-Champaign, United States, 2Center of Advanced Materials for the Purification of Water with Systems, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 3Department of Soil Science, North Carolina State University, Raleigh, NC, United States

Many microorganisms release Fe(III)-chelating siderophores in response to Fe limitations. The mechanisms controlling siderophore-bound Fe(III) bioavailability remain unclear, but reduction of the Fe(III) center is believed to be important for Fe release and cellular use. Previous studies suggest that reduction of Fe(III)siderophore complexes by physiological reductants is thermodynamically unfavorable over a wide pH range, and that reports of Fe(III)-siderophore reduction are an artifact of strong Fe(II)-chelating colorimetric agents present (to monitor reaction progress). This presentation describes studies on the reduction of Fe(III)-DFOB (desferrioxamine B, a trihydroxamate siderophore) complexes by flavin mononucleotide (FMN) in the absence of Fe(II) chelators, and Fe redox cycling in solutions containing DFOB plus oxidized and/or reduced FMN. Experiments demonstrate that the rate and extent of Fe(III)-DFOB reduction by FMN is strongly dependent on the redox status and speciation of reactants. At circumneutral pH, incomplete Fe(III)-DFOB reduction occurs due to two processes that re-oxidize the resulting Fe(II)-DFOB (auto-oxidation and reaction with oxidized FMN). Observations are consistent with thermodynamic constraints and a speciation-dependent kinetic model for Fe redox cycling. ENVR 117 Allelochemicals and other highly bioactive chemicals generated by the oxidation/reduction of natural products A. T. Stone, [email protected] Department of Geography and Environmental Engineering, Johns Hopkins University, Baltimore, MD, United States Several important natural products released by plants, fungi, and bacteria into surface waters, soils, and sediments must be activated by redox reactions to fulfill their biological function. Oxidations (or reductions) often yield products that are stronger electrophiles (or nucleophiles) than the originally biosynthesized compound. Relating natural product structure and prevalent biogeochemical conditions to pathways and rates of transformation can help explain natural product efficacy. The potent allelochemical sorgoleone, for example, can be generated by oxidation of its sorghum-biosynthesized precursor, a lipid resorcinol, by oxidants found in soils, including Fe(III) (hydr)oxides. DIBOA and DIMBOA, biosynthesized by a number of grain crops, undergo a series of hydrolysis and oxidation steps that generate two much more bioactive compounds, APO and AMPO. Some of these steps are undoubtedly enzymatic, while others could easily take place in soil interstitial media. ENVR 118 Sorption of organic matter to goethite in the presence of ferrous iron and its effect on surface reactivity S. Gocke, [email protected], C. Laskov, and S. B. Haderlein. Center of applied geoscience, University of Tuebingen, Tuebingen, Germany

Redox reactions at mineral surfaces play an important role in anoxic groundwater systems. Previous studies have shown that oxidation of surface bound ferrous iron causes remodelling of the surface and increase the redox reactivity of iron minerals. Commonly, these studies investigated model systems devoid of redox active organic matter, but including organic buffers. Recently, it was shown that these buffers (MOPS, HEPES) led to partial desorption of ferrous iron from goethite, resulting in a decrease in surface reactivity. In this study we investigated the sorption of selected humic substances and quinones (AQDS, Lawsone) to goethite in the presence and absence of surface bound ferrous iron. Aldrich humic acid sorbed up to 4 times higher than quinones. Furthermore, sorption of Aldrich HA increased significantly with increasing ferrous iron content, whereas no desorption of ferrous iron could be observed. It will be further investigated how sorption of redox-active organic matter effect the surface reactivity of goethite. ENVR 119 Fractionation of hydrophobic fractions of dissolved organic matter (DOM) by Fe3+ - montmorillonite T. Polubesova, [email protected], Y. Chen, R. Navon, and B. Chefetz. Department of Soil and Water Sciences, The Hebrew University of Jerusalem, Rehovot, Israel Water-dissolved organic matter (DOM) is the major carrier of heavy metals and organic contaminants in the environment. Fe3+ - saturated mineral surfaces can promote electron transfer reactions of adsorbed organic matter and thus change DOM binding properties. We investigated adsorption and fractionation of the major hydrophobic components of DOM (hydrophobic acid -HoA and hydrophobic neutral-HoN), by Fe3+-montmorillonite. Interactions of fulvic acid (FA) with Fe3+-monmorillonite also have been studied. A pH increase of about one unit was recorded followed by HoA and FA adsorption by Fe3+montmorillonite . The changes in the ratio of absorbance at 250 and 365 nm (E2/E3 ratio) followed by adsorption of HoA and FA indicated the preferable adsorption of larger-molecular-size fractions by Fe3+- montmorillonite. Changes in molar absorptivity at 280 nm and FTIR measurements showed preferential adsorption of aromatic moieties by Fe3+-montmorillonite. Spectroscopic measurements demonstrated distinct fractionation of HoA, HoN, and FA on the surface of Fe3+-montmorillonite. ENVR 120 Reductive dehalogenation of bromotrichloromethane by chemically reduced humic acids and quinones C. Laskov, [email protected], C. Lee, and S. B. Haderlein. Center of Applied Geoscience, University of Tuebingen, Tuebingen, Germany

The potential of natural organic matter (NOM) to reduce halogenated hydrocarbons under anoxic conditions was described already more than a decade ago. The mechanistic understanding of these redox transformations is, however, still limited with respect to target compounds as well as redox active moieties of NOM. In this study we investigated the reductive dehalogenation of BrCCl3 by chemically reduced humic acid and quinones. We used a common protocol from microbial electron shuttling research, which reduces OM with hydrogen and palladium as catalyst. Controls were run with OM incubated with Pd but under N2 atmosphere followed by filtration. As similar transformation rates were obtained for reduced humic acids and controls we postulate that the contact with palladium stimulates the reactivity of HA towards halogenated hydrocarbons. Hence, care has to be taken with regard to chemically reduced humic acids, as the potential for electron transfer processes might be overestimated. ENVR 121 Identifying the rate limiting steps in sustainable algae production for bioenergy A. F. Clarens, [email protected], E. Resurreccion, and L. M. Colosi. Civil and Environmental Engineering, University of Virginia, Charlottesville, VA, United States Algae are considered to be a promising source of next-generation biofuels even though significant technological barriers must be overcome before they can be cultivated on large scales. The results of a comparative life cycle assessment suggest that algae have a much larger environmental burden than either switchgrass or corn in several key impact areas, including greenhouse gas emissions and water use. These impacts are driven by the need to deliver large volumes of CO2 and nutrients to the algae ponds. Algae's one advantage, its inherently small land footprint, suggests that, with improvements, algae could produce bioenergy more effectively than conventional alternatives. Toward realizing these improvements experiments were conducted to evaluate the growth of two microalgae species in wastewater, particularly source-separated urine. Growing algae in these solutions was found to have important implications on algae harvesting processes using filtration. The effects of wastewater composition on algae growth and membrane filtration will be demonstrated. ENVR 122 Material science behind the Fleishmann and Pons effect V. Violante1, [email protected], F. Sarto1, E. Castagna1, S. Lecci1, G. Hubler2, D. Knies2, K. Grabowski2, M. McKubre3, F. Tanzella3, and T. Zilov4. 1 ENEA, Italy, 2NRL, Washington DC, United States, 3SRI, Menlo Park, United States, 4Energetics Technologies, Omer, Israel

Statistical data on excess power production during the electrochemical deuterium loading of palladium cathodes reveal a fundamental role of the metal's state in producing the effect. The metallurgy affects the loading dynamics as well as the deuterium equilibrium concentration; a minimum threshold loading (D/Pd 0.9) is necessary to observe the excess. The crystallographic orientation is also correlated with the phenomenon such that mainly <100> oriented samples gave the highest reproducibility. The third identified conditions concerns the character of the surface of the cathodes that has been identified by means of the power spectral density function. Materials having the above mentioned characteristics have been used to obtain a transportable reproducibility. Material design work has been performed leading to the manufacture of samples giving excess power. The amplitude of the excess is not yet reproducible. The role of the impurities in or on the metal, at the ppm level, seems to be crucial to obtaining the required palladium characteristics. ENVR 123 Cryogenic calorimetry of "exploding" PdDx wires F. Tanzella, [email protected], and M. Mc Kubre, [email protected] SRI International, United States Several groups have reported anomalous effects in thin PdDx materials stimulated by different forms of electro-diffusion. The ultimate extrapolation of this technology is the electrical heating of thin PdDx wires resulting in destructive high-speed melting - "exploding wires". Exploding wire technology has been used for over 150 years to make fine metal particles. Using the techniques of Celani. et al., we are loading thin Pd wires electrochemically up to high loading and sealing their surface electrochemically. Using a novel gas-tight cryogenic calorimeter we can explode the sealed loaded wires safely and measure any excess energy released. We will also measure He formation and isotopic distribution as well as any ionizing radiation that might be produced. ENVR 124 Method of low energy nuclear reactions acceleration by formation of correlated states of interacting particles V. Vysotskii1, [email protected], and S. Adamenko2. 1Radiophysical Dept, Kiev National Shevchenko Univ, Kiev, Ukraine, 2Electrodynamics Laboratory "Proton-21", Kiev, Ukraine In this work we considered a more universal mechanism that could help optimise low energy nuclear reactions on the basis of correlated states of interacting particles. To understand this mechanism, it may provide significant increase of the barrier penetrability under critical conditions (low energy, high barrier), at which the rate of "ordinary" tunneling events is negligibly small, and can be

applied to different experiments. The physical reason of the barrier penetrability increase is strongly combined with the modified uncertainty relation qph/2(1rqp2) of correlated states and with the increase of the momentum p and coordinate q variances as well as the correlation coefficient rqp. We considered preconditions and methods of formation of correlated coherent states of interacting nuclei. It was shown, for the first time, that in real nuclear-physical systems very sharp rise (up to 1030-1050 and more times!) of the Coulomb barrier penetrability at low energy with the increase of rqp is possible. Several successful low-energy correlated-induced fusion experiments will be discussed. ENVR 125 Observation of excess power and isotope effect using D-Pd codeposition methods D. Letts1, and P. Hagelstein2, [email protected] 1Lettslab, Austin, TX, United States, 2 MIT, Cambridge, MA, United States Results from a series of eight codeposition experiments using the methods originated by Szpak, Boss and Smith in 1990-91 are presented. Our preliminary findings appear to support the general claim that excess power is produced when palladium and deuterium are co-deposited on a metal substrate. We found further that a gold-plated copper cathode works better than bare copper. We also observed that excess power only appeared when the gold-plated copper cathode was electrolyzed inside a platinum wire anode cage with a deuterium-based electrolyte. ENVR 126 Cold fusion, LENR, CMNS, FPE: One perspective on the state of the science M. C. McKubre, [email protected] Department of Materials Research, SRI International, Menlo Park, CA, United States It has become important to clarify in non-specialist terms what is known and what is understood in the general field of so called Low Energy or Lattice Enhanced Nuclear Reactions (LENR). It is also crucial and timely to expose and elaborate what objections or reservations exist with regard to these new understandings. In essence we are concerned with the answers to the following three questions: What do we think we know? Why do we think we know it? Why do doubts still exist in the broader scientific community? Progress in the LENR field will be reviewed with primary focus on the experimental work performed at SRI by and with its close collaborators with a view to defining experiment-based nontraditional understandings of new physical effects in metal deuterides. Particular attention will be directed to the Fleischmann-Pons Effect, nuclear level heat from the deuterium-palladium, and the associated nuclear products: 4He; 3He; 3H.

ENVR 127 Catching CO2: Natural products, big molecules and small molecules as Hbonding CO2 receptors J. A. Tossell1, [email protected] 1Department of Chemistry, George Washington Univ., Washington, DC, United States, 2Department of Chemistry and Biochemistry, Univ. of Maryland, College Park, MD, United States There is a great need for the removal of CO2 both from power plant effluents and directly from the atmosphere. We recently studied an amidourea macrocyclic complex with CO3-2, which was formed by the direct removal of CO2 from the atmosphere. This macrocycle contains an already assembled binding site coordinating all the O atoms of CO3-2 through H-bonding to N-H groups. However such macrocycles are expensive. We need either a cheap natural product or a cheap small molecule which can be readily obtained and will bind CO2 or its hydrolysis products moderately strong. We have now used quantum chemical computational techniques to evaluate structures, stabilities and spectral properties for a number of complexes of CO2 and its hydrolysis products with Hbonding receptor molecules in solution. The receptor molecules studied include the natural product prodigiosin, large synthetic molecules containing multiple amine groups and cheap, small molecules such as urea and ammonia. ENVR 128 Beneficial uses of aluminum wastes instead of landfilling G. V. Calder1, [email protected], and T. D. Stark2, [email protected] 1 Environmental & Land Reclamation, Chemtech-Engineering, Racine, WI, United States, 2Department of Civil & Environmental Engineering, University of Illinois, Urbana, IL, United States Recent field experiences show that landfills accepting both raw municipal solid waste (RMSW) and incinerated RMSW (highly alkaline) can undergo a highly exothermic amphoteric reaction of aluminum metal and alkaline water by the following reaction: Al (metal) + (OH)-1(AQ) + 3 H2O(L) = [Al(OH-1)4]-1(AQ) + 3/2 H2 (Gas). This and other reactions can result in the emission of noxious fumes and damage to the engineered components of the landfill. This paper will investigate methods for the beneficial use of aluminum wastes instead of landfilling and how to benefit if a landfill is unfortunately impacted by an aluminum reaction such as "mining" the thermal energy produced using a Stirling type turbine to produce electricity, capturing the hydrogen gas for use as a fuel, and excavating the aluminum waste and using it as a fuel source. ENVR 129 Advances in new energy technologies with van der Waals and Casimir forces based on vacuum energy

T. Ludwig, [email protected] Deutsche Vereinigung für Raumenergie DVR, Berlin, Berlin, Germany One of the most promising new energy technologies are those that use a vast vacuum state energy (vacuum fluctuations, zero point energy) as an energy resource. A fascinating effect in quantum field theory is the Casimir effect, which leads from microscopic fluctuations to a macroscopic force. This effect could be the basis for new energy technologies using ZPE. The effect is also closely related to the van der Waals forces. This work shows how to engineer the vacuum in order to built machines that run on zero point energy. In this report the method based on quartz tuning forks is described towards their usability for Casimir force measurements. Furthermore a design for Casimir force measurements that was set up in Berlin will be described, and practical experimental aspects will be discussed. A status report on the Casimir experiments will be given, including the experimental setup. ENVR 130 Quantum field energy sensor based on the Casimir effect T. Ludwig, [email protected] Deutsche Vereinigung für Raumenergie DVR, Berlin, Berlin, Germany A number of new energy technologies aim to tap the quantum filed energy (vacuum fluctuations, zero point energy). In order to engineer this energy, the author saw the need to develop a sensor. The sensor is based on the Casimir effect. The sensor is necessary in order to study the effects of different geometries, materials and other external conditions on the quantum field energy. In this presentation the design and fundamental parameters of the sensor will be reported. The sensor uses a Casimir force measurement realized by a quartz tuning fork configuration. Furthermore an outlook will be given on which kind of new energy technologies can be studied with the sensor. ENVR 131 Appearance of palladium on zinc anode under vacuum E. Esko, [email protected] Quantum Rabbit LLC, Pittsfield, MA, United States In a vacuum discharge test conducted at Quantum Rabbit (QR) Lab in New Hampshire, USA, QR reserachers noted the anomalous appearance of palladium in test materials, including zinc and copper electrodes and sulfur oxygen catalyst. Significant traces of palladium were discovered by ICP (Inductively Coupled Plasma Atomic Admission Spectroscopy.) Results confirm prediction about possible low energy nuclear reaction between zinc and sulfur, with the applied formula: 30Zn + 16S = 46Pd (zinc plus sulfur into palladium).

ENVR 132 Nanostructured palladium electrochemistry J. Marwan, [email protected] Dr Marwan Chemie, Germany Electrochemical deposition of metals from hexagonal lyotropic liquid crystalline phases produces metal films with a unique ordered nanostructure in which the cylindrical pores of 1.7 to 3.5 nm running through the film are arranged in hexagonal arrays. Nanostructured Pd films were deposited electrochemically from the template mixture of either C16EO8 or BrijÒ 56. Electrochemical studies showed that the metal films have a high electroactive surface area with the specific surface area of the order of 91 m2/g. These values together with the TEM and X-ray data are consistent with the expected H1 nanostructure. The hydrogen region of nanostructured Pd in the cyclic voltammetry in 1 M H2SO4 was more resolved than that of plain Pd because of the thin walls of the nanostructure and the high surface area. We could distinguish the hydrogen adsorption and absorption processes. The permeation of hydrogen into the Pd metal lattice occurs with fast kinetics when the Pd surface is blocked by either crystal violet or Pt. We believe that the hydrogen absorption process takes place without passing through the adsorbed state so that hydrogen diffuses directly into the Pd bulk. This process speeds up when the formation of adsorbed hydrogen is suppressed by the coverage of poisons. These results were compared to those obtained in a heavy water solution to which the Pd electrode was exposed. Adsorption characteristics of deuterium on the Pd metal surface are slightly different to those obtained for hydrogen in previous studies. Diffusion of deuterium into the Pd metal lattice works with fast kinetics under appropriate surface modification. ENVR 133 Reactions at interfaces as significant drivers of indoor chemistry B. J. Finlayson-Pitts, [email protected] Department of Chemistry, University of California Irvine, Irvine, CA, United States Reactions at interfaces are increasingly recognized as being important in atmospheric processes both outdoors and indoors. These include the interface between air and the surfaces of organic and inorganic particles, as well as the interface between air and thin films on solid macroscopic surfaces such as buildings, walls, etc. Despite the potential importance of such chemistry, relatively little is known about the molecular composition and properties of species on the surfaces that determine the interactions with gases. Even the nature of thin films of adsorbed water, their reactivity and their role in chemistry on these surfaces is not well understood. This talk will highlight some areas where interface chemistry is likely to be significant indoors, with emphasis on the need for molecular level understanding in order to quantitatively assess their potential contribution to indoor air quality and impacts.

ENVR 134 Indoor chemistry of secondhand tobacco smoke M. Sleiman1, [email protected], L. A. Gundel1, J. F. Pankow2, [email protected], P. Jacob3, [email protected], M. Ahmed4, [email protected], J. Smith4, [email protected], K. Wilson4, [email protected], B. C. Singer1, [email protected], H. Destaillats1,5, [email protected], and C. Lin1. 1Indoor Environment Department, Lawrence Berkeley National Laboratory, Berkeley, California, United States, 2Portland State University, United States, 3 UCSF, United States, 4Chemical Sciences Division, LBNL, United States, 5 Arizona State University, Tempe, AZ, United States Little is known about how the chemical aging of secondhand smoke (SHS) influences its toxicity. We hypothesize that reactions taking place between SHS pollutants (such as nicotine and particles) and atmospheric reactive species (e.g., ozone and NOx) can be long-term sources of secondary pollutants. In this study we investigated heterogeneous reactions that take place on indoor surfaces and/or on the surface of SHS particles under realistic conditions. Gas chromatography ion trap tandem mass spectrometry (GC-IT-MS/MS), chemiluminiscence detector, scanning mobility particle sizer and vacuum ultraviolet aerosol mass spectrometry (VUV-AMS), were used to identify the reaction products. Our results show that low concentrations of reactive atmospheric species react quickly with SHS and produce carcinogenic, irritant pollutants and secondary organic aerosols (SOA). The formation of these products may lead to increased toxicity of SHS as it ages indoors. Our findings indicate that reactions at indoor interfaces influence the exposure of nonsmokers to SHS. ENVR 135 Chemistry of ozone and human skin lipids and its implications for indoor ozone and carbonyls A. Wisthaler1, [email protected], and C. J. Weschler2,3. 1Institute of Ion Physics and Applied Physics, University of Innsbruck, Innsbruck, Austria, 2 Environmental and Occupational Health Sciences Institute, University of Medicine and Dentistry of New Jersey and Rutgers University, Piscataway, NJ, United States, 3International Centre for Indoor Environment and Energy, Technical University of Denmark, Kgs. Lyngby, Denmark Ozonolysis of leaf lipids has been suggested as a sink for ozone and a source of carbonyls in the atmosphere. In this study, we have investigated the reactions of ozone with human skin lipids as a sink of ozone and a source of carbonyls, dicarbonyls, and hydroxycarbonyls in the indoor environment. An initial series of small-scale in vitro and in vivo experiments were followed by experiments conducted with human subjects in a simulated office. The observed spectrum of ozonolysis products is fully consistent with the Criegee mechanism for ozone

reacting with squalene, the single most abundant unsaturated constituent of skin lipids, and several unsaturated fatty acids in their free and esterified forms. Reactions between ozone and human skin lipids reduce the mixing ratio of ozone in indoor air, but concomitantly increase the mixing ratios of volatile products and, presumably, skin surface concentrations of less volatile products. ENVR 136 Influence of humans on the oxidative capacity of indoor environments C. J. Weschler1, [email protected], and A. Wisthaler2. 1Department of Occupational and Environmental Medicine, University of Medicine and Dentistry of New Jersey, Piscataway, New Jersey, United States, 2Institute of Ion Physics and Applied Physics, University of Innsbruck, Innsbruck, Austria We have recently reported that reactions occurring on exposed human hair, skin and clothing significantly reduce ozone mixing ratios in indoor environments. The same ozone/skin-surface-lipid chemistry responsible for this reduction also impacts the indoor mixing ratios of hydroxyl and nitrate radicals. In the present paper we report results from a modeling study designed to estimate the magnitude of this impact. Several of the primary and secondary products of ozone/squalene chemistry are themselves efficient anti-oxidants. 6-MHO sets an upper limit on the concentration of NO3 radicals in occupied indoor environments and influences the net concentration of OH radicals. Geranyl acetone is also expected to react rapidly with ozone, OH and NO3, producing additional 6-MHO in the process. 4-OPA influences the OH budget. As a consequence of these reactions the oxidative capacity of an otherwise identical room, occupied and unoccupied, can differ dramatically. ENVR 137 Terpenoid emissions from vegetation and their contribution to secondary aerosol formation: Observations from forests, urban areas, and smog chambers, and implications for the indoor environment A. H. Goldstein1, [email protected], N. Bouvier-Brown1, B. Williams1, D. R. Worton1, Y. Zhao1, J.-H. Park1, N. M. Kreisberg2, and S. V. Hering2. 1Department of Environmental Science, Policy, and Management, University of California at Berkeley, Berkeley, CA, United States, 2Aerosol Dynamics Inc., Berkeley, CA, United States Terpenoids emitted from vegetation are oxidized to form secondary aerosols. Terpenoids are also used in household cleaning products and air fresheners, and contribute to chemistry of indoor air. Our research focuses on emissions from vegetation, their oxidation to secondary gas and particle phase products, and their importance for atmospheric processes. We developed the Thermal Desorption Aerosol Gas chromatograph (TAG) system for in-situ speciation of organic compounds in aerosols including primary emissions and secondary

compounds. Recent TAG developments include incorporation of two-dimensional chromatography and a semivolatile collection system. We will present for the indoor air community recent developments in atmospheric organics measurement capabilities (TAG, 2DTAG, SVTAG, TAG-AMS), new observations of speciated semi-volatile gas/particle partitioning, and results from urban, forested, and controlled chamber source oxidation studies of terpenes and their oxidation products. We aim to increase the dialogue regarding mutually interesting research between the outdoor and indoor air communities. ENVR 138 Secondary organic aerosol in the Earth's atmosphere J. A. de Gouw1,2, [email protected] 1NOAA Earth System Research Laboratory, Boulder, Colorado, United States, 2Cooperative Institute for Research in Environmental Sciences, University of Colorado, Boulder, CO, United States In the Earth's atmosphere, secondary organic aerosol (SOA) is formed from the photo-oxidation of volatile organic compounds (VOCs). There are still many uncertainties about the relative importance of SOA from biogenic and anthropogenic VOCs. Based on the known emissions and the SOA yields from smog chambers, one would expect biogenic SOA to dominate over anthropogenic SOA over large areas of the globe. However, recent research has indicated that anthropogenic SOA is formed much more efficiently and may rival the importance of biogenic SOA at northern mid-latitudes. In this talk, I will review the science of SOA as it relates to the atmosphere, and will briefly detail the measurement techniques that are used to come to address these issues. ENVR 139 Reaction kinetics of ozone with four terpenese on glass, polyvinylchloride and paint surfaces G. C. Morrison, [email protected], S. Shu, and M. Springs. Department of Civil, Architectural and Environmental Engineering, Missouri University of Science and Technology, Rolla, MO, United States We have quantified the effective reaction probability and areal rate coefficients of the reaction of four terpenes with ozone on surfaces representative of indoor settings using a tubular fixed bed reactor filled with beads of glass, polyvinylchloride (PVC) or painted glass. A short residence time ensures that gas-phase conversion is inegligible and that only ozone-terpene reactions on bead surfaces are observed. Using terpene concentrations ranging from 27 to 66 ppb for -terpeneol and dihydromyrcenol (DHM) and 0.5 to 1.0 ppm, for -carene and -limonene, we find that the effective reaction probabilities range from 3×10-6 to 3×10-4. Increasing humidity reduces the areal reactivity by water displacement

of -carene and -limonene, but does not effect reactivity for -terpineol. Extrapolating to the surface-area-to-volume ratio typical of indoor environments, the ozone consumption rate due to surface reactions with -limonene is small compared with gas-phase conversion and somewhat higher for -carene. Lower vapor pressure terpenes (-terpineol and DHM) coat more surface sites and surface conversion rates will be greater than those due to gas-phase reactions. Room-sized chamber experiments have verified that ozone and DHM conversion rates are much higher than anticipated from gas-phase reactions alone, and that this increase is consistent with results from the reactor experiments. ENVR 140 Reaction products of indoor chemistry R. Wells, [email protected], and C. D. Forester. Exposure Assessment Branch, National Institute for Occupational Safety and Health, Morgantown, WV, United States The details of indoor chemistry are important to predict or determine occupant exposures and ultimately assess indoor air quality. Dicarbonyls are a class of compounds that could have health effects and have been routinely observed as reaction products in indoor chemistry experiments. Our recent work investigating dicarbonyl reaction product yields from a series of indoor-environment-relevant volatile organic compounds clearly demonstrated that indoor oxidation can result in the formation of other oxygenated organic compounds. Atmospheric research on particulate matter suggests that dicarboxylic acids are also possible reaction products. To further clarify indoor chemistry mechanisms new sampling techniques utilizing denuders and derivatization agents will be presented. The advantage of denuders to easily separate both gas-phase and particulate-phase species yields useful data to assess the partitioning of oxidation reaction products. Both laboratory and field measurements generate data that can be used in indoor air quality models, exposure assessments and occupant health effects studies. ENVR 141 Enhanced mercury removal efficiency with polysulfide-rubber (PSR) coating on activated carbon E. A. Kim1, [email protected], R. G. Luthy1, [email protected], S. Fendorf2, [email protected], Y. M. Slowey2, [email protected], and A. Seyfferth2, [email protected] 1Department of Civil and Environmental Engineering, Stanford University, Stanford, CA, United States, 2Department of Environmental Earth System Science, Stanford University, Stanford, CA, United States Here we report on the utilization of a modified activated carbon to enhance mercury removal efficiencies. We describe mercury removal from water using an

activated carbon coated with a sulfur-rich polymer, namely polysulfide-rubber (PSR) that consists of ethyl-tetrasulfide segments. The paper will discuss the method of preparation in which the polymer was synthesized by a simple one-pot reaction, and the chemical properties of PSR and PSR-Hg-complex. Mercury ions were strongly engaged with PSR even under low pH conditions. Sulfur loading levels were easily controlled by the polymer dose during the coating process. The polymer was effectively impregnated in TOG®-NDS activated carbon maintaining the micropore volumes and total BET surface area when an optimal amount of PSR was used. Mercury adsorption was monitored with Tekran 2600 CVAFS (Cold Vapor Atomic Fluorescent Spectrometry). The paper will discuss the adsorbed mercury distribution on the engineered particles using X-ray fluorescence mapping and microtomography. ENVR 142 Modeling in-situ application of activated carbon to sequester hydrophobic organic compounds in sediments Y.-M. Cho1, D. Werner2, and R. G. Luthy1, [email protected] 1Department of Civil and Environmental Engineering, Stanford University, Stanford, CA, United States, 2School of Civil Engineering and Geosciences, Newcastle University, Newcastle, United Kingdom Laboratory and pilot field studies have demonstrated the `proof of concept' for insitu treatment of sediment with highly-sorbent activated carbon (AC) to repartition persistent hydrophobic organic compounds, and thereby making the contaminants less available to pore water and biota. Models are needed to explain the differences between laboratory results with well-mixed systems and field results with minimally-mixed systems. From both regulatory and management perspectives, models are the only means for making long-term predictions towards an eventual quasi-equilibrium state. This presentation will discuss the formulation of such models that consider: 1. diffusive mass transfer under quiescent conditions, 2. advective pore water movement in intertidal and sub-tidal regions, 3. effects of dissolved organic matter on reducing the mass transfer and/or sorption capacity of the AC, and 4. the distribution of AC particles within the sediment, e.g., uniformly distributed as in a well-mixed laboratory test or heterogeneously distributed, as in a field trial. ENVR 143 Characterization of arsenic absorption by Fe2O3 supported on granular activated carbon (GAC) J. Terry1, [email protected], D. Olive1, Y. Ha1, Y. Gim1, Z. Gu2, and B. Deng2. 1 Department of Biological, Chemical, and Physical Sciences, Illinois Institute of Technology, Chicago, IL, United States, 2Department of Civil and Environmental Engineering, University of Missouri, Columbia, Columbia, MO, United States

Previous work [Gu, Z., et al., Environ. Sci. Technol. 39, 3833 (2005)] on iron­ impregnated granular activated carbon showed that it may be used in remediation of arsenic contaminated water, although the method by which the arsenic binds to the Fe-GAC was not determined. X-ray absorption (XAS) measurements were carried out at the iron and arsenic K­edges in order to determine the incorporation of the iron on/in the GAC and the geometry of the absorbed arsenic moiety to the surface. X-ray absorption near edge structure (XANES) and x-ray absorption fine structure (XAFS) results indicate that the iron exists as Fe3+ in the form of a thin iron oxide layer supported on the micropores of the GAC. XANES and XAFS show that the As exists on the surface as As5+. The arsenic compound on the surface is AsO43- and is bound to the iron oxide layer. No evidence of As-O-C bonding was observed. Density functional theory (DFT) calculations were performed to calculate the expected As surface geometry on Fe2O3. The observed surface geometry was in excellent agreement with that predicted by the DFT calculations. ENVR 144 Removing aqueous Hg(II) by sulfur-impregnated activated carbon and mesoporous carbon J. Zheng1,2, [email protected], B. Deng2, J. Wang3, and J. Yin2. 1State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, Jiangsu, China, 2Department of Civil and Environmental Engineering, University of Missouri, Columbia, MO, United States, 3 Institute of Chemistry, Henan Academy of Sciences, Zhengzhou, Henan, China Sulfur-containing activated carbons and ordered mesoporous carbons were prepared by impregnating elemental sulfur into a powdered activated carbon and an ordered mesoporous carbon under different temperatures for removing Hg(II) from aqueous solutions. Batch adsorption experiments were conducted to optimize the sulfur impregnation temperature and understand the impact of aqueous chemistry on Hg(II) removal. For the activated carbon, the optimal temperature was found to be 400 oC. The sulfur-impregnated activated carbon prepared at this temperature had a maximum adsorption capacity of about 800 mg/g at pH=5.5. At C0 = 43 mg/L, the Hg(II) removal rates were consistently above 98% in the pH range of 2-11. Ionic strength and the majority of water constituents, except for chloride and humic acid, did not show much impacts on Hg(II) uptake. Compared to their activated carbon counterparts, sulfurimpregnated mesoporous carbons had similar adsorption properties for Hg(II) removal, but their adsorption capacities were surprisingly lower. ENVR 145 Enhanced adsorption kinetics by adsorption site coverage on internal pore surface of activated carbon

L. Ding, [email protected], B. J. Mariñas, and V. L. Snoeyink. Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States Traditional activated carbon stays as the most popular adsorption material, in spite of the development in novel adsorbent research. The current study by our research group focuses on better understanding the competitive effect of competing compounds on target compound adsorption kinetics. In addition to the previously discovered pore blockage effect in which large competing compounds slow down the diffusion of the target compound, the competition may actually also speed up the kinetics when the similarly-sized competing molecules are present. The proposed hypothesis is that those molecules cover up some of the adsorption sites and therefore reduce the diffusion resistance due to surface affiliation between adsorbates and adsorbents. It was also found that using the equivalent background compound (EBC) for competing compound adsorption better related the extent of enhancement with competition. Continuing research is being carried out to confirm this enhancement effect and to better quantify it. The knowledge will build the basis for modeling trace organic compound removal by activated carbon in the presence of background organic matter. ENVR 146 Predicting natural water adsorption isotherms using polyparameter linear free energy relationships Q. W. Chow, [email protected], T. H. Nguyen, [email protected], and V. L. Snoeyink, [email protected] Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States Recently, the presence of emerging trace organic contaminants in our drinking water have become of great concern. Activated carbon has been widely used to remove both natural organic matter (NOM) and trace organic contaminants. Adsorption isotherms in for trace contaminants in the presence of NOM are needed to predict the performance of activated carbon for removing these compounds, but such data are not available for most of these emerging contaminants and it will be expensive to carry out isotherm tests for all the emerging contaminants. The approach presented here is intended to fulfill this need. Polyparameter linear free energy relationships (pp-lfer) of activated carbon adsorption for trace contaminants in organics free water have been well developed. However, in the presence of NOM, the adsorption capacity and kinetics for trace organic contaminants on activated carbon is greatly decreased. The objective of this research is to develop a model that can predict the adsorption capacity of activated carbon in natural water using available molecular descriptors of the trace contaminants. Pharmaceuticals, endocrine disrupting compounds and some industrial solvents are used in this study as trace compounds, Suwannee River NOM was selected, and oxidized graphite was used to represent a typical activated carbon surface. Results show that natural

water adsorption capacity predictions by the pp-lfer model are within a factor of 2 from the experimental values. ENVR 147 Metal grafted mesoporous SBA-15: Effect of transition metal incorporation on the adsorption of naproxen from water S. M. Rivera-Jimenez, [email protected], S. Mendez-Gonzalez, [email protected], and A. J. Hernandez-Maldonado, [email protected] Department of Chemical Engineering, University of Puerto Rico at Mayaguez, Mayaguez, PR, United States Incorporation of transition metals onto the surface of mesoporous silica via grafting techniques could become a potential strategy for the bottom-up design of sorbents for the removal of pharmaceutical drugs and other emerging contaminants from water sources. In this presentation, we will discuss the incorporation of Co2+, Ni2+ or Cu2+ onto the surface of SBA-15 using an aminoorganic grafting method. The resulting metal-modified materials have been fully characterized using XRD, SEM/EDAX, FT-IR, TGA and porosimetry. Aqueous phase single point adsorption experiments showed that Cu-based materials are excellent sorbents for the uptake of low-concentration Naproxen at 25o C and alkaline conditions. The materials uptake capacities decreased as follows: CuNH2_g_SBA-15 > NiNH2_g_SBA-15 > CoNH2_g_SBA-15. In general, the adsorption results correlate well with the observed structural and textural properties of the materials, suggesting also that the metal amino organic loading is highly dependent on the nature of grafting process and choice of metal. ENVR 148 Dinitrophenol adsorption by ordered nanoporous organosilicates M. Zavareh, [email protected], C. W. Ingram, and C. Parker. Chemistry, Clark Atlanta University, Atlanta, GA, United States Ordered nanoporous organosilicates, MCM-41 and SBA-15 containing amino and imidazole organic functionalities were evaluated for the adsorption of phenolic compounds from water. The presence of the imidazole group introduced a strong affinity for 2,4-dinitrophenol (2,4-DNP). The effect of pore size, type and concentration of organic functionalities, pH and concentration of 2,4-DNP on the adsorption selectivity, capacity and kinetics will be presented. ENVR 149 Elucidating the role of dissolved organic matter as a chemical reductant in anaerobic sediments

E. J. Weber1, [email protected], and H. J. Zhang2. 1National Exposure Research Laboratory, US EPA, Athens, GA, United States, 2Department of Chemistry and Environmental Sciences, Southern Illinois University Edwardsville, Edwardsville, IL, United States The pioneering work of Frank Dunnivant, René Schwarzenbach, and Donald Macalady (Environ. Sci. Technol. 1992, 26, (11), 2133-2141) demonstrated the reduction of substituted nitrobenzenes by dissolved organic matter (DOM). This finding provided much of the impetus for numerous studies designed to elucidate the role of DOM in the reduction of nitroaromatics and halogenated aliphatics in model systems designed to mimic natural systems. To extend this work to anaerobic sediments, we conducted a two-pronged investigation to measure (1) the reactivity of a probe chemical, which allowed for differentiation between surface-associated and solution-phase electron-transfer processes, in several anaerobic sediments, and (2) the reactivity of a soluble nitroaromatic in twentyone anaerobic sediments of different origins. The results of these studies indicate that Fe(II) associated with amorphous Fe(III) minerals and biologically-reduced DOM are the predominant reductants in anaerobic sediments, and that soluble Fe(II) and DOC will serve as readily measurable indicators of their reactivity. ENVR 150 Chiral probes for redox behavior in the biotransformation of PCBs C. M. Lee, [email protected] Department of Environmental Engineering & Earth Sciences, Clemson University, Anderson, SC, United States The reductive dechlorination of polychlorinated biphenyls (PCBs) is one of the few transformative mechanisms available for PCBs in natural systems. The reductive mechanism is more probable than the oxidative mechanism because the hydrophobic PCBs tend to associate with anaerobic, organic-rich sediments. The chiral nature of selected congeners allows researchers to explore the mechanisms and is supplementary to molecular biological techniques. Our research group published the first microcosm work showing enantioselective reductive dechlorination of chiral PCBs. Microcosms were incubated with sediment from Lake Hartwell, SC, a Superfund site with monitored natural recovery as the remediation. Additional work indicates that distinct microbial species are responsible for removal of each type of chlorine. We also found evidence that microorganisms colonizing different types of organic matter (fine benthic organic matter, coarse particulate organic matter, and periphyton) have different biotransformation pathways. Using chiral PCB congeners as probes can reveal interesting features of biological reductive-oxidation pathways. ENVR 151 Charging and decharging: The role of hydrology in controlling the redox state in DOM rich wetlands

S. Peiffer, [email protected], K. H. Knorr, [email protected], S. Frei, [email protected], and J. Fleckenstein, [email protected] Department of Hydrology, University of Bayreuth, Bayreuth, Germany Whether redox active DOM will act as electron donor or acceptor strongly depends on the redox state of the DOM-bearing waters which itself is regarded to be controlled by the coupling of microbial and geochemical reactions. In our presentation we will demonstrate that the variability and dynamics of biogeochemical reactions in such an aquatic system may mainly depend on the spectrum of different residence times in the system. We have performed simulations of biogeochemical turnover rates in a wetland as a function of residence times along reaction paths and found a reasonable agreement with measured and predicted concentration profiles of redox active species. We hypothesize that the loading of pore waters with redox active species, the contact time with organic matter and the exposure time to a certain redox state is controlled by the spectrum of hydraulic residence times and creates a broad variety of biogeochemical environments. ENVR 152 Rapid transformation of the antibiotic sulfamethoxazole under ironreducing soil conditions: Evidence in support of a biotically mediated abiotic mechanism J. L. Mohatt1, K. T. Finneran1, and T. J. Strathmann1,2, [email protected] 1 Department of Civil & Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 2Center of Advanced Materials for the Purification of Water with Systems, University of Illinois at UrbanaChampaign, Urbana, IL, United States Antibiotics are heavily used for livestock growth promotion and disease prevention. Agricultural soils receive large inputs of antibiotics from land applications of manure, leading to concerns about antibiotic fate and persistence. This contribution examines the mechanism responsible for rapid degradation of the antibiotic sulfamethoxazole in soil incubated under Fe(III)-reducing conditions. Soil microcosms incubated under different terminal electron accepting processes (TEAPs) showed, unexpectedly, that sulfamethoxazole degrades much more rapidly under Fe(III)-reducing conditions than other TEAP conditions (aerobic, nitrate-reducing, sulfate-reducing). Subsequent experiments suggest that the rapid transformation results from abiotic reactions with microbially generated Fe(II). Sulfamethoxazole degrades in sterile Fe(II)-amended suspension of goethite (-FeOOH(s)) by reductive cleavage of the five-member isoxazole ring, and reaction rates increase with increasing Fe(II) sorption to goethite. Results of this work show that abiotic reaction with Fe(II) may be an important, but previously unrecognized, contributor to the fate of sulfamethoxazole and related isoxazole-containing compounds in soils.

ENVR 153 Impact of iron salt anion identity on the reactivity of synthesized iron nanoparticles K. Moore1, [email protected], B. Forsberg1, B. Arnold1, D. Baer2, and L. Penn1. 1University of Minnesota, United States, 2Pacific Northwest National Laboratory, United States Zero-valent iron particles are an effective remediation technology for groundwater contaminated with halogenated organic compounds. In particular, nano-scale zero-valent iron is a promising material for remediation due to its high specific surface area, resulting in faster rate constants and more effective use of the iron. An aspect of iron nanoparticle reactivity that has not been explored is impact of varying the anion of the iron salt used for iron metal nanoparticle synthesis. Iron salts were used to generate iron oxide nanoparticles, which were dialyzed to remove dissolved byproducts and then dried and reduced by hydrogen gas at high temperature. The reactivity of the resulting zero-valent iron nanoparticles was quantified by monitoring the kinetics of carbon tetrachloride reduction, and significant differences in reactivity were observed. Furthermore, substantial variations in the solid-state products of oxidation; such as magnetite, iron sulfide, lepidocrocite, and goethite, among others; were also observed. ENVR 154 Redox driven atom exchange in goethite and magnetite M. Scherer1, [email protected], R. Handler1, C. Johnson2, B. Beard2, C. Gorski1, and K. Rosso3. 1Department of Civil and Environmental Enginering, University of Iowa, Iowa City, IA, United States, 2Department of Geology & Geophysics, University of Wisconsin, Madison, WI, United States, 3Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, Richland, WA, United States The redox reactions of iron (Fe) influence a variety of global elemental cycles such as carbon, nitrogen, and phosphorus. We are using stable Fe isotopes in conjunction with 57Fe Mössbauer spectroscopy to study redox reactions between ferrous Fe and Fe oxides. Our results show that sorbed Fe(II) is oxidized by Fe(III) in Fe oxides, such as goethite, hematite, ferrihydrite, and magnetite, and that Fe(II)-Fe(III) electron transfer initiates extensive mixing between the Fe oxide and aqueous Fe(II) in both goethite and magnetite. We propose that a redox-driven conveyor belt is established where sorption and dissolution sites are linked via conduction through the bulk crystal, as was recently demonstrated for hematite. Complete re-crystallization of Fe oxides in the presence of Fe(II) has significant implications for heavy metal sequestration and release (e.g., arsenic and uranium) and reduction of soil and groundwater contaminants.

ENVR 155 Assessing redox properties of structural Fe in smectites with electrochemical methods M. Sander1, D. Soltermann1, M. Aeschbacher1, M. Marques2, B. Baeyens2, C. A. Gorski3, R. P. Schwarzenbach1, and T. B. Hofstetter1, [email protected] 1Department of Environmental Sciences, IBP/ETH Zurich, Zurich, Switzerland, 2Nuclear Energy and Safety Department, Laboratory for Waste Management / Paul Scherrer Institute, Villingen, Switzerland, 3Department of Civil and Environmental Engineering, University of Iowa, Iowa City, United States Redox reactions involving structural iron in clay minerals such as smectites play a key role in the biogeochemical cycling of elements and the transformation dynamics of pollutants. Yet, the redox properties of structural Fe, including the dependence of its reduction potential, Eh, on the extent of Fe reduction and structural arrangement, remain poorly understood. In this study, we electrochemically reduced and oxidized structural Fe in model clays in the presence of redox-active organic radicals to facilitate the electron transfer between clay and the working electrode. We observed a decreasing Eh of structural Fe with increasing pH at constant extent of Fe reduction. At constant pH, Eh decreased with increasing degree of Fe reduction more strongly than explicable by the classical Nernst equation. These trends suggest that the Eh of structural Fe in clay minerals is highly variable because Eh is affected by several mineralogical properties including total Fe content, Fe(II)/Fe(III) ratio, and arrangements of Fe(II)-Fe(III) within the structure. H+/e- transfer ratios of unity during both reduction and oxidation of Fe point towards reversible dehydroxylation reactions of structural Fe and hence charge compensation by the uptake and release of protons. The determined redox properties help to rationalize the complex kinetics of organic contaminant reduction at clay mineral surfaces. ENVR 156 Influence of Al, Mn, and phosphate on the reaction of Fe(II) with goethite D. E. Latta, [email protected], and M. M. Scherer, [email protected] Department of Civil and Environmental Engineering, The University of Iowa, Iowa City, IA, United States In nature, iron oxides like goethite exist in a complex chemical milieu with sorbed species such as phosphate and with common structural impurities including Al and Mn. Cation substitution of Al for Fe is known to alter the redox behavior of goethite resulting in slower rates of reductive dissolution with increasing Al substitution. We are investigating the influence of Al and Mn substitution, as well as phosphate sorption on electron transfer and atom exchange between aqueous Fe(II) and goethite by measuring Fe(II) uptake isotherms and using the isotope

selectivity of 57Fe-Mössbauer spectroscopy. We observed significantly less Fe(II) uptake on Al-substituted goethite compared to pure goethite, and in contrast to pure goethite, we observed the formation of a stable Fe(II) species. Formation of the Fe(II) species indicates Fe(II)-Fe(III)oxide interfacial electron transfer did not occur for some of the Fe(II) on the Al-substituted goethite, which may influence the reactivity of goethite towards oxidized contaminants. ENVR 157 Ultrafine particle concentrations and exposures in Northern California houses W. W. Nazaroff, [email protected], S. Bhangar, and N. Mullen. Department of Civil & Environmental Engineering, University of California, Berkeley, California, United States Field monitoring of ultrafine particles and copollutants was conducted for a weeklong period at each of seven houses in the East Bay area near San Francisco, California. At each site, time-resolved measurements were made indoors and outdoors of particle number concentrations in addition to nitric oxide, ozone, and carbon dioxide. Data were also acquired through the use of questionnaires and temperature and proximity sensors. The information was analyzed to characterize (1) indoor and outdoor PN concentrations; (2) key factors that influence indoor PN concentrations; and (3) the exposure of building occupants to indoor PN and its determinants. The results provide important information about the interplay among building factors, human occupancy, and pollutant dynamics as they influence concentrations of and exposures to ultrafine particles in the houses. Particle levels indoors were much higher when occupied than when vacant. Indoor emission sources were important contributors to indoor PN levels. ENVR 158 Surfaces and particles in indoor and outdoor environments: From heterogeneous chemistry to occupational health hazards V. H. Grassian, [email protected] Department of Chemistry, University of Iowa, Iowa City, IA, United States In this talk, the importance of surfaces and particles in atmospheric chemistry and the role of heterogeneous chemistry on mineral dust in the fate and transport of trace gases and pollutants will be discussed. In the indoor environment, surfaces and particles are equally important from several perspectives including heterogeneous chemistry of trace gases on particles and surfaces and the potential health hazards of nanodust from the nanotechnology industry. The talk will focus on a wide range of issues associated with several different aspects of particles and surfaces in indoor and outdoor environment including: (i) the impact

of relative humidity on surfaces and surface chemistry; (ii) surface spectroscopy to unravel molecular speciation of pollutants on surfaces; (iii) changes in the physicochemical properties of surfaces and particles following reaction with pollutants; (iv) single particle characterization of particulate matter in the workplace. The approach to these studies combines surface chemistry and surface science, aerosol science, microscopy and spectroscopy to unravel the details of the role of particles and surfaces in indoor and outdoor environments. ENVR 159 Multi-tool formaldehyde measurement in simulated and real atmosphere for indoor air monitoring C. George1, [email protected], M. Sassine1, L. Chiappini2, F. Fuvel2, R. Dagnelie3, S. Fable2, and T.-H. Tran-Thi2. 1IRCELYON, CNRS, Villeurbanne, France, 2INERIS, Verneuil-en-Halatte, France, 3CEA Saclay, Gifsur-Yvette, France People spend most of their time in indoor environments where they can be exposed to many pollutants. Among them, formaldehyde is of particular concern due to its health effects and its abundance in domestic environment linked to continuous (resins, wood products...) and intermittent (cooking, cigarette smoke...) sources. In French public places, usually recorded formaldehyde mean concentrations range from 3 g m-3 to 60 g m-3. To define a formaldehyde measurement method suitable for usual indoor levels, five different techniques have been tested in the INERIS simulation chamber and in indoor environments: a passive and an active sampling methods based on formaldehyde DNPH reaction, two on-line, continuous monitoring system based on fluorescence and UV measurement, a portable commercialised analyser based on electrochemical reaction. Chamber experiments have been carried out under two formaldehyde concentration levels, 10 and 25 µg m-3 and controlled temperature (20 °C), relative humidity (50 %) and wind speed (1 m s-1) conditions, to asses their potential influence on passive sampling and continuous systems response. Two sampling periods have been tested, 8 and 48 hours, also to evaluate their influence on passive sampling. Real atmosphere experiments have been performed in four different indoor environments: an office, a furniture shop, a shopping mall and residential dwelling in which several potential formaldehyde sources have been tested (candle burning, cooking...). An overall agreement between each technique have been observed. Analytical and sampling problems associated with each one of them have been identified. ENVR 160 Squalene and cholesterol in indoor dust: Implications for indoor chemistry C. J. Weschler1,2, [email protected], S. Langer3, A. Fischer3,4, G. Beko1, J. Toftum1, and G. Clausen1. 1International Center for Indoor Environment and

Energy, Technical University of Denmark, Lyngby, Denmark, 2Department of Occupational and Environmental Medicine, Univeristy of Medicine and Dentistry of New Jersey, Piscataway, New Jersey, United States, 3Department of Chemistry and Material Sciences, SP Technical Research Institute, Boras, Sweden, 4Department of Chemistry, Atmospheric Sciences, University of Gothenburg, Goteborg, Sweden Mass-fractions of squalene and cholesterol have been measured in dust samples collected from non-floor surfaces in the bedrooms (n = 500) and daycare centers (n = 151) of children from Odense, Denmark. The mass fractions of squalene are log-normally distributed (homes: GM = 25 µg/g, GSD = 7.1; daycare centers: GM = 8.6 µg/g, GSD = 6.9). The mass-fractions of cholesterol are not well described by a log-normal distribution (homes: median = 356 µg/g; daycare centers: median = 135 µg/g). If squalene is present in the dust as a consequence of partitioning from the gas phase, then it is on all exposed indoor surfaces. Given the rapid surface reaction between squalene and ozone, this observation could help to explain the relatively similar deposition velocities that have been measured for ozone in numerous indoor environments. Squalene-soiled surfaces would contribute to the scavenging of ozone in all settings occupied by humans. ENVR 161 Indoor air purification/deodorization by TiO2 photocatalysis: Fundamentals, potentialities and problems P. Pichat, [email protected] Photocatalyse et Environnement, CNRS/Central School of Lyon, Lyon, France This keynote talk will start with some basic information about the mechanisms and active species involved in TiO2 photocatalysis. The influence of air relative humidity on the removal rate of pollutants as well as the competition between indoor air pollutants will then be discussed. The question of the effect of purifiers based on TiO2 photocatalysis upon the average concentration in indoor air of carbonyl compounds of low-molecular mass will also be addressed. ENVR 162 Molecular studies of chemical reactions relevant to remediating indoor air pollution F. Geiger, [email protected] Department of Chemistry, Northwestern University, Evanston, IL, United States Chemical ionization mass spectrometry (CIMS) is used to study the adsorption and photochemistry of the common indoor air pollutant acetone and several of its homologs on the surface of Degussa P25 TiO2, an inexpensive catalyst that can be used to mineralize volatile organic compounds. Using nonreactive uptake coefficients for acetone, formic acid, acetic acid, mesityl oxide, and diacetone

alcohol, and results from photochemical studies, we quantify, on a per-molecule basis, the room-temperature photocatalytic conversion of the species under investigation to CO2 and related oxidation products. The results imply that catalytic surfaces that enhance formate and acetate production from acetone precursors will facilitate the photocatalytic remediation of acetone in indoor environments even at room temperature. ENVR 163 Photocatalytic oxidation of indoor VOCs at ppb levels: Kinetics of byproducts formation O. Debono2, [email protected], F. Thevenet2, [email protected], V. Hequet1, [email protected], C. Raillard1, [email protected], L. Le-Coq1, [email protected], and N. Locoge2, [email protected] 1 Dept. Systemes Energetiques et Environnement, Ecole de Mines de Nantes, Nantes, France, 2Dept. Chimie et Environnement, Ecole de Mines de Douai, Douai, France In the present work the photocatalytic oxidation (PCO) of toluene and n-decane is individually performed in a 120L simulation chamber using Degussa P25 TiO2 as photocatalyst. The kinetic disappearance of toluene and n-decane is monitored for initial concentrations ranging from 100 to 800 ppb. Two levels of relative humidity are investigated (RH = 0% and RH = 50% at ambient temperature). Several by-products are identified and quantified in the gas phase. The reaction intermediates detected for toluene PCO are given in Table 1 below. Table 1.Identified reaction intermediates of toluene PCO. Retention time (min) 8.679 10.12 15.082 17.202 19.629 20.200 20.959 21.249 23.028 26.103 Reaction intermediate acetic acid benzene hexanal 1-hexanol benzaldehyde octanal o-cresol m-cresol+p-cresol decanal 4-octen-3-one

For the PCO of n-decane the observed reaction intermediates belong to the chemical groups of aldehydes, ketones, and alkenes. Their temporal evolution is thus investigated and finally pathways for the PCO of toluene and n-decane are proposed.

ENVR 164 Nitrate radical chemistry of the indoor environment: Gas-phase and surfaces J. E. Ham, [email protected], J. C. Harrsion, M. M. Flemmer, and R. Wells. Exposure Assessment Branch, National Institute for Occupational Safety and Health, Morgantown, WV, United States Indoor environments contain, or are treated with chemicals that result in the formation of oxygenated organics due to reactions initiated in the gas phase and/or on surfaces by the nitrate radical (NO3·). Previous work by this group has shown that the gas-phase chemistry of NO3· with fragrances can occur 1-3 times faster than an air exchange of 1 h-1 and lead to the formation of potentially asthmagenic species. Our group has also investigated the surface chemistry of fragrances with ozone (O3) which resulted in the formation of new reaction products compared to the gas phase. Combining these results has led to the development of instrumentation for the introduction of NO3· to a surface that has been coated with common fragrances found indoors. This system includes a cavity-ringdown system (CRDS) used for accurately measuring nitrate radicals in the outdoor environment and the previously designed FLEC Automation and Control System (FACS). ENVR 165 Experimental confirmation of the homogeneous hydrolysis of NO2 under atmospheric conditions: A new source of HONO and secondary inorganic aerosol-NH4NO3 B. Zhang1, [email protected], F.-M. Tao2, and Z. Li2. 1Department of Chemistry, NSC Environmental Science and Technology, Temple City, CA, United States, 2Department of Chemistry and Biochemistry, California State University, Fullerton, Fullerton, California, United States It has been shown from our recent theoretical studies that the homogeneous hydrolysis of NO2 is thermodynamically favorable under normal atmospheric conditions and the reaction is likely responsible for the production of atmospheric HONO. Furthermore, the same reaction may also directly lead to ammonium nitrate (NH4NO3) as a secondary inorganic aerosol through a homogeneous nucleation process. Laboratory experiments have been followed to confirm the theoretical prediction. Product species including HONO and NH4NO3 were observed by FT-IR spectroscopy. ENVR 166 Development and characterization of photocatalysts for water purification

W. Choi, [email protected] School of Environmental Science and Engineering, Postech, Pohang, Gyoengbuk, Republic of Korea The photocatalytic water treatment technologies based on the photo-induced redox reactions occurring on the illuminated semiconductor nanoparticles have been extensively studied for the last two decades. Although the popularity of this technology is widespread among environmental scientists and engineers, it is still waiting for breakthroughs in materials development, mechanistic understanding, and reactor engineering. In this talk, several examples related with photocatalytic water purification will be briefly introduced. The specific topics include the assessment of photocatalytic activity for water treatment and the development of visible light active photocatalysts. The substrate-specific nature of photocatalysts was systematically investigated for its implication for water treatment. As for the visible light photocatalysis, the synthesis and the characteristics of fullerol/TiO2, dye-sensitized TiO2 and Pt/WO3 will be introduced and their applications to water purification be discussed. ENVR 167 Photocatalytic degradation of the X-ray contrast agent diatrizoate by nanophase TiO2: Kinetics and mechanisms M. N. Sugihara1,2, [email protected], L. Hu1,2, D. Moeller1,2, and T. J. Strathmann1,2. 1Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 2Center of Advanced Materials for the Purification of Water with Systems, University of Illinois at Urbana-Champaign, Urbana, IL, United States Tri-iodinated X-ray contrast media have been widely detected in natural waters in relatively high concentrations compared to other micropollutants due to their inherent stability. Diatrizoate, an ionic tri-iodinated compound, is recalcitrant towards conventional wastewater and drinking water treatment processes. As a result, alternative treatment technologies are being explored to treat diatrizoate and other recalcitrant compounds. This study examines the photocatalytic treatment of diatrizoate using nanophase TiO2. Batch experiments demonstrate rapid degradation of diatrizoate in aqueous TiO2 suspensions illuminated with UVA light, whereas no degradation is observed in light-only controls, TiO2 suspensions under darkness, or illuminated with visible light. The predominance of oxidative versus reductive transformation pathways is being examined through scavenger/electron acceptor studies and organic product analysis by tandem mass spectrometry. The effects of solution conditions (e.g., the presence of nontarget water constituents) will also be discussed in addition to preliminary results for diatrizoate treatment in a flow-through photocatalytic reactor. ENVR 168

Controlling bromate formation following UV-TiO2 oxidation in brackish water R. M. Brookman, [email protected], R. Lamsal, and G. A. Gagnon. Centre for Water Resources Studies, Dalhousie University, Halifax, Nova Scotia, Canada The U.S. EPA has identified bromate as a contaminant and have set a maximum contaminant level (MCL) of 0.010 mgL-1 for drinking water, with a goal (MCLG) of reducing this limit to zero. Compliance with the MCLG will become increasingly difficult for treatment plants where bromide ions are inherent in the source water. The objective of this study is to show that bromate is controlled to levels below detection limits as a result of TiO2 photocatalysis in freshwater or seawater. The two water matrices are tested independently, as well as a mixture that contains half of the salinity (bromide concentration) found in seawater, thereby creating an artificial brackish water matrix. Samples are ozonated to provide a basis for comparing the results. Scanning electron microscope (SEM) images are taken of the nanoparticles and x-ray photoelectron spectroscopy (XPS) is performed to determine the amount of titanium lost during photocatalysis. Table 1 - Test Variables for 23 factorial design experiments in each of the three water matrices. TiO2 1 mgL-1 5 mgL-1 UV 5 mJ/cm2 50 mJ/cm2 Salinity (Br-) 15 ppt (22 mgL-1) 30 ppt (44 mgL-1)

On limited sample size and test variable, Brookman et al. (2009) reported that UV irradiation of TiO2 nanoparticles suspended in seawater did not produce bromate or bromoform when ozonation produced significant levels of both DBPs. Results of brackish water trials are expected to show photocatalysis of TiO2 nanoparticles does not produce bromate or bromoform in brominated water matrices. Results from the SEM and XPS analyses of the nanoparticles will show titanium is not released during photocatalysis, and provide insight to their stability when used for drinking water treatment applications. These results will illustrate that TiO2 photocatalysis is a promising solution for meeting the U.S. EPA MCLG for drinking water. Experiments are underway and results are expected February 2010. ENVR 169 Enhanced photocatalytic solar disinfection (ENPHOSODIS) of Escherichia coli using nitrogen and fluorine co-doped titanium dioxide M. Pelaez1, E. R. Bandala2, J. Castillo2, P. S. M. Dunlop3, A. Byrne3, and D. D. Dionysiou1, [email protected] 1Department of Civil and Environmental Engineering, University of Cincinnati, Cincinnati, Ohio, United

States, 2Department of Civil and Environmental Engineering, Universidad de las Americas-Puebla, Cholula, Puebla, Mexico, 3Nanotechnology and Integrated Bioengineering Centre, University of Ulster, United Kingdom Solar disinfection (SODIS) is a simple, environmentally friendly and low cost point-of-use treatment technology for drinking water purification. However, improvements of SODIS performance such as reduction of irradiation time and avoidance of bacteria re-growth are necessary. Visible light-activated TiO2 is a promising technology for the enhancement of SODIS. In this study, inactivation of Escherichia coli (E.coli) was determined using sol-gel based nitrogen and fluorine co-doped TiO2 (NF-TiO2) and control TiO2 nanoparticles under dark, visible and solar light at different pH conditions. The presence of NF-TiO2 enhanced the disinfection rate efficiency of E.coli when compared to those experiments where control or no photocatalyst was used. The value of pH of the suspensions was observed to have an important role in the inactivation mechanisms which seems to be related with the cell wall permeability and with particle's surface charge. Finally, the development of a simple UV dosimetric indicator for disinfection was also explored. ENVR 170 Virus inactivation is mediated by reactive oxygen species in photosensitized fullerol nanoparticle suspensions S. Chellam1, [email protected], A. R. Badireddy1, [email protected], E. M. Hotze2, [email protected], and M. R. Wiesner2, [email protected] 1Civil and Environmental Engineering, University of Houston, Houston, Texas, United States, 2Civil and Environmental Engineering, Duke University, Durham, NC, United States Production of reactive oxygen species through photosensitization of fullerol nanoparticles is shown to enhance viral inactivation rates. Singlet oxygen production in UV-A illuminated fullerol suspensions was confirmed via EPR spectroscopy, NBT reduction, and the SOSG procedure. The first-order MS2 bacteriophage inactivation rate nearly doubled due to the presence of singlet oxygen, and increased by 125% due to singlet oxygen and superoxide when compared with UV-A illumination alone. Mechanisms of loss of virus infectivity were also probed using dsDNA bacteriophages with capsids of different composition (T7 and PRD1). Capsid protein damage was identified using FTIR spectroscopy and SDS-PAGE. Inactivation rates varied as MS2 > T7 > PRD1 indicating the role of capsid composition in the susceptibility of viruses to singlet oxygen. Damages to phage membrane components could be resulting from protein oxidation and cross-linking. These results suggest that fullerenes can impact natural microbial populations as well as their potential as a disinfectant. ENVR 171

Tuning a ligand-promoted oxygen atom transfer system for perchlorate reduction Y. Zhang, [email protected], and J. R. Shapley, [email protected] Department of Chemistry and Center of Advanced Materials for the Purification of Water with Systems, University of Illinois at Urbana-Champaign, Urbana, IL, United States Previous work in this laboratory showed that a pyridine ligand stabilized rhenium (Re) center formed in-situ under hydrogen (H2) on the surface of activated carbon supporting palladium nanoparticles (5 wt. % Pd/C) provided an efficient heterogeneous catalyst for reduction of perchlorate to chloride in water. In this work, the activity and stability of this system have been tuned by systematic changes in the coordination environment of the Re center involved in the key oxygen atom transfer (OAT) step. A number of monodentate and bidentate ligands have been examined as addends, and the ligand properties were correlated with the catalyst behavior. Variations in H2-activating components and supports will be discussed as time permits. ENVR 172 Heavy metal removal by metal oxide nanoparticles in batch studies K. Engates, [email protected], and H. J. Shipley, [email protected] Department of Civil & Environmental Engineering, University of Texas at San Antonio, San Antonio, TX, United States One possible application of nanoparticles is as contaminant sorbents due to their enhanced properties such as increased surface area. Heavy metal sorption (Pb, Cd, Ni) to Fe2O3 and TiO2 nanoparticles was examined for potential use in water treatment technologies. Experiments showed metal adsorption was pHdependent, with 98% Pb being removed within 1 minute by TiO2 and 1 hour by Fe2O3 nanoparticles at pH 8. Simultaneous multi-metal removal in solution showed 0.5g/L Fe2O3 nanoparticles removed > 54% and TiO2 nanoparticles > 94% of the total metals within 2 hours. Exhaustion studies with 0.1 g/L TiO2 nanoparticles and 100 µg/L of each metal showed a non-detectable percent change in Pb adsorption over time while for Cd and Ni a percent change of 51%, and 98.4% was observed. Comparisons to similar bulk particles and naturally contaminated waters will also be presented to show the potential of metal oxide NP use in water treatment. ENVR 173 Characterization of Re speciation and its influence on stability and activity of the Pd-Re catalysts for perchlorate treatment J. K. Choe1,3, [email protected], T. J. Strathmann1,3, J. R. Shapley2,3, and C. J. Werth1,3. 1Department of Civil and Environmental Engineering, University of

Illinois at Urbana Champaign, Urbana, IL, United States, 2Department of Chemistry, University of Illinois at Urbana Champaign, Urbana, IL, United States, 3 The Center of Advance Materials for Purification of Water with Systems, Urbana, IL, United States Perchlorate contamination is widespread throughout the United States. Due to growing concerns about its health effects, the implementation of strict drinking water regulations is anticipated and new technologies to effectively treat perchlorate-contaminated water are needed. Heterogeneous palladium-rhenium (Pd-Re) bimetal catalysts, in combination with hydrogen, reduce perchlorate to chloride under mildly acidic conditions and ambient temperatures and pressures. However, long-term activity and stability of the catalyst needs to be assessed to develop a practical and sustainable treatment technology. This presentation describes studies examining how Re surface speciation changes under different operating conditions (e.g., exposure to hydrogen- versus air-saturated water) and how catalyst stability and activity is influenced by these changes. The molecular properties of sorbed Re species are characterized using X-ray photoelectron spectroscopy, and a model for redox cycling of Re surface species is proposed. Ongoing efforts to immobilize Pd/Re bimetal catalysts within perchlorate-specific ion exchange resins will also be discussed. ENVR 174 Water remediation using organosilica-based materials and nanoparticle composites that swell in the presence of organic contaminants P. L. Edmiston1,2, [email protected], L. A. Underwood1, and D. C. Pickett1. 1Department of Chemistry, College of Wooster, Wooster, Ohio, United States, 2Georgia Tech Research Institute, Georgia Tech, Atlanta, Georgia, United States Organosilica materials that energetically swell when exposed to organic molecules are being demonstrated as an effective water remediation tool. Swellable organically modified silica (SOMS) rapidly swells up to 8 times its dried volume upon exposure to non-polar chemical species whether found as a neat liquid, in gaseous form, or dissolved in water yielding forces on expansion in excess of 200N/g. SOMS has been demonstrated to be effective at removing solvents, pharmaceuticals, and pesticides from natural waters. Composite materials of SOMS with embedded nano-scale zero valent iron particles are currently being used for the in situ remediation of trichloroethylene (TCE) in groundwater to provide a system that combines the absorption properties of SOMS to accumulate and subsequently dechlorinate TCE. Pilot tests for TCE remediation in soil and through pump-and-treat systems have recently been completed. Additional applications of the material including MTBE remediation and produced water purification will be discussed. ENVR 175

Nanoparticle deposition under the influence of electrostatic repulsive conditions, surface roughness, and arbitrary flow direction K. E. Nelson, [email protected], and T. R. Ginn. Civil and Environmental Engineering, University of California, Davis, CA, United States Research is expanding dramatically on the use of nanoparticles as a costeffective means of remediating contaminated groundwater to yield suitable drinking water. Design and evaluation of such endeavors requires that we have a robust and detailed understanding of nanoparticle transport and deposition in natural porous media. Nanoparticles fall on the low end of the colloid size range and while classical Colloid Filtration Theory (CFT) has been relatively successful at predicting particle transport and deposition in well-defined systems in the absence of an electrostatic energy barrier, CFT has not been able to explain the magnitude nor dynamics of particle deposition in the presence of a barrier. We present the results of Lagrangian numerical experiments aimed at explaining nanoparticle deposition in the presence of: an energy barrier, porous media surface roughness, and arbitrary flow directions. Our preliminary results suggest that surface roughness can drive deposition under these conditions giving a fairly realistic representation of transport and deposition in natural porous media. Further simulations combined with experimental investigations are expected to provide an important contribution to enabling the use of nanoparticles for in situ groundwater remediation. ENVR 176 Polymer supported hybrid nanosorbent to mitigate global arsenic crisis A. K. SenGupta, [email protected] Civil and Environmental Engineering, Lehigh University, Bethlehem, PA, United States Nanoscale Inorganic Particles (NIPs) and their agglomerates offer excellent opportunities conducive to selective removal of a wide array of target compounds from contaminated water bodies. For example, hydrated Fe(III) oxides or HFO nanoparticles can selectively sorb trace arsenate and arsenite in the presence of other electrolytes. However, applications of NIPs in fixed-bed columns, in-situ reactive barriers and in similar flow-through applications are not possible due to extremely high pressure drops. Also, these NIPs are not durable and lack mechanical strength. In our work, we have successfully dispersed HFO nanoprticles within anion exchange resins. The resulting polymeric/inorganic hybrid nanosorbent shows extra-ordinarily high sorption affinity toward dissolved arsenic due to the Donnan membrane effect, is durable and amenable to fixedbed application and reuse through regeneration. The synthesis of hybrid nanosorbent has since been commercialized and the sorbent is currently in use in five countries including the United States to remove arsenic from naturally contaminated groundwater. The laboratory and field results will be presented.

ENVR 177 Development of a carbon footprint model for landfill disposal of solid waste M. A. Barlaz, [email protected], and F. Dela Cruz, [email protected] Department of Civil, Construction, and Environmental Engineering, North Carolina State University, Raleigh, NC, United States Landfills are an anaerobic ecosystem in which biogenic carbon decomposes to methane and carbon dioxide. Landfills are a leading source of anthropogenic methane in the U.S. and globally. A landfill carbon balance includes gas production and collection, the biological oxidation of methane in landfill cover soils, fugitive emissions, carbon sequestration and avoided emissions when methane is recovered for beneficial reuse. A spreadsheet model was developed to explore the sensitivity of various input parameters to the overall carbon footprint. Realistic ranges for key inputs will be presented along with the results of model simulations. The waste decay rate, extent of methane oxidation in landfill covers and collection efficiency all exerted a strong influence on the carbon footprint. Use of the model to evaluate changes in the landfill footprint as a function of waste composition is also explored. ENVR 178 Hydrothermal carbonization of municipal solid waste for carbon sequestration and energy generation N. D. Berge1, [email protected], J. R. V. Flora1, K. S. Ro2, and S. Bae3. 1 Department of Civil and Environmental Engineering, University of South Carolina, Columbia, SC, United States, 2Coastal Plains Soil, Water & Plant Research Center, USDA-ARS, Florence, SC, United States, 3Department of Chemistry and Energy and Environmental Studies Program, North Carolina A&T State University, Greensboro, NC, United States A fairly new, innovative technique, called hydrothermal carbonization (HTC), has the potential to change the way municipal solid waste (MSW) is managed. HTC is a wet, low temperature (180 ­ 350 oC), low pressure (in a closed system) thermochemical waste treatment/conversion technology that has been shown to convert biomass into a fixed carbonaceous residue (hydrochar). Utilization of such a technique has the potential to substantially reduce greenhouse gas emissions from the waste management sector. HTC of office paper was conducted at 250 oC for 20 hours. Results indicate the solid phase retains a significant fraction of carbon (;40%). The energy content of the carbonized paper was 21284 KJ/kg, equivalent to that of lignite coal (19200 kJ/kg). These results suggest carbonization of wastes may effectively sequester carbon and produce a feedstock for subsequent energy generation. Research is being underway to evaluate the feasibility of HTC of a typical MSW. Results from experiments over a range of reaction conditions will be presented.

ENVR 179 Vacuum assisted steam autoclaving as a front-end technology for converting waste to bioenergy K. M. Holtman, [email protected], D. Franqui, [email protected], D. V. Bozzi, [email protected], and W. J. Orts, [email protected] USDA-ARS, Western Regional Research Center, Albany, CA, United States Vacuum-assisted steam autoclaving is used to isolate organic materials from municipal solid waste (MSW). This study describes results from a pilot-scale system in Salina CA to convert autoclaved MSW to ethanol, biomethane (LNG/CNG/electricity), and electricity. MSW typically contains 30-40 % paper waste and 10-30 % food waste (total organic content ;60 %). Through volume reduction, autoclaving can result in 90% landfill diversion. Ethanol yields are ;48 gal/Ton, along with a ;4000 ft3 of biomethane and >350 kWh electricity per ton of processed MSW. Optimal bioenergy end-product depends upon the scale (MSW volume) and bioenergy prices, with biomethane being the primary product of a small scale rural operation (output = 11,000 ft3/Ton of processed MSW). Agricultural wastes are included as they become available on a seasonal basis, meaning that biofuels production using MSW can be extended to rural areas where crop waste densities are too low to justify an economical biorefinery. ENVR 180 Assessing the quality of PET bottles isolated from MSW by a novel, vacuum-assisted steam autoclaving technology W. J. Orts1, [email protected], K. M. Holtman1, A. Kodama1, A. P. Klamczynski1, A. Flynn2, D. V. Bozzi1, L. Torres2, E. Moe1, D. Franqui1, G. M. Glenn1, and J. Mao3. 1USDA-ARS, Western Regional Research Center, Albany, CA, United States, 2E. Khashoggi Industries (EKI), LLC, Santa Barbara, CA, United States, 3Department of Chemistry and Biochemistry, Old Dominion University, Norfolk, VA, United States Steam autoclaving of municipal solids wastes, MSW, followed by size-separation is introduced as a way to recover virtually 100 % of recyclable polyethylene terephthalate, PET, a yield not attainable by typical material recovery facilities (MRF). Polymer properties were evaluated by TGA, DSC, GPC, viscometry, and solid-state NMR, showing that properties critical for PET recycling are affected by the autoclave heating cycle. Molecular weight, Mw, decreases as a result of autoclaving from 64.0k for virgin PET to 57.4k for recycled-PET (RPET). Apparently, the autoclave heat cycle (high temperature and 20 min residence time) allows for reorganization of polymer chains resulting in property changes. Extruded samples,, which mimicked potential commercial application of the RPET samples show that, without special consideration to reduce contamination and discoloration, recovered RPET can only be used in small quantities in

recycled PET bottles. It will likely best be used in "downcycled" products such as fibers and injected molded products. ENVR 181 Effect of substrate concentration on methane fermentation of cattle dung J. Li, [email protected], and A. K. Jha, [email protected] State Key Laboratory of Urban Water Source and Environment, School of Municipal and Environmental Engineering, Harbin Institute of Technology, Harbin, Heilongjiang, China Methane fermentation of cattle manure (CM) with different total solid contents were conducted in the laboratory-scale batch reactors (2.5 L volume) in order to determine the substrate concentration performance and potential energy recovery at mesophilic (35o C ) and thermophilic (55o C) conditions. The three reactors containing CM and water in the ratio of 1:1w/w (dry fermentation), 2:1 w/w and 1:0 w/w (wet fermentation) were utilized for each above conditions. The work was performed for a period of 70 days to compare the volatile solids and DOC degradation, total and soluble COD removal, VFA generation and effect on total P, TKN and NH3-N. The experiment showed that anaerobic digestion of CM generated 0.07, 0.065 and 0.06 m3 methane/kg of CM for the ratios 1:1, 2:1 and 1:0 respectively. Comparing the digestions, it was shown that water promotes start up phase and biodegradability of the substrates with almost same methane content in the biogas yielded on the both conditions but increases the volume of the digesters. Keywords: Methane fermentation, cattle manure, substrate concentration, biodegradability, biogas ENVR 182 Bioreactor landfills: Chemical engineering and fermantation engineering perspectives D. Augenstein1, [email protected], R. Yazdani2, J. Benemann1, and P. Imhoff3. 1 Institute for Environmental Management, United States, 2Yolo County Public Works, United States, 3University of Delaware, United States Over half a billion tons of municipal solid waste (MSW) are discarded worldwide in landfills and dumps, where organic fractions decompose due to microbial action and generate landfill gas (LFG, a mix of methane and carbon dioxide). In typical landfills decomposition is slow, requiring decades, and is relatively unpredictable. Much LFG escapes to the atmosphere, where it contributes roughly 5% of anthropogenic greenhouse gas emissions, and wastes energy that, if recovered, could replace about 1% of worldwide fossil fuel supplies. Socalled "Controlled Bioreactor" landfills have been developed based on fundamental biochemical and chemical engineering principles, elevating microbial reaction rates as a function of moisture and temperature, making use of improved mass transfer and heat balances. These designs now allow for much

faster gas generation, completing gas production in under two decades, and capturing well over 90% of the LFG produced. This technology has been demonstrated at full-scale at the Yolo County Landfill in California; results of this 20 year project will be reported. ENVR 183 End of life, post-closure care, and the sustainable landfill J. W. F. Morris, [email protected], and M. F. Houlihan. Geosyntec Consultants, Columbia, MD, United States This study seeks to provide a useful definition of landfill sustainability based on performance-based post-closure care (PCC) requirements and the intended end use of the facility once PCC has been completed. By relating sustainability to the "functional stability" of the landfill (the landfill's long-term non-impacting relationship with its receiving environment in the absence of some or all active PCC provisions), it is argued that sustainability can be reached through a combination of enhanced waste degradation (bioreactor technology), use of passive fail-safe design and natural analog engineering features (wetlands, phytocaps, biocovers), and by defining PCC control systems and end-use conditions that emphasize environmental responsibility, engagement of the host community, and minimize the need for land use restrictions and buffers after completion of active PCC. In this way, the landfill property can be a community asset that requires minimal long-term active maintenance while remaining protective of human health and the environment. ENVR 184 Performance of enhanced aerobic landfill bioreactor under air flow and liquid addition R. Yazdani1, [email protected], E. Mostafid2, B. Han2, P. T. Imhoff2, P. Chiu2, M. Kayhanian1, and G. Tchobanoglous1. 1Civil and Environmental Engineering, University of California, Davis, California, United States, 2Civil and Engineering, Univeristy of Delaware, Newark, Delaware, United States A bioreactor landfill cell at Yolo County, California (USA) was operated aerobically for six months to evaluate the influence of air flow and liquid addition on aerobic degradation of solid waste. By measuring the gas composition of effluent gas and examining possible biodegradation reactions, the portion of the solid waste degraded anaerobically was estimated and tracked through time. From an analysis of in-situ aerobic respiration and gas tracer data, it was found that a large fraction of the gas-filled pore space was in immobile zones where it was difficult to maintain aerobic conditions, even at landfill cell-average moisture contents of 33-36%. Even with the intentional injection of air, anaerobic activity was never less than 13%, and sometimes exceeded 65%. The similarity of the respiration rates and the mobile/immobile mass transfer rates suggests that rates

of respiration in the waste were influenced significantly by rates of oxygen transfer to immobile gas zones. Coupling this observation with the relatively large portion of the gas phase that resided in immobile zones (32 to 92%), it is clear that in some portions of the solid waste oxygen transfer to immobile gas zones limited the degree of aerobic waste degradation, a condition that was exacerbated by liquid addition. Difficulties in maintaining conditions for aerobic degradation are of concern in other aerobically operated bioreactor landfills. ENVR 185 Waste plastic bags/films in landfill: A key contributor to leachate fluoroscency and a suspectable contamination indicator D. Wu, F. Lü, P.-J. He, and L.-M. Shao, [email protected] State Key Laboratory of Pollution Control and Resources Reuse, Key Laboratory of Yangtze River Water Environment, College of Environmental Science and Engineering, Tongji University, Shanghai, China Fluorescent analysis of dissolved organic matters in leachates from different municipal solid waste (MSW) landfill sites and aerobic compost confirmed the obvious existence of an intensively fluorescent compound with triple-peaks fluorophore. A survey on the fluorescent characteristics of MSW components showed that the aqueous leaching of waste plastic bags/films presented the similar triple-peaks fluorophores, which could only be found in plastic bags of special color regardless of the polymer materials. The peaks were of the same excitation wavelengths as leachate fluorophores, with a 40-60 nm red-shift in emission wavelengths. Pigments, dyes or fluorescent brightening agents then stood out from major plastics additives to contribute to this special fluorescency. Since plastics constituted 10%;20% of MSW (in wet basis), the leaching of plastics in landfill could significantly contribute to the fluorescency of leachate. The special fluorophore is able to distinguish the MSW contamination from other anthropogenic activities (e.g. wastewater discharge), so that it could be a potential indicator for landfill contamination. ENVR 186 Microbial reduction of solid substrates in aquatic environments via extracellular electron transport (EET) K. Nealson, [email protected] Department of Earth Sciences, University of Southern California, Los Angeles, CA, United States Shewanella is a gram negative bacterial genus renowned for respiratory versatility, being capable of enzymatic reduction of 15 or more electron acceptors, including several solid metal (oxy)hydroxides. A number of strategies are now hypothesized to be used by various Shewanella species to accomplish the reduction of solid substrates, including: 1) direct extracellular electron

transport (EET) via outer membrane bound enzymes: 2) the use of soluble electron shuttles (exogenous or endogenous) to move electrons to the solid substrates; 3) the production of inorganic reductants; and/or 4) the utilization of conductive "nano-wires" to carry electrons between cells and solid electron acceptors. We report here the use of dual cell flow chambers to observe biofilm formation and measure electron transfer to solid surfaces, investigating the potential role of EET in the metabolism of MR-1. Using this approach, it has been possible to quantify the rate of electron transfer to solid substrates, and begin to estimate the impact of EET on sedimentary environments. If indeed, if long-range EET occurs, it may force us to reexamine our view of the dynamics of stratified aquatic environments like sediments, biofilms, and other sites of extreme biogeochemical activity. ENVR 187 Microbial redox niches: Predictive power and analytical challeges J. L. Macalady, [email protected], D. S. Jones, and D. Tobler. Department of Geosciences, Pennsylvania State University, University Park, PA, United States Underground streams in limestone karst offer a unique opportunity to investigate microorganisms populating redox gradients. Geochemistry and microbial community composition were mapped at spatial scales ranging from centimeters to kilometers. Initial data were used to construct a simple ecological model incorporating two niche dimensions: water shear stress and the ratio of sulfide to oxygen in bulk stream water. The model sucessfully predicts the taxonomic affiliation of the dominant microbial population at each sample site in the full data set, despite strong differences in temperature (10-50° C), conductivity (100010,000 microS/cm), and sulfide concentrations (<1-1000 micromolar) among locations. The predictive power of the niche model suggests that members of globally distributed microbial taxa show fidelity to narrow redox niches, and that redox specialization in these groups originated in the distant evolutionary past. Precise measurements of dissolved oxygen or other redox indicators in natural waters are required to extend the model. ENVR 188 Non-reductive dissolution of iron oxides by endogenous organic ligands of S. oneidensis during dissimilatory Fe(III) reduction M. E. Jones1, [email protected], C. M. Fennessey2, T. J. DiChristina2, and M. Taillefert1. 1School of Earth and Atmospheric Sciences, Georgia Institue of Technology, Atlanta, Georgia, United States, 2School of Biology, Georgia Institue of Technology, Atlanta, Georgia, United States Dissimilatory iron reducing bacteria (DIRB) impact many environmental processes, including biogeochemical cycling of carbon and iron and bioremediation of contaminants. Several pathways for the respiration of iron

oxides have been proposed, including: direct contact, electron shuttling, and nonreductive solubilization of iron oxides by organic ligands followed by reduction of the organic-Fe(III) complex. In this study, we demonstrate the solubilization of iron oxides by endogenous ligands of Shewanella oneidensis. Solubilization of Fe(III) by S. oneidensis is observed during the reduction of iron oxides and not in the presence of more favorable electron acceptors. Genes responsible for solubilization were disabled by chemical mutagenesis and impaired strains were identified with a novel Microelectrode Screening Array (MESA). For S. oneidensis and all mutant strains, rates of soluble organic-Fe(III) production were proportional to rates of iron reduction indicating soluble organic-Fe(III) may be an important intermediate step in anaerobic respiration of Fe(III) by S. oneidensis. ENVR 189 Biogenic lead sulfide formation and reactivity E. Peltier1, [email protected], B. Haring2, P. Ilipilla1, and D. Fowle2. 1Department of Civil, Environmental and Architectural Engineering, University of Kansas, Lawrence, KS, United States, 2Department of Geology, University of Kansas, Lawrence, KS, United States The structure and reactivity of metal sulfide precipitates formed in anoxic wetland sediments are not well known, but have important implications for trace metal sequestration and remobilization in contaminated systems. In a previous study, we have shown that biological sulfate reduction can lead to the formation of well ordered ZnS phases that are more resistant to oxidation than amorphous precipitates. This work assesses the reactivity of lead sulfides in model anoxic systems. Sulfate-reducing Desulfovibrio sp. were grown in a high-sulfate, minimal metal complexing media amended with up to 100 micromolar dissolved lead for 5 days. The resulting precipitates were characterized using x-ray absorption spectroscopy and x-ray diffraction. Subsequently, lead remobilization due to reoxidation was assessed using a continuous stirred-flow reaction chamber. Initial results show decreases in dissolved lead concentration occurring within 4-12 hours after sample inoculation, corresponding to sulfate reduction and increased levels of free sulfide species. ENVR 190 Coupled biotic-abiotic redox transformations of uranium near the mineralmicrobe interface K. M. Kemner1, [email protected], M. Boyanov1, E. O'Loughlin1, D. SholtoDouglas1, K. Nemec1, B. Lai1, R. E. Cook1, E. Carpenter2, V. G. Harris3, S. D. Kelly4, and K. Nealson5. 1Argonne National Laboratory, Argonne, Illinois, United States, 2Virginia Commonwealth University, United States, 3Northeastern University, United States, 4EXAFS Analysis, Bolingbrook, Illinois, United States, 5 University of Southern California, United States

The region within ;10 mm of the mineral-microbe interface is a fundamental, yet poorly understood, spatial regime that exerts critical control on heavy metal and radionuclide transformations. Reactions that occur in this region can dominate subsurface reactivity, often exerting the greatest effect on coupled biological, chemical, and physical transformations of a contaminant and the biogeochemical milieu in which it resides. We have used a hard x-ray nanobeam (150 nm spatial resolution) to probe the spatial distribution of uranium on a thin film of lepidocrocite with actively respiring surface-adhered Shewanella oneidensis MR1. Results identify U(VI) associated with the surface-adhered cells and partially reduced uranium associated with the solid phase just a few microns away from the surface-adhered cells. The implications of these results and others towards understanding the coupled biotic-abiotic redox transformations of uranium near surface-adhered bacteria will be presented. ENVR 191 Effects of phosphate doping on the bioreduction of iron oxide E. O'Loughlin1, [email protected], C. Gorski2, K. Kemner1, M. Boyanov1, R. Cook3, and M. Scherer2. 1Biosciences Division, Argonne National Laboratory, Argonne, Illinois, United States, 2Department of Civil and Environmental Engineering, University of Iowa, Iowa City, Iowa, United States, 3Materials Science Division, Argonne National Laboratory, Argonne, Illinois, United States The bioreduction of Fe(III) oxides may result in the production of a suite of Fe(II)bearing secondary mineralization products (Fe(II)SMPs), including magnetite, siderite, ferrous hydroxy carbonate, vivianite, and green rusts. In an effort to better understand the effects of iron oxide structure and composition on the formation of particular Fe(II)SMPs of Fe(III) oxide bioreduction, we examined the effects of phosphate doping on the bioreduction of lepidocrocite (-FeOOH) by the dissimilatory iron-reducing bacterium Shewanella putrefaciens CN32. In the absence of structural phosphate, lepidocrocite was rapidly and stoichiometrically reduced to magnetite, which over time was partially transformed to ferrous hydroxy carbonate. Doping with between 0.2 ­ 0.7 mass % P significantly inhibited the initial reduction of lepidocrocite but ultimately resulted in greater overall Fe(II) production and the formation of carbonate green rust as the dominant Fe(II)SMP; doping with 3.0 % P resulted in the formation of green rust and vivianite ENVR 192 New insights in the electron transfer pathway of dissimilatory Mn(IV) reduction by Shewanella oneidensis H. Lin1, [email protected], M. Taillefert1, J. L. Burns2, and T. J. DiChristina2. 1 School of Earth and Atmospheric Seciences, Georgia Institute of Technology,

Atlanta, GA, United States, 2School of Biology, Georgia Institute of Technology, Atlanta, Ga, United States The mechanisms of dissimilatory Mn(IV) and Fe(III) reduction have to be characterized to predict their impact on the biogeochemical cycles of carbon and other metal contaminants. In contrast to the recent progress made on dissimilatory Fe(III) reduction, the mechanism of electron transfer from bacterial cells to solid Mn(IV) oxides remains poorly defined. In the present study, dissimilatory Mn(IV) reduction was studied in anaerobic incubations of Shewanella oneidensis MR-1 wild-type and Mn(III) reduction-deficient mutants strains, fed Mn(IV) oxides as terminal electron acceptor. Analytical speciation of Mn and measurements of CO2 production demonstrated that Mn(III) accumulates during Mn(IV) oxide reduction by both wild-type and the mutant strains. These findings, for the first time, suggest that dissimilatory Mn(IV) reduction proceeds via two successive one-electron transfer steps (as opposed to a single two-electron transfer reaction). In addition, CO2 measurements during these incubations indicate that only the second electron transfer step is coupled to energy generation. The implications of these findings on the contribution of dissimilatory Mn(IV) reduction to carbon mineralization will be discussed. ENVR 193 Characterization of a trans-outermembrane icosaheme complex for electron exchange between bacteria and their environment J. N. Butt1, [email protected], R. S. Hartshorne1, A. J. Gates1, T. A. Clarke1, P. C. Mills1, D. J. Richardson1, L. Shi2, A. S. Beliaev2, M. J. Marshall2, C. L. Reardon2, J. K. Fredrickson2, J. M. Zachara2, M. Tien3, D. Ross3, J. Nuester4, and S. Brantley4. 1Schools of Chemistry and Biological Sciences, University of East Anglia, Norwich, Norfolk, United Kingdom, 2Pacific Northwest National Laboratory, Richland, Washington, United States, 3Department of Biochemistry and Molecular Biology, Pennsylvania State University, University Park, Pennsylvania, United States, 4Department of Geosciences, Pennsylvania State University, University Park, Pennsylvania, United States ATP synthesis in Gram-negative bacteria is driven by a proton motive force across the inner membrane generated alongside quinone reduction. For electron acceptors that are external to the bacterium, e.g., mineral-oxides, recycling the quinol pool requires a conductive pathway that spans the periplasm and outer membrane. To assess the potential for products of the mtrCAB gene cluster to support electron transfer across the outer membrane of Shewanella we have characterised MtrC, MtrA, MtrAB and MtrCAB. The results suggest MtrB forms a sheath tightly embedding MtrA such that MtrA hemes can come into close proximity to MtrC hemes to support transmembrane electron transfer. Homologues of MtrA and MtrB are associated with extracellular DMSO reduction by Shewanella and phototropic Fe(II) oxidation by Rhodopseudomonas palustris.

Thus, the MtrAB module may be widely used for electron exchange between bacteria and the extracellular environment. [Hartshorne et al. (2009) Proc. Nat. Acad. Sci. in press] ENVR 194 Challenges in the study of the interactions of metals with dissolved organic matter G. Aiken1, [email protected], J. Ryan2, [email protected], and K. Nagy3, [email protected] 1US Geological Survey, Boulder, CO, United States, 2 Department of Civil, Environmental and Architectural Engineering, University of Colorado, Boulder, CO, United States, 3Department of Earth and Environmental Sciences, University of Illinois at Chicago, Chicago, IL, United States The intrinsic complexity of dissolved organic matter (DOM) presents unique challenges in determining chemical factors and mechanisms describing interactions of DOM with metals and colloids. Metal-DOM binding interactions are controlled by specific functional groups appropriate for the metals of interest. For instance, soft metals, such as mercury, interact with soft acids, such as thiol groups, whereas hard metals, such as iron and calcium, interact with hard acids, such as carboxyl groups. In contrast, surface active molecules rich in aromatic moieties appear to control the interactions of DOM with colloids such as iron oxides, calcite and cinnabar. These interactions are independent of the presence of the strongest binding sites, however, and their surface chemistry is poorly understood. Future advances in analytical approaches and experimental design to study those DOM compounds that interact most strongly with metals and colloids are key for understanding the factors controlling metal cycling in aquatic systems. ENVR 195 Bacterial mercury methylation and the role of natural dissolved organic matter D. P. Krabbenhoft1, [email protected], J. Moreau2, and E. Roden3. 1U.S. Geological Survey, Middleton, WI, United States, 2School of Earth Sciences, University of Melbourne, Melbourne, Australia, 3Geology and Geophysics, University of Wisconsin, Madison, WI, United States Sulfate-reducing bacteria (SRB) are the primary known environmental producers of the neurotoxin methylmercury (MeHg). Dissolved natural organic matter (DOM) is ubiquitous and contains reduced sulfur sites capable of complexing aqueous Hg(II). Given field and lab observations that DOM promotes methylation and neutral HgS(aq) exhibits hydrophobicity, respectively, we hypothesized that presence of a hydrophobic DOM should enhance methylation in the presence of ambient sulfide. We conducted methylation assays using natural hydrophobic DOM, Hg isotope tracers, and Desulfobulbus propionicus. Results showed 1-3

percent tracer methylation in both DOM+ and DOM- cultures. However, a similar amount of non-tracer mercury associated with the DOM fraction was also methylated, revealing that naturally-partitioned mercury was at least as bioavailable as the tracer. Methylation of natural DOM-hosted Hg suggests a commonality with respect to the form of Hg(II) that can be methylated by SRB. The amount of time of interaction between Hg and DOM may play a previously unrecognized role. ENVR 196 Rate of formation and dissolution of mercury sulfide nanoparticles: The dual role of natural organic matter A. J. Slowey, [email protected] Water Resources Discipline, U.S. Geological Survey, Menlo Park, California, United States The objective of this study was to determine how dissolved organic matter (DOM) affects the reaction between dissolved inorganic mercury (Hgaq) and sulfide to form HgSs nanoparticles. Using ultracentrifugation and chemical analysis, we periodically quantified Hgaq (<5 nm) following ;1 to 100 M sulfide amendment to model aqueous solutions containing 0.001 to 10 M Hg and 10 mg C/L as DOM. Hg-bearing particles were characterized using EXAFS spectroscopy and DLS. Three fractions of Hg­DOM species were observed with respect to reactivity toward sulfide. Following an initial sulfide-driven precipitation of HgSs nanoparticles resembling HgS, HgSs continued to form but also was dissolved presumably by DOM. The extent of HgSs precipitation versus dissolution is counterintuitive with respect to sulfide concentration, suggesting the influence of supramolecular DOM-HgS associations. Our results clarify the importance of DOM as a mediator of Hg-sulfide reactions and HgS nanoparticle dissolution. ENVR 197 Effects of natural organic matter on methylmercury production by pure cultures of Desulfovibrio desulfuricans ND-132 A. Biswas1, S. C. Brooks1, [email protected], C. L. Miller1, M. M. Drake2, and X. L. Yin1. 1Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, United States, 2Biosciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, United States Methylmercury (MeHg) produced by sulfate-reducing bacteria (SRB) in sedimentary environments bioaccumulates up marine food webs to directly impact human populations. Studies of MeHg formation by SRB suggest that Hg speciation plays an important role in the uptake of Hg by bacterial cells, though the effect may be species-specific. Due to its ubiquitous presence in natural systems, natural organic matter (NOM) is an important environmental variable whose influence on the bioavailability of Hg for methylation is incompletely

understood. We conducted pure culture studies to investigate the effect of NOM and growth stage on Hg methylation by the known methylating SRB Desulfovibrio desulfuricans ND-132. Results offer a first step toward a better understanding of the controls on MeHg production under natural environmental conditions. ENVR 198 Identification of metacinnabar in mixed mercury, sulfide, and dissolved organic solutions through chromatographic concentration and EXAFS C. A. Gerbig1,2, [email protected], G. R. Aiken2, C. S. Kim3, J. W. Moreau4, J. N. Ryan1, and J. Stegemeier3. 1Department of Civil, Environmental, and Architectural Engineering, University of Colorado at Boulder, Boulder, CO, United States, 2Water Resources Division, United States Geological Survey, Boulder, CO, United States, 3Department of Chemsitry, Chapman University, Orange, CA, United States, 4School of Earth Sciences, The University of Melbourne, Parkville, VIC, Australia There is an ecological and human health impetus to identify mercury speciation in environmental systems that contain mixtures of mercury, sulfide, and dissolved organic matter (DOM). Using synthetic systems with 10 or 50 mg L-1 DOM, 100 µM total sulfide, and a range of mercury concentrations (350 pM to 1.4 µM), we have identified evidence of colloidal metacinnabar despite the absence of particulates that can be removed via conventional methods. Mixed solutions were run through a column of C18 resin to concentrate hydrophobic mercury species. EXAFS of the mercury on the resin indicates a mercury­sulfur bond distance of 2.52 Å, but with only 2.5-3.0 sulfur atoms coordinating the mercury atom. While the coordination number is lower than expected, the bond distance is indicative of metacinnabar, does not match the sulfide-free mercury-DOM model that was also produced, and provides the first direct evidence of metacinnabar in systems of this complexity. ENVR 199 Species specific enriched stable isotopic spikes elucidate binding differences between mercury species in forest soils B. P. Jackson, [email protected], and V. F. Taylor. Department of Earth Sciences, Dartmouth College, Hanover, NH, United States Inorganic sulfur and NOM thiols play major roles in the fate and transport of Hg species in soil and sediment systems. Using enriched species specific stable isotope spikes and size exclusion chromatography ICP-MS we have studied differences in binding between inorganic Hg and methylHg in OM extracted from New England forest soils. Despite its high affinity for DOC, Hg2+ binds preferentially in a colloidal phase that is excluded from the SEC column while methylHg binds to lower molecular weight DOC. The methylHg isotopic signal correlates well with the sulfur signal from the DOC. The use of SEC-UV-Fl

coupled to high resolution ICP-MS allows for the study of Hg partitioning at environmentally relevant concentrations. ENVR 200 Decrease in net mercury methylation following an iron amendment to tidal wetland sediments P. D. Ulrich, [email protected], and D. L. Sedlak. Department of Civil and Environmental Engineering, University of California, Berkeley, Berkeley, California, United States Tidal wetlands are important methylmercury (MeHg) sources in aquatic ecosystems, and there is concern that wetland restoration may increase MeHg concentrations. We evaluated an iron amendment for minimization of MeHg production and export from wetland sediments. The presence of Fe(II) decreases S(-II) concentrations via FeS(s) formation, resulting in reduced concentrations of dissolved mercury-sulfide complexes bioavailable for methylation. Porewater organic matter also influences MeHg production, since wetland plant root exudates can stimulate microbial activity and form complexes with Hg(II), affecting microbial bioavailability. Wetland microcosms under simulated tidal conditions were amended at three iron doses. Following iron addition, porewater S(-II) concentrations decreased for each dose relative to the control and surface water MeHg concentrations decreased by over 90% for the highest dose. Our research suggests that iron addition may provide a practical MeHg control, however, additional research is needed to evaluate this approach under varied wetland conditions (e.g., plant communities, tidal elevation). ENVR 201 Dissolved methylmercury concentrations in two headwater streams: Influence of geochemical factors on differences between results from distillation/ethylation and thiourea-catalyzed SPE R. J. M. Hudson1, [email protected], G. R. Aiken2, P. M. Bradley3, M. E. Brigham4, D. A. Burns5, J. F. DeWild6, D. P. Krabbenhoft6, and B. R. Vermillion1. 1 Department of Natural Resources and Environmental Sciences, University of Illinois, Urbana, IL, United States, 2U.S. Geological Survey, Boulder, CO, United States, 3U.S. Geological Survey, Columiba, SC, United States, 4U.S. Geological Survey, Mounds View, MN, United States, 5U.S. Geological Survey, Troy, NY, United States, 6U.S. Geological Survey, Madison, WI, United States We report a comparison of dissolved MeHg in freshwater samples analyzed by: a) distillation plus ethylation/GC (MeHgDE) and b) thiourea-catalyzed SPE with Hg speciation analysis by Hg-thiourea ion chromatography (MeHgTU). Both methods employ CVAFS to quantify the MeHg and have been internally validated by standard addition and artifact formation tests. Split samples (N=139) were obtained during a study of headwaters streams in the Upper Hudson and Edisto

River basins conducted by the USGS NAWQA program. [MeHgDE] and [MeHgTU] are significantly correlated (r2=0.69-0.72), but the [MeHgDE]: [MeHgTU] ratio (R) is less than unity (P<0.0001) both at Fishing Brook (median=0.69) and McTier Creek (median=0.50), suggesting that thiourea-catalyzed SPE recovered a stable form of MeHg that was not distilled. The geochemical factors that appear to influence the differences between the measurements include strongly anaerobic conditions, which cause R to approach 1, and hydrophobic organic matter, which may stabilize the refractory MeHg.

ENVR 202 Using transmission X-ray microscopy, XAS, and µ-XRF to study Hg accumulation and transformation in Spartina foliosa and Medicago sativa J. C. Andrews1,2, [email protected], S. Carraso-Gil3,4, D. L. LeDuc2, C. Patty1, R. Millan3, and L. E. Hernandez4. 1SSRL, SLAC National Accelerator Laboratory, Menlo Park, CA, United States, 2Department of Chemistry and Biochemistry, California State University East Bay, Hayward, CA, United States, 3 Ciemat, Madrid, Spain, 4Universidad Autonoma de Madrid, Madrid, Spain Visualization of Hg accumulation within cordgrass roots (Spartina foliosa) and alfalfa (Medicago sativa) grown hydroponically in Hg(II) was accomplished using micro X-ray fluorescence (u-XRF; beam line 2-3) and full-field transmission x-ray microscopy (TXM; BL 6-2) at the Stanford Synchrotron Radiation Lightsource (SSRL, USA). The TXM has been designed to operate in the photon energy range from 5-15 keV in absorption contrast, and at 8 keV and 5 keV in Zernike phase contrast with resolution as high as 30 nm. Micro-XRF, and TXM with 2D absorption contrast images and 3D nano-tomography have revealed microorganisms within the rhizosphere of S. foliosa, presumably sulfate reducing bacteria, with Hg bound to the surface. Speciation of plant roots using X-ray absorption spectroscopy (XAS; BL 9-3) as well as micro-XAS (Hg L3 XANES) revealed Hg transformation from HgCl2 to thiol-bound Hg, methylmercury and

metacinnabar compounds, consistent with a view of Hg methylation in progress. Imaging and speciation/transformation results will be presented for Hg in alfalfa as well. ENVR 203 Effectiveness of nanoscale zerovalent iron (NZVI) to reduce contaminant mass emission from a NAPL source zone in an intermediate-scale aquifer system T. Phenrat1,2, [email protected], M. Mittal2, H.-J. Kim1, F. Fagerlund2, T. Illangasekare2, and G. Lowry1. 1Center for Environmental Implications of Nanotechnology (CEINT) and 1 Department of Civil & Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA, United States, 2Center for Experimental Study of Subsurface Environmental Processes (CESEP) at, Colorado School of Mines, Golden, CO, United States This study demonstrates NZVI delivery and NAPL targeting in situ by polymer modified NZVI, and quantifies the effect of NZVI treatment on mass emission from a perchloroethylene (PCE) source zone in small and intermediate scale twodimensional (2-D) flow tanks. The NAPL targeting was demonstrated in a 2-D flow cell of 20 cm x 30 cm x 2.5 cm. The effect of NAPL saturation in the source zone (50, 75, and 100% volume of NAPL/void space in the source zone) on NZVI targeting was evaluated. Polymer modified NZVI (20 g/L) was injected from a well and had a radial flow pattern analogous to a single well injection used in the field application. The targeting is dependent on the degree of NAPL saturation, with lower NAPL saturation providing better targetability of NAPL. Presumably, high NAPL saturation promotes flow bypass around the source zone which decreases transport of polymer modified NZVI into the source. In a larger 2-D tank (1.2m x 2.4m x 0.5 m), we studied both targetability and the effectiveness of NZVI treatment of a PCE source zone (40% saturation) using polymer modified NZVI. Approximately 30 g of polymer modified NZVI was injected into the tank using a single well injection to create a reactive NZVI treatment zone (15cm x 15cm x 5.5cm) around the PCE source. Up to 60% reduction of PCE mass emitted from the source was observed after NZVI injection. Acetylene, ethene, and ethane were the major intermediates and byproducts. NZVI in the direct vicinity of the PCE NAPL generated a lot of gaseous byproducts (hydrogen, acetylene, ethene, ethane) which accumulated in the tank. A tracer test was conducted to evaluate the effect of gas formation on flow field and treatment efficiency. ENVR 204 Sorption studies of Chromium(VI) and Chromium(III) to open and microwaved synthesized nano-magnetite particles (Fe3O4)

J. E. Hernandez1, [email protected], C. M. Gonzalez1, [email protected], J. G. Parsons2, [email protected], and J. L. Gardea-Torresdey1, [email protected] 1Department of Chemistry, University of Texas-El Paso, El Paso, TX, United States, 2Department of Chemistry, University of Texas-Pan American, Edinburg, TX, United States Chromium exists in two common oxidation states which are Cr(III) and Cr(VI). Chromium(III) is relatively non-toxic whereas chromium(VI) is very toxic to most living organisms. In this study we investigated the binding of chromium(III) and chromium(VI) to engineered nano-magnetite, which was synthesized using two different techniques. The synthesis were performed through the titration of Iron(II) chloride with sodium hydroxide at a ratio of 3 OH to 1 Fe(II) ion. Subsequent to the titration the samples were aged using 1.) traditional heating source in and open vessel at 90ºC for 60 minutes and 2.) microwave oven with closed vessel at 90ºC for 30 minutes. The batch studies showed that chromium(III) and chromium(VI) bind to the nanomaterials differently at different pHs. Only the chromium(VI) showed differences in the binding to the open vessel and the closed vessel nano-magnetite. Further data obtained from batch studies from interference and isotherm experiments will be presented. ENVR 205 Sorption and interference batch studies of selenite (SeO32-) and selenate (SeO42-) to engineered nano-Jacobsite in aqueous solutions C. M. Gonzalez1, [email protected], J. E. Hernandez1, J. G. Parsons2, and J. L. Gardea-Torresdey1. 1Chemistry, University of Texas El Paso, El Paso, TX, United States, 2Chemisty, University of Texas at Pan American, Edinburg, TX, United States Selenium is essential in the biological systems of both humans and animals. Elevated concentrations of selenium in the environment can lead to improper biological functions in animals. In this study, we investigated the binding of selenite and selenate to engineered nano-Jacobsite. Batch pH studies were performed using 100 ppb of either selenate or selenite and the time dependency and isotherm studies were performed at pH 4. Potential interference of Cl-, NO3-, SO42-, and PO43- on selenite and selenate binding to both nanomaterials were investigated. Results showed that both selenium species bound better to the nanomaterials at pH 4 within the first five minutes of contact time and remained constant, with high binding capacities. Both Cl- and NO3- had no significant effect on binding while SO42- and PO42- ions decreased the selenium binding only when present at concentrations above 10 ppm. ENVR 206 Elucidation of nitrate reduction mechanisms on a Pd/In bimetallic catalyst using isotope labeled nitrogen species

R. Zhang1,3, [email protected], K. A. Guy2,3, T. J. Strathmann1,3, C. J. Werth1,3, and J. R. Shapley2,3. 1Department of Civil & Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois, United States, 2Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois, United States, 3The Center of Advanced Materials for the Purification of Water with Systems, University of Illinois at Urbana-Champaign, Urbana, Illinois, United States Nitrate contaminated drinking water resources pose significant hazards to human health, including methemoglobinemia and increased cancer risk. Catalytic hydrogenation over Pd-based catalysts has shown promise as an economic, as well as ecological, treatment approach for nitrate and related oxyanions (e.g., perchlorate), but full-scale catalytic reduction technologies will require improved selectivity for the end product di-nitrogen over ammonia. Pathways for nitrate reduction have been proposed but reaction intermediates have not been confirmed. The goals of this work are to elucidate nitrate reduction pathways that yield di-nitrogen and ammonia, and to determine the factors that affect the preference of one pathway over another. Experiments are conducted with isotope-labeled nitrate and nitrite, alone and in combination with other proposed intermediates, to evaluate reduction pathways with an Al2O3-supported Pd/In bimetallic catalyst. By examining their reaction rates and NO, N2O and N2 product mass ratios (by GC/MS), intermediate steps in the reaction pathways are elucidated. ENVR 207 How nC60(aq) production method affects nanoparticle physiochemical properties C. D. Vecitis, [email protected], and M. Elimelech, [email protected] Department of Chemical Engineering, Environmental Engineering Program, Yale University, New Haven, CT, United States Aqueous fullerene nanoparticles (nC60(aq)) have been previously produced by a number of methods such as organic-water solvent exchange via distillation, air stripping, and high power ultrasonication, as well as extended stirring in pure water. nC60(aq) physiochemical properties such as diameter, polydispersity, crystallinity, shape, and surface charge are highly dependent upon the specific particle formation process. Here, we investigate how extensive low-power ultrasonication affects the physiochemical properties of aqueous nC60. It is of note that the nC60(aq) produced by bath sonication mediated solvent transfer from toluene yields particles with much less negative electrophoretic mobilities and an isoelectric point at pH ;2. ENVR 208

Water-soluble C60 derivatives as novel photocatalyst: Photochemical properties J. Lee1, [email protected], Y. Mackeyev2, M. Cho3, J.-H. Kim3, L. J. Wilson2, and P. J. J. Alvarez1. 1School of Civil and Environmental Engineering, Rice University, Houston, Texas, United States, 2Department of Chemistry, Rice University, Houston, Texas, United States, 3School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, Georgia, United States Despite photoexcitation with low photon energy and extraordinary photochemical properties for production of reactive oxygen species, the use of C60 as environmental photocatalyst is limited because of its extremely low aqueous availability. In an effort to enable C60 application for water remediation, highly water-soluble hexakis C60 derivatives were synthesized and their photochemical activities were investigated. Based on consumption kinetics of furfuryl alcohol (FFA) as a singlet oxygen (1O2) indicator, all synthesized C60 derivatives showed much higher photochemical performance for 1O2 generation than fullerol. Their higher 1O2 yields were also confirmed by electron paramagnetic resonance spectra as a function of UV illumination time. The decay kinetics of a triplet state for each derivative, monitored through nanosecond laser flash photolysis, is well correlated to the measured 1O2 production kinetics. The oxidation of emerging contaminants by these novel functionalized C60 will be demonstrated and considered within a context of photochemical and surface properties. ENVR 209 Water-soluble C60 derivative as novel photocatalyst: Biocidal properties M. Cho1, [email protected], J. Lee2, Y. Mackeyev3, L. J. Wilson3, P. J. J. Alvarez2, and J. Kim1. 1School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA, United States, 2School of Civil and Environmental Engineering, Rice University, Houston, TX, United States, 3 Department of Chemistry, Rice University, Houston, TX, United States The objective of this study is to evaluate the efficiency of a newly synthesized water-soluble cationic hexakis C60 derivative, C60(CR2)6 (R = CO2(CH2)2NH3+CF3CO2-), for inactivation of various indicator microorganisms. Results suggest that this C60 derivative efficiently inactivates MS2 bacteriophage under UVA more efficiently than commercial TiO2 photocatalyst. A relatively fast inactivation kinetics was also observed under visible light irradiation. The inactivation was found to result from photochemically generated singlet oxygen, as inactivation was prohibited in the presence of excess amount of L-histidine (singlet oxygen scavenger). The microbial inactivation with singlet oxygen was quantitatively evaluated: the exposure of photochemically produced singlet oxygen was determined using the degradation of furfuryl alcohol at specific time, expressed as CT (the product of singlet oxygen concentration and contact time), and the target microbial inactivation level was also observed at these times (Log(N/N0)). These findings collectively suggested that this newly synthesized

functionalized C60 might have a potential as a new antimicrobial agent which functions under visible light as well as UV light.

ENVR 210 Antimicrobial mechanisms of single-walled carbon nanotubes (SWNTs) C. D. Vecitis, [email protected], S. Kang, and M. Elimelech, [email protected] Department of Chemical Engineering, Environmental Engineering Program, Yale University, New Haven, CT, United States Single-walled carbon nanotubes (SWNTs) have been previously observed to be strong antimicrobial agents. SWNT-bacterial interactions result in membrane damage and release of intracellular contents (membrane stress), as well as production of reactive oxygen species, ROS (oxidative stress). We propose a mechanism where SWNTs act as an electrically conductive bridge across the insulating lipid bilayer, which results in conversion of intracellular energy into extracellular ROS. The plausibility of this mechanism is investigated by comparing the cytotoxicity of electronically metallic SWNTs to electronically semiconducting SWNTs. The metallic SWNTs are observed to have a significantly greater antimicrobial activity towards E. coli than the semiconducting SWNTs, in agreement with the proposed mechanism. The possible environmental implications and applications of the electronic structure dependent cytotoxicity of SWNTs are discussed. ENVR 211 Single-walled carbon nanotube (SWNT) composite membranes for reduction of biofouling in water treatment M. S. Mauter, [email protected], and M. Elimelech. Chemical Engineering, Environmental Program, Yale University, New Haven, CT, United States

Ultrafiltration membranes perform critical pre-treatment functions in advanced membrane treatment processes. As the first barrier for bacteria, the resistance of these membranes to biofouling is fundamental to their performance. Prior work on the toxicitiy of shortened, functionalized single-walled carbon nanotubes (SWNTs) in the biomedical field suggests that incorporating SWNTs into UF membranes may impart antimicrobial activity to the membrane surface and delay the onset of biofouling. The present work optimizes the dispersion and surface coverage of SWNTs in UF membranes and assesses the antimicrobial activity of SWNTs sequestered in polymer films. Additional work on nanocomposite membranes also suggests that the incorporation of SWNT into the membrane active layer affects the hydrophilicity of the surface and modifies the polymer packing structure. Tailored incorporation of nanomaterials into ultrafiltration membranes shows promise for improving flux performance through enhanced permeability and reduced biofouling. ENVR 212 Activity, selectivity and anti-fouling tests of Pd/carbon nanofiber (Pd/CNF) catalysts for nitrite hydrogenation D. Shuai1,3, [email protected], J. R. Shapley2,3, and C. J. Werth1,3. 1 Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 2Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 3The Center of Advanced Materials for Purification of Water with Systems, University of Illinois at Urbana-Champaign, Urbana, IL, United States Nitrite is formed during nitrate reduction; it is toxic and can form carcinogens during disinfection and in the human body. Catalytic hydrogenation is one feasible approach to remove nitrite from drinking water; however, the activity, selectivity, and anti-fouling potential of nitrite reduction vary among different catalysts. In this work, carbon nanofiber (CNF) was used as a new catalyst support. Different preparation methods were evaluated for loading Pd inside and outside of the fibers, and nitrite reduction kinetics, ammonia to di-nitrogen formation ratios, and transmission electron microscopy (TEM) were used to characterize the suite of prepared Pd/CNF materials. Results show that nitrite reduction rates were comparable to those with commercially available Pd on activated carbon (Pd/AC), but that selectivity increased significantly with Pd/CNF regardless of whether loading was interior or exterior. The fouling potential of the Pd/CNF with natural organic matter (NOM) and sulfide are presently being evaluated. We anticipate that Pd loaded inside CNF is protected from fouling by NOM and sulfide. To summarize, novel Pd-based catalysts with CNF as a support were prepared, and they show promising future applications in nitrate and nitrite removal. ENVR 213

Escherichia coli inactivation mechanism by zero-valent iron nanoparticles and ferrous ion J. Y. Kim1, H.-J. Park2, C. Lee3, C. Lee3, and J. Yoon2, [email protected] 1 Department of Civil and Environmental Engineering, University of California, Berkeley, Berkeley, California, United States, 2School of Chemical and Biological Engineering, Seoul National University, Seoul, Republic of Korea, 3School of Urban and Environmental Engineering, Ulsan National Institute of Science and Technology, Ulsan, Republic of Korea Although nano particulate zero-valent iron (nZVI) and ferrous ion (Fe[II]) were previously reported to exhibit strong bactericidal effects on E. coli under deaerated conditions, no good explanation with substantial evidence has been provided for exact inactivation mechanisms. This study shows that the extent of E. coli inactivation under deaerated conditions successfully correlated with the production of intracellular oxidants measured by fluorescence assay, which suggests that the oxidants are produced by the reactions of nZVI and Fe(II) with the oxygen present inside or on the surface of the cells under deaerated conditions. The oxidative stresses by ·O2- and H2O2 were negligible, indicating that more reactive oxidants such as ·OH or Fe(IV) produced by the Fenton reaction are responsible for the inactivation of E. coli. Significant disturbances of the cell membrane and respiratory activity were also observed in the E. coli cells treated by nZVI and Fe(II) under deaerated conditions. ENVR 214 Paper filters impregnated with silver nanoparticles for the removal of bacterial pathogens T. Dankovich, [email protected], and D. G. Gray, [email protected] Department of Chemistry, McGill University, Montreal, QC, Canada Our aim in this work is to incorporate silver nanoparticles into paper filters suitable for treatment of bacteria-contaminated water in emergency situations. Silver nanoparticles have been used in many different types of antimicrobial applications, and a couple studies have explored the use of silver nanoparticles in filtration applications, but not with paper as the supporting medium. Our filtration tests examined the effectiveness of silver to deactivate bacteria while passing through the paper. The filters were tested with a range of silver contents and with nonpathogenic strains of gram negative bacteria, E. coli, and gram positive bacteria, E. faecalis. The gram negative bacteria appear to be more susceptible to silver nanoparticle toxicity than the gram positive bacteria, although both showed high lethality, with a greater than log 4 reduction in bacteria. Additionally, the effluent water was analyzed for leached silver, which was found to be below the US-EPA guideline of 100 ppb.

ENVR 215 Role of end-of-life management on sustainable building material selection T. G. Townsend1, [email protected], H. Kim1, and T. Tolaymat2. 1Department of Environmental Engineering and Sciences, University of Florida, Gainesville, FL, United States, 2Office of Research and Development, U.S. Environmental Protection Agency, Cincinnati, OH, United States Both virgin and recycled materials serve as the feedstock for construction products in modern buildings and infrastructure. Importance is now placed on the sustainability of modern construction materials and construction. One aspect often ignored in such evaluations is the potential impact of construction material quality on end-of-life management of building products. The incorporation of waste materials into building products fosters sustainability through materials recycling, but may end up impacting long-term management of the materials, once discarded. For example, waste ash may be used in cement, synthetic gypsum is frequently recycled in new drywall manufacture, and discarded treated wood has been proposed as an ingredient in composite building materials. All of these applications could impact the ability to recycle these materials when the structure is removed from service. In this paper, a framework to incorporate endof-life management into building material sustainability decision-making will be described, including examples of actual applications. ENVR 216 Trace element leaching from recycled pavement materials stabilized with fly ash C. Benson, [email protected], J. O'Donnell, and T. Edil. Recycled Materials Resource Center, University of Wisconsin-Madison, Madison, Wisconsin, United States Recycled pavement materials are being used with increasing frequency for sustainable construction and rehabilitation of the nation's roadway infrastructure. To ensure recycled pavement materials have adequate strength and stiffness, they are often blended with cementitous fly ashes from coal fired power plants. This strategy has been shown to reduce construction costs by as much as 33%, reduce energy consumption and greenhouse gas emissions, and result in pavements with longer service life. The field data indicate that the percolation rate from the base of a pavement profile varies seasonally in response to seasonal variations in meteorological conditions (thermal and hydrological). The highest percolation rates occur in the spring and early summer in response to spring melting and heavier storm events. In the winter, the percolation rate is near zero, especially when the pavement profile is frozen. Percolation rates typically range between 0.1-0.5 mm/d, with the average percolation rate falling between 0.1-0.2 mm/d depending on site conditions. Concentrations of many trace elements, particularly those with relatively low water quality standards,

diminish over time as water flows through the pavement profile. In most cases, concentrations below US water drinking water quality standards are attained within 2-4 pore volumes of flow at the bottom of the pavement profile. ENVR 217 Counting solid waste D. J. Tonjes, [email protected] Department of Technology and Society, Stony Brook University, Stony Brook, NY, United States Whenever new solid waste policies are implemented, impacts should be assessed. Garbage is tangible, and is managed in very large quantities. Nonetheless, solid waste has proven to be difficult to count well. Methodology and definitional issues abound, so that the two most credible national waste generation assessments differ by at least 50 percent ­ over 100 million tons. The EPA modeled waste stream, widely accepted and cited, clearly does not match especially well with sampling of actual waste streams. Regulations and adopted goals can drive solid waste assessors to over- or undercount wastes for various well-meant or self-serving reasons. I will discuss these difficulties through particular examples, showing that counting differences can affect choices we need to make. There is no simple means to make solid waste assessments congruent, but better understanding can lead to better decisions on waste and sustainability issues. ENVR 218 Complete removal of inks from substrates assisted by intricate environmental benign neutral de-inking chemistry H. T. Ng, [email protected], M. K. Bhattacharyya, L. Mittelstadt, and E. G. Hanson. HP Labs, Hewlett-Packard Co., Palo Alto, CA, United States Successful removal of inks (a.k.a., de-inking) from various substrates (i.e., inorganic fillers and cellulose fibers) is important towards fulfilling a greener recycling ecosystem and a lower carbon footprint. There are significant challenges towards fulfilling the recyclability of waste paper streams. We show here that total removal of inks from various substrates can be achieved successfully via an environmental friendly neutral de-inking chemistry. More specifically, we have adopted a so-called `two-stage' pulping process while introducing the de-inking chemicals, to control the intricate effective interactions with the ink particles, thereby facilitating successful deinking during the subsequent flotation process. We show also that advanced molecular modeling can provide deep insights to the underlying working mechanism of our neutral de-inking chemistry, and can be used to predict the performance of the de-inking materials set.

ENVR 219 Incineration technology for MSW disposal in JAPAN: Development and experience K. Kawamoto, [email protected] Research Center for Material Cycles and Waste Management, National Institute for Environmental Studies, Japan, Tsukuba, Ibaraki, Japan Japan incinerates huge amounts of municipal solid waste (MSW): about 80% of the 52 million tons produced each year (FY 2006) is incinerated. These statistics probably reflect the country's relatively small land area and large population. The fact that there are still over 1300 MSW incineration facilities in Japan has focused much attention on dioxin problems and has brought progress in incineration technology and advanced flue-gas cleaning. This study reviews these developments, focusing on dioxin emission reduction in combustion and flue gas control systems. The introduction of gasification and melting plants as new incineration systems has also been a big issue in this field. The development of this equipment and the experience gained in its application to MSW disposal-- and to the control of pollutants and residues--are described here for use by other countries in further developments in this field. ENVR 220 Production and management of municipal solid waste incineration residues in China: Challenges toward the new pollution control standards H. Zhang, P.-J. He, [email protected], and L.-M. Shao. State Key Laboratory of Pollution Control and Resources Reuse, Key Laboratory of Yangtze River Water Environment, College of Environmental Science and Engineering, Tongji University, Shanghai, Shanghai, China Due to stricter requirements for environmental protection and greater pressure on limited landfill space, municipal solid waste (MSW) incineration in China is playing a more and more important role in MSW management. Increasing attention has been paid to the production and management of MSW incineration residues. It was estimated that, about 3.6 million tons of bottom ash and 0.4 million tons of air pollution control residues were produced in 2007 in China. The increasing amount of incineration residues poses an urgent requirement for environmentally-sound treatment, disposal and beneficial reuse. In this study, the production and current status of treatment, disposal and beneficial reuse of MSW incineration residues in China were investigated. The related pollution control standards and management regulations were introduced. Based on which, the technical and economic aspects regarding to the treatment and disposal of incineration residues were analyzed. The prospects and challenges for management of incineration residues were then discussed. ENVR 221

Evaluation of test methods for assessing the environmental risks from road marking glass beads B. K. Dubey1, [email protected], and N. Singhal2, [email protected] 1 Department of Environmental Health, East Tennessee State University, Johnson City, TN, United States, 2Department of Civil and Environmental Engineeirng, University of Auckland, Auckland, Auckland, New Zealand Glass beads used for road marking are typically manufactured from recycled glass and depending on the origin of recycled glass the beads may contain different amounts of heavy metals. There has been ongoing debate among transportation management professionals around the world on the risks posed to human health and environment by the heavy metals present in glass bead. Risk assessment procedures are based on examining the exposure to a target constituent through a variety of pathways and have been commonly used to assess the risks posed by contaminated soils. In recent past, a similar approach has also been used to assess the beneficial reuse and management options of various waste materials. This presentation will do an overview of risk assessment methodologies and the testing protocols used for making these assessments with the goal of assessing the appropriateness of prescribed thresholds for heavy metal levels present in glass beads used for road marking. The data generated as part of an ongoing study will be presented and the appropriateness of using an analytical technique for a realistic beneficial reuse risk assessment of this material will be discussed. ENVR 222 Sustainable development of oil shale processing: Synthesis and environmental challenges of oil shale wastes based geopolymers U. Kirso1, [email protected], J. Reinik1, N. Irha1, G. Urb1, and E. Steinnes2. 1 Group of Environmental Chemistry, National Institute of Chemical Physics and Biophysics, Tallinn, Estonia, 2Department of Chemistry, Norwegian University of Science and Technology, Trondheim, Norway The use of oil shale (OS) for energy generation and oil production started to be a strategic issue for several countries, including the U.S. Processing of OS results in vast quantities of solid wastes. There are both economical and ecological needs to convert these wastes into a resource. The special treatment strategy of OS ash for syntheses of geopolymers was found to be promising. The silicon in the original ash was converted into calcium-alumino-silicate hydrates, e.g., into tobermorite structures with long silicate chains and a small number of bridging sites. The mobility of toxic trace metals in ash was investigated in leaching tests. The negligible release (0.1% or less) was found for V, Mn, Zn, Pb, Ni, and Co, Cu (0.5-1.0%), Cr and Cd (2.5-3.1%) were the metals of medium mobility. The strategy for utilization of OS wastes should include treatment of material to eliminate toxic ingredients or decrease their mobility.

ENVR 223 Engineered bioractor landfills as energy technology: Comparison with alternatives A. Wang3, [email protected], D. Augenstein1, J. Benemann1, and R. Yazdani2. 1Institute for Environmental Management, Inc., United States, 2Yolo County Public Works, United States, 3Golder Associates, Inc., United States Processes converting waste to fuels are being reintroduced as alternatives to landfill disposal. Developed technologies include in-vessel fermentation, digestion and gasification / pyrolysis. Fundamental thermodynamic and economic hurdles have historically limited commercial process applications to selective minor waste streams. These hurdles and other performance limitations are not widely recognized in the waste management industry, nor are project failures publicized. Meanwhile, as these process investigations continue, engineered bioreactor landfills are yielding significant net positive energy, while successfully balancing economic, environmental and social factors. The authors evaluate and compare these factors for four commercial processes and the bioreactor landfill, applying a multi-dimensional sustainability model to data provided by operators and in the literature. The model results suggest that the lifecycle energy output of bioreactor landfills compare positively to more active waste-to-fuel processing. The significant limitations common to most of the waste-to-fuel processes included intensive pre-treatment and pre-processing to obtain a suitable substrate; small but highly detrimental substrate contamination; high parasitic energy inputs; and substantial waste remainders to be managed. Field data show performance of bioreactor landfills comparing well to vessel alternatives in terms of total fuel value yields (up to 50% higher net energy); fraction of potentially convertible MSW organics entering conversion (100% vs. <50%); parasitic energy inputs (<2% vs. >30% of product fuel energy); economics (<10% of the costs of other processes) and environmental benefits. Bioreactor landfills provide higher ultimate net energy returns and comparable total waste mass reductions than vessel processes, with lower overall environmental impacts. ENVR 224 Photochemistry of dissolved organic material and its role in aquatic ecosystems D. M. McKnight, [email protected] INSTAAR, University of Colorado, Boulder, CO, United States Approaching questions of aquatic biogeochemistry from the perspective of "hotspots" and/or "hot moments" allows for integration of these results within the broad concepts of aquatic ecosystem function. This approach also allows for forging connections to the dynamic chemistry of the reactive constituents of interest to limnologists. One example is the role of sunlight in determining the structure of lake and stream ecosystems, not only by controlling photosynthesis,

but also by driving photochemical processes. These photochemical processes can transform dissolved organic material (DOM), nutrients and many trace constituents. Studies have shown that direct photochemical processes influence the chemistry of the DOM pool, changing its bioavailability and its reactivity with trace metal and organic contaminants. From a biogeochemical perspective, the noonday sun irradiating a stream or river reach represents a "hot moment" that can have a sustained ecological effect through the rest of the diel cycle. The hydrologic transport of these reactive photochemical constituents to downstream reaches and to adjacent reducing environments, such as hyporheic zones, may influence ecosystem function. These changes are especially important in the context of the bioavailability of toxic metals, such as copper, to invertebrates and fish in streams receiving acid mine dranage in their headwaters, as will be illustrated based on studies in the Colorado Rocky Mountains. Further, the changes occurring over a day-night cycle are superimposed upon seasonal changes in light regime and in hydrologic regime. Incorporating these dynamic processes into models for lake and stream ecosystems function and into monitoring approaches may be useful in understanding the effects of the substantial changes in water quality, land use and hydrologic regime. ENVR 225 Effect of borohydride reduction on the optical properties and ultra-high resolution mass spectra of humic substances J. Ma1, E. Boyle1, N. Allen1, K. Longnecker2, E. Kujawinski2, R. Del Vecchio3, and N. V. Blough1, [email protected] 1Department of Chemistry and Biochemistry, University of Maryland, College Park, MD, United States, 2Department of Marine Chemistry and Geochemistry, Woods Hole Oceanographic Institution, Woods Hole, MA, United States, 3Earth System Science Interdisciplinary Center, University of Maryland, College Park, MD, United States The reduction with sodium borohydride of Suwannee River humic and fulvic acids, a commercial lignin, and a series of solid phase C18 extracts from fresh, estuarine, coastal and offshore waters of the middle Atlantic bight produces a preferential loss of long wavelength (visible) absorption and enhanced, blueshifted emission. These results are consistent with and interpreted within a previously proposed charge transfer model. High resolution mass spectra of borohydride-reduced samples exhibit clear mass shifts (M+2) for only a subset of the masses observed in the original sample, suggesting that it should prove possible to identify the molecular formulae of those species contributing to the absorption and emission properties of these materials. ENVR 226 Tracing fluorescent whitening agents in stream water

K. Walton-Day1, [email protected], D. L. Macalady2, and L. B. Barber3. 1 Colorado Water Science Center, U.S. Geological Survey, Denver, CO, United States, 2Department of Chemistry and Geochemistry, Colorado School of Mines, Golden, CO, United States, 3National Research Program, U.S. Geological Survey, Boulder, CO, United States Fluorescent whitening agents, also known as optical brighteners, are present in many household products and can be used to trace wastewater in aqueous environments. Samples collected from a suburban stream in Utah where homes have individual sewage disposal systems (septic) were analyzed for optical brighteners using standard, commercially available fluorescence analysis. An observed downstream increase in fluorescence may be attributable to optical brighteners and indicates possible leakage of septic systems along the stream. Select samples were sent to a specialty laboratory that confirmed an optical brightener signal in only a few of the samples that exhibited the greatest fluorescence. It is possible that natural organic matter in the samples, and not wastewater, may have caused the fluorescence signal in the remaining samples. Experiments using diluted, pure optical-brightener solutions and environmental samples were conducted to better separate the fluorescent signals of optical brighteners and natural organic matter. ENVR 227 Correlations between the degradation of pharmaceuticals and personal care products and changes of the absorbance spectra of wastewater and surface water in ozonation G. V. Korshin1, [email protected], V. Nanaboina1, and F. Chen2. 1Deparment of Civil and Environmental Engineering, University of Washington, Seattle, WA, United States, 2College of Environmental Science and Engineering, Nankai University, Tianjin, China This study explored the degradation by ozone of selected pharmaceuticals (e.g., diclofenac, ibuprofen, iodopromide, others), personal care products (e.g., oxybenzone, musks) in wastewater and surface water. Their breakdown and attendant changes of the absorbance spectra at varying ozone doses were quantified. Strong correlations were observed to exist between the decrease of the absorbance NOM and the degradation of the PPCP species. However, the target species were degraded only when the ozone dose and/or reaction time were sufficiently high to cause the absorbance of NOM to decrease below a characteristic threshold value. Its existence appears to correspond to the oxidation of rapidly reacting groups in NOM, after which ozone and hydroxyl become abundant enough to participate in reactions with trace-level species. Practical implications of the observed phenomena will be discussed during the presentation. ENVR 228

Oxidation of organic contaminants occurring on zero-valent metals W. Choi, [email protected], A. Bokare, S. H. Kang, and J. Lee. School of Env. Sci. Eng., Pohang Univ. Sci. Technol., Pohang, Republic of Korea The reductive transformation of aquatic pollutants occurring on zero-valent iron (ZVI) surface has been extensively investigated. Recently, it has been also reported that the reduction of O2 on Fe0 leads to in-situ production of H2O2 and Fe2+ that was responsible for the OH radical-induced oxidation. In this work, we have demonstrated that the oxidation pathways on ZVI can be accelerated in the presence of suitable electron shuttles such as polyoxometalate (POM) and natural organic matter (NOM). The performance and the characteristics of each POM and NOM mediated system were investigated for the oxidation of 4chlorophenol. The oxidative degradation of aquatic organic contaminants using zero-valent aluminum (ZVAl) in the presence of dissolved oxygen was also investigated. The metal corrosion process in acidic conditions was accompanied by the electron transfer from ZVAl to O2, which led to the simultaneous generation of Al3+ and hydrogen peroxide that was subsequently decomposed into OH radical. ENVR 229 Pyrite driven ROS formation in simulated lung fluid: Implications for coal workers' pneumoconiosis A. D. Harrington, [email protected], S. Hylton, M. A. Folkin, and M. A. A. Schoonen. Department of Geosciences, Stony Brook University, Stony Brook, New York, United States Coal continues to play a crucial role in meeting the energy needs of the world, and its use will only increase in the future. The hazards of coal mining are not just mechanical, but also medical. The most common disease related to coal exposure is Coal Workers Pneumoconiosis (CWP). While some studies argue the main factors contributing to CWP are coal rank and length of exposure, recent works show the amount of bioavailable iron in the coal correlates best with incidences of CWP. Additionally, pyrite oxidation experiments performed on coal with varying amounts of pyrite determined that pyrite, rather than the organic fraction, caused the formation of Reactive Oxygen Species (ROS). In the present study, pyrite oxidation experiments performed in simulated lung fluid, show that not only do ROS form, but hydrogen peroxide forms at a rate of more than 2.5 times faster than in water alone. ENVR 230 Degradation kinetics of trichloroethylene in heterogeneous pyrite Fenton reaction

H. Che, [email protected], and W. Lee, [email protected] Department of Civil and Environmental Engineering, Korea Advanced Institute of Science and Technology, Yuseong-gu, Daejeon, Republic of Korea The degradation of trichloroethylene (TCE) by heterogeneous pyrite Fenton reaction was investigated in a closed batch system. Pyrite was used as a catalyst to decompose hydrogen peroxide (H2O2) to hydroxyl radical (OH·). The oxidative degradation of TCE was properly fitted by a pseudo-first-order rate law contradict to that by classic Fenton reaction. The rate constants of TCE degradation increased linearly with an increase of pyrite contents from 0.21 to 12.82 g/L (slope normalized by pyrite surface concentration = 0.0126 L m-2 min-1). TCE removal increased more than 99% and its kinetic rate constant showed a saturation pattern as the concentration of H2O2 increased from 27 to 326 mM. The kinetic rate constants decreased linearly as initial pH increased from pH 3 to 10. TCE was fully degraded in the pH range tested here due to its decrease during the oxidative degradation of TCE. ENVR 231 Hydroxyl radicals form in natural sediments: Effects on sedimentary organic matter A. Skoog, [email protected], and V. A. Arias-Esquivel. Department of Marine Sciences, University of Connecticut, Groton, Connecticut, United States We show that hydroxyl radicals form at the oxic anoxic interface in marine sediments from Fe2+ reacting with H2O2 in the Fenton reaction. The aggressive nature of hydroxyl radicals makes it likely that they participate in degradation of sedimentary organic matter (SOM). We used terephthalic acid (TPA) to trap the hydroxyl radicals in sediment cores - TPA reacts with hydroxyl radicals to form the highly fluorescent product TPAOH. Results indicated formation of TPAOH at high concentrations at the oxic-anoxic interface. We also subjected SOM to hydroxyl radicals formed by the Fenton reaction, which resulted in changes in fluorescence properties and chemical composition. This is the first study showing formation of hydroxyl radicals and their effect on SOM, which is a previously unknown mechanism in the global carbon cycle. ENVR 232 Influence of dissolved natural organic matter on the photochemical cycling of mercury D. E. Latch1, [email protected], and G. R. Aiken2. 1Department of Chemistry, Seattle University, Seattle, WA, United States, 2Water Resources, USGS, Boulder, CO, United States Natural organic matter and photochemical processes are important controls for mercury in aquatic systems. Photochemical processes have been demonstrated

to oxidize Hg(0), reduce Hg(II), and degrade methylmercury. Natural organic matter is a strong ligand for Hg(II) and is a major source of an array of photochemically produced reactive intermediates in sunlit natural waters. We have undertaken a laboratory study aimed at elucidating the mechanistic underpinnings and the role of natural organic matter in Hg(II) photoreduction and Hg(0) photooxidation processes. We have found that the photoreduction kinetics observed for Hg(II) in natural organic matter solutions are similar to those of Hgthiolate species. This finding is consistent with recent reports which indicate that thiolate sites dominate Hg(II) binding at environmentally relevant Hg concentrations. Our results also show that a direct photoreduction process is operative. Photostationary state experiments indicate that photooxidation of Hg(0) is faster than photoreduction of Hg(II). ENVR 233 Thiol complexation of methylmercury enhances indirect photodemethylation by singlet oxygen T. Zhang, and H. Hsu-Kim, [email protected] Department of Civil & Environmental Engineering, Duke University, Durham, NC, United States Photodemethylation of monomethylmercury (CH3Hg) is an important component of the mercury cycle that maintains CH3Hg at low concentrations in natural waters. Rates of photodemethylation, however, can vary drastically between different types of surface waters for reasons that are largely unknown. In this research we studied photodemethylation by sunlight-sensitization of dissolved natural organic matter (NOM) and examined the importance of CH3Hg -binding ligands for demethylation rates. We quantified rate constants for demethylation reactions involving singlet state oxygen (1O2) and hydroxyl radicals ·OH. Our results indicated that 1O2 was capable of demethylating CH3Hg. Binding of CH3Hg+ ions to thiol-containing organics, such as glutathione, mercaptoacetate, and humic substances, increased 1O2 demethylation rates to values that are consistent with rates observed in lakes. In contrast, reaction rates with CH3HgCl complexes were at least one order of magnitude slower. Hydroxyl radicals were capable of demethylating CH3Hg complexes with rate constants near 2×109 M-1s1 . However, when we considered typical steady state ·OH concentrations in NOM-rich lakes, this rate was too slow to account for field observations. Our results provide an explanation to why photodemethylation is rapid in NOM-rich freshwater lakes, and relatively slow in coastal marine waters where CH3HgCl complexes dominate methylmercury speciation. ENVR 234 Effects of humic acid and cations on photocatalytic activity and aqueous transport of fullerene-based nanoparticles (FNPs)

S. Chae1, [email protected], Y. Xiao1, [email protected], A. R. Badireddy1, [email protected], J. Farner Budarz1, [email protected], A. Valladares2, [email protected], S. Mitra3, [email protected], and M. R. Wiesner1, [email protected] 1Department of Civil and Environmental Engineering, Duke University, Durham, NC, United States, 2Dept. Environmental, Earth, and Geospatial Sciences, North Carolina Central University, Durham, NC, United States, 3University High School, 4771 Campus Dr. Irvine, CA, United States Fullerene-based nanomaterials (FNMs) are emerging in a variety of potential applications, including cosmetics, energy production, semiconductors, and medical treatments. Although engineered nanomaterials have had an increasing presence in the consumer products, they are believed to pose a viable threat to the environment. Since they have a large surface area to mass ratio, they can be used as drug delivery devices, as imaging agents, and in consumer products like sunscreens, paints, cosmetics. However, while their applications are beneficial to society, their environmental implications such as oxidative stress could impact the ecosystem and pose severe health risk to humans. In this study, we explored the effects of various water chemistries, such as the presence of humic acids and mono- and di-valent cations on: 1) production of reactive oxygen species (ROS) from the photosensitized FNP aggregates, 2) T-7 bacteriophage inactivation by photosensitized FNP aggregates, and 3) transport of the aggregates from water to toluene for quantitative analysis of fullerene using a liquid chromatograph. As a result, it was found that the presence of humic acid and salts increased size of aggregates, decreased ROS generation, and consequently resulted in either limited or no viral inactivation. Also humic acid prevented transport of the FNP aggregates from water to toluene phase resulting in decrease of extraction efficiency for the quantitative analysis. ENVR 235 Effect of natural organic matter on the light-initiated transformation of fullerenes L. L. Kong, [email protected], K. Chan, R. Zepp, C. Ma, D. Bouchard, and C. Isaacson. US Environmental Protection Agency, Athens, GA, United States Natural organic matter (NOM) is ubiquitous in natural environments. Previous research has observed enhanced dispersion of Buckminster fullerene (C60) in water in the presence of NOM. It is also well-known that NOM can impact the photoreaction of many organic compounds by producing reactive oxygen species (ROS) such as, singlet oxygen (1O2), superoxide (O2-) and hydroxyl radical (·OH). Here we show that the phototransformations of C60 and fullerenol have very different dependencies on NOM concentrations. Corrected for light attenuation effects, C60 photoreaction rates generally decreased on addition of NOM but fullerenol rates were enhanced compared to controls without added NOM. Determination of 1O2, O2- and ·OH in the C60/NOM and fullerenol/NOM systems during irradiation suggested that photoreaction via ROS in the bulk water is not a

major pathway for both C60 and fullerenol, but an intramolecular pathway in aggregates is potentially possible. Although NOM can act as both scavenger and generator of ROS, the balance between scavenging and generation of ROS may be altered because of microheterogeneous formation and reactions of the transients in fullerene or fullerene-NOM clusters. ENVR 236 Aggregation of C60 fullerene water suspension in the presence of structurally different dissolved matters H. Mashayekhi, S. Ghosh, and B. Xing, [email protected] Department of Plant, Soil & Insect Sciences, University of Massachusetts, Amherst, MA, United States Stability of C60 aggregates in water may affect their mobility, bioavailability and toxicity. The objective of this study was to examine the effects of NOM structural properties on the aggregation behavior of fullerene water suspension (FWS). Fulvic acid (FA), tannic acid (TA), and two structurally different humic acids (HA1 and HA7) were used. Zeta potential (), size and aggregation rate of FWS were measured. The of pure FWS decreased (more negative) after adding any type of NOM, leading to a more stable colloidal system. Addition of Ca2+ to the FWS+NOM system increased the value. Critical coagulation concentration (CCC) was calculated at 14.5, 6.5, 5.4, and 3.7 mM Ca2+ for HA7, HA1, FA, and TA, respectively. The CCCs increased with NOM molecular size, suggesting a steric stabilization mechanism. This study highlights the role of NOM structural properties in the environmental fate of manufactured nanoparticles. ENVR 237 Mass spectrometry of non-colloidal fullerenes in waters containing natural organic matter W. C. Hockaday1, [email protected], Y. S. Hwang2, [email protected], C. A. Masiello1, [email protected], and Q. Li2, [email protected] 1Department of Earth Science, Rice University, Houston, TX, United States, 2Department of Civil and Environmental Engineering, Rice University, Houston, TX, United States Characterizeing engineered carbonaceous nanoparticles is environmental matrices present a substantial analytical challenge. We used atmospheric pressure photoionization mass spectrometry (APPI MS) to quantify aqueous fullerene C60 and identify C60 oxides in waters containing natural organic matter (NOM). Over 99% of aqueous C60 fullerene is suspended in the form of nanoscale colloids (nC60), where it is undetectable by APPI MS. However, APPI MS can detect non-colloidal C60 in water, even in the presence of NOM (see figure). The presence of NOM (20 mg/L) (see Figure 1) increased the dispersable concentrations of nC60 and non-colloidal C60(OH)0-3 by 5 fold (to 8µM) and 40-fold

(to 1nM), respectively. Work is ongoing to determine how environmental factors (e.g., NOM concentration and UV exposure) control the concentration and chemical transformation of non-colloidal fullerenes in aquatic systems.

ENVR 238 New insights in Mo(VI) speciation in sulfidic waters: Importance of natural organic matter A. Chappaz1, [email protected], A. Dhenain1, G. Druschel2, J. P. Fitts3, C. S. Kim4, and T. W. Lyons1. 1Department of Earth Sciences, University of California, Riverside, Riverside, CA, United States, 2Department of Geology, University of Vermont, Burlington, VT, United States, 3Environmental Sciences Department, Brookhaven National Laboratory, Upton, NY, United States, 4Department of Chemistry, Chapman University, Orange, CA, United States Molybdenum (Mo) is one of our best proxies for reconstructing the redox history of the early ocean. Although many studies point to a governing link between organic delivery/burial and Mo sequestration, the details of this relationship are unknown. We have explored the complexation of Mo by different kinds of dissolved organic matter (DOM) at varying DOM concentrations, pH, and Mo speciation. Here, we present results collected by an array of complementary analytical methods. Using UV-vis absorption spectroscopy, we show that MoS42is complexed by DOM with varying efficiency and kinetic behavior as a function of the type of organic matter and pH. We have also been able to uncover an intermediate Mo-DOM complex using electrochemistry methods that might have important implications for Mo uptake. Finally, x-ray absorption spectroscopy is providing information on the distance, coordination number, and identity of the nearest neighbor atoms, which define the Mo coordination environment. ENVR 239

Differential absorbance spectroscopy in the analysis of metal complexation to dissolved organic matter D. J. Dryer1, [email protected], G. V. Korshin1, and M. Benedetti2. 1 Department of Civil & Environmental Engineering, University of Washington, Seattle, WA, United States, 2Laboratoire de Géochimie des Eaux, Université Paris Diderot-Paris 7-IPGP, Paris, France This study examined the change in absorbance behavior of Suwannee River Fulvic Acid (SRFA) during interactions with copper ions. The absorbance spectra of SRFA underwent consistent changes during complexation with varying levels of copper (5-1000 g/L). At copper concentrations greater than 40 g/L, distinct features became discernible in the differential absorbance spectra. These features could be correlated to the engagement of particular protonation-active functional group types, such as carboxylic and phenolic-type chromophores. The differential absorbance results were also shown to correlate strongly with predicted copper binding results based on the NICA-Donnan model. It is predicted that this technique can also be applied to interactions with other metals of interest, and has the potential to provide a sensitive method for elucidating metal-NOM binding at low metal concentrations. ENVR 240 Metal complexation with dissolved organic matter in soil and groundwater remediation D. Tsang, [email protected] Department of Civil and Natural Resources Engineering, University of Canterbury, Christchurch, New Zealand High complexing ability of dissolved organic matter (DOM) often controls the speciation and fate of metals in the subsurface environment. This study investigated the kinetic change of metal speciation, particle size distribution, and binding mechanisms during soil and groundwater remediation that uses chelating agent and zero-valent iron, respectively. Complexes with DOM were shown to be the predominant forms of dissolved lead, aluminum, and iron during chelant washing between 1-min and 7-day reaction times. This indicated that DOM effectively complexes with these metals and controls their fate and bioavailability even if a strong chelant is applied for soil remediation. On the other hand, in groundwater remediation using zero-valent iron, DOM was found to form innersphere complexes with colloidal iron precipitates, which as a result agglomerated into larger particles with increasing reaction time. These changes in chemical and physical properties influence the collision efficiency and deposition of iron colloids during groundwater remediation. ENVR 241

Energy efficient production of caustic soda from wastewater using bioelectrochemical systems K. Rabaey, [email protected], R. A. Rozendal, [email protected], and J. Keller, [email protected] Advanced Water Management Centre, The University of Queensland, Brisbane, Queensland, Australia A key issue observed in bioelectrochemical systems (BESs) is the development of a pH gradient between the anode and the cathode. This is due to the fact that the majority of the charge balance between the anode and the cathode is restored by cations other than protons. Here, we have reversed this disadvantage to an advantage ­ by allowing the pH to increase at the cathode, caustic soda is effectively produced. To demonstrate the concept, we constructed a litre scale reactor, which delivered up to 1050 mA from synthetic feed, and up to 400 mA from real brewery wastewater. At the cathode, caustic was generated with a concentration of up to 3.5%, which is a concentration used, for example, for cleaning in place in breweries. The energy requirement for caustic production decreased by about 60%, relative to the existing production processes, thus highlighting how BESs can contribute to energy efficiency. ENVR 241.5 Extracellular electron transfer in microbial fuel cells Y. Gorby, [email protected], O. Bretschger, S. Ishii, G. Wanger, and M. ElNaggar. Microbial fuel cells provide potential for transforming wastewater and other organic-rich waste streams into electricity, hydrogen and methane. New engineering designs and a deeper understanding of the microbial communities that form on electrode surfaces under a variety of operational conditions are helping to increase power output and expand the applicability of MFC technologies. Still, components and mechanisms of electron transfer between microorganisms and electrode surfaces are poorly understood. It is generally accepted that extracellular electron transfer occurs through either (1) direct cellelectrode contact, (2) small redox-reactive compounds that serve as dissolved mediators, or (3) electrically-conductive appendages called bacterial nanowires. This presentation will provide an update on the approaches and progress we are making toward developing a mechanistic understanding of extracellular electron transfer in wastewater microbial fuel cells. Particular attention will be given toward electron transport processes that defy diffusional limitations. ENVR 242 Understanding and optimizing the biofilm anode of microbial electrochemical cells

C. I. Torres, [email protected] Center for Environmental Biotechnology, Arizona State University, Tempe, AZ, United States Microbial electrochemical cells (MXCs) rely on the catalytic activity of anoderespiring bacteria (ARB) to generate electrical current from the electrons contained in organic compounds. ARB form a biofilm at the surface of the anode, thus creating a 3-dimensional structure that catalyzes the anodic reaction. Being micron-size catalysts, ARB produce lower current densities than typical chemical catalysts. Therefore, the ARB biofilm anode often limits current generation in MXCs. In order to optimize the biofilm anode, we must understand the transport processes occurring inside the biofilm: substrate diffusion, proton and ion diffusion, and electron transport to the anode. Moreover, we must understand how the MXC design affects these processes and limit ARB activity at the biofilm anode. I discuss the design specifications (e.g., anode surface area, electrode size, distance between anode and cathode) required to achieve optimal conditions at the biofilm anode and maximize current and power density in MXCs. ENVR 243 Laboratory and field tests using microbial electrolysis cells for hydrogen production from agricultural and domestic wastewaters B. E. Logan1, [email protected], R. Cusick1, [email protected], M. D. Merrill1, [email protected], S. Cheng1, [email protected], B. Bryan2, [email protected], and D. S. Parker2, [email protected] 1 Department of Civil & Environmental Engineering, Penn State University, University Park, PA, United States, 2PO Box 8045, Brown and Caldwell, Walnut Creek, CA, United States Microbial electrolysis cells (MECs) are a new method for electrochemical hydrogen production at the cathode based on bacterial electrolysis of organic matter at the anode. The translation of laboratory findings to the field presents several challenges in terms of determining the suitability of wastewaters for treatment (pH, organic matter concentration, and conductivity), architectures needed (scalability of electrode designs, flow through the reactor), variability in conditions (temperature, flow, and composition of the wastewater, and gas evolution and capture. We report here on the first ever translation of laboratory studies to the field using MECs for recovery of energy as hydrogen gas from wastewaters. Several different agricultural wastewaters were first evaluated in the laboratory for electricity generation in a microbial fuel cell, and then they were used for current generation in an MEC. In order to examine the feasibility of the MEC process for an actual wastewater at a larger scale, chose one wastewater type, and we designed and built a 1000 liter pilot scale reactor. The reactor was deployed to a test site in the Napa Valley in California (Napa Wine Company, Oakville, CA). In this talk we will present our findings on the reactor tests begun in September, 2009.

ENVR 244 Development of non-platinum based cathodes for hydrogen production in microbial electrolysis cells H. Hu, [email protected], Y. Fan, and H. Liu, [email protected] Biological and Ecological Engineering, Oregon State University, Corvallis, OR, United States We recently developed non-platinum based cathodes by electrodepositing NiMo on carbon cloth, which demonstrated good electrocatalytic activity for hydrogen evolution in microbial electrolysis cells (MECs). To further optimize the loading of NiMo and electodepositing conditions, the effects of applied current density and durition of electrodeposition were systematically investigated. The developed cathodes were then characterized by various methods, including energydispersive X-ray spectroscopy (EDS) and electrochemical impedance spectra (EIS). The developed cathodes were also evaluated in chemical cell and in MECs for hydrogen production. Results demonstrated that NiMo loading can be reduced to 1-1.5 mg/cm2 and the hydrogen production rate of MECs with NiMo cathodes was comparable to that with Pt cathode with similar loading. ENVR 245 Microbial fuel cell cathodes with poly(dimethylsiloxane) diffusion layers constructed around stainless steel mesh current collectors F. Zhang1, [email protected], T. Saito1,2, S. Cheng1,3, M. A. Hickner2, and B. E. Logan1. 1Department of Civil and Environmental Engineering, Penn State University, University Park, PA, United States, 2Department of Materials Science and Engineering, Penn State University, University Park, PA, United States, 3 Department of Energy Engineering, Zhejiang University, Hangzhou, Zhejiang, China A new and simplified approach for making cathodes for microbial fuel cells (MFCs) was developed by using metal mesh current collectors and inexpensive polymer/carbon diffusion layers (DLs). We constructed the cathode around the metal mesh itself, thereby avoiding the need for the carbon cloth or other supporting material. A base layer of poly(dimethylsiloxane) (PDMS) and carbon black was applied to the air-side of stainless steel mesh, and Pt on carbon black with Nafion binder was applied to the solution-side as catalyst for oxygen reduction. Multiple PDMS/carbon layers were applied in order to optimize the performance of the cathode. Two PDMS/carbon layers achieved the highest maximum power density of 1610 ± 56 mW/m2 (47.0 ± 1.6 W/m3), with coulombic efficiency of 15-67%. These findings demonstrate that cathodes can be constructed around metal mesh materials such as stainless steel, and that an inexpensive coating of PDMS can be used for diffusion layer. ENVR 246

Structure-property relationship of polymeric cathode binders in microbial fuel cells T. Saito1,2, [email protected], T. H. Roberts1, M. A. Hickner2, and B. E. Logan1. 1 Department of Civil and Environmental Engineering, The Pennsylvania State University, University Park, PA, United States, 2Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA, United States Microbial fuel cells (MFC) are a promising renewable energy production technology. Air-fed MFCs use a microbe-laden anode to liberate electrons from organic compounds, and a cathode where oxygen is reduced on the surface of an inorganic electrocatalyst, such as platinum. The electrochemical reactions to reduce oxygen to water at the cathode involve the impingement of electrons, protons, and oxygen at a catalytic site. Our previous study demonstrated that the presence of sulfonate groups in polymeric binders for the cathode impeded the oxygen reduction activity of the platinum catalyst. Here, we report the effect of hydrophilic character of non-ionic polymeric binders. Increasing the hydrophilicity by increasing length of poly(ethylene oxide) (PEO) in polystyrene-b-PEO diblock copolymer catalyst binders enhanced the electrochemical response and MFC performance due to more catalyst area being exposed to the ionic buffer. Our recent progress on understanding the electrochemical environment of the cathode catalyst will be reported. ENVR 247 Treatment of carbon fiber brush anodes for improving power generation in air-cathode microbial fuel cells Y. Feng1, yu[email protected], Q. Yang1, X. Wang1, and B. E. Logan2. 1State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, Heilongjiang, China, 2Dept of Civil & Environmental Engineering, Penn State University, Armenia Carbon brush electrodes have been used to provide high surface areas for bacterial growth and high power densities in microbial fuel cells (MFCs). Three different treatment methods were first used to examine the power generation of carbon fiber (CF) brushes. It was proven that heat treatment (CF-) can improve power production to 1280 mW m-2, which was 25.4% larger than the untreated control (CF-C, 1020 mW m-2). Different heat treatment temperature was applied to carbon fiber and different power generated. XPS and NMR analysis of the treated and untreated anode materials indicated that power increases were related to higher N1s/C1s ratios and a lower C-O composition. These findings demonstrate efficient and simple methods for improving power generation, and provide insight into reasons for improving performance that may help to further increase power through other carbon fiber modifications.

ENVR 248 Progress in development of a microbial fuel cell system for treating municipal wastewater S. A. Wallin1, [email protected], S. T. Matteucci1, and R. D. Watt2. 1Core R&D, The Dow Chemical Company, Midland, MI, United States, 2Environmental Technology Center, The Dow Chemical Company, Midland, MI, United States Sustainable solutions in the areas of energy, water, and human health are crucial to continuing human progress and, at the same time, represent areas of significant economic growth. Microbial fuel cells (MFCs) have the potential to impact each of these areas. We will report progress in the development of a cost effective MFC for treatment of municipal waste water. Compared to the typical synthetic feeds used in laboratory studies, municipal waste water has low conductivity and low buffering capacity. We will present data comparing the performance of MFCs operating on highly buffered acetate feeds, acetate feeds having low buffering capacity, and municipal waste water. Critical aspects for the development of an economically viable system will be discussed. ENVR 249 Enhance potential in membrane-less biocathode upflow microbial fuel cell C. Sukkasem1, [email protected], and P. Boonsawang2, [email protected] 1Department of Food Science and Technology, Thaksin University, Phattalung Campus, Amphur Phapayom, Phattalung, Thailand, 2 Department of Industrial Biotechnology, Faculty of Agro-Industry, Prince of Songkla University, Hat Yai, Songkhla, Thailand The novel technology of microbial fuel cells (MFCs) has paid much attention recently which revealed many advantages. However, the high cost investment and high internal resistance are majority limits to scale-up to an economic scale. In this study, the reactor was designed to enhance potential on the low cost concept and reduce the internal resistance concomitant such as hook reactor without membrane, decrease electrodes distance, increase electrodes surface (using granular activated carbon), prevented air diffusion backward to the anode part, high sufficient air in cathode part and using biocatalyst cathode. The biodiesel wastewater (initial COD 187,308 mgL-1, pH 9.83) had been fermented until pH drop down to 5.5. The supernatant (132,308 mg COD L-1, 8,459 mg VFA L-1, pH 5.5) was fed in continuous mode at various conditions. The result illustrated that this $150 m-3 reactor obtained the maximum power density 7.12 mWm-3 at 10.0 kW. About 50% of supernatant COD was removed at OLR 76.21 g COD L-1d-1 and HRT 1.736 day. These results indicate that it is possible to scale-up this design for wastewater treatment. However it still needs to integrate the reactor by stacking to enhance COD removal and power generation.

ENVR 250 Impact of water chemistry on the removal of arsenic from drinking water by electrocoagulation W. Wan, [email protected], T. Pepping, and D. Giammar. Department of Energy, Environmental & Chemical Engineering, Washington University in St. Louis, St. Louis, MO, United States Exposure to arsenic through drinking water poses a threat to human health, especially in rural developing regions with limited water treatment infrastructure. Electrocoagulation is an emerging water treatment technology that involves electrolytic oxidation of anode materials and in situ generation of coagulant. The electrochemical generation of coagulant is an alternative to using chemical coagulants that may be beneficial for communities with better access to electricity than to chemicals. Batch electrocoagulation experiments were performed using iron electrodes. The experiments quantified the effects of pH, arsenic concentration and oxidization state, and concentrations of dissolved phosphate, silica and sulfate on the arsenic removal efficiency and rate. Arsenic concentration was determined by inductively coupled plasma mass spectrometry, while the solid phases formed in these experiments were characterized by X-ray diffraction and scanning electron microscopy. The experimental results were used to identify the mechanisms and rate-limiting steps of arsenic removal by electrocoagulation. ENVR 251 Disinfection of drinking water using solar UV: A low cost system applicable in developing countries E. G. Mbonimpa, [email protected], and E. R. Blatchley III, [email protected] Civil and Environmental Engineering, Purdue University, West lafayette, IN, United States Drinking water-related diseases affect low-income communities in sub-Saharan Africa , this tropical region is located where solar radiation is abundant and intense throughout the year. This study consists of designing a simple point-ofuse solar ultraviolet (UV) system to disinfect drinking water for these communities. The solar radiation spectrum, depending on location and time, will include UV wavelengths that are germicidally active; UV radiation is known to induce alterations in microbial DNA which prevent microorganisms from replicating. Dose- response behaviors of microorganisms were performed using surrogate microorganisms MS2, T4 and E-coli. They were subjected to UV wavelengths that can be obtained from solar radiation in these regions; between 290nm and 400nm. These surrogate microorganisms showed inactivation mainly between 290 and 320nm. An Irradiance field and a dose distribution for a model reactor was simulated using a CFD software; Fluent. Then, the dose distribution

and dose-response curve permitted to predict the performance of the solar UV reactor model. ENVR 252 Water treatment using ceramic filters amended with activated carbon J. A. Smieja1, [email protected], A. Vernon1, and B. Striebig2. 1Department of Chemistry and Biochemistry, Gonzaga University, Spokane, Washington, United States, 2School of Engineering, James Madison University, Harrisonburg, Virginia, United States Porous ceramic filters have been shown to be effective at removing microbes from drinking water. The possibility of amending this point-of-use technology with activated carbon to remove inorganic ions was explored. Granulated activated carbon was prepared in a kiln by steam activation of carbonized coconut shells. The surface functional groups, pore structure, and adsorption capacity of the prepared carbon was compared to two commercially available activated carbons. Ceramic filters amended with the prepared carbon and non-amended ceramic filters were compared with respect to their ability to remove a variety of contaminants from water. ENVR 253 Inorganic contaminants in scales formed in drinking water distribution systems: Examination of occurrence and release C.-Y. Peng1, [email protected], G. Korshin1, and A. Frenkel2. 1 Department of Civil and Environmental Engineering, University of Washington, Seattle, Washington, United States, 2Stern College, Yeshiva University, New York, New York, United States Accumulation and mobility of inorganic contaminants in drinking water distribution system have implications for long-term sustainability of drinking water distribution systems. In this study, we examined the occurrence in and release of a wide range of inorganic contaminants from representative samples of corrosion scales and assessed impacts of pH, exposure time and correlations between the release of major (iron, manganese) and minor scales' components. The chemical status of arsenic was also examined by EXAFS analyses. Notable levels of arsenic (40-630 µg/g), nickel (90-300 µg/g) and lead (15-110 µg/g) were found to be present in selected scales. Examination of their release demonstrated the existence of strong correlations between the behaviour of nickel, barium and manganese or, on the other hand, that of arsenic, lead and iron. EXAFS measurements for arsenic indicated that a major part of the retained arsenic exhibited the presence of As-O-Fe bonds and that the arsenic was primarily constituted by As(V) species.

ENVR 254 Polymer templated porous TiO2 monoliths doped with gadolinium(III) and their photocatalytic efficiency toward water purification D. L. Rogow1, [email protected], H. Fei1, X. Fan2, Y. A. Abdollahian1, M. R. Bresler1, and S. R. J. Oliver1. 1Department of Chemistry & Biochemistry, University of California Santa Cruz, Santa Cruz, California, United States, 2 Department of Physics, Marshall University, Huntington, West Virginia, United States Free-standing porous titanium dioxide monoliths were prepared using solvent swollen agarose polymer gel as a template. The TiO2 was doped with gadolinium(III) by addition of Gd(NO3)3·6H2O or Gd2(CO3)3NH3H2O (Denoted SLUG-8 for University of California Santa Cruz, structure number 8) to the prepolymer solution before swelling and inclusion of the TiO2 precursor. The photocatalytic degradation of aqueous methylene blue under ultraviolet irradiation was used to evaluate the materials for photocatalytic efficiency toward water purification. The monoliths doped with 0.2 wt/V % SLUG-8 showed improved catalytic efficiency compared with the Gd(NO3)3·6H2O doped TiO2 and undoped TiO2. The monoliths have an added advantage in that they do not require filtration and/or centrifugation to separate the catalyst from the solution. The results of the photocatalytic experiments for the materials containing varying amounts of Gd(III) dopant and different types of dopant precursors will be presented.

ENVR 255 Removal of polar pharmaceuticals from treated drinking water by commercial faucet-style water filters S. Baik, [email protected], and D. S. Aga. Chemistry, The State University of New York at Buffalo, Buffalo, NY, United States The removal of polar pharmaceuticals from drinking water by faucet-style water filters was investigated. The pharmaceuticals included carbamazepine,

carisoprodol, dilantin, meprobamate, sulfamethoxazole and trimethoprim. The commercial water filters tested were Brita® and PUR® brands which are claimed to have the efficiency to remove some organic compounds with a capacity of at least 100 gallons of water. The water filters were connected to the tap water system and 1 ml of 100 ppb pharmaceutical mixture was injected to the filters to collect 1 L of filter-treated tap water at 0, 50, 100, 200, and 300 gallons of water passing through the filter. The removal efficiencies for both brands of filter showed more than 90% for all 6 pharmaceuticals within 100 gallons of drinking water passing through the filters. The removal efficiencies after the filter's capacity, however, decreased for meprobamate and carisoprodol down to 85% and 80%, respectively, after 300 gallons of drinking water were passed through the filters. ENVR 256 Desalination and sustainability of drinking water distribution systems: Effects of blending of desalinated and conventionally treated surface water on iron corrosion and release H. Liu1, [email protected], G. Korshin1, [email protected], J. Ferguson1, [email protected], K. Schonberger1, H. Luckenbach2, E. Desormeaux3, and P. Meyerhofer3. 1Department of Civil and Environmental Engineering, University of Washington, Seattle, WA, United States, 2City of Santa Cruz, Water Department, Santa Cruz, CA, United States, 3CDM Inc., Walnut Creek, CA, United States Desalination has become a globally important drinking water technology. However, desalinated water is low in alkalinity, hardness, dissolved organic matter concentration and has a low pH. These characteristics make it potentially corrosive but its interactions with materials found in drinking water systems have not been well explored. This study assessed impacts of water quality changes caused by the blending of surface and desalinated water (produced at the Santa Cruz pilot desalination plant) on iron release from new iron coupons and corrosion scales from the Santa Cruz distribution system. Results show that blends with higher desalinated water fractions exhibit lower soluble iron levels. However, corrosion rates increase as the percentage of desalinated water increases while corrosion scales formed in these conditions exhibit susceptibility to colloidal mobilization. These concurrent processes indicate a possibility of red water episodes following the introduction of desalinated water and needs to address this aspect of the behaviour of drinking water systems. ENVR 257 Implementation of biosand filters in the village of Estanque de Leon a sustainable option: Field case study

M. Rabago Smith1, [email protected], N. Thor2, E. Santos1, D. LeCronier1, J. DeKoekkoek1, N. Findlay1, and N. Huthman1. 1Department of Chemistry and Biochemistry, Kettering University, Flint, Michigan, United States, 2 Health and Safety, Kettering University, United States Potable drinking water and sanitation are recognized as human rights but about 1.1 billion people worldwide lack access to safe drinking water supplies. The point-of-use water treatment technology has emerged as a feasible option to provide some communities with better water quality in the home. Slow sand filters, along with SODIS (UV purification systems), were implemented in a village located in a deserted area in the north of Mexico in October 2008, greatly increasing the quality of drinking water. This talk discusses the results obtained after one year of the implementation of Biosand-filters in the village of Estanque de León. ENVR 258 Photochemical production of superoxide and hydrogen peroxide from natural organic matter T. D. Waite1, [email protected], S. Garg1, and A. L. Rose2. 1School of Civil and Environmental Engineering, The University of New South Wales, Sydney, NSW, Australia, 2Southern Cross GeoScience, Southern Cross University, Lismore, NSW, Australia Irradiation of Suwannee River fulvic acid (SRFA) at pH 8.1 with simulated sunlight resulted in production of nanomolar concentrations of superoxide and hydrogen peroxide by reduction of singlet oxygen.

Similarity between superoxide and hydrogen peroxide concentrations over time obtained in this study and those observed during photolysis of simple quinones suggests that quinone-like moieties present in SRFA may be responsible for production of superoxide and hydrogen peroxide during SRFA irradiation. A kinetic model based on quinone photochemistry is proposed, with modifications to account for key differences. Implications of the photochemistry of natural organic matter to transformations between iron species are discussed.

ENVR 259 Kinetics of oxidation of manganese(II) by superoxide in natural waters S. P. Hansard, H. Easter, and B. M. Voelker, [email protected] Department of Chemistry and Geochemistry, Colorado School of Mines, Golden, CO, United States The kinetics of the reaction of Mn2+ with O2- were examined at environmentally realistic concentrations of both reactants in seawater samples and in simulated freshwaters. O2- decay kinetics were followed using MCLA chemiluminescence to quantify subnanomolar [O2-]. From the measured effect of an excess of Mn2+ on O2- decay kinetics, we obtained effective second-order rate constants for the oxidation of Mn2+ by O2- of ;106 M-1s-1. Further experiments with initial [O2-] in excess of [Mn2+] show that Mn is also capable of catalytic O2- decay, implying that redox cycling of Mn occurs under these conditions. We conclude that Mn may be a significant sink of O2- in some waters. More significantly, since recent studies have measured [O2-] on the order of 10-10 M in surface seawater, the results of our study imply that reaction with O2- is a surprisingly rapid pathway of abiotic oxidation of Mn(II), with a Mn(II) half-life on the order of hours. ENVR 260 Free radical induced oxidative and reductive degradation of pharmaceutically active compounds (PhACs) W. Song, [email protected], and W. J. Cooper. Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA, United States Many pharmaceutically active compounds (PhACs) are found in surface and ground waters suggesting their ineffective removal by conventional wastewater treatment technologies. Advanced oxidation/reduction processes (AO/RPs) are alternatives to traditional treatment and have received considerable attention for PhACs removal. AO/RPs typically involve the formation of hydroxyl radicals (·OH) as oxidizing species and either hydrated electrons (e-aq) as reducing species, both can be utilized in the destruction of organic pollutants present in drinking or waste water. However, to provide a fundamental understanding of the applicability of these processes to degrade PhACs, it is necessary to determine the bimolecular reaction rate constants between the reactive species and the PhACs of interest. These data are required for both evaluating the potential use of AO/RPs for the destruction of these compounds and for studies of their fate and transport in surface waters where radical chemistry may be important in assessing their lifetime. ENVR 261

Nitro reduction by zero-valent iron: Reactivity vs. particle size, structure, and polymer coatings J. T. Nurmi, [email protected], Z. Shi, E. Jackson, G. O'Brien Johnson, R. L. Johnson, and P. G. Tratnyek, [email protected] Division of Environmental and Biomolecular Systems, Oregon Health & Science University, Beaverton, OR, United States Nano-sized zero-valent iron (nZVI) is being used for remediation of contaminated groundwater, but questions remain whether its mobility and reactivity are suitable for reliable and sustained performance under field conditions. Recently, we have shown that the presence of natural organic matter (NOM) greatly increases its mobility in porous media by slowing aggregation and attachment to stationary surfaces. NOM could also affect the reactivity of nZVI, altering its rate of transformation (e.g., aging) or the rate at which it reduces contaminants. Here we use nitrobenzene as a probe contaminant, in part because its reduction products may form polymeric coatings on the nZVI with properties analogous to NOM. It appears that NOM adsorbed to the nZVI acts as an anodic inhibitor (physical barrier) to reduction processes, and the products of nitrobenzene reduction have an equivalent effect. NOM also decreases the rate at which nZVI is oxidized to magnetite. So far, we have found no evidence for enhanced interfacial electron transfer mediated by the quinonoid-moieties associated with NOM. ENVR 262 Abiotic dechlorination of cis-dichloroethylene (cis-DCE) and vinyl chloride (VC) by reduced iron minerals Y.-S. Han1, [email protected], S. P. Hyun1, H. Y. Jeong2, and K. F. Hayes1. 1 Department of Civil and Environmental Engineering, University of Michigan, Ann Arbor, MI, United States, 2Pohang Accelerator Laboratory, Pohang University of Science and Technology (POSTECH), Pohang, Republic of Korea Cis-dichloroethylene (cis-DCE) and vinyl chloride (VC), partial dechlorination products of commonly used chlorinated ethylenes such as tetrachloroethylene (PCE) or trichloroethylene (PCE), have been considered more problematic contaminants compared to their parent compounds due to their higher toxicity and persistence in the environment. Although several Fe(II)-bearing minerals may reductively dechlorinate cis-DCE and VC under anoxic conditions, the geochemical variables leading to complete dechlorination or build-up of both chloroethylenes remain to be clearly delineated. The goal of this study is to identify the geochemical conditions and reduced Fe species that promote the complete abiotic dechlorination of cis-DCE and VC. To simulate reducing redox conditions, several batches containing different Fe species were prepared by a chemical precipitation under a range of geochemical conditions (e.g., the initial concentrations of Fe(II), Fe(III), and S(-II), the initial pH, and background anions). The resultant batches were evaluated for the reductively dechlorinating reactivity

with cis-DCE and VC, and further examined for the solid-phase Fe speciation using x-ray absorption spectroscopy (XAS). ENVR 263 Ab initio simulation study on the reaction of chloroethylenes with iron (Fe) and iron sulfide mackinawite (FeS) D.-H. Lim1, [email protected], and C. M. Lastoskie2, [email protected] 1 Materials Science and Engineering, University of Michigan, Ann Arbor, MI, United States, 2Civil and Environmental Engineering, University of Michigan, Ann Arbor, MI, United States Adsorption and dissociation of perchloroethylene (PCE), trichloroethylene (TCE), and cis- dichloroethylene (cis-DCE) on iron (Fe) and iron sulfide mackinawite (FeS) are investigated using density functional theory (DFT) to evaluate hypotheses concerning the relative reactivity of these compounds on iron and iron-containing mineral. On the pristine iron surface, the ordering of the adsorption energies of chloroethylenes is in agreement with experimental observation (PCE > TCE > cis-DCE). The relative reactivity order among chloroethylenes on Fe(110) is also found to be PCE > TCE > cis-DCE. On the FeS with a functional group, a sulfide functional group (SH0) is found to be favored over an iron(II) hydroxyl functional group (FeOH0). The electronic structures of Fe-SH bonds on mackinawite surface are investigated to analyze the characteristics of water-adsorbed mackinawite. This model is used to understand contradictory results reporting the reactivity ordering with respect to degree of chlorination for chloroethylene reduction on iron and mackinawite. ENVR 264 Reaction behavior of nanoscale magnetite and nitrate ions in simulated groundwater G. C. C. Yang1, [email protected], and Y.-H. Chen2. 1Institute of Environmental Engineering, National Sun Yat-Sen University, Kaohsiung, Taiwan, Taiwan Republic of China, 2Institute of Environmental Engineering, National Sun Yat-Sen University, Kaohsiung, Taiwan, Taiwan Republic of China The aim of this study was to investigate the reductive adsorption behavior of laboratory-prepared nanoscale Fe3O4 and NO3- in simulated groundwater. Experimental results showed that nanoscale Fe3O4 had a greater adsorption amount when the initial NO3- concentration was higher than lower. It was also shown that at a higher pH environment or the existence of humic acid in simulated groundwater would decrease the removal efficiency of NO3-. Analysis of NO3- adsorption on nanoscale Fe3O4 in simulated groundwater indicated that a Langmuir-type of chemical adsorption would have a better fit. In this study, it was also found that nanoscale Fe3O4 not only adsorbed nitrate ions but also further

reduced NO3- to NO2- and NH4+ at pH=3. A possible reaction scheme for this reductive adsorption behavior was proposed accordingly. ENVR 265 Iron coordination and its role in the production of reactive oxidants from hydrogen peroxide D. L. Sedlak1, [email protected], C. K. Remucal1, A. L. Pham1, and F. M. Doyle2. 1Department of Civil & Environmental Engineering, University of California at Berkeley, Berkeley, CA, United States, 2Department of Materials Science & Engineering, University of California at Berkeley, Berkeley, CA, United States The reaction of Fe(II) with H2O2 (i.e., Fenton's reagent) is important to oxidation of contaminants in both sunlit natural waters and engineered treatment systems. In the absence of ligands, the reaction produces hydroxyl radical under acidic conditions and a less reactive oxidant, presumed to be Fe[IV], at circumneutral pH values. Addition of organic ligands, such as EDTA, NTA or oxalate, alters the reaction mechanism, resulting in production of hydroxyl radical over a wide pH range. In the presence of polyoxometalates or inorganic Fe(II)-complexing surfaces (e.g., Si or Al oxides) a similar shift in oxidant production also occurs. Therefore, Fe(II) coordination is critical to the fate of H2O2. By manipulating Fe[II] coordination, it is possible to enhance the yield of hydroxyl radical in the Fenton's reagent reaction by up to two orders of magnitude allowing for effective treatment of contaminants over a wide range of pH values. ENVR 266 Atomic-scale characterization of the effect of fulvic acid on heavy metal uptake at the muscovite (001)-solution interface S. S. Lee1,2, [email protected], P. Fenter1, C. Park3, and K. L. Nagy2. 1Division of Chemical Sciences and Engineering, Argonne National Laboratory, Argonne, IL, United States, 2Department of Earth and Environmental Sciences, University of Illinois at Chicago, Chicago, IL, United States, 3HPCAT, Advanced Photon Source, Argonne National Laboratory, Argonne, IL, United States The vertical distributions of divalent metal cations adsorbed at the muscovite (001)-fulvic acid (FA) interface were investigated at pH 2.0 to 3.7 using in-situ resonant anomalous X-ray reflectivity with sub-Å resolution. When muscovite was reacted in premixed metal-FA solutions, the distribution of some cations, but not others, was changed compared to adsorption from solutions of metal salts alone. For example, organophilic Hg2+ became broadly distributed within the entire FA film formed on the muscovite surface, suggesting that Hg2+ adsorbed mostly as organic complexes. In contrast, adsorption of less organophilic Sr2+ in an inner-sphere position was impeded by the directly-adsorbed FA fraction, while

some additional Sr2+ sorbed in the outer portion of the FA film. Compared to Hg2+ and Sr2+, FA had less effect on the adsorbed distributions of Cu2+ and Zn2+, cations with larger hydration enthalpies, suggesting that metal hydration strength is also a controlling factor. ENVR 267 Metal ion partitioning and speciation at complex natural organic mattermineral interfaces Y. Wang1, [email protected], F. M. Michel1,2, Y. Choi3, P. J. Eng3, J. R. Bargar2, B. Gu4, and G. E. Brown, Jr1,2,5. 1Surface & Aqueous Geochemistry Group, Department of Geological & Environmental Sciences, Stanford University, Stanford University, CA, United States, 2Stanford Synchrotron Radiation Lightsource, MS 69, SLAC National Accelerator Laboratory, Menlo Park, CA, United States, 3Consortium for Advanced Radiation Sources, University of Chicago, Chicago, IL, United States, 4Environmental Sciences Division, P.O. Box 2008, MS-6036, Oak Ridge National Laboratory, Oak Ridge, TN, United States, 5Department of Chemical Engineering, Stanford University, Stanford, CA, United States Mineral surfaces are often coated by natural organic matter (NOM). Changes in local nm-scale environments and the abundant binding sites in NOM coatings may induce significant changes in metal(loid) sorption and sequestration. However, such effects are still poorly understood at a molecular level. Here we applied long-period X-ray standing wave-florescence yield spectroscopy to measure partitioning of metal(loid) ions between Elliott soil humic acid (ESHA) and single crystal -alumina (0001) and (1-102) and hematite (0001) surfaces as well as hematite nanoparticles. Results show that a significant amount of Pb(II) in the ESHA coatings redistributes to reactive -alumina (1-102) and hematite (0001) surfaces, and hematite nanoparticle surfaces, whereas Cu(II) and Zn(II) strongly complex with ESHA and are relatively immobile. These results show that intrinsic properties (nature of binding sites and binding affinities) of NOM and minerals are key factors governing the distribution and speciation of metal(loid) ions at complex NOM/mineral interfaces. ENVR 268 Surface and organic speciation of Europium(III) in the -Al2O3 - humic acid system: Macroscopic and spectroscopic investigations P. E. Reiller1, [email protected], N. Janot1,2, [email protected], and M. F. Benedetti2. 1Department of Physical Chemistry, CEA, Gif-sur-Yvette, France, 2Laboratory of Water Geochemistry, IPGP, Paris, France The fate of lanthanides (Ln) and actinides (An) +III in the environment is strongly influenced by inorganic and organic colloids including natural organic matter

(NOM) [1]. The distribution of the metal between immobile and potentially mobile fractions is mainly driven by pH and NOM to surface concentration ratio. In a system consisting of surface/NOM/metal, it is up to now not clear which compartment influences most An/Ln(III) chemistry. The partitioning and chemical environment of Europium(III) in the presence of -Al2O3 and humic acid vs. pH and NOM concentration is studied combining batch experiments and spectroscopic characterisation by time-resolved luminescence spectroscopy (TRLS). The fate of Eu(III) seems to be mostly linked to NOM from its chemical environment probed by TRLS. Nevertheless, some subtle differences are evidenced pointing to a modification in the structure of NOM sorbed on oxide surface. 1. McCarthy, J.F., et al: Environ. Sci. Technol. 32, 3901 (1998). ENVR 269 Chromium(III) and cadmium binding to natural organic matter from surface water and landfill leachate A. Masion1, [email protected], S. Grimal1, F. Ziarelli2, J.-M. Garnier1, and J. Rose1. 1CEREGE UMR6635 Aix-Marseille University, CNRS, Aix en Provence, France, 2Spectropole, Aix-Marseille University, Marseille, France It is known that Natural Organic Matter (NOM) strongly binds metals. Here the interaction of two types of NOM (leachate, river NOM) and two trace metals (Cd2+, Cr(III)) was investigated. Standard IHSS protocols were applied to separate NOM samples into hydrophilic and hydrophobic fractions. The binding of Cd and Cr to NOM was investigated at the molecular scale using spectroscopic tools, viz. C-13 NMR, IRTF, Cd K-edge EXAFS. With the hydrophobic fraction of the landfill leachate, Cd is in the form of oligomers. This metal is strongly bound to NOM (on average one C is present in the first coordination sphere of Cd), most likely through the carboxylic acid functions. These functions were also identified as the main binding site for Cr(III) in both hydrophilic and hydrophobic fractions of the two NOM sources. Additionally, for this cation, NMR provided evidence for binding to NOM via -complexes. ENVR 270 Role(s) of siderophores and other natural organic ligands in Fe acquisition from hematite by an aerobic soil microorganism P. A. Maurice1, [email protected], C. A. Dehner2, and J. L. Dubois2. 1Civil Engineering & Geological Sciences, University of Notre Dame, Notre Dame, IN, United States, 2Chemistry and Biochemisry, University of Notre Dame, Notre Dame, IN, United States Siderophores are low molecular weight organic ligands that are released by aerobic microorganisms to acquire Fe. We investigated the role of siderophores in Fe acquisition from the mineral hematite by Pseudomonas mendocina ymp, an

obligate aerobic bacterium previously shown to secrete siderophore(s). Using a mutant incapable of producing functional siderophores (i.e., siderophore (-) strain), it was shown that siderophores are necessary for appreciable growth in the presence of hematite. However, a large excess of small-molecule reductant (ascorbate) alone could restore the siderophore(-) culture to WT growth levels. We also observed that siderophores and reductant could work synergistically. Excess carboxylic acid (oxalate) alone had little effect on mutant growth, but oxalate had a pronounced effect when siderophores were present (either WT or added siderophores). Our results demonstrate that the process of Fe acquisition from mineral substrates can involve a complex array of natural organic ligands typically found in soil environments. ENVR 271 Chemical weathering processes in the Rio Negro Basin (Brazil): Insights from colloidal organic matter and iron speciation M. F. Benedetti1, [email protected], T. Allard2, H. Gallard3, J.-P. Croué3, E. Fritch2, and P. Turcq4. 1Laboratoire de Géochimie des Eaux, Université Paris Diderot - IPGP UMR CNRS 7154, Paris Cedex 13, France, 2IMPMC, Université Paris 6 - IPGP, Paris Cedex 05, France, 3Laboratoire de Chimie et Microbiologie de l'eau UMR CNRS 6008, Université de Poitiers, Poitiers, France, 4LMTGHYBAM, Institut de Recherche pour le Dévelopement - IRD, Bondy, France The interactions between iron and colloidal organic matter from representative porewaters of soil sequences from laterite-podzol transitions and associated brooks as well as major rivers of the Rio Negro watershed (Brazil) are studied to reveal processes of chemical weathering. All samples contain dissolved Fe(II), Fe(III) bound to organic matter (FeOM) as well as iron oxides in the broad sense. In soil sequences, iron is equally concentrated in organic particulate and colloidal fractions, which is consistent with the aggregation of small units of organic matter with similar reactivity. By contrast, iron concentration is higher in colloidal fractions of rivers, which is consistent with a higher reactivity of riverine colloidal matter or with an iron rich soil horizon as the source of the colloidal fraction. Modelling of the iron organic matter interaction is developed to account for field data. ENVR 272 Iron-bridged complexation of arsenite with dissolved organic matter G. Liu1, Y. Cai1,2, [email protected], and A. Fernandez1. 1Department of Chemistry & Biochemistry, Florida International University, Miami, FL, United States, 2 Southeast Environmental Research Center, Florida International University, Miami, FL, United States

Metal-bridged (e.g., Fe) complexation between arsenic (As) and dissolved organic matter (DOM) has been proposed as one of mechanisms underlying AsDOM complexation, but chromatographic evidence remains lacking due to the difficulties in differentiation between free and DOM-bound arsenic. By employing a newly developed speciation method, which consists of size exclusion chromatography (SEC), UV/Vis detection, and inductively coupled plasma mass spectrometry (ICP-MS), we investigated As-DOM complexation in the presence of iron. Only a small fraction of arsenite could form complexes with Aldrich humic acid (HA) without the addition of Fe. However, the fraction of DOM-bound As increased significantly in the presence of Fe. Moreover, the coelution of DOM, As, and Fe was observed on the SEC column. This chromatographic evidence confirmed the occurrence of Fe-bridged As-DOM complexation. Rosenthal plot was used to calculate the apparent stability constant (Ks) of As-Fe-DOM ternary complex, with the log Ks ranging from 4.4 to 5.7. ENVR 273 Influence of dissolved organic carbon molecular weight and structure on copper complexation S. P. McElmurry1,3, [email protected], T. C. Voice1, and D. T. Long2. 1 Civil and Environmental Engineering, Michigan State University, East Lansing, MI, United States, 2Geological Sciences, Michigan State University, East Lansing, MI, United States, 3Civil and Environmental Engineering, Wayne State University, Detroit, MI, United States In freshwater systems, Cu is predominantly complexed with dissolved organic carbon (DOC), yet it remains unclear how the molecular size and molecular structure of DOC influence complexation. Using an assortment of humic standards, with known structural composition, high and low molecular weight (MW) Cu-DOC complexes were isolated by solid-phase extraction and quantified. High MW fractions of DOC were found to have a greater number of binding sites than low MW fractions. The number of binding sites present in high MW DOC was found to be related to structure (aromaticity) and composition (oxygen functional groups). The relative strength of complexation, determined by cation exchange, was found to be dependent on aromaticity. Results demonstrate the importance of aromatic structure in Cu-DOC complexation and suggest mechanisms for the preferential complexation of Cu by select size fractions. ENVR 274 Uptake of fullerene (nano-C60) by Lumbriculus variegatus J. Wang1,2, [email protected], J. M. Maul1,2, T. A. Anderson1,2, Q. Cai1,2, and G. P. Cobb1,2. 1Department of Environmental Toxicology, Texas Tech University, Lubbock, Texas, United States, 2The Institute of Environmental and Human Health, Lubbock, Texas, United States

Nanotechnology applications and uses have expanded rapidly for electronics, textiles, drug delivery, waste remediation, cosmetics, and agriculture. These compounds are unique due to their small unit size and large surface area. The emerging presence of engineered nanoparticles in the environment may introduce new toxicological issues. Few investigations have been performed to determine the toxicity and bioaccumulation of fullerenes to aquatic invertebrates, especially those that inhabit the benthos. This project is to determine the uptake of nano-C60 by Lumbriculus variegates which leads to the potential bioaccumulation by ecological receptors. In the preliminary test, nano-C60 was spiked into sediments at concentrations from 0.05 µg/g to 11.33 µg/g. With a 10day test, 4 replicates were set for each concentration, controls and vehicle controls were both performed. The number of worms surviving in each treatment group was not significantly decreased relative to controls after 10 days. The lack of mortality suggests no acute toxicity of nano-C60 to L. variegatus in the testing range. However, the amount of nano-C60 in sediment decreased after 10 days, indicating a possible uptake of nano-C60 by L. variegates. Quantification of nano-C60 in worms is underway. The potential bioaccumulation of nano-C60 is currently being investigated using the highest concentration tested during preliminary studies. ENVR 275 Give and take of Geobacter microbe-electrode interactions D. R. Lovley, [email protected] Department of Microbiology, University of Massachusetts, Amherst, MA, United States Geobacter species generate the highest current densities of any known microorganisms; are often the predominant microorganisms that naturally colonize the anodes of high-current-density, high-columbic-efficiency microbial fuel cells; and are effective in oxidizing organic contaminants with an electrode serving as the electron acceptor. Geobacter species can also reduce a diversity of contaminants and other electron acceptors with an electrode serving as an electron donor. A series of studies with Geobacter sulfurreducens including: adaptive evolution coupled with genome resequencing; microarray and real-time analysis of gene expression; genetic manipulation of gene expression; genomescale metabolic modeling; and electrochemical analyses have suggested a model for long-range electron transfer through conductive anode biofilms. Similar approaches indicate that electron transfer in the reverse direction from electrodes to the cells proceeds through different mechanisms. These findings have important implications not only for the design of microbial fuel cells but also for a number of emerging bioelectronic applications. ENVR 276 Electrochemical modeling of the anode reducing ability of Geobacter sulfurreducens

L. Tender1, [email protected], S. Strycharz1, H. Yi2, K. P. Nevin2, B.-C. Kim2, A. Franks2, A. Klimes2, and D. R. Lovley2. 1Center for Bio/Molecular Science and Engineering, Naval Research Laboratory, Washington, DC, United States, 2 University of Massachusetts, Amherst, United States Geobacter sulfurreducens possesses the ability to directly transfer electrons to anodes of microbial fuel cells without addition of soluble redox mediators. This property allows for growth of high current-density generating biofilms supplying uninterrupted power from complete oxidation of acetate. We have recently reported qualitative modeling of the catalytic properties of mutants of G. sulfurreducens strain DL1 analyzed using cyclic voltammetry. Here we report our most recent results advancing this modeling and its application investigate the cause of enhanced power generation by G. sulfurreducens strain KN400 analyzed by cyclic voltammetry and impedance spectroscopy. ENVR 277 Investigations of mechanisms of extracellular electron transfer in anode biofilms of Geobacter sulfurreducens N. S. Malvankar1, [email protected], K. P. Nevin2, A. E. Franks2, M. Vargas2, K. Inoue2, T. Mester2, M. T. Tuominen1, and D. R. Lovley2. 1Department of Physics, University of Massachusetts, Amherst, Amherst, MA, United States, 2 Department of Microbiology, University of Massachusetts, Amherst, Amherst, MA, United States Previous studies in our laboratory demonstrated that the biofilms of Geobacter sulfurreducens that grow on the anodes of microbial fuel cells are electronically conductive, with conductivities rivaling those of synthetic conductive polymers. To investigate the components conferring the conductivity, we studied novel strains of G. sulfurreducens capable of enhanced power production and mutants deficient in various outer surface components. Strains producing more current, produced biofilms with higher conductivity, demonstrating that higher biofilm conductivity facilities higher current density and suggesting that conduction is an important mechanism for long-range electron transfer through the biofilms.There was a direct correspondence between biofilm conductivity and the abundance of pili, referred to as microbial nanowires. There was no correspondence between cytochrome abundance and conductivity. An electrochemical gating technique revealed the direct role of pili in biofilm conductance. The results are being incorporated into a physical model of electron transfer through the biofilms. ENVR 278 Periplasmic hydrogenases role for extracellular electron transfer X. Wu1, N. Rahunen2, F. Zhao1, [email protected], J. Varcoe1, C. AvignoneRossa2, A. Thumser3, and R. Slade1. 1Chemical Sciences, University of Surrey, Guildford, United Kingdom, 2Microbial Sciences, University of Surrey, Guildford,

United Kingdom, 3Biological Sciences, University of Surrey, Guildford, United Kingdom Bioelectrochemical systems have more recently gained considerable attention because of their environmental significance and practical applications. To date, only membrane-bound cytochromes have been extensively studied for direct electron transfer between microbes and electrodes. A better knowledge of other enzymes for electrode reactions is essential to improve performance of bioelectrochemical systems since a wide range of proteins are present in microbial cells. In the present work we have demonstrated that periplasmic hydrogenases play an important role for extracellular electron transfer. This work was supported by the UK's ESPRC as part of the Supergen5 Biological Fuel Cells Consortium programme (contract EP/D047943/1). ENVR 279 Are all electron shuttles created equal? E. V. LaBelle, [email protected], and D. R. Bond, [email protected] BioTechnology Institute, University of Minnesota, Saint Paul, MN, United States Bacteria reducing extracellular acceptors utilize immobilized mediators or soluble shuttles. Investigation of two soluble compounds, anthraquinone-2,6-disulfonate and riboflavin, revealed similar redox potentials and diffusion coefficients. However, riboflavin showed more facile interfacial kinetics. Additions of each shuttle caused dose-dependent increases in current production by Shewanella oneidensis. The two shuttles behaved similarly at high applied potentials, but riboflavin mediated higher current at lower applied potentials. These results demonstrate how electron shuttle behavior can be diffusion-controlled at higher potentials, while interfacial kinetics can become dominant at potentials closer to these compounds' midpoint potentials. In general, the fact that added shuttles increased electron flux as much as 10-fold shows substrate oxidation is not always the rate-limiting step in electron transfer to electrodes. The potentialdependent behavior highlights differences that likely manifest during both environmental mineral reduction and in microbial fuel cells operated to achieve maximum power density. ENVR 280 Investigations into the extracellular electron transfer mechanisms of Geobacter and Shewanella species W. C. Sanders1, [email protected], L. A. Fitzgerald1, E. R. Petersen1, S. M. Strycharz1, P. E. Sheehan1, L. M. Tender1, D. R. Lovley2, and B. R. Ringeisen1. 1U.S. Naval Research Laboratory, United States, 2University of Massachusetts-Amherst, United States

With the recent discoveries that electrochemically active bacteria may use conducting nanofilaments and/or soluble electron mediators to enhance electron transport to insoluble electron acceptors, the elucidation of the mechanism for extracellular electron transfer (EET) has become complex. We have studied both Shewanella oneidensis MR-1 and Geobacter sulfurreducens DL-1 using nanoscale and macroscopic electrochemical techniques to determine how the EET mechanisms change under different environmental conditions. By performing these analytical experiments while exposing the microorganisms to differing levels of oxygen (MR-1), nutrients (MR-1, DL-1) and electron acceptors (MR-1, DL-1), we have made conclusions about when cell attachment occurs and biofilms are formed, when conducting nanofilaments are present, and when extracellular electron transfer is enhanced or reduced. We also used novel strains and deletion mutants to help understand the role different electron transfer mechanisms play in current generation in MFCs. ENVR 281 What influences Pseudomonas aeruginosa current production in bioelectrochemical systems? L. Angenent, [email protected] Biological and Environmental Engineering, Cornell University, Ithaca, NY, United States Pseudomonas aeruginosa, known for its pathogenicity, is also able to function as an electrode-reducing bacterium in bioelectrochemical systems (BESs), such as microbial fuel cells (MFCs), because it produces phenazines that act as electron mediators. For this reason, P. aeruginosa has become a model organism to study mediator-based electron transport in BESs. Seven single gene loss-offunction mutant strains and a wildtype strain of P. aeruginosa were investigated for their electrochemical properties. The mutants were deficient in the pathway for phenazine production or involved in biofilm formation. The mutant DeltaretS exhibited significantly higher current production than the wildtype and all other mutants. With this research we are deducing the biological reasons why P. aerigunosa generates is an electrode-reducing bacterium and also how the wildtype strain can increase its electric current. The latter information may be important for scientists and engineers to increase the electric power output of BESs. ENVR 282 Understanding electrochemical power extraction from Shewanella oneidensis at the single cell level J. Hu1, [email protected], X. Jiang1, C. M. Lieber1,2, J. C. Biffinger3, L. A. Fitzgerald3, and B. R. Ringeisen3. 1Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts, United States, 2School of Engineering and Applied Science, Harvard University, Cambridge,

Massachusetts, United States, 3Chemistry Division, US Naval Research Laboratory, Washington, DC, United States Microbial fuel cells (MFCs) represent a promising approach for sustainable energy production, yet fundamental factors and limits determining charge transport and power extraction remain controversial and/or poorly understood. This presentation will focus on studies designed to understand electrochemical power extraction from microbes, such as Shewanella oneidensis, down to the single cell level so as to reveal fundamental limits and factors affecting electron transport and power output. Well-defined, optically-transparent nanoelectrode arrays coupled with high-resolution phase-contrast microscopy, were developed to enable highly-controlled real-time electrochemical measurements while simultaneously resolving individual cells and cell assemblies on and interacting with different electrodes. The influence of the cell culture, electrode interface and measurement conditions on short-circuit current and other electrochemical properties will be described. These results provide new insight into the intimate cell-electrode interaction in MFCs, and open up the potential to advance significantly our understanding of power extraction from microbial fuel cell systems. ENVR 283 Reactivity of effluent organic matter towards hydroxyl radical as a function of molecular weight and its effects on the application of advanced oxidation M. M. Dong1, [email protected], F. Rosario1, [email protected], and S. Mezyk2, [email protected] 1 Department of Civil, Environmental and Architectural Engineering, University of Colorado, Boulder, Boulder, CO, United States, 2Department of Chemistry and Biochemistry, California State University at Long Beach, Long Beach, CA, United States Advance oxidation processes (AOP) are applied for the removal of organic contaminants in reuse applications. AOPs generate hydroxyl radical (OH), which non-selectively react with a wide range of organic contaminants. However, OH is scavenged by effluent organic matter (EfOM), reducing the overall efficiency. Recently the reactivity of EfOM towards OH was investigated as a function of molecular weight to understand the specific relationship between chemical properties and reactivity to OH. Four tertiary wastewater samples were collected. Each sample was fractionated by ultra-filtration membrane with cutoffs of 1, 3, 5 and10 kDa. Then second order rate constants (kEfOM-OH) for each filtrates and non-isolated water were measured by pulse radiolysis. The low molecular weight fraction (<1kDa) was the most reactive fraction, with a value for kEfOM-OH approximately 2.3 times higher than for the raw water. In general, the reactivity between the fractions and OH decreased as a function of molecular weight.

ENVR 284 Development of a novel hybrid UAFB-anoxic-aerobic MBR for energy production and nutrients removal from domestic wastewater D. Gao, [email protected], and R. An. Department of Environmental Science and Engineering, Harbin Institute of Technology, Harbin, Heilongjiang, China Facing an energy crisis and shortage of water resources, domestic wastewater showed an enormous potential for reclaiming energy and reusing wastewater. In this study, the combined treatment process made up of up-flow anaerobic sludge fixed bed (UAFB), anoxic tank and aerobic membrane bioreactor (MBR) was used to treat domestic wastewater, and the ability of reclaiming methane and reusing wastewater was investigated. The efficiency of the combined treatment process treating wastewater at optimized parameter was studied in this paper. The combined treatment process treating domestic wastewater run at optimized parameter (20° C, HRT were 3h, 3h, 3.5h) indicated that the anaerobic gas production was 1.55 L/d, the COD and NH+4-N removal efficiency were 93.28% and 90.60% respectively, UAFB effluent including 54.74 mg/L of total VFAs, corresponding NO-3-N accumulating rate was 45.19% and TN removal efficiency was 45.51%. At the same time, it was found that sludge concentration of anoxic tank and aerobic MBR could be maintained at a low level, which is so rich in significance for sludge reduction and delaying membrane fouling. ENVR 285 Electro-enzymatic removal of nitrate from wastewater Y. J. Yoo, [email protected], and J. Cho, [email protected] Department of Chemical and Biological Engineering, Seoul National University, Seoul, Republic of Korea Biological denitrification among various denitrification methods is the most widely accepted process because of its economical and environmental advantages. Four enzymes in microorganisms, nitrate reductase, nitrite reductase, nitric oxide reductase, and nitrous oxide reductase, are known to be involved in biological denitrification process. However, the biological denitrification process has some problems. Most of all, the process needs carbon sources for microbial activities. The carbon sources cause cost increase and second pollution. In this research, Ochrobactrum anthropi SY509 was used as biocatalyst containing 4 enzymes for denitrification. And the microorganisms were treated by organic solvent for permeablization. The permeablized microorganisms and conducting material were immobilized by polymer material. As the result, the biocatalysts and conducting material formed 3-dimensional bioelectrode. And in the bioelectrode, the electrons for denitrification were transferred directly to the biocatalysts. The electrode was applied to batch and continuous reactor. Using this bioelectrode, high denitrification efficiency was obtained.

ENVR 286 Comparative evaluation on fate and treatability of estrogenic contaminants in conventional wastewater treatment plants P. A. Ruiz-Haas1, [email protected], K. D. Cho2, and K. G. Linden3. 1 Department of Chemistry and Physics, Mary Baldwin College, Staunton, VA, United States, 2District Department of the Environment, Washington, DC, United States, 3Department of Civil, Environmental, and Architectural Engineering, University of Colorado at Boulder, Boulder, CO, United States The elimination of endocrine disrupting compounds (EDCs) in three advanced wastewater treatment plants (WWTPs), which employ different solids and liquids treatment processes, was evaluated. The study was conducted over the course of one year to assess the effectiveness of the operational design, sequences of processes employed, and seasonal variation to determine fate, presence and treatability of EDCs. Solid and liquid samples were collected from individual unit operations in the WWTP train; analysis of samples was conducted by GC/MS and a yeast estrogen screening assay to determine total estrogenic activity. The plants studied employ different activated sludge processes, with final disinfection consisting of chlorination or UV disinfection. A high loading of EDCs was observed in biosolids (1-200 µg/kg); however finished biosolids dried at high temperatures had low (< 0.5 µg/kg) concentrations of EDCs. Removal of EDCs from the liquid stream was correlated to total TOC removal in the wastewaters examined. ENVR 287 Incomplete rejection of low molecular weight compounds in reverse osmosis systems and their potential impacts on potable water quality D. L. Sedlak1, [email protected], E. Agus1, L. Zhang2, and M. Lim2. 1 Department of Civil & Environmental Engineering, University of California at Berkeley, Berkeley, CA, United States, 2Centre for Advanced Water Technology, Public Utilities Board of Singapore, Singapore, Singapore The ability of reverse osmosis (RO) systems to reject neutral organic compounds depends upon the molecular weight of the compound, with compounds below 250 Daltons exhibiting rejections as low as 50%. To assess the potential presence of low molecular weight compounds in RO permeate, samples were collected from several full-scale advanced wastewater reclamation plants and analyzed for a broad suite of low molecular weight compounds by GC/MS/MS and GC/olfactometry/MS. Several compounds with very low odor thresholds were detected occasionally after RO. Although the concentrations of these compounds were always below levels that pose human health concerns, the presence of the compounds could diminish the aesthetic quality of the water. These odorous compounds are volatile and therefore should dissipate readily when the RO water is discharged to surface reservoirs. Advanced treatment plants that

discharge directly to groundwater may need to consider monitoring these compounds and possibly using advanced oxidation processes to remove them if they are present at concentrations above organoleptic thresholds in potable water. ENVR 288 Treatment of hydrogen sulfide contaminated sour water with potassium permanganate M. T. Doyle, [email protected] Department of Chemistry, California State University Dominguez Hills, Carson, California, United States Sour water samples containing high concentrations of dissolved hydrogen sulfide gas were treated with pH 9.5 buffered potassium permanganate solution to oxidize hydrogen sulfide to elemental sulfur, water and manganese ion. Treatment allowed the safe disposal of the sour water without the danger of hydrogen sulfide gas. A series of four trials were performed and it was determined that 17.1 mL of permanganate solution was required to treat 100mL of sour water. ENVR 289 Pharmaceutical compounds in our water supply: Advanced oxidation processes to remove antibiotics from water H. B. Santoke, [email protected], W. Song, and W. J. Cooper. Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, California, United States Fluoroquinolones, as a class of broad-spectrum antibiotics, have been detected in both surface and ground waters, and advanced oxidation/reduction processes (AO/RPs) are currently under development to remove these and other pharmaceuticals from wastewater. This work reports the reaction kinetics of six common fluoroquinolones with hydroxyl radicals and hydrated electrons, which are the major reactive species involved in AO/RPs, and identifies the byproducts formed in the process. The rate constants are related to the functional groups attached to the quinolone core, particularly the steric hindrance of the piperazine ring, making it possible to obtain a preliminary estimate of the ·OH rate constant of an arbitrary fluoroquinolone by observing the ring constituents. In addition, the products of gamma-irradiation degradation of fluoroquinolones were analyzed by LC-MS to elucidate the probable pathways of AO/RPs degradation, and three major pathways were identified. ENVR 290

Rapid and selective removal of perchlorate from water using ion exchange resin/glass fiber composites J. L. Langer, [email protected], K. J. Lim, M. Dejarld, and J. Economy. Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States Perchlorate is a potentially toxic anionic contaminant found in many groundwater supplies throughout the United States. In order to effectively remove perchlorate from water, it is desirable to use ion-exchange resins with hydrophobic quaternary ammonium exchange sites. Use of such functional groups leads to slow diffusion in the resin, resulting in poor exchange kinetics. As an engineered form, ion-exchange fibers provide an alternative solution for selective removal of perchlorate, allowing rapid exchange kinetics in concert with high selectivity. We report the preparation and properties of ion-exchange fibers based on non-woven glass substrates coated with poly(vinyl benzyl chloride), cross-linked with 1,4diazabicyclo[2.2.2]octane (DABCO). These composite fibers display an order of magnitude increase in ion-exchange kinetics as compared to the Purolite A-530E perchlorate-selective resin. We propose this new class of ion-exchange materials as an excellent treatment option for point-of-use applications. ENVR 291 Photochemical disinfection after contamination with Escherichia coli: Role of singlet oxygen formation N. Barashkov1, [email protected], D. Eisenberg1, S. Eisenberg1, I. Irgibayeva2, G. Shegebayeva2, Y. Sakhno3, [email protected], and T. Sakhno3. 1Micro-Tracers, Inc, San Francisco, CA, United States, 2Department of Chemistry, Eurasian National University, Astana, Kazakhstan, 3Academy of Sciences Technological Cybernetics, Poltava, Ukraine Deionized water, highly contaminated with Escherichia coli and containing ammonium sulfate as an electrolyte, was treated in a circulating system with use of the active layer of photosensitizer during its irradiation with a visible light. It was shown that the polymer films, such as ethylcellulose, doped with aluminium salt of fluorescent dyes are able to generate a singlet oxygen which is responsible for sanitizing effect. Such parameters, as choice of spectral region of the visible light with low intensity, which is able to excite the fluorescent dye molecules; concentration of electrolyte and flow rate are investigated and an experimental proof of the singlet oxygen generation is provided. ENVR 292 Implementation of pallidized iron-impregnated reactive activated carbon system for PCB clean-up: Effects of PCB loading, reaction pH, and coexisting NOM and ionic species

H. Choi1, [email protected], and S. R. Al-Abed2. 1Department of Civil Engineering, University of Texas at Arlington, Arlington, Texas, United States, 2National Risk Management Research Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio, United States For the treatment of chlorinated organic compounds in the environment such as polychlorinated biphenyls (PCBs), we have developed reactive activated carbon (RAC) impregnated with Fe/Pd bimetallic nanoparticles. The RAC system can couple adsorption of PCBs to activated carbon with their dechlorination on Fe/Pd. Subsequently, there has been a great advance in the RAC research for the remediation of PCB-contaminated sites, including tests on the ageing and longevity of RAC and its treatability towards various PCB congeners. However, most recent studies have not addressed the complexities of treating actual sites, and rather neglected the potentially adverse impacts of co-existing species in the environment. In this presentation, we will discuss some practical reaction conditions relevant in natural systems, including PCB loading, reaction pH, and coexisting natural organic matter and ionic species, which greatly influence the trapping and treatment strategy of RAC system towards PCBs. ENVR 293 Effects of high-volume pharmaceutical products on a model land plant, Arabidopsis thaliana K. Butzine, [email protected], and C. Chan, [email protected] Department of Biological Sciences and Chemistry, University of Wisconsin-Whitewater, Whitewater, WI, United States The accumulation of pharmaceutical products in the environment is a growing concern as the consumption of such chemicals increases. They have been detected in surface water, where they primarily enter the ecosystem through effluent from wastewater treatment plants. They also exist in soil, mainly from wastewater runoff during flooding and application of biosolids. The presence of select pharmaceutical products in surface water has been correlated with negative developmental consequences in aquatic organisms. However, the effects of these chemicals on terrestrial plants are not well documented. Our research focuses on characterizing the effects of select high-volume pharmaceuticals on a model land plant, Arabidopsis thaliana. We will present the effects of these pharmaceuticals on the development of Arabidopsis, and link the phenotypic observation with specific patterns of mineral nutrient accumulation. Our results will serve as a foundation for future work on the effects of pharmaceutical products on agriculturally- and environmentally-important plant species. ENVR 294

Pilot scale testing of swellable organosilica-nano zero valent iron composite materials for the in situ remediation groundwater contaminated with trichloroethylene D. C. Pickett, [email protected], and P. L. Edmiston. Department of Chemistry, College of Wooster, Wooster, Ohio, United States Composite materials composed of swellable organosilica with embedded nanoparticles of zero valent iron (nZVI) have been tested for the dechlorination of trichloroethylene in groundwater. Laboratory testing has shown that such materials are effective in rapidly dechlorinating TCE to ethane and chloride ion. The glass matrix serves to concentrate the TCE and protect the nZVI from deactivation by dissolved ions. Both nZVI and bimetallic particles in the glass matrix were tested under a variety of conditions. In conjunction with laboratory testing, two pilot projects were carried out in central Ohio at industrial sites with groundwater contaminated by either TCE or perchloroethylene. Composite materials were injected into the aquifer to create a soft curtain up-gradient from a string of monitoring wells. Soil testing was used to determine the distribution of the material post-injection using fluorescently labeled particles. Chlorinated solvent concentrations were measured as a function of time to assess the effectiveness. ENVR 295 Comparative degradation of textile dye with homogeneous/heterogeneous iron systems J. Vergara-Sánchez1, [email protected], R. Suárez- Parra1, [email protected], I. Hernández-Pérez2, [email protected], and M. Ocampo-Gaspar1, [email protected] 1Materiales Solares, National Autonomous University of Mexico, Temixco, Morelos, Mexico, 2Basic Science, Metropolitan Autonomous University, México, Federal District, Mexico The dye reactive red-120 degradation was carried out by Fenton, photo Fenton reagent and hetero-photocatalytic processes with a suspension of iron oxide (Fe2O3) nanoparticles (NPs), and with Fe2O3 NPs supported on a mesoporous material (SBA-15) and hydrogen peroxide (H2O2) as oxidizing agent in mildly acidic aqueous solutions. The iron ions concentration was 0.1 and 1 mM, equal concentration (0.0428 M) of H2O2 for all cases, and 100 mg/l of reactive red-120. The evolution of the catalytic reaction was followed by UV-Vis spectroscopy (190 to 900 nm). The oxidation degree was monitored by measurements of chemical oxygen demand (COD), total organic carbon (TOC) and catalytic activation of H2O2 efficiency. It was found that the processes with illumination were the most efficient, reducing TOC over 99%. ENVR 296

Nonylphenol interferes with the immune function of human natural killer cells R. Etherton, [email protected], and M. M. Whalen, [email protected] Department of Chemistry, Tennessee State University, Nashville, TN, United States Nonylphenol (NP) is a degradation product of compounds used as surfactants in a wide variety of applications including household products. It has been found in human blood samples. Human natural killer (NK) lymphocytes are able to lyse virally-infected and tumor cells. Agents that interfere with the ability of NK cells to lyse targets may increase tumor development or viral infection. We examined the effects of varying concentrations of NP on the lytic function of human NK cells. Exposures to 2.5, 5 and 10 µM NP for 24 h decreased lytic function 13%, 32%, and 46%, respectively. Exposures to 1, 2.5 and 5 µM NP for 48 h decreased lytic function by 13% (2.5 M) and 18% (5 M). A 6 day exposure to 1, 2.5 and 5 µM NP decreased the ability of NK cells to lyse tumor cells by 28% (1 M), 45% (2.5 M), and 55% (5 M).These results indicated that exposures to NP can cause significant loss of lytic function, which increases with length of exposure after 48 h. Supported by NIH grant S06 GM008092-34. ENVR 297 Triclosan causes persistent suppression of the immune function of human natural killer cells M. M. Whalen, [email protected], and T. Martin. Department of Chemistry, Tennessee State University, Nashville, TN, United States Triclosan (TC) is an antimicrobial compound that is in widespread use in antibacterial soap products as well as other personal hygiene products such as toothpaste. It contaminates the aquatic environment and has been found in human blood, breast milk, and urine. It likely enters humans through absorption through the skin or by ingestion. Human natural killer (NK) lymphocytes are able to destroy (lyse) virally-infected and tumor cells. Agents that interfere with the ability of NK cells to lyse targets may increase tumor development or viral infection. We examined the effects of varying concentrations and lengths of exposure to TC on the lytic function of NK cells. Exposures to 5 and 10 µM TC for 1 h decreased lytic function 46%, and 92%, respectively. Exposures to 2.5 and 5 µM TC for 24 h decreased lytic function by 64% (2.5 µM) and 87% (5 µM). NK cells exposed to 10 µM TC for 1 h followed by 24 h, 48 h or 6 day periods in TC-free media continued to show suppression of NK function. 24 h following a 1 h exposure to 10 µM TC the lytic function of NK cells was still suppressed by 67%. This maintained out to 6 days, where the decrease in lytic function was 75%. These results indicated that exposures to TC can cause significant loss of lytic function, which persists for at least 6 days following a 1 h exposure. Supported by NIH grant S06 GM008092-34.

ENVR 298 Treatment of arsenic in ash and scrubber pond effluents using nanoparticulate pyrite (FeS2) D. Han1, [email protected], A. Abdel-Wahab1, and B. Batchelor2. 1 Chemical Engineering, Texas A&M University, Education City, Doha, Qatar, 2 Civil Engineering, Texas A&M University, College Station, TX, United States The purpose of this study is to evaluate the ability of nanoparticulate pyrite to remove arsenic from ash and scrubber pond effluents. Pyrite is expected to produce stable residuals for ultimate disposal after removing arsenic from solution, so that removal of resenic from wastewaters will not result in contamination of soils and groundwaters. A batch reactor system was employed in an anaerobic chamber to conduct experiments to characterize both the removal of arsenic from solution and their subsequent reactions with pyrite. In addition, the stability of pyrite combined with arsenic was investigated by measuring the ability of arsenic to resist release to the aqueous phase after removal. ENVR 299 Paraoxon causes brain injury and increases the total power of EEG (Electroencephalography) in rats Z. Gu, [email protected], R. A. Bauman, [email protected], and J. B. Long, [email protected] Department of Closed Head Injury Research, Walter Reed Army Institute of Research, Silver Spring, MD, United States Intoxication of paraoxon (O,O-diethyl O-p-nitrophenyl phosphate), a metabolite of the insecticide can induce headaches, convulsions, respiratory arrest as well as even death. However, the effects of paraoxon on brain function are still poorly understood. The present study examined the brain injury and EEG changes after paraoxon exposure in 32 male Sprague-Dawley rats (in the control group, n=8; in the paraoxon exposure group, n=24). Telemetric EEGs were recorded and analyzed using the software Spike 2 (CED, Cambridge, England). After paraoxon (1.575 mg/kg) injection, seizure was quickly developed starting at 8.3 ±1.6 min. EEG total power sharply increased within minutes and was 12 folds higher than the baseline at 1st hour post-exposure. EEG total power remained 3 times higher than the base line at 72nd hour after exposure. These results suggested that exposure to paraoxon can cause acute cortical/ subcortical brain injury and dysfunction. The increase of EEG total power may be useful for the detection of acute paraoxon poisoning. ENVR 300

Improvement of chitosan adsorption towards dyes by low concentration hydrogen peroxide pretreatment C. Shen, [email protected], Y. Wen, [email protected], and W. Liu, [email protected] Institute of Environmental Science, Zhejiang University, Hangzhou, Zhejiang, China A new simple pretreatment of chitosan, using low concentration of hydrogen peroxide, was applied to improve the adsorption of dye C. I. acid red 73 onto chitosan without depolymerization. The results indicated that the improvement of C. I. acid red 73 adsorption on chitosan could achieve ca. 60% after the pretreatment with 200mM hydrogen peroxide for 2 h. Additionally, the minor changes in pretreated chitosan samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), static water contact angles (CA), and fourier transform infrared spectroscopy (FTIR). Then the effect of pH, the adsorption isotherms, the adsorption of other dyes and the regeneration of chitosan were discussed next. In conclusion, the hydrogen peroxide pretreatment could be suggested as a simple, efficiently and environmentally friendly method to improve the adsorption capacity of chitosan towards anionic and non-ionic dyes in acid and neutral solution. ENVR 301 Determination of total cyanide in municipal wastewater and drinking samples by ion-exclusion chromatography and pulsed amperometric detection T. T. Christison, [email protected], R. F. Jack, B. M. De Borba, and J. S. Rohrer. Dionex Corporation, Sunnyvale, CA, United States Cyanide is a well known acute toxin and therefore, regulated as an environmental contaminant by the US Environmental Protection Agency for drinking, surface, and wastewater. To protect animal life, lower maximum contaminant levels of 1-5 µg/L are proposed for effluent discharges, wastewater, and saline water sources. Therefore, accurate and sensitive analytical methods are needed. In this paper, we describe an ion exclusion method with pulsed amperometric detection (ICE-PAD) using a Pt electrode to determine total cyanide in acid-digested drinking and wastewater samples. ICE-PAD has the advantages of eluting cyanide before sulfide with Rs > 3, and excluding other interferences, and selectively detecting cyanide and sulfide. The cyanide peak area response to concentration was linear from 1 to 25 g/L, an r2 of 0.9999, and the estimated LOD was 0.3 g/L. In this paper, we demonstrate accuracy and precision for the determination of total cyanide in samples of drinking and wastewater using ICE-PAD. ENVR 302

Improving dye-sensitized solar cells: Increasing Voc and Jsc for ZnO based cells C. H. C. Giammanco, [email protected], and H. Van Ryswyk. Department of Chemistry, Harvey Mudd College, Claremont, California, United States Dye-Sensitized Solar Cells (DSSC) are a cheap and easy to make alternative to solid-state semiconductor solar cells, but need to be more efficient to be economically competitive. The most efficient cell to date has been the Grätzel cell, with TiO2 nano-particles as the anode and a ruthenium based dye, which has been optimized to give ;11% efficiency. ZnO is a good candidate to replace the TiO2 anode, as it has a higher electron mobility and it can be formed into the more optimized nanotube geometry, and porphyrin dyes are cheaper than Grätzel's dye and have the possibility of extending absorption of light farther out into the red. Acid etching of the ZnO anodes is shown to lead to better charge injection of otherwise inefficient dyes. Pre-intercalation of Li+ into the anodes leads to a larger open-circuit photovoltage, which leads to an increased efficiency. ENVR 303 Analysis of organotins in polyvinyl chloride pipe and their diffusion into water over time W. A. Adams1, [email protected], C. A. Impellitteri1, G. Rice2, A. Fristachi3, Y. Xu4, H. Carlson-Lynch5, and J. C. Little6. 1National Risk Management Research Laboratory, U.S. Environmental Protection Agency, Cincinnati, OH, United States, 2National Center for Environmental Assessment, U.S. Environmental Protection Agency, Cincinnati, OH, United States, 3Battelle, Columbus, OH, United States, 4Department of Civil, Architectural and Environmental Engineering, The University of Texas at Austin, Austin, TX, United States, 5Syracuse Research Corporation, Syracuse, NY, United States, 6 Department of Civil & Environmental Engineering, Virginia Tech, Blacksburg, VA, United States Organotins are commonly used as thermal stabilizers in the manufacturing of PVC pipes, which are widely used in drinking water distribution systems. Additives, such as organotins, have been shown to leach through PVC pipe into water. While tri-substituted organotin compounds have shown high toxicity, the presence of any alkylated tin compound in a water system should be of concern. This research examines the presence of monomethyltin, dimethyltin, monobutyltin, and dibutyltin in a small-scale simulated PVC distribution system. The analysis of the organotins is conducted using water samples taken from the system, which are then extracted and derivatized using liquid-liquid extraction and ethylation derivatization. The samples are analyzed using GC/PFPD. The diffusion coefficient for the system is then calculated based on organotin concentrations and compared with predicted diffusion models for the leaching of organotin additives in PVC pipe over time.

ENVR 304 Effect of nano-sized metal oxides on the oxidation of triclosan by -MnO2 S. Taujale, [email protected], P. Bick, [email protected], and H. J. Zhang, [email protected] Department of Chemistry and Environmental Sciences, Southern Illinois University Edwardsville, Edwardsville, Illinois, United States The antibacterial agent triclosan has been reported to be rapidly oxidized by manganese oxide (d-MnO2). To properly extend the reaction with pure MnO2 to the environment where multiple metal oxides co-exist, it is important to understand how the presence of an additional metal oxide affects the oxidation of triclosan by MnO2. For this purpose, oxidation studies were performed on systems containing both MnO2 and nano-sized metal oxides. Kinetic results show that the addition of nAl2O3 significantly inhibited the oxidation of triclosan by MnO2, particularly under acidic conditions. nSiO2 slightly inhibited triclosan oxidation while nTiO2 was inhibitory only when a limited amount of triclosan was present. Based on the obtained SEM images and the reported pHzpc values, nAl2O3 and nSiO2 most likely inhibit MnO2 oxidation through hetero-aggregation between oxide particles, but nTiO2 inhibits triclosan oxidation most likely by competitively adsorbing triclosan and limiting its availability towards oxidation by MnO2. ENVR 305 Heteroaggregation of oxide particles and the impact on the oxide reactivity H. J. Zhang, [email protected], and F. J. Murillo, [email protected] Southern Illinois University Edwardsville, United States Oxidation of organic contaminants by Fe oxides has been reported to be an important pathway in natural environment. To properly extend the results obtained with pure oxides to the environment where multiple metal oxides coexist, it is important to understand how the presence of an additional metal oxide affects the oxidation of organic contaminants. For this purpose, oxidation studies were performed on systems containing hydroquinone, goethite (FeOOH) and Si or Ti oxides. Kinetic results on hydroquinone oxidation (as monitored by quinone formation) show that the inhibition effect of TiO2 is much more significant than that of SiO2. When a constant amount of TiO2 was added, quinone formation was inhibited more at lower hydroquinone or FeOOH initial concentrations. Based on the obtained SEM images and the reported pHzpc values, the second metal oxide most likely inhibits hydroquinone oxidation through hetero-aggregation between oxide particles. ENVR 306

Effects of acid/abandoned mine drainage on semipermeable membrane devices (SPMDs) N. R. McElroy, [email protected], C. Lewis, A. Devlin, and F. Opayemi. Department of Chemistry, Indiana University of Pennsylvania, Indiana, PA, United States Semipermeable membrane devices (SPMDs) can be used to detect the presence of several types of nonpolar organic contaminants in aqueous systems, and have been successfully used in lakes, rivers, and seawater. In western Pennsylvania, several streams are affected by the discharge of abandoned deep coal mines, resulting in low stream pH (2-4), discoloration from iron hydroxide, and eventual loss of stream life. Before SPMDs are employed in local streams where mine drainage exists, the effects of low pH on the efficiency of SPMDs to uptake nonpolar organic contaminants are examined. ENVR 307 Analysis of dried, powdered, kelp food supplements for the presence of heavy metals via energy dispersive X-ray fluorescence D. Garshott, [email protected], E. MacDonald, [email protected], M. A. Benvenuto, [email protected], and E. Roberts-Kirchhoff, [email protected] Department of Chemistry & Biochemistry, University of Detroit Mercy, Detroit, MI, United States A series of kelp dietary supplements, all of which can be purchased at health food or drug stores, have been analyzed using energy dispersive X-ray fluorescence (EDXRF) spectroscopy. The supplements were examined to determine the presence of arsenic, lead, and mercury within them. Before doing so, a set of standards for such analyses was created, because there appear to be no established, NIST standards for this material. The findings for the complete set of supplements are presented and discussed, as is the method for production of the standards. ENVR 308 Active soil acidity and reserve soil acidity as influenced by N-fertilization and irrigation K. P. Gidda, [email protected], J. S. McConnell, C. J. Altfillisch, S. L. Bilderback, L. R. Morgan, B. M. Mullins, S. M. Nicioli, T. M. Pedigo, K. E. Ribordy, D. R. Sheppard, and S. M. Stenger. Department of Chemistry, Western Illinois University, Macomb, IL, United States Soil acidity has two components: active soil acidity which is estimated by soil pH; and reserve acidity which is determined by titration techniques. Soil pH is considered the single most informative soil test regarding the overall soil productivity. Acid soils are typically defined as having soil pH values less than

optimum for plant growth. Generally, soils with pH values below 5.5 impede plant growth. The source of soil acidity may be classed as either geologic or anthropic. Geologic soil acidity results from the weathering of sulfide and aluminum bearing minerals. Anthropic produced soil acidity may be generated from the application of ammoniacal-nitrogen fertilizers, sulfur and sulfide fertilizers, and the removal of basic cations of the soil with crop harvest. Irrigation water with high salt and bicarbonate content is known to add basic cations to soils and neutralize soil acidity, thereby raising soil pH and reducing soil acidity. Long-term studies were conducted to determine the acidifying effects of ammoniacal-nitrogen fertilizer treatments in conjunction with irrigation with high bicarbonate content water on cotton. These studies were conducted in side-by-side irrigation blocks at the Southeast Branch Experiment Station at Rohwer, Arkansas, on an Hebert silt loam (fine-silty, mixed, thermic Aeric Ochraqualfs) soil. Combinations of specific urea-N fertilization rates (acidifying effect) with specific irrigation methods (basifying effect) were found to produce soil acidity levels unique to the treatment combinations. ENVR 309 Aqueous photolysis of ultraviolet filter chemicals M. L. Tse, J. Klein, A. Kracunas, and L. A. MacManus-Spencer, [email protected] Department of Chemistry, Union College, Schenectady, NY, United States In order to make decisions about the regulation and remediation of pharmaceuticals and personal care products (PPCPs) it is important to understand their fate in the aquatic environment. One class of PPCPs of current environmental concern comprises ultraviolet filter chemicals (UVFCs), used in sunblock, lip balm, and other personal care products to protect the skin from harmful UV radiation. These chemicals enter the environment via direct (e.g., swimming) and indirect (e.g., washing clothes) routes. The aqueous photolysis of three UVFCs, benzophenone-3 (oxybenzone), octyl methoxycinnamate (octinoxate), and homomenthyl salicylate (homosalate), has been investigated. Experiments were conducted under natural and simulated sunlight to determine quantum yields, environmental half-lives, and the relative importance of direct and indirect photolysis for each chemical. In addition, gas chromatography ­ mass spectrometry (GC-MS) and liquid chromatography ­ tandem mass spectrometry (LC-MS/MS) were used to identify photolysis products in the case of octinoxate, which degrades almost completely by direct photolysis. ENVR 310 Comparisons of organic carbon content of native prairies, prairie restoration areas, and conventionally tilled soils in Illinois

L. R. Morgan, [email protected], J. S. McConnell, C. J. Altfillisch, S. L. Bilderback, K. P. Gidda, B. M. Mullins, S. M. Nicioli, T. M. Pedigo, K. E. Ribordy, D. R. Sheppard, and S. M. Stenger. Department of Chemistry, Western Illinois University, Macomb, IL, United States Carbon is a fundamental component of all living organisms, the atmosphere, non-living organic matter, fossil fuels, certain minerals, and dissolved gases and solutes in water. Carbon is dynamic in the environment and readily changes oxidation state and physical form as it moves among the biosphere, atmosphere, hydrosphere and lithosphere. Atmospheric carbon occurs primarily as carbon dioxide, a bio-respiration product and a "greenhouse gas." Atmospheric carbon dioxide is increasing rapidly raising concerns regarding global warming. A potential way to reduce atmospheric carbon dioxide is to increase the amount of atmospheric carbon held in soils as organic carbon. As plants die, some of their carbon may be retained in the soil as decaying organic matter. Current efforts in Midwestern states are directed toward the restoration of farmland to native prairie conditions by both private agencies and state governments. The restoration of land to near-native conditions should increase soil carbon content. Our research investigated native prairies; restored prairies of various ages; and compared the soil organic carbon content and character with analogous soils under crop production and cultivation. The soils of native prairies, restored prairie and the analogous conventionally farmed land were extensively sampled. The organic carbon content of the soil samples was determined using oxidation techniques with chromic acid. The organic carbon contents of analogous soils of native prairies and prairie restoration areas with farmed land were compared using statistical techniques such as analysis of variance and regression analysis. Statistical analyses of soil organic carbon means indicated more organic carbon is retained in the native prairies and restored prairies that analogous conventionally tilled soils. These results imply that prairie restoration may be potentially beneficial in reducing atmospheric carbon dioxide. ENVR 311 Colloidal behavior of fullerenes (nC60): Role of coions B. Mukherjee1, [email protected], and J. Weaver2, [email protected] 1National Research Council/U.S. Environmental Protection Agency, Athens, Georgia, United States, 2Office of Research and Development, U.S. Environmental Protection Agency, Athens, Georgia, United States The effects of coions on the average initial aggregate size (DH) and zeta potential (ZP) of nC60 in mono and divalent counterion (10 mM) systems were investigated at pH 3, 5.8, and 10. Differences in the effects of SO42- and Cl- could not be established, in presence of Na+, for any pH treatment. The same was true at pH 3 and 5.8 when Mg2+ was present. However, a strong coion-dependent surface charge reversal occurred at pH 10. ZP and DH were measured at +4 mV and 1450 nm for SO42- and +40 mV and 225 nm for Cl- treatments. In contrast, ZP and DH for nC60 in DI water were -65 mV and 115 nm, respectively at pH 10.

These findings provide a better understanding of the interaction characteristics of colloidal nC60 with coions and may allow us to better assess the behavior of nC60 in aquatic environments. ENVR 312 Selective uptake of antidepressant pharmaceuticals in fish neural tissue M. M. Schultz1, [email protected], E. T. Furlong2, D. W. Kolpin3, A. Logue1, M. M. Painter4, and H. L. Schoenfuss4. 1Department of Chemistry, The College of Wooster, Wooster, OH, United States, 2National Water Quality Laboratory, U. S. Geological Survey, Denver, CO, United States, 3U. S. Geological Survey, Iowa City, IA, United States, 4Aquatic Toxicology Laboratory, St. Cloud State University, St. Cloud, MN, United States Antidepressant pharmaceuticals are widely prescribed, and wastewater effluent disposal is a point source of these pharmaceuticals to stream ecosystems. Fish residing in the effluent-influenced streams are receiving continuous exposure to antidepressants. This exposure to nontarget organisms is a concern. A method using liquid chromatography/tandem mass spectrometry measured antidepressants in brains from white suckers residing in effluent-influenced streams at points upstream and progressively downstream of the effluent outfall. Fluoxetine, sertraline, and their degradates, were the principal antidepressants observed in fish brain tissue at low ng/g concentrations, a different analyte profile than what was observed in the stream-water samples. Analyses were also performed on neural tissue collected from male fathead minnows that were exposed in the laboratory to antidepressants (fluoxetine, sertraline, venlafaxine, and bupropion). These studies show that the compositions of antidepressants in neural tissue from exposed fish differ substantially from the compositions observed in the water and sediment, suggesting preferential uptake. ENVR 313 Degradation and products of diclofenac during UV photolysis V. O. S. Keen1, [email protected], E. M. Thurman2, I. Ferrer2, A. D. Dotson1, and K. G. Linden1. 1Department of Civil, Environmental and Architectural Engineering, University of Colorado at Boulder, Boulder, Colorado, United States, 2Center for Environmental Mass Spectrometry, University of Colorado at Boulder, Boulder, Colorado, United States Diclofenac is one of the most commonly detected pharmaceuticals in wastewater discharges. As more wastewater treatment utilities switch to ultraviolet (UV) disinfection, it becomes important to understand the fate of synthetic microconstituents during UV light exposure of the effluent. Degradation pathways of diclofenac were analyzed after exposure to low pressure (monochromatic) and medium pressure (polychromatic) UV irradiation. The analysis of the products was performed in lab grade water as well as natural water from participating

waterworks. Using high performance liquid chromatography tandem mass spectrometry, it was determined that under UV irradiation diclofenac loses both chlorine atoms which likely reduces the toxicity of the compound to aquatic life. This important finding has not been previously reported in prior studies of degradation pathways of diclofenac subjected to other types of water treatment processes. ENVR 314 Metal extraction from aqueous solutions using thiosemicarbazone and semicarbazone chelating resins A. Crook, [email protected], D. D. Ensor, and E. C. Lisic. Department of Chemistry, Tennessee Technological University, Cookeville, TN, United States The presence of heavy metals in natural waters is an increasing problem due to industry practices and man-made disasters, such as the ash spill at the TVA power plant in Harriman, TN. As the environmental consciousness of the population is raised, the demand for stricter regulations on the amounts of metals present in water sources will increase. This study presents the results of removing metal ions from aqueous solutions using a series of chelating resins. Dry weight distribution, Dw, values were measured by a batch technique for a series of resins containing different functional moieties at selected pH values. The results for the uptake of nickel, cadmium, and cobalt as a function of pH, resin loading, and structure of the chelating group will be presented. These materials offer the potential to effectively extract and separate metals at environmentally important aqueous conditions. ENVR 315 Effects of pH, temperature, and salinity on microbial communication: Speciation of autoinducer-2 in the aquatic environment R. L. Frey1, [email protected], P. J. Pellechia1, A. W. Decho2, and J. L. Ferry1. 1 Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC, United States, 2Arnold School of Public Health, University of South Carolina, Columbia, SC, United States Microbial communication in biofilms and solution is mediated by a family of extracellular molecular signals. Autoinducer-2 (AI2) is a furanosyl borate diester used by Archaea, Gram positive and Gram negative bacteria. The extent of autoinduction correlates with the extracellular concentration of AI2, therefore the environmental stability of this molecule plays a critical role in the establishment of cooperative microbial behaviors (i.e. biofilm construction; enzyme production, etc). In this work we report the stability of AI2 as a series of independent functions of temperature, borate, salinity and pH. NMR techniques were applied to qualify the identity and quantify the speciation of AI2 across several different environmentally relevant conditions. Speciation was used to estimate molecular

diffusivity under the various conditions. Diffusivity was correlated to the lifetime of AI2 to estimate the maximum distances between cells to ensure communication in less than one half-life. ENVR 316 Simultaneous ground level ozone and NOx measurements in Ventura County, California using portable ozone and NOx instruments P. E. Kolic, [email protected], and S. Aloisio, [email protected] Department of Chemistry, California State University Channel Islands, Camarillo, CA, United States Ground level ozone (O3) is a major atmospheric pollutant that is harmful to human health. In the human body, ozone can cause respiratory problems. In polluted air, ozone is formed by the reaction of nitrogen oxides (NOx), which are constituents of photochemical smog, with volatile organic compounds (VOCs). Simultaneous measurements of ozone and NOx are reported using inexpensive, commercially available, spectroscopic instruments. Ozone is detected using a portable instrument utilizing ultraviolet-visible spectroscopy. Ozone concentrations are determined using a mercury lamp which emits light at a wavelength of 254nm - ozone's absorption maximum. This work is part of an undergraduate research project, and the measurements can be developed into a lab for a general or an environmental chemistry course. Local measurements are currently made in Ventura County, California. The longer term goal of the project is to remotely measure ozone and NOx in areas with little or no pollution emission, but where these species are transported in with polluted air masses; for example, Channel Islands National Park. ENVR 317 Rapid immunoassays for the pentabrominated diphenyl ether BDE-47 banned in polyurethane foam K. C. Ahn1, [email protected], H. J. Kim1, S. J. Gee1, A. Blum2, E. Fishman2, and B. D. Hammock1. 1Department of Entomology, University of California Davis, Davis, CA, United States, 2Green Science Policy Institute, Berkeley, CA, United States Polybrominated diphenyl ethers (PBDEs) are flame retardants that have been commonly added into indoor consumer products. PentaBDEs including BDE-47 were largely banned due to potential human toxicological effects. We produced a selective rabbit antiserum against a BDE-47 structural mimic hapten. This antiserum was used for development of both a competitive indirect ELISA and a noncompetitive dipstick immunoassay for the rapid detection of BDE-47 in polyurethane foam. The dipstick assay uses a phage specific to an immunocomplex of BDE-47 and its antibody. The immunoassays were performed on 10- or 50-mg foam sample following simple dilution of a DMSO extract. We

found that some current commercial furniture in stores, and furniture or carpet foam existing in homes contain BDE-47. The ELISA was a selective detection tool compared to XRF with a LOQ of 0.03% for BDE-47. There was good agreement (r2 = 0.835) with a slope of 0.675 between the data obtained by ELISA and GC-FID. A dipstick assay provided as a rapid premonitoring tool to distinguish negative and positive results with a LOQ of 0.2%. The ELISA provided excellent quantitative results when performed on foam samples of small weight following simple sample extraction only, suggesting a useful convenient screening tool for enforcement and regulation. ENVR 318 Determination of hydrazines in aqueous and soil samples by LC/MS/MS J. Wang, [email protected], and C. J. Neslund. Environmental Sciences, Lancaster Laboratories, Lancaster, PA, United States Hydrazines (hydrazine, monomethylhydrazine and 1,1-dimethylhydrazine) are commonly known for their use as rocket propellants. The use of LC/MS/MS for hydrazines analysis has not been reported. Recovery of hydrazines in soil samples can be challenging. The objective of this study was to develop a sensitive and specific LC/MS/MS method for the analysis of hydrazines. Furthermore, the objective was to develop an extraction procedure that would recover hydrazines from soil samples. Data will be presented to demonstrate how the LC/MS/MS method was successfully applied to aqueous and soil samples. The method sensitivity, accuracy, and precision will be discussed. The LC/MS/MS method has the following advantages: a) The use of tandem mass spectrometer provides greater confidence for quantification and identification of hydrazines; b) The sensitivity of the tandem mass spectrometer allows for reductions in sample preparation volumes ­ a "green" analytical technique; c) Soil extraction procedure overcomes previous recovery difficulties observed in solid matrices. ENVR 319 Where strong acids become weak: Vibrational sum frequency spectroscopy investigations of nitric acid adsorption at the air/water interface P. Blower, [email protected], and G. Richmond. Chemistry, University of Oregon, Eugene, OR, United States Nitrogen species play an important role in the chemistry of the atmosphere. Specifically, aqueous nitric acid is present as aerosols in both the stratosphere and troposphere as well as on surfaces located on terra firma. These systems can be considered as binary solutions or as aqueous solutions with ions present. By interrogating the chemical structure and orientation at a vapor/aqueous interface, nitric acid can be examined for relevant atmospheric properties. Recent

studies of this interface using Vibrational Sum Frequency Spectroscopy (VSFS) have shown that unlike in bulk systems, nitric acid displays weak dissociation. By performing isotopic dilution studies of nitric acid and water via VSFS, conclusions can be made about the local bonding environment aiding in our understanding of atmospheric reactions on aerosol surfaces. In addition, the presence of various environmentally relevant ions is being explored for their ability to suppress/promote molecular nitric acid adsorption to the vapor/aqueous interface. ENVR 320 Characterization of organic materials recovered from municipal solid waste by steam autoclaving and sieving S. M. Steinberg1, [email protected], J. R. Batista2, D. W. Emerson1, T. A. Nartker4, and S. F. Moujaes3. 1Department of Chemistry, University of Nevada Las Vegas, Las Vegas, NV, United States, 2Depatment of Civil and Environmental Engineering, University of Nevada Las Vegas, Las Vegas, NV, United States, 3Department of Mechanical Engineering, University of Nevada Las Vegas, Las Vegas, NV, United States, 4School of Computer Science, University of Nevada Las Vegas, Las Vegas, NV, United States Annually millions of tons of solid municipal wastes are sent to landfills where they decompose, producing odor, CO2 and methane. Municipal waste landfills are a potential source of water and soil pollution. Futhermore the green house gases that they produce exacerbate global climate change. Recently autoclave technology has been demonstrated that can be used to recover the majority of the organic fraction of municipal solid waste for potential reuse. We have utilized pyrolysis GC/MS and chemopyrolysis GC/MS to examine this organic material in order to gauge its potential for fuel and char conversion. This work has demonstrated that the cellulosic material contains measureable quantities of lignin, fatty acids, and hydrocarbons as well as synthetic polymers, in addition to the dominant cellulosic component. We propose that this material can be harvested to provide a viable source of biodiesel, ethanol and char. ENVR 321 Novel treatment technology for perchlorate: Partially oxidized titanium and ion exchange membrane hybrid system S. Park, [email protected], and B. Batchelor. Zachry Department of Civil Engineering, Texas A&M University, College Station, TX, United States The objective of this study is to determine the feasibility of new treatment technology for perchlorate using partially oxidized titanium ions and ion exchange membrane hybrid system (TMHS). From the previous research, our lab demonstrated that Ti(II) and Ti(III) can reduce perchlorate ions successfully, but it

needed extreme condition such as high acid concentration. Here, we applied an ion exchange membrane to overcome the weakness. This system is composed of three parts as shown in figure 1; dialysis cell, ion exchange membrane and reductant solutions. We examined removal mechanism of this system; adsorption, diffusion and reduction.

Three kinds of membranes were evaluated to investigate the effect of initial perchlorate and acid concentration. This system is fast to remove high concentration of perchlorate in relatively short time.

ENVR 322 Combustion flow visualization through Schlieren method T. Guillaume1, [email protected], T. K. Pham2, [email protected], D. Guillaume2, [email protected], C. Rauda1, H. Luong2, A. Ramos1, and C. S. Khachikian1, [email protected] 1Department of Civil

Engineering, California State University Los Angeles, Los Angeles, California, United States, 2Department of Mechanical Engineering, California State University Los Angeles, Los Angeles, California, United States Two methods for visualizing fluid flow (one for inside a combustion chamber and one for monitoring the effluent) during combustion have been investigated. The Schlieren method ­ which makes use of parabolic mirrors, lenses, high-speed cameras, and the diffraction of light ­ is used during active combustion: when a flame is present. Experiments were conducted using a mock chamber (approximately 70 mm long and 9 mm in diameter) with iso-octane as the fuel source. Swirl number, ratio of axial air flow to tangential air flow was varied to investigate combustion under various flow conditions. Captured images show varying density gradients for the emissions from the combustion chamber. Further work will include creating a visual data set from the captured images and connecting aspects of the data (i.e., size, shape of effluent) to swirl numbers. The second method of visualization involves the use of a laser sheet and a smoke source for flow visualization in the absence of a flame. Preliminary results indicate that the actual swirl inside a combustion chamber can be visualized using this technique. ENVR 323 Exploring atmospheric chemistry on aqueous surfaces: Examining the effects of temperature on the formation of a SO2:H2O surface complex S. T. Ota, [email protected], and G. L. Richmond. Department of Chemistry, University of Oregon, Eugene, Oregon, United States The surfaces of aqueous aerosol particles act as a platform for many interactions that drive chemistry in the atmosphere. For example, acid rain formation begins with the uptake of sulfur dioxide gas; a process that is facilitated by the formation of a water:SO2 surface complex. Unfortunately, most of the information regarding surface reactions is obtained through inference from chemistry occurring in the bulk. The unique set-up used in our laboratory allows us to study the molecular impact of gas uptake on the water surface using VSFS while monitoring and controlling the bulk solution temperature. This work builds on previous observations of the room temperature surface species, and demonstrates that lowering the temperature has a distinct effect on the bonding interactions between water and SO2(g) at the water surface. ENVR 324 Investigating the toxicity of metal oxide nanoparticles to bacterial biofilms using a fluorescence-based viability assay O. Mileyeva-Biebesheimer1, C. L. Gruden1, [email protected], and Y. Seo1,2, [email protected] 1Department of Civil Engineering, University of

Toledo, Toledo, Ohio, United States, 2Department of Chemical Environmental Engineering, University of Toledo, Toledo, Ohio, United States Nanoparticles are being integrated into consumer products at an ever-increasing rate. Since their eventual disposition will be the environment, determination of the associated environmental and ecological risks is vital. One significant area of concern is the microbiological fate of metal oxide nanoparticles. While most previous studies have been conducted with planktonic bacteria, most bacteria exist as a biofilm in the environment. The goal of this research was to investigate the impact of nanoparticles on planktonic cells as compared to biofilms, which typically include extracellular polymeric substances (EPS). In bench scale experiments, we studied the impact of nano-sized (10-20nm) titanium dioxide (TiO2) (0, 10, 100, 500 mg/L) on bacterial cell (E. coli) viability by employing a membrane integrity stain in conjunction with a non-specific DNA stain. Fluorescent microscopy yielded results that indicated a statistically significant impact on planktonic cells at 100 and 500 mg/L of nano-sized TiO2. Biofilm experiments are ongoing. ENVR 325 Equations of climate change: Svante Arrhenius vs. Andrew Angus A. C. Angus, [email protected] Department of Research, Andrew Angus Research Institute, San Jose, California, United States The author introduces two equations called "Andrew's Laws of Climate Change." The equation of the First Law of Climate Change is expressed as: PV / nR = T. The equation of the Second Law of Climate Change is expressed as (mc^2) / (nR) = T. The first equation reveals that the moles of gas is inverse to the global temperature. The second equation reveals that nuclear reactions emit tremendous amounts of heat energy that can affect global temperature if a critical amount of radioactive material is released to the environment. The two equations are very significant because the two equations debunk Nobel Laureate Svante Arrhenius's equation on climate change that claims CO2 causes global warming. This paper is a revolutionary breakthrough in environmental science. ENVR 326 Magnetic mediated solid-phase extraction with LC/MS/MS for analysis of biomolecules in H295R cell M. H.-W. Lam, and Q. Li, [email protected] Biology and Chemistry Department, City University of Hong Kong, Kow Loon, Hong Kong, China Liquid chromatography tandem mass spectrometry detection technique has been used to investigate the behavior of many biomolecules, such as hormones. This detection technique helps investigations into the mechanisms of disorders of endocrine disrupter chemicals. Further advances are still needed in the sample

preparation. In the present study, a new Fe3O4/poly(divinylbenzene-comethacrylic acid) core-shell magnetite microspheric material has been successfully developed as magnetic-mediated solid-phase extraction microparticle sorbent in dispersion mode (MM-SPE-MP) for the determination of steroids. Analysis of cell lysate spiked with steroids showed that most analytes can be detected at sub-nanogram amount. The accuracies of all steroids after derivative are above 80%. The steroid amounts between the control and treated cells were compared in the present study. The study shows that metabolite detection with MM-SPE-MP-LC-MS2 is a promising approach to investigate steroid hormone in cells. ENVR 327 Stabilization of H2O2 in Fenton and Fenton-like reaction using tartaric acid Y.-H. Kim1, [email protected], K. Chaehoon1, J. Jun2, L. Woo Taik2, and H. Oh2. 1Department of Environmental Engineering, Andong National University, Andong, Kyungpook, Republic of Korea, 2Department of Applied Chemistry, Andong National University, Andong, Kyungpook, Republic of Korea Fenton oxidation is one of the most feasible chemical treatments for the removal of organic contaminants in water and soil. The degradation rate is generally proportional to the concentration of H2O2 and ferrous iron. Some organic acid is known to stabilize H2O2 in Fenton reaction. Tartaric acid is studied for the purpose of H2O2 stabilization. Tartaric acid stabilized H2O2 through complexation reaction with ferrous and Ferric iron and the complexation was monitored with UV-Vis spectrophotometer. The effect of stabilization was highly dependent on the solution pH. The protonated organic acid at below pKa1 was the most effective species in the stabilization. The stabilization of H2O2 resulted in a prolonged life time of Fenton reaction and this means that the oxidant can flow into a deep soil layer in Fenton-like reaction. ENVR 328 PAHs and particle emissions from a combustion chamber M. Ghadiri1, [email protected], C. Khachikian1, [email protected], D. Guillaume2, [email protected], T. Pham2, [email protected], S. Esparza2, T. Guillaume2, M. Ortega2, and E. Bautista2. 1Department of Civil Engineering, California State University, Los Angeles, United States, 2California State University, Los Angeles, United States Polycyclic aromatic hydrocarbons (PAHs), some of which are carcinogenic, are released as byproducts of the combustion of organic materials. Here, we evaluate the presence of 16 PAHs attached to particulates in the exhaust of jet engines. We collected 24 effluent samples of the combustion of kerosene in a chamber that was assembled to simulate a scramjet combustion engine. The engine was operated at varying swirl numbers (the ratio of tangential to axial air

flow) to determine the effects of swirl on the effluent. Particles were captured in the effluent air on filter papers. The abundance of particles was inferred from analysis of digital photographs of the filter papers. Furthermore, the concentration of PAHs associated with the particles was determined by extraction with dichloromethane followed by analysis via gas chromatography/mass spectrometry. All 16 PAH compounds were found in all of the samples, with lower concentrations found at higher swirl numbers. ENVR 329 Characteristics of heavy metal uptake in plant: Relationship among BCF, heavy metals, and plant species H. S. Moon1, [email protected], S. Jeong2, [email protected], and K. Nam2, [email protected] 1School of Earth and Environmental Sciences, Seoul National University, Republic of Korea, 2Dept. Civil and Environmental Engineering, Seoul National University, Republic of Korea Phytoextraction has demonstrated its beneficial use in the removal of heavy metals from polluted soil. Bioconcentration factor (BCF), as the ratio of a metal concentration in a plant to that in a soil, can be used as an indicator representing a potential for the plant to remediate metals from the soil. This study is being conducted to characterize how BCF is affected by different metals (Zn, Cu, Pb, Cd and As), plants, and initial metal concentrations in soil by reviewing a vast of published data. Copper and arsenic (BCF value is a 0.951±2.11 and 502.9±747.68, respectively) showed higher BCF values than the other metals regardless of plant species. BCF increased with an increase in initial metal concentration up to a certain initial concentration range and then BCF decreased in all metal types. Plant- and metal-specificity was also evident. Along with the types of metals and plant species, soil properties may also influence on BCF, which is being studied. ENVR 330 Understanding selenium metabolism and detoxification in the hyperaccumulator, Stanleya pinnata W. M. Amos1, [email protected], X. Huang1, Q. Chan2, J. Caruso2, J. A. Hayter3, and D. LeDuc1, [email protected] 1 Chemistry & Biochemistry, California State University, East Bay, Hayward, CA, United States, 2Department of Chemistry, University of Cincinnati, Cincinnati, Ohio, United States, 3Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA, United States We are using an array of techniques (proteomics, transcriptomics, GC-ICP-MS, FAAS, and synchrotron radiation, TXM, µ-XRF and XAS) to construct a complete understanding of the selenium hyperaccumulation pathway in S. pinnata. S.

pinnata tolerates extreme levels of selenite, 6.4 times more than S. albescens, a non-accumulating relative. Transmission x-ray microscopy images of seleniteexposed roots suggest that Se moves into the xylem where it is sequestered into vacuoles in clusters approximately 4 µm in diameter. Micro x-ray fluorescence multiple speciation state tomographic maps indicate that SeCys synthesis and its subsequent methylation occurs primarily in the shoot. GC-ICP-MS has allowed quantification of the volatile metabolites, dimethylselenide and dimethyldiselenide. Finally, MALDI-TOF/TOF proteomics analysis has revealed differential protein expression induced by Se exposure. Connecting the expression of key proteins with changes in the production and localization of Secontaining metabolites will provide a holistic picture of the mechanism of selenium hyperaccumulation in this species. ENVR 331 Ambient synthesis of Pd/Fe bimetallic nanotubes and their application in dechlorination reactions E. M. Zahran1, [email protected], D. Bhattacharyya2, and L. G. Bachas1. 1 Department of Chemistry, University of Kentucky, Lexington, Kentucky, United States, 2Department of Chemical and Material Engineering, University of Kentucky, Lexington, Kentucky, United States The synthesis of bimetallic Pd/Fe nanoparticles and their application in remediation of halogenated organic pollutants have been extensively studied. Yet, because the nanoparticles aggregate, their effective catalytic surface area is reduced. Nanotubes and nanofibers maintain high surface area even when aggregated. In this poster, we describe the synthesis of a new class of bimetallic nanotubes based on Pd/Fe and demonstrate their efficacy in the dechlorination of polychlorinated biphenyls (PCBs). One-dimensional iron metal nanotubes of different diameters were prepared by electroless deposition within the pores of polycarbonate membranes using a simple technique under ambient conditions. Specifically, a track-etch polycarbonate membrane template was mounted between two halves of a custom made U-tube cell. The longitudinal nucleation of the nanotubes along the pore walls was achieved by the localized electroless reduction of ferrous sulfate, stabilized by ascorbic acid, placed in one side of the U-tube cell, upon diffusion of sodium borohydride from the other side of the cell. The effect of concentration of the electrolytes and time of reaction on the structure and morphology of the nanotubes were studied. Shell/core Pd/Fe nanotubes were prepared by soaking Fe nanotubes liberated from the template in an ethanolic solution of palladium acetate. The size, morphology, and structure of the Pd/Fe nanotubes were characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The as-prepared Pd/Fe bimetallic nanotubes were used in dechlorination of 3,3',4,4'-tetrachlorobiphenyl (PCB77). In comparison with Pd/Fe nanoparticles, the Pd/Fe nanotubes demonstrated higher efficiency in the dechlorination reaction.

ENVR 332 Chromate bioremediation is enhanced by bacteria engineered to produce the compatible solute trehalose T. Frederick, and P. J. Woodruff, [email protected] Departments of Biology and Biochemistry, Bowdoin College, Brunswick, ME, United States Chromium(VI), often found as chromate, is a potent carcinogen that can easily leach into the ground and contaminate the water supply. Despite its acute toxicity, chromate contamination can be diminished by the action of microbes, which reduce chromium(VI) to its less toxic form chromium(III). However, the bacteria are damaged by oxygen radicals released as a byproduct of the reduction process. Trehalose is a small molecule that protects key biological macromolecules in living systems. Trehalose can protect against osmotic stress, thermal stress, oxygen radicals, and even radioactivity. Bacteria engineered to overproduce trehalose grew more robustly than wild-type bacteria, and were also able to reduce more chromium(VI) to chromium(III). Thus, engineering trehalose biosynthesis assists chromate bioremediation, and may have an impact on the bioremediation of other environmental contaminants as well. ENVR 333 Effective nutrient replacement and erosion control using non-toxic natural polymers T. James, [email protected], C. Saito, [email protected], S. Hutson, [email protected], J. Jamison, [email protected], A. Osler, [email protected], E. Benjamin, [email protected], and E. Benjamin, [email protected] Department of Chemistry and Physics, Arkansas State University, State University, AR, United States Many problems arise while trying to restore ecosystems that have been modified through anthropogenic interaction. Two such problems are that of soil erosion and nutrient loss due to the increased intensity of forest fires. Nutrient loss caused by intense forest fires has led to decreased soil fertility and plant survivability. Currently, polyacrylamide, a non-toxic polymer that is used as a soil binder has been found to contain its neurotoxic precursor acrylamide. To aid water retention, a mixture of non-toxic polymers was engineered to stabilize pH, create a binding agent for water and nutrient retention, and reestablishment soil fertility. These polymers are water absorbent, all-natural, and non-toxic which have been infused with Hoagland solution. The mediums used different soil gradient slopes, with and without polymers, to test erosion control. Our results showed significant efficacy in preventing erosion, lowering the amount of runoff to levels of .04% of the total. ENVR 334

Contamination of cultured marine organisms by oil spill accidents K. Sung1, [email protected], Y. A. Kim1, Y. Kang1, S. Park2, [email protected], and S. Yi3. 1Department of Ecological Engineering, Pukyong National University, Busan, Republic of Korea, 2Department of Ocean Engineering, Pukyong National University, Busan, Republic of Korea, 3Department of Statistics, Pukyong National University, Busan, Republic of Korea Oil spills in the sea adversely affect various marine organisms, but the effects of oil spills on cultured marine organisms are particularly harmful. In this study, the contamination of cultured marine organisms (sea cucumber, oyster, abalone, marine clam, corb shell, sea mustard, and larver) at oil spill sites was monitored. EPA's 16 priority pollutant polycyclic aromatic hydrocarbons (PAHs) obtained from 200 marine organisms were analyzed, along with total petroleum hydrocarbons (TPHs) and 16 PAHs and 18 PAHs obtained from sediment samples. In addition, the benzo-a-pyrene (BaP) equivalence approach was employed to evaluate PAH toxicity in marine organisms with the help of five different estimates of relative PAH potency. The results showed that among the five estimates used, the Nisbet & LaGoy estimates produced the highest total equivalent toxicity in all the investigated marine organisms. The TPH and PAH concentrations in the sediment samples were strongly correlated, but no statistically significant relation in terms of PAH concentrations or patterns was observed between sediments and marine organisms. ENVR 335 Estimation of mercury bioavailability in contaminated soils of the Mexican state of Queretaro using chemical speciation and a physiologically based extraction test I. Gavilan-Garcia1,2, [email protected], E. Santos-Santos1, R. Navarro1, A. Gavilán-García3, and S. Suárez1. 1Chemistry Faculty - Unidad de Gestión Ambiental, National Autonomous University of Mexico, Mexico City, D.F., Mexico, 2 Centro Interdisciplinario de Investigaciones y Estudios sobre Medio Ambiente y Desarrollo, National Polytechnic Institute, Mexico City, D.F., Mexico, 3DISQRE, National Institute of Ecology, Mexico, D.F., Mexico Chemical form of pollutants is related to their bioavailability, transformation and elimination degree. The towns of Pinal de Amoles and San Joaquin in the State of Queretaro were highlighted from previous research for the presence of several silver and mercury old mines where amalgamation was used. However, some of these mines are being re-opened since the demand of mercury is increasing in international market. The aim of this study is to identify the potential risk to health and the environment due to the availability of mercury from mining wastes using a chemical speciation method. Preliminary results show that most of the mercury is found in stable species (41.54% for HgS, and from 48.66-92.34% for Hg0 in the form of amalgamated mercury). In-vitro bio-availability tests show that this

species are not absorbed in stomach conditions, but there is a potential risk due to the new mining activities developed in the site. ENVR 336 Polybrominated diphenyl ethers (PBDEs) flow analysis in commercial products in Mexico A. Gavilán-García2,3, [email protected], E. Santos-Santos1, I. GavilánGarcía1,2, J. Castro-Díaz1, and S. Aburto-Mejía4. 1Chemistry Faculty - Unidad de Gestión Ambiental, National Autonomous University of Mexico, Mexico City, D.F., Mexico, 2Centro Interdisciplinario de Investigaciones y Estudios sobre Medio Ambiente y Desarrollo, National Polytechnic Institute, Mexico City, Mexico, Mexico, 3DISQRE, National Institute of Ecology, Mexico City, D.F., Mexico, 4 Engineering Faculty, Division of Basic Science, National Autonomous University of Mexico, Mexico City, D.F., Mexico Polybrominated diphenyl ethers (PBDEs) have been used in a variety of manufactured products, including foam cushioning used in furniture and plastic housings for televisions and computers, automobiles and large and small household appliances. The ratification of the Stockholm Convention committed Mexico to the reduction in the use of these substances. Currently, a large number of goods manufactured or imported to Mexico contain an unknown percentage of PBDEs; in addition, the environmental fate of these substances is unknown and an inappropriate management might represent a potential risk to human health and the environment. The aim of this study is to develop an inventory of penta-, octa- and deca-BDEs, either as pure chemicals or as previously applied additives in products. The methodology includes: 1) review of official databases (INEGI, Customs, Economy Bureau, PRTR, US and Canada databases), 2) Official reports (OECD, Basel & Rotterdam Conventions, 3) Industry reports, 4) Polymer applications. ENVR 337 Effect of natural organic matter on CO2 hydrate formation for its sequestration R. B. Lamorena, [email protected], and W. Lee, [email protected] Department of Civil and Environmental Engineering, Korea Institute of Science and Technology, Daejeon, Daejeon, Republic of Korea A study was conducted to investigate the effect of natural organic matter on CO2 hydrate formation. We collected three types of marine sediments from different coastal sites to identify the role of organic matter and its controlling factors for the hydrate formation. 1H-NMR, FTIR, MLOI (0.10 ­ 55%) and TOC (13-15 ppm) analyses of the sediment samples showed that significant amounts of organic matter exist in the samples. CO2 hydrate formation tests were conducted using

the marine sediments at 0.30 C and 30 bar. Control sample was also prepared with kaolinite suspension. All marine sediment suspensions, whether in an inhibited growth medium such as the suspension with electrolyte, or pH-modified suspensions (extremely basic and acidic suspensions) showed fast hydrate formation compared to that in the control test . The experimental results can contribute to our understanding of hydrate formation processes and its feasible application to the CO2 sequestration in natural and engineered deep-sea environments. ENVR 338 Biogeochemistry of iodine in soil environments P. R. Grossl1, [email protected], M. J. Eick2, and T. P. Luxton3. 1Department of Plants, Soil, and Climate, Utah State University, Logan, Utah, United States, 2 Crop & Soil Environmental Sciences, Virginia Polytechnic Institute & State University, Blacksburg, Virginia, United States, 3National Risk Management Research Laboratory, US Environmental Protection Agency, Cincinnati, Ohio, United States Iodine deficiency is the number one preventable cause of mental retardation worldwide. Proper management of iodine deficient systems will require an understanding of iodine behavior in soil environments in order to safeguard against any threats to public health and possible toxicity to plants and animals. Likewise, proper management of iodine-based pesticides warrants a thorough understanding of the biogeochemical cycling of iodine in soils. We studied the sorption behavior of iodate and iodide, the most common forms of iodine in soil environments, on soil and soil constituent surfaces. Experiments included column transport studies, sorption isotherms and edges, surface complexation modeling, and iodine volatility studies. Sorption of both iodate and iodide was minimal (Kd < 1) especially in calcareous soils. Both ions formed outersphere surface complexes with ferrihydrite and goethite. Organic matter, pH, and electrochemical potential appear to be the most important factors regulating iodine retention in soils. ENVR 339 Adsorption of both fluoride and arsenic on surface modified cellulose fibers Y. Tian1,2, M. Wu3, R. Liu1, [email protected], X. Lin1,2, D. Wang1,2, J. Tan1,2, and Y. Huang1,3,4. 1State Key Laboratory of Polymer Physics and Chemistry, Beijing National Laboratory of Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China, 2Graduate University, Chinese Academy of Sciences, Beijing, China, 3National Engineering Research Center of Plastics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing, China, 4Laboratory of Cellulose and Lignocellulosics Chemistry,

Guangzhou Institute of Chemistry, Chinese Academy of Science, Guangzhou, China Cellulose fibers were surface modified by grafting poly(N,N-dimethyl aminoethyl methacrylate) (PDMAEMA). The adsorption of fluoride (F-) and arsenic (AsO2and AsO43-) arsenic on the PDMAEMA modified cellulose fibers were studied under equilibrium and dynamic conditions. The equilibrium adsorption capacities increased with the initial concentrations. The adsorbent was still effective for removing As and F ions at low initial concentrations. The pH value has little effect on the adsorption characteristics, and the adsorption can be performed at pH of 3-10. The presence of other anions such as Cl-, HCO3- and SO42-, has almost no obviously affect on the adsorption of As ions onto the adsorbent, whereas will compete with F- adsorption and reduce its adsorption efficiency. The distribution coefficient KD keeps at a constant value with the increasing adsorbent dose, which suggests that the surface polymer chains are homogeneous in water and corresponds to a quite fast adsorption kinetics (reaching equilibrium within 3 minutes). The isothermal adsorption can be well fitted by the Langmuir equation and the adsorption capacity increased with rising temperature, which indicates that the fluoride and arsenic anions are adsorbed in the form of monolayer coverage on the adsorbent surface. The adsorbed anions can be de-adsorbed using dilute HCl aqueous solution and the adsorbent can be re-used for several times. This work provides helpful information for preparing low cost, high efficiency adsorbent using biomass such as agro- and plant-wastes. ENVR 340 Preparation of TiO2 film and its photocatalytic activity for methylene blue decolorization Y. Jun1, and W. Chaoxia1,2, [email protected] 1Department of Textile and Clothing, Jiangnan University, Wuxi, Jiangsu, China, 2Department of Fiber Science and Apparel Design, Cornell University, Ithaca, New York, United States A spin coating process was employed to prepare TiO2 thin film at 60°C without being calcined at a high temperature. X-ray diffraction (XRD) patterns mainly consisted of anatase peaks of TiO2 film. The analysis of the transmission spectra showed that TiO2 film was transparent in the visible range and opaque in the ultraviolet range. The transmittance decreased and the absorption edge shifted as the layers increased. The scanning electron microscopy (SEM) images revealed that the films had a porous structure and the surface was smooth. The average size of the TiO2 particles was found to be about 50 nm in diameter. The photocatalytic activity of the films was evaluated by measuring the degradation of methylene blue (MB) aqueous solution. The film exhibited high photocatalytic activity and could be reused for several times without obvious decrease in photodegradation. ENVR 341

Incorporation of transition metals into inorganic-organic pillared clays for the selective adsorption of naproxen from water M. Lehner, [email protected], S. M. Rivera-Jimenez, [email protected], and A. J. Hernandez-Maldonado, [email protected] Department of Chemical Engineering, University of Puerto Rico at Mayaguez, Mayaguez, PR, United States The incorporation of transition metals (M = Cu2+ and Co2+) into inorganic-organic pillared clays (IOPCs) was used to study the selective adsorption of Naproxen from water. The IOPCs were synthesized by modifying bentonite clays with hexadecyltrimethylammonium bromide (HDTMAB) and aluminum hydroxide. Cobalt and copper were introduced to the IOPCs by ion exchange. All the materials were characterized by X-ray Diffraction (XRD), porosimetry, thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) as well as tested toward the adsorption of Naproxen using an initial concentration of 14 ppm at room temperature. The adsorption performance was studied as a function of pH. It was found that Cobalt based IOCPs are promising candidates for the selective adsorption of Naproxen at all pH ranges, with pH of 6.5 having the highest adsorption capacity (3.29 mmol/g). In general, the characteristics of the clays, including the size of the interlayer, and overall surface area had little to no effect on the ability to adsorb Naproxen. The attraction of naproxen to the bentonites relies mainly on interaction with the functional species. ENVR 342 Effect of anions on separation efficiency of trace Cd2+ and SDS using continuous multi-stage ion foam fractionation V. Rujirawanich1, [email protected], S. Chavadej1,2, R. Rujiravanit1,2, and J. H. O'Haver3. 1Deparment of petrochemical technology, The Petroleum and Petrochemical College, Chulalongkorn University, Pathumwan, Bangkok, Thailand, 2The Center for Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University, Pathumwan, Bangkok, Thailand, 3Department of Chemical Engineering, University of mississippi, Oxford, Mississippi, United States Due to severe toxicity of heavy metal accumulation in the environment, removal of heavy metal ions is of particular interest in recent hazardous waste research. However, current techniques are considerably uneconomical for treating large volumes of dilute wastewaters due to the high operational cost. In this study, a multi-stage foam fractionation column using bubble-cap trays with 5 trays connected in series [Figure 1] was developed to remove cadmium (Cd) at low concentrations, and the effects of anions (NO3-, Cl- SO42-) were studied. Sodium dodecyl sulfate (SDS) was used to generate foam in the present study. The removal, residual factors and enrichment ratios of both Cd and SDS were used to evaluate the process performance. It was found that an increase in NaCl

concentration up to 0.005 M caused a small reduction of the residual factor of Cd. Beyond this optimum NaCl concentration of 0.005 M corresponding to the maximum Cd removal close to 100%, the residual factor of Cd tended to increase significantly whereas the Cd removal decreased sharply. A good correlation between the residual factor of Cd and theoretical CdCl2 formation was also found. Hence, the reduction of the effectiveness for Cd removal is due to the presence of negative chloride ions to neutralize the positive cadmium ions.

ENVR 343 Speciation and leaching behaviors of heavy metals in dredged river sediments during solidification/stabilization K.-Y. Hwang, [email protected] Department of Civil & Environmental Engineering, Pusan National University, Busan, Republic of Korea The behavior of heavy metals in river sediment after their disposal to land has important implications for the environmental management of dreged river sediments. Sediments contaminated with heavy metals were obtained from Seonakdong River in Korea and were solidified/stabilized with various binders such as fly ash, oyster shell, red mud, furnace blaster slag and cement. The chemical speciation and leaching behaviors of heavy metals (Cr, Ni, Cu, Zn, Cd, Pb and As), and compressive strength of the treated sediments were investigated.. The fractionation of heavy metals by a sequential extraction procedure showed that more than 30% of the metals were associated with fraction 1 to 3 (except Pb). A maximum compressive strength was observed when the water content of the sediment was 50%. When Korean Leaching Test (KLT) and Korean Soil Test (KST) were used to test toxicity reduction, heavy metals concentrations in the leachate of the sediments treated by a oyster shell were well below the regulation standards. The oyster shell were selected as a best binder for safe disposal and beneficial use of sediments. ENVR 344

Separation of cobalt, strontium and cesium using silicotitanate in radioactive laundry wastewater Y.-J. Park1, [email protected], Y.-C. Lee3, S. R. Gajulapalle1, Y.-H. Kim2, W. S. Shin1, [email protected], and S.-J. Choi1. 1Department of Environmental Engineering, Kyungpook National University, Daegu, Republic of Korea, 2Andong National University, Republic of Korea, 3Korea Hydro & Nuclear Power Co., LTD, Republic of Korea Silicotitanate was applied to decontaminate laundry wastewater from nuclear power plant that includes salts, surfactants and dissolved solids. Single- and bisolute competitive adsorption of Co, Sr and Cs onto silicotitanate were investigated. Freundlich, Langmuir, Dubinin-Radushkevich models were fitted to the single-solute adsorption data. Generally Freundlich and Langmuir models fitted better than Dubinin-Radushkevich model. Bi-solute competitive adsorptions were analyzed by competitive Langmuir model (CLM) coupled to the singlesolute adsorption model. The predictions of those models were successful in most of adsorption except a few cases. The effect of cations and surfactants were also investigated. The distribution coefficients (Kd) of cesium slightly decreased in the presence of Na+ and Ca2+ ions. The presence of surfactants (non-ionic, cationic and anionic) also affected the adsorption of metals onto silicotitanate due to the change in surface charge of silicotitanate and the formation of metal-surfactant complexes. ENVR 345 Comparative study of composite materials isolated from the humic acid and humin of a mineral soil G. Chilom1, A. Baglieri2, and J. A. Rice1, [email protected] 1Department of Chemistry and Biochemistry, South Dakota State University, Brookings, SD, United States, 2DACPA, University of Catania, Catania, Italy Humic acid (HA) and humin(HU), obtained from a mineral soil by a traditional aqueous, alkaline extraction method, were separated into two fractions; a humiclike (HAs, HUs) and a lipid-like (Ls, LUs) by a combination of aqueous alkaline and organic solvent extractions. All the fractions were characterized by 13C DPMAS solid-state NMR and the relative carbon-type distributions determined. In addition, the lipid-like fractions and a nanocomposite formed by their interaction with the amphiphilic humic-like molecules were characterized by differential scanning calorimetry and their respective surface activity of the amphiphilic fractions determined by tensiometry. The data showed that humic acid and humin isolated from this particular soil consisted of similar fractions though the amphiphilic components are present in smaller proportions in humin but are stronger amphiphiles. ENVR 346

Accelerated TiO2 photocatalytic oxidation of sulfonamide antibiotics in the presence of carbonate alkalinity K. M. Parker1,2, [email protected], M. N. Sugihara1,2, and T. J. Strathmann1,2. 1Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 2Center of Advanced Materials for the Purification of Water with Systems, Urbana, IL, United States Recent studies have documented widespread occurrence of antibiotics and related pharmaceutical micropollutants in drinking water sources, and many of these compounds are recalcitrant to conventional water treatment technologies. Advanced oxidation processes (AOPs), including heterogeneous photocatalysis with nanophase TiO2, are capable of oxidizing a wide range of contaminants, but the non-selective reactivity of hydroxyl radicals generally leads to poor treatment efficiency in complex natural water matrices. Dissolved carbonate typically inhibits photocatalytic oxidation processes by scavenging hydroxyl radicals, but here we report on the enhanced UVA-TiO2 photocatalytic oxidation of sulfamethoxazole (SMX) and related sulfonamide antibiotics in the presence of aqueous carbonate species. Reaction kinetics and products are examined with sulfonamides and substructural analogues in solutions of variable carbonate concentration and acid-base speciation. A mechanism is proposed involving formation of carbonate radicals that, although less reactive than hydroxyl radicals, are selective for aniline moieties present in the structures of sulfonamides. ENVR 347 Photolytic breakdown of fullerene C60 cages in an aqueous suspension R. Gelca1, [email protected], K. Surowiec2, T. A. Anderson1, and S. B. Cox1. 1Department of Environmental Toxicology, Texas Tech University, Lubbock, Texas, United States, 2Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, Texas, United States Fullerene C60, a class of carbon nanomaterials, is widely used and is likely to reach the environment. The degradation and transformation of C60 aqueous suspensions exposed to environmentally relevant conditions were studied. C60 aqueous suspensions prepared by stirring pristine C60 in water under sunlight exposure undergo breakdown with formation of a mixture of compounds with unknown chemical structure. The mass and infrared spectrometric analysis of the breakdown products shows the presence of broken C60 cages, as well as of oxygen and hydrogen atoms in their structure. This demonstrates that fullerenes C60 are not stable in the environment and that the breakdown products should be considered when evaluating the environmental impact of fullerene C60. ENVR 348

Degradation of bromotrichloromethane by humic acid in the presence of palladium C.-C. Lee1, [email protected], C. Laskov2, S. Haderlein2, and R.-A. Doong1. 1Department of Biomedical Engineering and Environmental Sciences, National Tsing-Hua University, Hsinchu, Taiwan Republic of China, 2Center for Applied Geoscience, University of Tuebingen, Tuebingen, Germany Humic acid is an organic matter which is widely found in the environment especially in the soil and groundwater. Because of its quinone-like structure, humic acid was frequently utilized as the electron shuttling compound to enhance the dehalogenation efficiency of the reductive system. It has been proven that not only quinone-like structure but also the reactive functional groups in humic acids can be used to reduce pollutants under anaerobic conditions. Those reactive functional groups are often protected by the structures of humic acid preventing the oxidation under atmosphere conditions. Therefore, humic acid can reactively decompose halogenated hydrocarbons, but the dehalogenation efficiency is usually low. Therefore, the purpose of this study is to enhance the reactivity of humic acid by addition of pure Pd(0). The experiment was conducted by adding Pd(0) in humic acid solution to decompose BrCCl3 under anaerobic condition. The results revealed that 84% of BrCCl3 was decomposed into chloroform by humic acid in the presence of Pd(0) in 10 hours. The increase in Pd(0) loading from 0.2 to 0.8 g/L also increased the dehalogenation efficiency of BrCCl3. Chloroform was also found to be decomposed by humic acid, showing that the reactivity of humic acid was significantly enhanced in the presence of Pd(0). In addition, the reaction rate kinetics as well as mechanisms for BrCCl3 dehalogenation was also evaluated. ENVR 349 Degradation of 2-chlorophenol and 4-chlorophenol with iron oxide nanoparticles dispersed on mesoporous silica E. Montiel-Palacios1, [email protected], R. Suárez-Parra1, [email protected], and I. Hernández-Pérez2, [email protected] 1 Materiales solares, Universidad Nacional Autónoma de México, Temixco, Morelos, Mexico, 2Ciencias Básicas, Universidad Autónoma Metropolitana-A, México, D.F., Mexico Halogenated aromatic compounds, 2-chlorophenol and 4-chlorophenol, present in wastewater were removed by a photocatalytic process using visible radiation. It was monitored by UV-Vis spectroscopy, chemical oxygen demand (COD) and total organic carbon (TOC). After 50 minutes of reaction, over 95% of chlorophenol was removed. Both compounds were mineralized by 70% after 5 hours of degradation. Iron oxide nanoparticles dispersed on mesoporous materials, MCM-41 and SBA-15, were used as photocatalysts. They were obtained by impregnation of silica with iron salt (FeCl3) in aqueous solution, and then calcined at 823 K. The catalysts were characterized by X-ray diffraction

(XRD), X-ray fluorescence (XRF), nitrogen physisorption and transmission electron microscopy (TEM). MCM-41 and SBA-15 were used as supports. These materials were obtained by hydrothermal synthesis and characterized by XRD, nitrogen physisorption and transmission electron microscopy (TEM). ENVR 350 LC-MS/MS analysis of selected perfluorinated alkyl acids in drinking water, EPA Method 537, a validation study J. Wang1, [email protected], C. J. Neslund1, [email protected], J. Beck2, and C. T. Yang2. 1Environmental Sciences, Lancaster Laboratories, Lancaster, PA, United States, 2Thermo Fisher Scientific, San Jose, CA, United States Recently, the U.S. Environmental Protection Agency promulgated a method for the analysis of perfluorinated alkyl acids in drinking water using solid phase extraction by LC-MS/MS. As one of the labs that was involved with this method as a "secondary laboratory," we were able to test this method in conjunction with the EPA. Good separation and recovery of fourteen perfluorinated alkyl acids and sulfonates in fortified reagent water and drinking water under conditions of EPA method 537 was achieved. Sensitivity in ppt range was obtained for all analytes. The performance of EPA method 537 was demonstrated, with results similar to those reported in the method. The results of our experiments will be discussed in detail. Our experience demonstrates that slight adjustment of certain method conditions following EPA Method Flexibility guideline can influence the ability to meet method criteria. These findings can provide helpful advice to others who are considering the use of EPA's method. ENVR 351 Using in-situ colorimetric assays to document enzyme activity in soils X. Yuan1,2, [email protected], L. Liermann1, E. Herndon1, S. Williams3, S. Geib4, M. Tien4, and S. Brantley1. 1Department of Geosciences, The Pennsylvania State University, University Park, Pennsylvania, United States, 2Department of the Environment, Hohai University, Nanjing, Jiangsu, China, 3Department of Biochemistry, University of West Alabama, Livingston, Alabama, United States, 4 Department of Biochemistry, Microbiology and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania, United States We used colorimetric and fluorescence assays, wherein substrate-imbued filter papers were placed against exposed plant roots in root boxes, to test for enzyme activity in situ in the Shale Hills watershed in central Pennsylvania. Four different enzymes were tested: acid phosphatase, aminopeptidase, chitinase, and Bglucosidase. All of the assays were successfully tested in the laboratory to establish standard curves. In the field, activity for all four enzymes was detected at various times, though acid phosphatase was the most consistent. Most of the

acid phosphatase activity was localized to primary roots, including possibly associated microorganisms and fungi. An experiment was conducted wherein pieces of apatite, a calcium phosphate mineral, were placed into the soil near the roots to test if phosphatase activity was changed over time by the presence of the mineral. These types of in-situ assays may be beneficial in documenting responses of plants and soil microorganisms to changes in nutrient availability and environmental pollutants. ENVR 352 Analysis of steroid hormones in surface water runoff from animal farms using sulfuric acid preservation and isotope dilution S. Havens1, [email protected], T. Barry1, C. Hedman2, J. Hemming2, M. Mieritz2, M. Shafer1,2, and J. Schauer1. 1University of Wisconsin - Madison, Madison, WI, United States, 2Wisconsin State Laboratory of Hygiene, Madison, WI, United States The goal of this research was to validate the use of sulfuric acid (H2SO4) for the preservation of a suite of steroid hormones and their metabolites in runoff from confined animal feeding operations (CAFOs) in conjunction with the use of isotope dilution. Target and isotopically-labeled hormone standards were spiked into Type 1 water samples and samples composed of CAFOs runoff, extracted via solid phase extraction and analyzed using HPLC-MS/MS. Most or all of the spiked hormones in the unpreserved CAFOs runoff samples were degraded within days of sample collection. The isotopically-normalized recovery of spiked hormones in H2SO4 preserved (pH 2) samples was sufficient (78-124%) after 14 days. The results of this study provides a much needed method for preventing microbial degradation of hormones and incorporates a technique for accounting for hormone adsorption to colloids and extraction inefficiencies. ENVR 353 Microtextural analysis of weathering in CO2 saturated soils P. Vahmani, [email protected], and C. S. Khachikian, [email protected] Department of Civil Engineering, California State University, Los Angeles, Los Angeles, CA, United States Laboratory experiments were conducted with volcanic ash soils from Mammoth Mountain, California to examine the dependence of soil weathering rates on pH and CO2. In batch experiments over the pH range of 2.5­4.0, the dissolution rates exhibited a fractional order dependence on pH determined from H+ consumption data and Si release data. The relationship between the texture and dissolution behavior of fresh, CO2 exposed and low pH exposed soils from Mammoth Mountain, where concentrations of soil CO2 have been elevated over the last decade, has been investigated by scanning electron microscope (SEM) and atomic force microscope (AFM). SEM was used to compare soil texture

micro-morphological characteristics before and after exposure to CO2 and different levels of pH; AFM was used to observe those characteristics changing during weathering processes. ENVR 354 Oxidation of isoprene via photolysis of HONO and PT/MS detection K. E. Edelen, [email protected], C. Quist, and D. R. Hanson. Chemistry, Augsburg College, Minneapolis, MN, United States Isoprene is one of the foremost volatile hydrocarbons found naturally within the atmosphere. Yet, a third of isoprene's carbon has not been accounted for in oxidation studies. Here the HONO photoxidation of isoprene was studied with PT/MS detection, where NO levels were typical of the atmosphere. Ion break-up processes of the products were taken into account, but overall sensitivities were crudely estimated. The parent ion of MVK/MACR was the most prominent product ion, and the yield of this species was discussed regarding PT/MS detection. The C5-hydroxylcarbonyl products represented 5%-20% yield, where the ion was the dehydrated parent ion. In separate experiments, dehydration of the product ions of aliphatic hydroxycarbonyls, 3-acetyl-1-propanol and 4hydroxy-4-methyl-2-pentanone, was shown to be dominant. On the other hand, the ion observed at 87u comprised ;5% yield and was attributed to the C4hydroxylcarbonyl parent ion; apparently the parent ion does not undergo dehydration. The hydroxynitrates poor detection at 148u was disrupted by breakup processes that lead to primarily 101u and 85u, with a yield of 2-3%; with the parent ion contributing 0.02% of that yield. The flow reactor was modeled with OH isoprene + NO kinetics and a unified oxidation scheme was developed. ENVR 355 Use of synchrotron- and plasma-based spectroscopic techniques to determine the uptake and biotransformation of chromium(III) and chromium(VI) by Parkinsonia aculeata Y. Zhao, [email protected], J. R. Peralta-Videa, M. L. Lopez-Moreno, and J. L. Gardea-Torresdey. Chemistry, University of Texas at El Paso, El Paso, TX, United States In this study, a combination of inductively coupled plasma-optical emission spectroscopy and x-ray absorption spectroscopy (XAS) was used to study the uptake and speciation of chromium in Parkinsonia aculeata, commonly known as Mexican Palo Verde. Plants were treated for 30 days in a soil containing chromium(III) or chromium(VI) at several concentrations. Results show that in all cases plants treated with Cr(III) accumulated significantly more Cr in roots, stems, and leaves, but neither Cr(III) nor Cr(VI) affected the uptake of phosphorus and sulfur. More calcium was in leaves of Cr(III) treated plant, but no

clear differences were observed in potassium and magnesium concentrations. XAS data show that chromium(VI) was reduced to chromium(III) in/on plant roots and transported as Cr(III) to stems and leaves. The XAS studied also showed that chromium(III) within plants was present as an octahedral complex. ENVR 356 Enhancement of Fenton degradation of TNT by organic modifiers S. M. King, [email protected], C. W. Jarand, and M. A. Tarr. Department of Chemistry, University of New Orleans, New Orleans, Louisiana, United States 2, 4, 6-Trinitrotoluene (TNT) is a common contaminant in military sites. Since TNT is toxic, remediation is of great interest. The Fenton reagent provides an advanced oxidation process capable of remediating TNT. Degradation of TNT via Fenton reagent was studied at neutral pH in the presence of several organic modifiers: -cyclodextrin, carboxymethyl--cyclodextrin, and polyethylene glycols (MW 200, 400, 600 g/mol). Pseudo first order rate constants were compared for the Fenton reactions with and without modifiers present. At higher iron concentrations (1 mM - 10 mM), enhancement of the rate constant for TNT degradation was observed in the presence of each of the modifiers. However, at lower iron concentrations (0.25 mM - 0.75 mM), inhibition of TNT degradation was observed with modifiers present. The greatest enhancement (12 fold) in TNT degradation rate was observed for -cyclodextrin. The observed enhancements in degradation rate likely involve free radical intermediates of the organic modifiers. ENVR 357 Heavy metals in Callinectes sapidus from the Caño Tiburones wetland A. I. Calderon Pagan, [email protected], and M. E. Diaz, [email protected] Physic- Chemistry, University of Puerto Rico Arecibo, Arecibo, Puerto Rico, United States Crabs of the genus Callinectes (C. sapidus, C. bocourti and C. danae) are taken from people who live nearby the Caño Tiburones Wetland for personal and commercial consumption. This hydrological system is adjacent to various sources of pollution including waste disposal sites, local or municipal sewage, sludge treatment facilities, agricultural activities, pharmaceutical industries among others. Heavy metals may come from these sources. It is well known that these pollutants accumulate in tissues of aquatic animals. Heavy metals can reach levels that can be harmful to public health because of their toxicological effect. To date, no studies have examined tissue burdens of selected toxic metals in C. sapidus from the Caño Tiburones Wetland, despite the active recreational fishing of these crustaceans in the area. This study evaluates levels of metals of environmental and toxicological importance such as lead (Pb),

cadmium (Cd), copper (Cu) and nickel (Ni) in C. sapidus from the Caño Tiburones wetland. Crab samples were collected from the Barrio Islote (BI) sampling station and a station nearby the Arecibo Regional Landfill (ARL). Approximately 1 to 10 crabs are collected from each sampling site. Edible tissues of C. sapidus, C. bocourti and C. danae included muscles, hepatopancreas and gonads. Wet tissue samples were digested with HNO3 70% w/w and H2O2 30% w/w. Edible crab tissues from the species found were digested using a microwave laboratory oven (CEM MARS X). These samples were analyzed for its metal content by means of an atomic absorption spectrophotometer (PE AAnalyst-800). Toxic metals were found in edible tissues of all crab species under study. ENVR 358 Use of recycled tire crumb rubber to remove toluene from aqueous and gaseous effluents L. Alamo-Nole1, [email protected], F. R. Roman1, and O. Perales-Perez1,2. 1 Department of Chemistry, University of Puerto Rico, Mayaguez, Puerto Rico, United States, 2Department of Engineering Science & Materials, University of Puerto Rico, Mayaguez, Puerto Rico, United States The sorption capability of waste tire crumb rubber and its major components: carbon black and styrene-butadiene polymer for toluene in aqueous solutions were evaluated at room-temperature. The concentration of toluene ranged from 100.0 to 0.05 mg/L. The concentration of crumb rubber mesh 14-20 was 5 g/L. The amounts of carbon black and styrene-butadiene polymer used in the sorption tests were calculated considering their concentration in tire crumb rubber. The sorption process was fast; 68% of toluene was removed from the aqueous phase in the first 30 minutes. The removal of toluene in vapor phase (10 to 40 mg/L) when passed through a static bead of crumb rubber at 50 mL/minute was also evaluated. Results confirmed the capability of crumb rubber to remove toluene in both phases. The fitting of experimental data suggested a two-stage sorption process when crumb rubber was used, that contrasted with the one-stage process for its components. ENVR 359 Degradation of microcystin-LR by UV/H2O2 advanced oxidation process X. He, M. Pelaez, [email protected], and D. D. Dionysiou, [email protected] Department of Civil and Environmental Engineering, University of Cincinnati, Cincinnati, Ohio, United States The destruction of a commonly formed cyanobacteria toxin, microcystin-LR (MCLR), by UV/H2O2 advanced oxidation process was studied. Experiments were carried out in a laboratory scale collimated beam system with low pressure

germicidal lamps set at 254 nm. A 97.5% removal of MC-LR with an initial concentration of 1 mg/L was achieved with a UV dose of 80 mJ/cm2 and an initial H2O2 concentration of 24 mg/L. When increasing the concentration of MC-LR only, a lower removal was observed; while increasing H2O2 only, the removal increased. However, the scavenger effect of H2O2 became pronounced at high concentration ranges. The effects of water quality parameters, such as pH, alkalinity and the presence of natural organic matter, were also studied. Real water samples from Lake Erie, Michigan; St. Johns River, Florida; and the Greater Cincinnati Water Works have also been used to evaluate the utility of this technology on the degradation of MC-LR. ENVR 360 Light-initiated transformation of C60 clusters in water L. L. Kong, [email protected], K. Chan, R. Zepp, C. Ma, D. Bouchard, and C. Isaacson. U.S. Environmental Protection Agency, Athens, GA, United States Although Buckminster fullerene (C60) has an extremely low water solubility (;8 ng/L), the formation of stable clusters (aqu/nC60) not only greatly increases the mass of C60 dispersed in water, but also alters its physicochemical properties. This research focused on investigating the light-initiated transformation processes of aqu/nC60 aggregates in water. The irradiation kinetics of aqu/nC60 with simulated solar and monochromatic irradiation were investigated. The direct photoreaction of aqu/nC60 over a 3-day period exhibited first-order kinetics with reaction quantum yields of 1.48 (± 0.05) × 10-5 and 2.95 (± 0.13) × 10-5 at 366 and 435 nm, respectively. Following irradiation by simulated solar radiation the fluorescence excitation-emission matrix scans (EEMs) of the aqueous phase of aqu/nC60 extracted with toluene showed an initial increase (7 days) and an ultimate decrease (12 days) with the emission peak shifted to a shorter wavelength. This result displays the same pattern observed with fullerenol, a hydroxylated C60, under simulated solar irradiation, suggesting that the photolysis of aqu/nC60 leads to formation of hydrophilic functional groups (i.e. -OH or -C=O). MALDI-TOF-MS of both the toluene and water phase of C60 extracted with toluene also implies the possible formation of more hydrophilic products following irradiation. ENVR 361 Steroid hormones degradation in active slurry solution R. Xuan1,2, [email protected], and S. R. Yates1. 1USDA-ARS, U.S. Salinity Laboratory, Riverside, CA, United States, 2Department of Environmental Science, University of California, Riverside, CA, United States Estrongenic hormones, including natural hormones and artificial hormones, are regarded as endocrine disrupters in environment. Trace amount of estrogen can

cause the feminization of male trout in river. The main parts of these hormones from human beings are excreted and enter into sewage. To reduce their influence in environment, the efficacy of sewage treatment plants (STPs) on their degradation is critical. 17-estradiol (-E2), 17-estradiol (-E2), estradiol (E3), and estrone (E1) are natural hormones; 17-ethynylestradiol (EE) comes from the contraceptives; they likely exist in sewage. In the batch experiment, hormones stock solution (dissolve in acetonitrile) was added in diluted activated sludge solution at room temperature. The concentration of each hormone spiked was 2mg/l. During their transformation, as the first step, both -, -E2 were gradually oxidized to E1; E3 was oxidized to 16-ketone-estradiol or 17hydroxylestrone; as the second step, E2, 16-ketone-estradiol and 17hydroxylestrone were transformed to other compound. EE is very stable in this sludge solution because its 17-hydroxyl cannot be easily oxidized to ketone. The transformation kinetic of single hormone is similar to that in several hormones mixture solution. Though methanol and acetone could be oxidized and transformed like hormones E1, E2 and E3, they did not hinder these hormones' transformation. Though more attention should be paid on EE degradation, what the products of E1 and E3 are after their transformation remains to be known. ENVR 362 Cellular uptake and toxicity of PCBs adsorbed onto nanoparticles B. J. Newsome1, [email protected], E. Fourie1, T. D. Dziubla2, D. A. Puleo3, and L. G. Bachas1. 1Department of Chemistry, University of Kentucky, Lexington, KY, United States, 2Department of Chemical and Materials Engineering, University of Kentucky, Lexington, KY, United States, 3Center for Biomedical Engineering, University of Kentucky, Lexington, KY, United States Nanoparticles are prevalent in the environment and can be found readily in soil and airborne. With the growing use of nanoparticles in industrial and environmental applications, the toxicological effects of these materials have increasingly come into question. Nanoparticles are able to passively and actively pass through cell membranes primarily due to their small size. Although polychlorinated biphenyls (PCBs) have well-known toxicology, they are preferentially stored in adipose tissue after entering the body instead of readily being taken up by other cells. Presumably PCBs can adsorb onto nanoparticles due to hydrophobic effects and subsequently enter cells using nanoparticles as carriers. Various PCBs were adsorbed onto alumina and polystyrene nanoparticles and adsorption was confirmed using GC-MS. Dynamic light scattering was used to confirm that particles were of a relevant size for entry into cells and cell viability of A549 alveolar endothelial cells was subsequently studied to determine if nanoparticle-PCB complexes cause increased cytotoxicity as compared to nanoparticles and PCBs alone. Continued testing with a bacterial cell model will help to determine further environmental effects of this complex.

ENVR 363 Effect of the presence of oxalate on the cloud condensation nuclei activity of calcium-containing mineral dust aerosol K. M. Gierlus, [email protected], O. Laskina, and V. H. Grassian. Department of Chemistry, University of Iowa, Iowa City, IA, United States Dicarboxylic acids, which make up a significant portion of organics in the atmosphere, are emitted directly through biomass burning and automobile combustion as well as produced through oxidation of volatile organics. In recent field studies, oxalic acid has been shown to be present in mineral dust aerosol. The presence of this internally mixed organic compound can alter water uptake and cloud condensation nuclei (CCN) abilities of dust particles in the Earth's atmosphere. In this study, CCN measurements indicate that the internally mixed oxalate/calcite particles were more active than the unreacted calcite particles, but showed a much smaller enhancement in CCN activity compared to sulfate/PSL and oxalic acid/PSL internally mixed particles due to the reaction of calcite with oxalic acid to yield calcium oxalate. Our results show that atmospheric processing of mineral dust through heterogeneous reactions can alter CCN activity to an extent which depends on mineralogy and chemical speciation. ENVR 364 Preliminary study for the development of carbon nanotube-based biosensor for monitoring MC-LR C. Han1, A. Doepke2, W. Cho3, A. A. de la Cruz4, W. R. Heineman2, H. B. Halsall2, V. N. Shanov3, M. J. Schulz5, P. Falaras6, and D. D. Dionysiou1, [email protected] 1Department of Civil and Environmental Engineering, University of Cincinnati, Cincinnati, Ohio, United States, 2 Department of Chemistry, University of Cincinnati, Cincinnati, Ohio, United States, 3Department of Chemical and Material engineering, University of Cincinnati, Cincinnati, Ohio, United States, 4Office of Research and Development, National Exposure Research Laboratory, US EPA, Cincinnati, Ohio, United States, 5Department of Mechanical Engineering, University of Cincinnati, Cincinnati, Ohio, United States, 6Institute of Physical Chemistry, NCSR Demokritos, Aghia Paraskevi, Attiki, Greece Cyanobacteria are ubiquitous inhabitants of freshwater lakes and reservoirs throughout the world. Under favorable conditions, they can form massive blooms and can severely affect animal and human health via oral, recreational and aerosol exposures. Cyanobacteria produce unfavorable taste, odor, color, and more importantly toxic metabolites, cyanotoxins. The most frequently reported cyanotoxins are microcystins (MC), a group of cyclic hepatotoxins and microcystin-LR (MC-LR) is the most commonly occurring variant in the US. Current methods to detect cyanotoxins in various matrices require long processing time, sophisticated instruments, complex procedure and high cost. A

sensitive, specific, and simple method for monitoring MCs is necessary to immediately institute remedial measures to prevent exposure to these toxins. Carbon nanotubes have electrical and physical properties that are desirable for developing novel submicron sized electrochemical sensors. An innovative, fieldportable continuously monitoring carbon nanotube (CNT)-based biosensor can detect MC-LR at low detection limits. Dense arrays of multi-walled carbon nanotubes were grown in controlled shapes by using patterned catalyst. Electrochemical, mechanical, and laser ablation methods were applied to functionalize CNT-based sensors and fluorescent spectroscopy was used to measure fluorescent labels after conjugated with functional molecules on CNT arrays. Raman spectroscopy and cyclic voltammetry were used to measure the number of oxygen sites. Results from preliminary study on the physical characteristics and functionalization of CNT-based electrodes prior to the development and application for CNT-based biosensors to detect MC-LR will be presented and discussed. ENVR 365 Interpretation of the evolution of fluorescence spectra of dissolved organic matter during metal complexation D. J. Dryer1, [email protected], G. V. Korshin1, and M. Benedetti2. 1 Department of Civil & Environmental Engineering, University of Washington, Seattle, WA, United States, 2Laboratoire de Géochimie des Eaux, Université Paris Diderot-Paris 7-IPGP, Paris, France The occurrence of fluorescence quenching during the complexation of metals to natural organic matter (NOM) is well-known, but it is generally considered insufficiently sensitive to provide detailed information about binding functionalities of NOM. This study examined the evolution of the emission spectra of Suwannee River Fulvic Acid (SRFA) and NOM of other provenance with copper ions at copper concentrations of 5-1000 g/L. While the general shape and placement of the maxima of the fluorescence spectra do not change significantly with metal complexation, there is evidence that quenching is preferential at wavelengths greater than max. Probing this preferential quenching by looking at the ratio of I500/I400 shows a close correlation between these intensity ratios and, on the other hand, a corresponding increase in UV absorbance. Additionally, both fluorescence quenching and this indicative intensity ratio very closely correlate with copper binding predicted by NICA-Donnan modeling. ENVR 366 Production of a biogas on a small scale S. Bremer, [email protected], W. J. Glauser, J. Wilburn, T. Feagin, [email protected], P. Iles, R. Valcarce, L. Giddings, and N.

Bastian, [email protected] Chemistry, Salt Lake Community College, Salt Lake City, UT, United States The process of breaking down human and animal waste into methane has been used effectively throughout the world for large-scale applications. Our goal has been to create a small-scale approach to this system. The initial two cycles of this experiment have provided proof of the functionality of our design, while defining control standards for comparison. In the most recent run, we converted human and animal waste into a clean-burning hydrocarbon fuel. Ultimately, this technology could be put to use in developing nations where large-scale infrastructure is lacking and facility construction is not yet feasible. ENVR 367 Heterogeneous mercury reaction chemistry in coal combustion flue gases E. Sasmaz, [email protected], B. Padak, S. Lee, and J. Wilcox. Energy Resources Engineerng, Stanford University, Stanford, CA, United States While the oxidized mercury in coal-fired flue gases is readily controlled by the interaction with fly ash and co-benefit of existing sulfur dioxide controls, elemental mercury is hardly controlled without the application of a specific control method for mercury. Therefore, it is important to understand heterogeneous mercury reaction mechanisms to predict the levels of mercury emissions from coal-fired power plants and determine the best applicable control technologies. Experimental studies will be conducted using a bench-scale packed-bed system to further understand heterogeneous mercury reaction mechanisms. Methane will be combusted in a tubular burner and mixed with mercury and chlorine to simulate the flue gas environment. The effect of combustion products on the sorption of mercury will be investigated. The activated carbon-based sorbent materials before and after simulated flue gas exposure will be analyzed using Xray photoelectron spectroscopy (XPS). The speciation of the resultant mercury will be conducted by direct measurement using an electron ionization quadrupole mass spectrometer specially designed for mercury measurements in our laboratory. ENVR 368 Development of a sensitive method to concentrate and detect microbial contamination in communal water supplies R. B. Hayman1, ryan.h[email protected], C. A. Lipovsky1, D. K. Toubanaki1, C. Rich2, U. Zuckerman2, S. Tzipori2, and D. R. Walt1. 1Department of Chemistry, Tufts University, Medford, MA, United States, 2Division of Infectious Diseases, Tufts Cummings School of Veterinary Medicine, North Grafton, MA, United States

Microbial contamination of water supplies used for consumption, recreation, or agriculture is a growing concern for industrialized and developing nations. We have developed a nucleic acid detection method that is more sensitive, specific, and rapid than current culture-based techniques. We targeted bacterial species such as S. enterica and E. coli O157:H7 identified by the U.S. Environmental Protection Agency's Contaminant Candidate List (CCL3). These highly virulent pathogens often have a low infectious dose and typically contaminate water supplies exposed to runoff from livestock fields. Bacteria are first concentrated by continuous flow centrifugation (CFC) and lysed. Amplification of species-specific virulence genes by PCR is followed by detection with oligonucleotide microarrays or disposable lateral flow biosensors. We have demonstrated the ability to detect less than 100 CFU of bacteria spiked in 10 L of water. Our technique is promising for online monitoring of water supplies, as results are available within hours of sampling. ENVR 369 Carbon dioxide adsorption on nanomaterials P. Galhotra1, [email protected], J. B. Knapp4, [email protected], J. Navea3, [email protected], and V. H. Grassian1,2, [email protected] 1Department of Chemistry, Univerist of Iowa, Iowa city, Iowa, United States, 2College of Engineering, University of Iowa, Iowa city, Iowa, United States, 3Department of Chemistry, Lawrence University, Appleton, Wisconsin, United States, 4Department of Chemistry, Wittenberg University, Springfield, Ohio, United States In this study, CO2 adsorption on different nanomaterials including nanocrystalline NaY, ZnO nanoparticles and aluminum oxyhydroxide nanowhiskers has been investigated with transmission FTIR spectroscopy. In the case of NaY nanocrystals, FTIR spectroscopy shows that a majority of CO2 adsorbs in the pores of these zeolites in a linear complex with the exchangeable cation. Most interesting is the formation of carbonate and bicarbonate on the external surface of nano-NaY zeolites suggesting unique sites for CO2 adsorption on the surface of this nanomaterial. For nanoparticulate zinc oxide and aluminum oxyhydroxide nanowhiskers, CO2 reacts with surface hydroxyl groups to form adsorbed bicarbonate and carbonate in the absence of co-adsorbed water. In the presence of co-adsorbed water, only carbonate is formed. Isotope studies with H216O and C18O2 show that there is extensive exchange between oxygen in adsorbed water and oxygen atoms in gas-phase carbon dioxide. Implications for the use of these nanomaterials in carbon dioxide uptake and storage are discussed. ENVR 370 Environmental analysis of switchgrass impact on soil and utilization of biomass

G. Geme1, [email protected], B. C. Banach1, [email protected], C. G. Brown1, [email protected], D. M. Gant1, [email protected], E. R. Holcomb1, [email protected], R. D. Seelinger1, [email protected], H. N. Short1, [email protected], F. Kidwaro2, [email protected], and S. E. McKay1, [email protected] 1Department of Biochemistry, Chemistry & Physics, CAFES, University of Central Missouri, United States, 2Department of Agriculture, CAFES, University of Central Missouri, United States Conversion of biomass to fuel is quickly gaining popularity due to its carbon neutral status and the cost volatility of the traditional fossil fuel resources. Sulfur and nitrogen emissions from biomass fuels are greatly reduced compared to fossil fuels. Biomass feedstocks, such as switchgrasses, require minimal fertilizers, labor, and land management. For sustainable switchgrass production to occur, we must understand environmental effects associated with switchgrass, such as any changes soil is undergoing during the growth of switchgrass and quality of runoff water. This particular study focuses on concentrations of potassium, calcium, zinc, phosphorus, nitrogen and lead in soil. Numerous soil samples were taken from four different species of switchgrass at different times of the year and in areas with different amounts of nitrogen fertilization. The study has also focused on determining potential biomass (switchgrass) production from non-tilled lands such as roadsides and waste areas for University of Central Missouri. ENVR 371 Potential risk of reused creosote-treated railway ties in Korea H. S. Moon1, [email protected], K. Yang2, [email protected], H. Ryu2, [email protected], and K. Nam2, [email protected] 1School of Earth and Environmental Sciences, Seoul National University, Republic of Korea, 2 Department of Civil & Environmental Engineering, Seoul National University, Republic of Korea In Korea, a nation-wide study has been initiated to characterize the current risks of creosote-treated old railway ties reused in recreational and residential areas and to establish guidelines on their reuse. As a preliminary report, generic human protection levels of the hazardous substances found in old railway ties and the environmental media nearby are presented here. Ingestion, dermal absorption, dermal contact-ingestion, and inhalation were identified as possible exposure routes. Generic protection levels (based on risk assessment) for 24 substances (6 BTEXs, 5 Phenols, and 13 PAHs) were calculated. Calculated generic protection levels based on noncarcinogenic effects were higher than that based on carcinogenic effects. Generic protection levels of soil were 0.382 mg/kg (Benzo(a)pyrene) ; 9.85X104 mg/kg (Chrysene) based on carcinogenic effects and 1.13X103 mg/kg (Benzene) ; 2.85X107 mg/kg (Phenol) based on noncarcinogenic. Concentrations of target substances in ties and environmental media will be compared to calculated generic potential levels.

ENVR 372 Influence of aquatic structures made of Portland cement and coal combustion fly ashes on water quality: Improvement of nitrification P. Torres, [email protected], S. Hwang, [email protected], and Y. Lugo, [email protected] Department of Civil Engineering, University of Puerto Rico at Mayaguez, Mayaguez, PR, Puerto Rico Due to the presence of fish, discharges or nutrients in water resources, ammonia can become a problem to the water environment since the presence of high concentrations of this compound has proven to be toxic. A lab-scale physical simulation of an aquatic environment was conducted to test a hypothesis that the aquatic structures made of Portland cement with fly ashes could enhance nitrification so as to decrease ammonia toxicity. Two identical physical aquatic environment models were constructed with 30-L aquarium tanks. The treatment reactor had the aquatic structures, whereas the control reactor did not. Nitrifying bacteria obtained from a local wastewater treatment plant were initially introduced into the systems. Ammonia was added with glucose and nutrients in a weekly basis to provide an adequate environment to the nitrifying bacteria. Monitored water quality parameters included: pH, turbidity, conductivity, dissolved oxygen, chemical oxygen demand, total phosphate, ammonia, hardness, alkalinity and nitrate. Alkalinity and hardness reductions were observed in the tank with the aquatic structures due to the nitrification process occurring within the system. A more decrease in the ammonia concentration and a more increase in the nitrate concentration were observed from the system with the aquatic structures. Turbidity was observed to decrease in the system with the aquatic structures due provably to the surface area provided by the aquatic structures for an attachment of turbidity-causing compounds. Therfore, it can be construed that the initial hypothesis has met, imporiving overall water quality decreasing the ammonia concentrations due to the addition of the auquatic structures made of Portland cement and coal combustion fly ashes. ENVR 373 Photolysis of antibiotics in natural sunlight vs. surrogates and identification of metabolites S. R. Batchu1, [email protected], and P. R. Gardinali1,2, [email protected] 1 Dept. of Chemistry and Biochemistry, Florida International University, Miami, FL, United States, 2Southeast Environmental Research Center, Florida International University, Miami, FL, United States Two types of photolysis reactions namely direct and indirect photolysis play an important role in determining the environmental fate of antibiotics. Kinetic data was obtained for three antibiotics namely nalidixic acid, clindamycin and roxithromycin in rayonet photochemical reactor (350 nm), SunTest (surrogate of natural sunlight, 300-800 nm) and natural sunlight. The results from Sun Test

and natural sunlight were compared. As an example, nalidixic acid is least stable of all the three compounds tested and it degrades at 350 nm with a calculated half life of ;8 min in distilled deionized water and with a half life of ;60 min in canal water and salt water. Three types of water matrices were used to compare direct photolysis versus indirect. Photodegradation products were identified using LC-MS/MS in ESI+ mode. At 350 nm roxithromycin degraded with a half life of 170 hrs and produced degradation products namely DP 734, DP 575 and DP 576. ENVR 374 Application of calcium carbonate based permeable reactive barriers for remediating iron-contaminated groundwater at a landfill site Y. Wang1, [email protected], J. H. Ko1, A. Gale1, A. Oppong-Anane1, J. Hou1, T. Townsend1, T. Boyer1, S. Jennings2, and R. Hixson2. 1Department of Environmental Engineering Sciences, University of Florida, Gainesville, FL, United States, 2Department of Solid Wast Management, Escambia County, Cantonment, FL, United States Research is being conducted at a closed unlined MSW landfill site in Escambia County, Florida. Groundwater at this site has elevated iron concentrations typically ranging from 10 to 50 mg/L. A pilot study is evaluating in situ remediation of groundwater contaminated with iron using permeable reactive barriers (PRBs). PRBs were installed in two trenches at the Klondike landfill. Each PRB was filled with limestone or crushed concrete. The dimension of each trench was 3 feet in width, 15 feet in depth, and 20 feet in length. Eighty tons of limestone and ninety tons of crushed concrete were used. Twenty eight groundwater monitoring wells were installed in the test area (down-gradient and up-gradient). Preliminary results show an iron reduction of 95% for the crushed concrete and 93% for the limestone. ENVR 375 Simultaneous analysis of multiple classes of antibiotics in South Florida surface waters using LC-MS/MS V. R. Panditi1, [email protected], and P. R. Gardinali1,2, [email protected] 1 Department of Chemistry and Biochemistry, Florida International University, Miami, FL, United States, 2Southeast Environmental Research Center, Florida International University, Miami, FL, United States Liquid chromatography coupled with ion trap mass spectrometry (LC-MS/MS) technique was used for the simultaneous analysis of multiple classes of 17 antibiotics in surface waters (i.e., reclaimed water and wastewaters) in South Florida. Representative samples were collected from C-1 Creek Canal which receives waters from agricultural, residential and landfill areas. Samples were

extracted using solid phase extraction with Oasis HLB cartridges prior to analysis by LC-MS/MS. The separation was achieved using zorbax C-18 column (25 cm * 5µ particle size) using ternary gradient mobile phase composed of methanol, acetonitrile and 0.1% Formic acid in water using sulfamethazine 13C-6 as an internal standard. Samples were analyzed using Thermo Finnigan LCQ advantage plus in ESI positive mode. The method developed had detection limit of 1µg/L for direct analysis and 10 ng/L for waters processed by SPE for all antibiotics except doxycycline and erythromycin. ENVR 376 Electrokinetic behavior of metal contaminations in soil and their electrochemical recovery Z. Wu, wuz[email protected], B. Yu, X. Ma, and Y. Cong. Department of Environmental Engineering, State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, Zhejiang, China The electrokinetic process shows much promise for the remediation of contaminated soil and groundwater. Removal of toxic heavy metals from a soil matrix and groundwater by the addition of chelating agents like phosphoric acid and ethylenediamine tetraacetic acid is an effective means of remediation. The pH can significantly affect the migration of contaminants, and partial degradation of organic components occurred close to the electrodes. Potentials applicable for metal deposition and, consequently, regeneration of the chelating agents were established. The contaminated soil can be remediated by the combination of the electrokinetic process and electrochemical reaction. A site remediation was demonstrated and the results will be presented at the meeting. ENVR 377 Development of highly active rhenium coordination complexes for heterogeneous catalytic treatment of perchlorate-contaminated water J. Liu1,3, [email protected], J. R. Shapley2,3, C. J. Werth1,3, and T. J. Strathmann1,3. 1Department of Civil & Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 2Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 3 Center for Advanced Materials for the Purification of Water with Systems, Urbana, IL, United States Catalysts combining nanophase palladium (Pd) with rhenium (Re) species on carbon support materials (Pd/Re-C catalyst) promote rapid reduction of perchlorate (ClO4-) by dihydrogen in acidic aqueous media, with the Re(V) species acting as an oxygen atom acceptor. Re complexes with organic ligands show enhanced reactivity with ClO4- and broader pH tolerance. This study explores the activity of new complexes with oxo-Re(V) centers, based on

structure-activity features of previously reported 2-(2'-hydroxyphenyl)-2-oxazoline (hoz) and dimethylaminopyridine (DMAP) ligands. Ligands with imine, phenol, pyridine, and other heteroatomic coordination moieties, as well as electron donating and steric bulk groups are rationally designed, synthesized and coordinated with oxo-Re(V) via ligand-exchange reactions. The perchloratereducing activity, stability, and pH tolerance of the synthesized Re complexes is quantified in the Pd-Re-C catalyst system. Results from this study support a longterm goal of developing an economical and sustainable catalytic treatment system for ClO4-. ENVR 378 Degradation of pyrene by pyrite-Fenton reaction in cationic surfactant solution with electrolyte M. B. Mannan, [email protected], and W. Lee, [email protected] Department of Civil and Environmental Engineering, Korea Advanced Institute of Science and Technology, Daejeon, Yuseong-gu, Republic of Korea This study was carried out to investigate the adsorption and degradation of pyrene by pyrite-Fenton reaction in a cationic cetylpyridinium chloride (CPC) surfactant solution with NaCl. Pyrene-surfactant solution (5 mg/L) was prepared by doubling the critical micelle concentration of CPC. 32% and 78% adsorption of pyrene were observed in 25 g/l and 50 g/l pyrite suspensions. Addition of 0.67 mM H2O2 into 25 g/l pyrite can degrade 92% pyrene (0.038 min-1). The presence of 0.17 M NaCl can reduce the adsorption by 19% and 32% in 25 g/l and 50 g/l pyrite suspension, respectively. In this system, a synergistic effect on pyrene degradation was observed in the presence of NaCl by decreasing the adsorption resulting in 100% degradation within 15 min. The experimental result shows an interesting effect of electrolyte in pyrite-surfactant system on the adsorption and degradation of pyrene where it can provide a novel remediation alternative for waste water produced from soil washing processes. ENVR 379 Simulated wastewater treatment of triclocarban and caffeine P. G. House, [email protected], D. M. Anton, and T. E. Zimmerman. Department of Chemistry, University of Wisconsin-Whitewater, Whitewater, WI, United States Personal care product and pharmaceutical (PPCP) pollutants in the environment are an emerging issue that is of high priority. Two of these compounds are the antimicrobial triclocarban and caffeine which is a non-prescription drug among other sources. Some PPCPs, including acetaminophen, have been shown to produce toxic compounds under conditions that simulate wastewater treatment. We have separately studied the reactions of triclocarban and caffeine with

hypochlorite under conditions that simulate the use of chlorine gas as a disinfectant in wastewater treatment. Reversed phase liquid chromatography has shown production of transformation products with caffeine which are being characterized by NMR. Work on triclocarban is progressing more slowly due to its hydrophobic nature. Solid phase extraction methods are being utilized to isolate triclocarban and possible reaction products. ENVR 380 Inhibition effect of natural organic matter on the reductive dechlorination of PCE by nZVI in the presence of vitamin B12 A. Amir, [email protected], and W. Lee, [email protected] Department of Civil and Environmental Engineering, Korea Advanced Institute of Science and Technology, Daejeon, Yuseong-gu, Republic of Korea This study presents the effect of natural organic matter (NOM) on the reductive dechlorination of PCE by nZVI in the presence of vitamin B12. NOM and vitamin B12 occurs naturally in soil and could affect the reductive dechlorination of chlorinated compounds by nZVI. Characterization study on the interaction between nZVI and vitamin B12 for the degradation of PCE showed enhanced dechlorination kinetics of PCE. Removal of PCE by nZVI-Vitamin B12 was 78% in 6 hours at pH 8.17. The dechlorination kinetic of PCE by the interaction was 30 times faster than that of nZVI (0.05g) alone. The predominant cobalt specie under the reaction condition was Co (II) (vitamin B12r). The observed reduction kinetic of PCE by nZVI-vitamin B12 decreased by 27% in the presence of NOM (humic acid, 20mg/L) due probably to its adsorption on the nZVI surfaces. The experimental results showed that the reductive dechlorination of chlorinated compounds could be inhibited by NOM in natural and engineered systems. ENVR 381 Novel method to detect and characterize electron shuttles used by ironreducing bacteria: Electrochemical detection coupled with electrospray ionization liquid chromatography mass spectrometry (EC/ESI/LC/MS) D. M. Brown1, [email protected], G. S. Rahn1, E. J. O'Loughlin2, and M. L. McCormick1, [email protected] 1Hamilton College, Clinton, NY, United States, 2Argonne National Laboratory, Chicago, IL, United States Electron shuttles are freely-diffusible redox-active molecules that can increase rates of iron oxide reduction by dissimilative iron-reducing bacteria (DIRB). Such shuttles may be directly produced by DIRB (endogenous) or may be provided from other sources (exogenous), both natural and synthetic. In this work we are developing a novel analytical method to detect and characterize electron shuttles using electrochemical screening coupled to LC/MS detection. In proof of concept experiments a mixture of flavin mononucleotide (FMN) and riboflavin was used to test the chromatographic separation, electrochemical detection and mass

spectral identification of these putative endogenous electron shuttles. Baseline resolution and identification of FMN and riboflavin was achieved. Subsequent analysis of spent media from a culture of fumarate grown Shewanella oneidensis MR-1 indicated the presence of FMN, consistent with recent reports of other investigators. These preliminary data suggest that EC/ESI/LC/MS may be a promising technique for rapidly detecting and identifying electron shuttles used by DIRB. ENVR 382 Fractionation and characterization of dissolved organic carbon from the Allequash Creek wetland in northern Wisconsin A. L. Kolpin, [email protected], J. Creswell, and D. Armstrong. University of Wisconsin Madison, United States Dissolved Organic Carbon (DOC) is a significant parameter affecting the bioavailability of Hg(II), although of the mechanisms underlying this relationship are not well understood, primarily due to the complex nature of DOC. In order to investigate Hg-DOC interactions, DOC was separated from pore water samples collected at the Allequash Creek Wetland in Northern Wisconsin. The samples were then fractionated into hydrophobic organic acids, hydrophilic organic acids, and short-chain hydrocarbons using a two column nonionic macroporous resin system. These fractions were concentrated and characterized by C13NMR, SUVA (Specific Ultra-Violet Absorbance), LC-Mass Spectroscopy, and TOC (Total Organic Carbon) measurements. Mercury and methylmercury concentrations in pore waters were also measured. These data were compared to previously measured Hg(II) methylation rates from this site to gain insight into the influence of Hg-DOC speciation and its role in controlling bioavailability. ENVR 383 Determination of acetaminophen, naproxen, ibuprofen and caffeine in rivers that disembogue to Mayagüez Bay, Puerto Rico V. Aponte, [email protected], and A. M. González. Department of Biology, Chemistry and Environmental Sciences, Inter American University of Puerto Rico, San Germán, PR, United States Environmental monitoring already has new challenges: "emerging contaminants". Among those compounds pharmaceuticals are very important, since they are continuously released to the environment, and its effect on different ecosystems is not widely known. A reason for the lack of knowledge is that pharmaceuticals are difficult to analyze due to their low concentration and the complexity of the sample matrix. USGS has determined some pharmaceuticals in water samples from the East and Central area of Puerto Rico. They reported the presence of acetaminophen and ibuprofen. However, the West ­ Southwest area of Puerto Rico was not reported. This work presents the concentration levels of

acetaminophen, naproxen, ibuprofen and caffeine in water from three different rivers that disembogue to the Mayagüez Bay. ENVR 384 Increasing the efficiency of the enzymatic decomposition of cellulose to glucose as a feedstock for biofuels A. Singh1, [email protected], H. Singh2, [email protected], T. Pham3, [email protected], and C. Khachikian4, [email protected] 1Department of Chemistry and Biochemistry, California State University, Los Angeles, United States, 2Department of Kinesiology and Nutritional Science, California State University, Los Angeles, United States, 3Department of Mechanical Engineering, California State University, Los Angeles, United States, 4Department of Civil Engineering, California State University, Los Angeles, Los Angeles, California, United States Glucose is a feedstock for many alternative fuels from ethanol to algae derived gasoline. Cellulose is a renewable and naturally abundant polymer of glucose present in almost all waste plant biomass in significant quantities. Current methods of chemical/mechanical decomposition of cellulose to glucose are economically unfeasible and environmentally unfriendly. Enzymes provide an eco-friendly means of decomposing cellulose, but the process is too slow and therefore uncompetitive for large-scale industrial use. This project was designed to elucidate the kinetics and to increase the efficiency of the enzymatic decomposition of cellulose. Using a cellulase system from Tricoderma Reesei, sonication (ultrasound) was looked at as a possible eco-friendly and efficient means of increasing the accessibility of the enzymes to the cellulose structure (Avicel), thereby significantly increasing glucose yields. Two methods of analysis were used to quantify results: A glucose assay kit analyzed using a microplate spectrofluorometer, and a HPLC/Photodiode Array (PDA) interface. ENVR 385 Cadmium removal by nano zerovalent iron: Influence of physicochemical parameters H. K. Boparai, [email protected], M. Joseph, and D. M. O'Carroll. Department of Civil & Environmental Engineering, University of Western Ontario, London, Ontario, Canada Nano zerovalent iron (nZVI) is an emerging nanoscale environmental technology for treating various organic and inorganic contaminants. In this study, nZVI was synthesized using the borohydride reduction method and tested for the removal of cadmium (Cd2+), a toxic heavy metal found at contaminated sites throughout the world. Batch experiments were performed to determine the feasibility of using nZVI as an adsorbent for Cd removal from groundwater. The impact of initial Cd2+

concentration, temperature, pH, competitive cations and ionic strength on cadmium removal were investigated. The maximum adsorption of Cd2+ on nZVI calculated using the Langmuir and Freundlich adsorption isotherms will be presented in addition to the thermodynamic parameters governing Cd2+ adsorption on nZVI. The adsorption increased significantly with increasing pH. The effects of competing cations showed that Zn2+, Co2+, and Mg2+ are potential inhibitors to Cd2+ adsorption by nZVI. Our results suggest that nano zerovalent iron is a promising approach for remediation of cadmium contaminated groundwater. ENVR 386 What's in the pool? A comprehensive identification of disinfection byproducts and assessment of mutagenicity of chlorinated and brominated swimming pool water S. D. Richardson1, [email protected], D. M. DeMarini2, M. Kogevinas3,4,5,6, P. Fernandez7, E. Marco7, C. Lourencetti7, C. Balleste7, D. Heederik8, K. Meliefste8, A. B. McKague9, R. Marcos10, L. Font-Ribera3,4, J. O. Grimalt7, and C. M. Villanueva3,4,5. 1National Exposure Research Laboratory, U.S. Environmental Protection Agency, Athens, GA, United States, 2National Health and Environmental Effects Research Laboratory, U.S. Environmental Protection Agency, Research Triangle Park, NC, United States, 3Centre for Research in Environmental Epidemiology (CREAL), Barcelona, Spain, 4IMIM Hospital Del Mar, Municipal Institute of Medical Research, Barcelona, Spain, 5 CIBER Epidemiologia y Salud Publica (CIBERESP), Spain, 6Medical School, University of Athens, Athens, Greece, 7Department of Environmental Chemistry, Institute of Environmental Assessment and Water Research, Barcelona, Catalonia, Spain, 8Division for Environmental Epidemiology, University of Utrecht, Institute for Risk Assessment Sciences, Utrecht, The Netherlands, 9CanSyn Chem. Corp., Toronto, Ontario, Canada, 10Grup de Mutagenesi, Dept. de Genetica i de Microbiologia, Edifici Cn, Universitat Automona de Barcelona, Bellaterra, Cerdanyola de Valles, Spain Swimming pool disinfectants and disinfection by-products (DBPs) have been linked to human health effects, including asthma and bladder cancer, but no studies have provided a comprehensive identification of DBPs in the water and related that to mutagenicity. We performed a comprehensive identification of DBPs using gas chromatography (GC)/mass spectrometry (MS) and disinfectant species in waters from public swimming pools in Barcelona, Spain, that disinfect with either chlorine or bromine, and we determined the mutagenicity of the waters to compare to the analytical results. We identified more than 100 DBPs, including many nitrogen-containing DBPs that were likely formed from nitrogencontaining precursors from human inputs, such as urine, sweat, and skin cells. Many DBPs were new and have not been reported previously in either swimming pool or drinking waters. Bromoform levels were greater in the brominated vs. chlorinated pool waters, but many brominated DBPs were also identified in the

chlorinated waters. The pool waters were mutagenic at levels similar to that of drinking water. ENVR 387 Holistic framework for sustainable and resilient design of urban energy and water infrastructure H. Jeong, [email protected], J. C. Crittenden, A. Pandit, and M. Xu. Institutes for Sustainable Energy and Technology, School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, Georgia, United States The population growth coupled with industrialization and urbanization augments the future demand of water and energy as shown in figure 1. Water and energy infrastructure being interdependent, their interactions or the energy water nexus should be better understood for the sustainable water and energy infrastructure design to satisfy the increased demand without conflicting with environmental and economic contraints. To this end, this research compares centralized energy and water systems with decentralized alternatives in terms of their life-cycle environmental impact and economic performance using a hybrid life cycle assessment (LCA) tool and cost benefit analysis, respectively. The goal is to develop a model optimizing the combination of alternatives based on the physical and socio-economic environments. Furthermore, this model will be able to examine infrastructure resiliency against physcial and socio-economic challenges such as population growth, severe weather, energy and water shortages, economic crisis, and so on.

ENVR 388 Degradation pathway of electrochemical oxidation of phenol on Ti base SnO2 anode J. Liu1, Y. Feng1, [email protected], X. Li2, B. Cui1, and Y. Cui1. 1State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, Heilongjiang, China, 2Department of Civil Engineering, The University of Hong Kong, Hong Kong, China The degradation pathway of phenol, as model pollutant organic pollutant was researched on antimony-doped tin dioxide electrode based on titanium (Ti/SbSnO2) anode and rare earth doped SnO2 anodes. Large amounts of intermediates of electrochemical degradation of phenol on Ti/Sb-SnO2 and rare earth doped SnO2 anodes were identified and quantified by HPLC. These intermediates were assured as aromatic ring-compounds (hydroquinone, catechol, benzoquinone, et al) and short chain fatty acids (maleic acid, fumaric acid, formic acid, cis muconic acid and 2-oxoglutaric acid, et al). Electrochemical degradation tests were conducted with some intermediates as substrates, including the electrochemical oxidation of formic acid, acetic acid, oxalic aicid, malonic acid, acrylic acid, succinic acid, fumaric acid, maleic acid, 2-oxaglutaric acid, and hytroquinone, catechol, benzoquione, et al. Different decompose pathway of phenol on Sb/SnO2 anode and rare earth doped Sb/SnO2 anodes was concluded. It is proven that the pathway relates to the element composition

on the electrode surface. These findings provide insight into reasons and demonstrate EC degradation of organic pollutants mechanism and help to construct effective structures of catalytic anodes materials. ENVR 389 Impact of sample processing procedures on the quality of environmental monitoring data influencing policy decisions R. P. Deo, [email protected], and R. U. Halden. Center for Environmental Biotechnology, The Biodesign Institute at Arizona State University, Tempe, Arizona, United States Environmental monitoring is an important aspect of public health protection. In this paper, we examined the influence of sample filtration on the accuracy of quantification of organic wastewater compounds in municipal sewage. Filtration of samples is known to preclude a potentially significant fraction of chemical mass from both chemical measurements and mass flow analyses at municipal sewage treatment plants. Sorption theory indicates that the loss of analytes during sample filtration will be particularly notable for hydrophobic organic compounds featuring a pH-dependent organic carbon-water distribution coefficient (DOC) of 10^3. Among some 30 organic wastewater compounds considered, the extent of sorption to filterable materials was calculated to range from 22 to as high as 99%. Sample filtration also was found to have a profound impact on the outcome of environmental fate studies. When the chemical mass residing on filterable particulates was considered, the concentration range doubled between maximum and minimum concentrations reported for raw sewage. In addition, sewage treatment plant removal efficiencies calculated for sorptive organics increased by up to 60% simply by changing the method of accounting. It is concluded that some of the data discrepancies reported in the literature concerning chemical mass loadings, contaminant concentrations in raw sewage, and removal efficiencies of similarly designed treatment works are caused by sample processing protocols and the method of mass accounting, as opposed to other factors such as sewage composition, geographic locations and treatment unit design. Greater consistency in data analysis strategies and reporting will be required to enable reliable monitoring for enforcement of environmental protection policies. ENVR 390 Inhibition of biofilm formation by allicin in Staphylococcus epidermidis G. C. Villalon, [email protected] Microbiology Department, Faculty of Medicine, Badajoz, Badajoz, Spain Allicin (diallyl thiosulfinate) is the active principle of garlic with medicinal properties. Among another properties, allicin shows antibacterial and antifungal

activity. In this work we describe a novel property of allicin: The inhibition of biofilm formation in the bacteria Staphylococcus epidermidis strain ATCC35984 (RP 62). Allicin produces inhibition at sub-minimal inhibitory concentration (MIC) of 4 micrograms/mL. Interestingly, we have found the allicin vapors produces similar inhibitory effects to that of the substance in solution. Similar assays were made with papain, an enzyme containing sulphydryl group in the active center. Finally a comparative study of the production of PIA (Polysaccharide Intercellular Adhesin), a bacterial agglutination factor has been made in cultures trated with allicin and a control without allicin. Our results show a significant reduction of PIA production in bacteria treated with allicin at sub MIC. A possible interpretation of this effect is made in the discussion.

strain Control ATCC 2.8±0.5 35984 2893 9542 12 2526 2.5±0.3 1.4±0.5 1.9±0.5 2.9±0.6

1/32 MIC 1/2 MIC 0.1±0.12** 0.10±0.05* 0.1±0.1** 0.08±0.05** 0.2±0.15* 1/4 MIC 0.2±0.2** 0.2±0.1* 0.3±0.3 0.2±0.1 0.2±0.2* 0.55±0.4 0.7±0.4 2±1.0 3.4±0.4 0.14±0.1*


1/8 MIC 1.50±1.0 0.6±0.8

1/16 MIC 2.8±0.7 1.9±0.6 0.5±0.5* 0.2±0.2** 3.0±0.5 2.2±0.1 0.8±0.5 0.5±0.2

ENVR 391 Role of extracellular polymeric substances of biofilm on bacteria inactivation

Z. Xue, [email protected], and Y. Seo, [email protected] Department of Civil Engineering, University of Toledo, Toledo, OH, United States Previous reports from water utilities in the U.S. have shown that biofilms survive in water distribution systems despite the continuing presence of disinfectants. Immobilized microbial cells grow and produce extracellular polymeric substances (EPS), together known as biofilm. The interaction between disinfectants and EPS leads to the transport limitation of disinfectants in biofilms and their destruction helps microorganisms embedded in EPS to re-grow. The purpose of this study was to investigate the role of biofilm EPS on the disinfection of microorganisms. In this study, strains from an opportunistic pathogen, Pseudomonas aeruginosa (both wild type and mutant strains) with different EPS secretion capabilities were tested to monitor the role of EPS on the susceptibility of bacteria to three disinfectants (chlorine, chloramines, and chlorine dioxide). Reaction kinetics and consumption rates of disinfectants with EPS were observed. The results indicated that biofilm EPS reacted with disinfectants and decreased the susceptibility of bacteria cells. ENVR 392 Silver as a sustainable biocide J. R. Ellis1,2, [email protected] 1Senior Technology Consultant, The Silver Institute, Washington, DC, United States, 2Project Administrator, The Silver Research Consortium, Durham, NC, United States Silver in the form of bulk metal, metal particles or dispersions of both soluble and insoluble compounds has been used since ancient times as a biocide. Its effectiveness against microorganisms is in the order of parts per million by weight. It is generally harmless to mammals, and because of its affinity to ambient sulfur and to other ligands is of very low toxicity to other life forms and is environmentally benign. Silver has long been used for water purification and is now increasingly being used on medical devices and to provide inhospitable surfaces for bacteria and viruses in hospitals and in food preparation areas. Appliances such as refrigerators and washing machines are also using silver in an effort to control bacteria. Preparations involving biocidal silver are long-lasting, essentially harmless to the environment, and are cost effective. This review of the literature, commercial applications, and ongoing research is designed to educate the public and the scientific community about the many uses of antimicrobial silver and the advantages of using the metal and its compounds in efforts to obtain antimicrobial activity with minimal damage to the environment. ENVR 393 Novel nanostructure-based methods for highly sensitive in-situ detection of heavy metal ions in drinking water

S. Hong, [email protected], S. Lee, [email protected], Y. I. Yang, [email protected], H. D. Song, [email protected], and J. Yi, [email protected] School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Seoul, Republic of Korea Highly sensitive and selective methods for the detection and in-situ analysis of heavy metal ions in drinking water were proposed, based on the selective complexation of the metal ions via the proof of concepts using receptors and excitation of surface plasmon coupling in metallic nanostructures. The resulting complexation between target metal ions with receptors then derives the changes in the refractive index of metallic nanostructures, leading to significant changes in optical responses. Importantly, the limit of detection of these methods for Hg2+, Pb2+, Cu2+, and AsV ions in drinking water is 10 to 100 times more sensitive than other detection methods as well EPA regulation levels. In addition to the fast response in real-time analyses, they can be used to selectively detect the heavy metal ions without any interference in the presence of other divalent metal ions. ENVR 394 Erzion interpretation of Oriani, SPAWAR, our IPRIM and Baranov results by erzioatom introduction Y. N. Bazhutov, [email protected] Russian Academy of Science, Pushkov Terrestrial Magnetism, Ionosphere and Radiowave Propagation Institute (IZMIRAN), Troitsk, Moscow region, Russian Federation To explain Oriani & SPAWAR experimental results in CR-39 films and also our abnormal experimental results received at the electrolysis with gas discharge on the anode in IPRIM it was proposed their Erzion model (EM) interpretation. In framework of EM nuclei of the hydrogen (in Oriani & SPAWAR case) or oxygen (in IPRIM case), being Enions carriers, dump Enions inside of the electrode during the electrolysis where they are converted into neutral Erzions with large energy up to ; 1MeV, leaving a cell outside. Neutral Erzion in organic material of CR-39 films (in Oriani & SPAWAR case) or in organic composition of scintillator detector (in IPRIM case) on the nuclei of group (H,C,N,O) creates catalytic Erzion-nuclear chain of exothermic reactions. To explain by EM Baranov results of Bi212 generation from Bi209 nuclei it is proposed at first the creation of alone neutral Erzioatom (Triton-Erzion - {-,H3}). Bond energy of such Triton-Erzion ;100 keV and its size - R;10 fm. In the reaction Bi209 + {-,H3} = Bi212 + 0 + 7.6 MeV the transmutation of Bi209 to Bi212 is running. The triplet tracks observed earlier in our IPRIM experiment in photo emulsions and later in CR-39 films in SPAWAR experiment can be also explained by Triton-Erzion creation and its nuclear reaction with HCNO nuclei where can be produced up to 6 daughter light nuclei (n, p, He4 ...) with energy up to 20 MeV. The same explanation is for observation of high energy neutrons and -particles. ENVR 395

Solubilization of organotin compound in surfactant solutions in single and mixed oils S. Damrongsiri1,2, [email protected], C. Tongcumpou1,2,3, P. Weschayanwiwat1,2, and D. A. Sabatini4. 1International Postgraduate Programs in Environmental Management, Chulalongkorn University, Bangkok, Thailand, 2 National Center of Excellence for Environmental and Hazardous Waste Management (NCE-EHWM), Chulalongkorn University, Bangkok, Thailand, 3 Environmental Research Institute, Chulalongkorn University, Bangkok, Thailand, 4 School of Civil Engineering and Environmental Science, The University of Oklahoma, Oklahoma, United States Enhanced removal via surfactant solubilization is considered a potential method for remediation of organometallic cpompound. However, the solubilization process of the organometallic compounds needs to be more understood. Dibutyltin dichloride (DBT) was selected for this study. The synergistic effect of DBT solubilization in the presence of perchloethylene (PCE) was also determined. The results indicate that PCE was solubilized in the core for both single and mixed systems. While DBT tended to be solubilized only near the surface of micelle in the single oil system, the solubilization of DBT was found to increase in the mixture with PCE. This may be because when the PCE were solubilized in the core of micelle they facilitated the solubilization of DBT. From this study it may be concluded that DBT behaves similarly to polar oil such as dodecanol. Thus, the solubilization of organometallic may be considered analogous to a general organic compound. ENVR 396 Desorption behavior of toxic tributyltin from sandy clay loam soil in a presence of sodium dihexyl sulfosuccinate L. Mathurasa1,2, [email protected], C. Tongcumpou1,2,3, D. A. Sabatini4, and E. Luepromchai1,2,5. 1International Postgraduate Programs in Environmental Management, Chulalongkorn University, Bangkok, Thailand, 2 National Center of Excellence for Environmental and Hazardous Waste Management (NCE-EHWM), Chulalongkorn University, Bangkok, Thailand, 3 Environmental Research Institute, Chulalongkorn University, Bangkok, Thailand, 4 School of Civil Engineering and Environmental Science, University of Oklahoma, Oklahoma, United States, 5Department of Microbiology, Chulalongkorn University, Bangkok, Thailand This research aimed to investigate desorption behavior of high concentration tributyltin (TBT) from sandy clay loam soil in a presence of anionic surfactant; sodium dihexyl sulfosuccinate (SDHS). The experiment was carried out in batch. The pH of all tested conditions was 5.5-6.0. The adsorption isotherm of TBT onto soil was linear over 0.1 to 1 mgSn/ml. With surfactant, the desorption equlibria was reached much earlier than using water. At sub-CMC, desorption of TBT was found to decrease with the increased concentrations of SDHS. It may cause by

adsolubilization which was able to trap TBT onto soil surface. At supra-CMC, the function of surfactant's concentration on the amount of desorbed TBT was linear. In comparing with desorption without surfactant, TBT was found to be desorbed more than the system with surfactant at sub-CMC. These could predict the phase of TBT in post-flushing, consequently useful to estimate the bioavailability to soil bacteria. ENVR 397 Study of the electric explosion of titanium foils in uranium salts L. I. Urutskoev1,2, [email protected], and D. V. Filippov1,2, [email protected] 1 Moscow State University of Printing Arts, Moscow, Russian Federation, 2 RECOM, National Research Center "Kurchatov Institute," Moscow, Russian Federation The results of experiments on electroexplosion titanic foil in water solutions of salts of uranium are presented. The experiments was carried out as with enriched as with natural uranium. It is shown, that as a result of electroexplosion occurs appreciable (to 20%) distortion of an initial isotope parity of uranium. In the most solution parts, observable isotope distortion occurs in favour of enrichment by 235U. At the instant of electric explosion, no induced uranium fission is observed and no fission neutrons are detected. Within 1­3 ms after the end of current pulse, gas counters filled with 3He detected some signals having, in all probability, electromagnetic origin. By means of Cs label and by methods by , , -spectrometry and mass-spectrometry it have been shown, that isotope distortion occurs at the expense of non-uniform "disappearance" of both isotopes from a solution, giving rise to "enrichment effect". Isotope distortion leads to infringement of the 234Th secular equilibrium in the uranyl solution. The most pronounced disturbance of the secular equilibrium was observed in "lower" samples, and subsequently the equilibrium was restored with the period T = 24.5 days. In the "upper" samples, the 234Th equilibrium was disturbed to a much lesser extent and the time variation was almost missing. The equilibrium infringement between the 234Th and 234mPa, i.e. within the proper thorium decay chain, was observed also. In some experiments, -measurements of the "upper" samples revealed disturbance of the equilibrium between the 234Th 92.5 keV doublet and the 1001 keV -line of its daughter product, 234mPa. The assumption about course of low-energy nuclear reactions at the moment of electroexplosion is suggested. ENVR 398 Investigation on the electrocatalytic characteristics of SnO2 electrodes with nanocoating prepared by sol-gel method

J. Liu, [email protected], and Y. Feng. State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, Heilongjiang, China SnO2 electrodes have many advantages in the degradation of toxic or biorefractory organic wastewater, and SnO2 is a kind of anode material which has the potential to be widely used. In order to enhance the electrocatalytic characteristics of TiSnO2 electrodes, a type of electrocatalytic electrode with nanocoating was prepared by sol-gel method and thermal oxidation technique. With phenol as the model pollutant, the electrochemical degradation efficiencies of electrodes with nanocoating and non-nanocoating were investigated. It was demonstrated that the electrodes with nanocoating have higher efficiency than that of electrodes with non-nanocoating. The degradation time was decreased 33.3% for the same amount of phenol's degradation. The crystal structure of surface coating, the micrograph of electrode surface and the chemical environment of Sn and Sb in the electrode surface were analyzed with the help of XRD, SEM and XPS. The results showed that the surface of electrode was mainly SnO2 crystal with rutile structure and that much adsorbed oxygen in nanocoating was the dominant factor for enhancing the electrocatalytic characteristics. ENVR 399 Total degradation of trinitroaromatic explosives by catalytic oxidation with FeIII-TAML and H2O2 S. Kundu, [email protected], A. Chanda, S. K. Khetan, and T. J. Collins. Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, United States Trinitroaromatic explosives suchas 2,4,6-Trinitrotoluene (TNT), 1,3,5trinitrobenzene (TNB) and 2,4,6-trinitrophenol(TNP) are electron deficient oxidation resistant molecules. These toxic compounds are soil and groundwater contaminants and present hazards to human health and environment. There is a need for a sustainable method for degradation of nitroaromatic explosives. Methods for the green and efficient catalytic oxidation process of trinitroaromatics in water will be presented. The oxidative resistance of TNT and TNB can be overcome by forming Meisenheimer complexes in basic solution in the presence of a cationic surfactant, such as CTAB. On treatment with FeIII-TAML/H2O2, these complexes degrade into small aliphatic acids and minerals. A facile oxidative degradation of TNP has been achieved by treatment with FeIII-TAML/H2O2 at pH 6.5­7 without surfactants. Several intermediate compounds have been identified and the degradation paths have been traced. Results of mineralization by TOC and IC analysis, detoxification by Microtox assay will be presented. ENVR 400

Photochemical disinfection of pathogens: Role of bacterial extracellular polymeric substances (EPS) coverage in systems with nitrate A. S. Gong, [email protected], C. Lanzl, D. M. Cwiertny, and S. L. Walker. Department of Chemical and Environmental Engineering, University of California, Riverside, Riverside, California, United States Photochemical batch experiments were used to investigate the ability of hydroxyl radicals (OH·) generated from the photolysis of nitrate to facilitate E. coli kill. A solar simulator was utilized to determine relative rates of E. coli die-off under a range of aquatic chemical conditions. The effectiveness of hydroxyl radicals (OH·) in promoting E. coli die-off as a function of EPS coverage, nitrate concentration, and wavelength were investigated. Specifically, various amounts of EPS have been removed from cell surfaces by sonication prior to the disinfection. Experiments have revealed rates of E. coli die-off were enhanced in the presence of nitrate, indicating the role of nitrate as an indirect photochemical sensitizer. The rate also was found to increase with increasing sonication times, which enhances EPS removal. When more EPS were removed, lower level of surface polymers remain surrounding the cells, the blocking effect of EPS may be lost, leading to greater disinfection. ENVR 401 Toxicity of disinfection by-product intermediates associated with the reaction of haloamines and formaldehyde Y. Komaki1,3, [email protected], S. Kimura1,3, J. Pals2,3, E. D. Wagner2,3, M. J. Plewa2,3, and B. J. Marinas1,3. 1Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 2Department of Crop Sciences, University of Illinois at UrbanaChampaign, Urbana, IL, United States, 3Center of Advanced Materials for the Purification of Water with Systems, University of Illinois at Urbana-Champaign, Urbana, IL, United States Disinfection byproducts (DBPs) form as a consequence of reactions between disinfectants and background constituents in water. The cytotoxicity and genotoxicity of various groups of DBPs has been evaluated with biological methods designed to develop consistent databases. However, such assays have mainly focused on assessing the cyto/genotoxicity of single pure chemicals which might not represent more realistic exposure conditions involving complex mixtures of DBPs and intermediate compounds involved in their formation. Our study attempts to elucidate the combined toxicity of chemical pathways involving DBPs and key intermediates, the latter group never considered before because they are not present in samples treated to quench the disinfectant residual for preservation. We specifically examine the toxicity of formaldehyde and other DBPs and intermediate compounds formed from formaldehyde and haloamines. The cytotoxicity and genotoxicity of compounds associated with the reactions initiated by haloamines and formaldehyde is assessed using mammalian cells.

ENVR 402 Potentiometric detection of iron nanoparticles Z. Shi, [email protected], J. T. Nurmi, R. L. Johnson, and P. G. Tratnyek, [email protected] Division of Environmental and Biomolecular Systems, Oregon Health & Science University, Beaverton, OR, United States Assessing the results of injecting nano zero-valent iron (nZVI) into the subsurface for groundwater remediation currently relies heavily on measuring the oxidationreduction potential (i.e., ORP) of water samples. However, the significance of such measurements is unclear because the electrochemistry of potentiometric measurements on the target materials (i.e. suspensions of highly reactive, variably aggregated, surfactant-coated, Fe(0)-core Fe(II)oxide-shell, 20-60 nm particles) has never been investigated. We hypothesize that the electrode response is a mixed potential dominated by dissolved Fe(II) species but also includes some direct contribution of the particles. Dissolved hydrogen--which is abundant due to reduction of the medium by Fe(0)--may also contribute to the mixed potential, depending on the condition of the working electrode. The corresponding exchange currents are strongly influenced by pH, the concentration of oxidants that stimulate dissolution of the Fe(0), the degree of aggregation of the nanoparticles, and the concentrations of additives to control the particle aggregation. ENVR 403 Dechlorination of trichloroethylene and 2,4-dichlorophenol by Fe/TiO2 nanocomposite materials under anoxic conditions P. Ganesh, and R.-A. Doong, [email protected] Department of Biomedical Engineering and Evironmental Sciences, National Tsing Hua University, Hsinchu, Taiwan Republic of China The simultaneous removal of priority pollutants by nanocomposites materials has received much attention. In this study, the trichlorothylene (TCE) and 2,4dichlorophenol (DCP) were removed by Fe(0)/TiO2 nanocomposite under anerobic conditions in the absence and presence of UV light at 365 nm. Fe0/TiO2 nanocomposite was synthesized by a novel and simple route using PEG and NaBH4 as the cross-linker and reducing agent, respectively. Electron probe microanalysis elemental maps showed thatthe distribution of iron and TiO2 inside nanocomposite was uniform. The dechlorination of TCE and DCP by Fe(0)/TiO2 followed the pseudo-first-order rate equation and rate constant (kobs) for TCE and DCP dechlorination was 1.3×10-2 and 1.0´10-2 h-1, respectively, which are more efficient than nanoscale Fe. The effect of various quinone compounds including lawson, benzoquinone, AQDS and naphthoquinone on dechlorination of TCE was invesrigated. Naphthoquinone showed the highest rate constant with kobs of 5.9 ×10-2 h-1. Although the dechlorination efficiency and rate of DCP by Fe/TiO2 was slower than that of TCE, the illumination of UV light at 365 can significant

enhance the removal efficiency of DCP by Fe/TiO2. However, only DCP can be photodegraded by Fe/TiO2 within 2 h. The relationship between dechlorination and photodegradtion was further discussed. ENVR 404 Study on the extracellular electron transport in the dissimilatory metal oxides reduction H. Li, [email protected], and L. Zhou, [email protected] State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Beijing, Beijing, China To study the extracellular electron transport process through which electrons can be transported from metal oxides to the cells, two experiment systems were established: traditional anaerobic biochemical cultivation system in which Fe(OH)3 particles were reduced by Geobacter metallireducens and novel microbial fuel cell system,the following results are obtained: (1) Chelators can accelerate the reduction of metal oxides through chelation of the metal oxides; (2) Electron shuttles can increase the rate of reduction by transporting the electrons between microorganisms and metal oxide particles; (3) The reduction of metal oxides by direct attachment involves biofilm formation, and biofilm formation always takes a long period of time; (4) After the biofilm becomes mature, it will affect the diffusion and reaction inside the film, thus weakening the effect of electron shuttles and metal chelators, then the reduction of metal oxides take place mostly by direct contact. Keywords: dissimilatory iron reduction, electron transport, microbial fuel cell, electron shuttle, biofilm ENVR 405 Bifunctional composites Fe(0)/D201 for effective elimination of Arsenite through simultaneous oxidation and adsorption Q. Du, [email protected], and W. Zhang, [email protected] State Key Laboratory of Pollution Control and Resources Reuse, Nanjing University, Nanjing, China Bifunctional Fe(0)/D201 composites are successfully developed by immobilize nZVI particles onto an anion-exchange resin D201. The composites are characterized by SEM-EDS, TEM, and XRD. The "bifunctional" means that the composites possess synergy of the catalysis oxidation ability of Fe(0)+H2O2 for As(III) to As(V) and the adsorption performance of D201 and fresh formed Fe2O3 for As(V). Experimental results show that the Fe(0)/D201 composites can oxidize higher toxic As(III) to lower toxic As(V) with high efficiency at ambient conditions and without the catalysis of noble metals. At the same time, As(V) is effectively removed by adsorption onto the surface of composites. Additionally, As(V) can be easily desorbed from the composites by NaOH solution. The bifunctional

composites are expected to have significant applications in treating water contamination. ENVR 406 Iron and manganese species distribution in the Black Sea: Importance of complexed forms in the redox zone structure formation S. Pakhomova, [email protected] P.P. Shirshov Institute of Oceanology RAS, Moscow, Russian Federation Distribution of different species of iron and manganese (valent, complexed, dissolved, colloidal, and suspended) were studied in NE and SW Black Sea. It was found that iron bound in stable complexes with organic matter amount up to 98% of total dissolvable iron in the Black Sea with highest concentrations (up to 2 uM) in upper 50 m, where its distribution can be determined by river run-off and metabolism of organisms. It seems that bound iron does not play any important role for processes in the redox zone. Mn bound in stable complexes with hypothetical P-containing compounds or organic matter is observed in the redox zones in significant (up to 5 uM, average: 0.5-1.0 uM) concentrations and is likely present as Mn(III), an intermediate product of Mn(II) oxidation. Bound Mn plays an important role in processes in the redox zone both as an oxidant and as a complexing agent. ENVR 407 Quantifying the effect of dissimilatory iron reduction on bulk electrical properties: Does iron reduction increase electrical conductivity? A. B. Regberg1, [email protected], K. Singha1, D. R. Bond2, Q. Zheng3, F. Picardal3, E. E. Roden4, and S. L. Brantley1. 1Department of Geosciences, Pennsylvania State University, University Park, Pennsylvania, United States, 2 Department of Microbiology, University od Minnesota, St. Paul, MN, United States, 3School of Public and Environmental Affairs, Indiana University, Bloomington, IN, United States, 4Department of Geology and Geophysics, University of Wisconsin, Madison, WI, United States We demonstrate that dissimilatory iron reduction rates are measurable as changes in electrical conductivity. In batch experiments, reaction rates calculated from geophysical and geochemical changes were within 25% of each other. This relationship extends to systems involving porous media, but may be obscured by microbial activity. In flow-through reactors a three-fold increase in electrical conductivity (0.02 S/m ­ 0.06 S/m) was recorded over 10's of cm. after 11 weeks. The abiotic addition and sorption of Fe(II) only accounts for 1/15 of this signal. However, models based on percolation theory indicate that biofilms 25-33 times more conductive than pore fluid may account for the measured conductivity increase. These models are supported by preliminary data from electrochemical experiments demonstrating a thousand-fold increase in electrical conductivity as

biofilms form. The presence of electron shuttles, pH gradients, extra-cellular DNA and or microbial nano-wires may affect biofilm electrical conductivity. ENVR 408 Preparation and reactivity assessment of polymer-supported nanoscale zerovalent iron for nitrate removal Z. Jiang, [email protected], and W. Zhang, [email protected] State Key Laboratory of Pollution Control and Resources Reuse, Nanjing University, Nanjing, Jiangsu, China A novel hybrid polymer, namely D201-Fe(0), is fabricated for enhanced removal of nitrate in water by immobilized nanoscale iron particles into a porous polymeric anion exchanger D201. D201-Fe(0) is characterized by SEM, TEM, and XRD. The zerovalent iron is adjusted and concentrated in the outer layer of the anion exchanger as core-shell structure in nanoscale. The kinetics of nitrate removal by D201-Fe(0) present that the process included ion exchanging and reduction simultaneously. The effect of pH indicates that the stability and reactivity of D201-Fe(0) can be maintained in the range of pH 3-7. The results show that, when the concentration of nitrate solution increases or the content of Fe in hybrid polymer decreases, the utilization efficiency of zerovalent iron in D201-Fe(0) increased, but the proportion of reduction in nitrate removal decreases. Both polymer and iron can be recovered and reused by ion exchanging and reducing reactions. ENVR 409 Uraninite reoxidation by Fe(III)-(Hydr)oxides: Thermodynamic and kinetic considerations M. Issarangkun1, [email protected], N. F. Spycher2, B. M. Peyton3, R. K. Sani4, B. Stweart3, and T. R. Ginn1. 1Department of Civil and Environmental Engineering, University of California, Davis, Davis, California, United States, 2 Earth Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, United States, 3Departmento of Chemical and Biological Engineering, Montana State University, Bozeman, Montana, United States, 4Department of Chemical and Biological Engineering, South Dakota School of Mines and Technology, Rapid City, South Dakota, United States Uranium contamination in groundwater is a concern because of the chemical toxicity and the volume of polluted subsurface media at many U.S. Department of Energy sites. One potential option for immobilizing uranium from groundwater is in situ precipitation under enzymatically catalyzed reaction by sulfate reducing bacteria (SRB). This is typically done by amending groundwater with an organic electron donor to stimulate SRB, reducing soluble U(VI) and precipitating it as UO2. However, it has been shown that the precipitated uranium can re-oxidize in the presence of Fe(III)-(hydr)oxide minerals once the electron donor is

exhausted. Multi-component biogeochemical simulations (using PHREEQCII and TOUGHREACT) are used to evaluate thermodynamic and kinetic constraints affecting uranium reduction and the subsequent onset of re-oxidation, including biotic and abiotic effects. The effect of nanoscale particle size on the solubility of biogenic UO2 is evaluated and taken into account to determine biogenic UO2 dissolution and chemical fate. For ;3nm particles, the calculated UO2 solubility increases by 3 orders of magnitude compared to bulk uraninite, and agrees closely with reported solubility values for amorphous UO2. It is also shown that Fe(III) oxidizes sulfide preferentially to biogenic UO2. As a result, the relative rates of sulfide and UO2 oxidation by Fe(III) play a key factor on rates and extent of UO2 reoxidizes or not. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering Fe(II) in solution and increasing the potential for UO2 reoxidation. Simulations include formation of U(VI) carbonate and calcium-carbonate complexes and show that the dominance of these species is enhanced by carbonate produced by the degradation of the organic electron donor used for bioreduction. ENVR 410 Influence of sorption on reactions of dichloroacetamide herbicide safeners with iron oxide-associated Fe(II) J. D. Sivey, [email protected], and A. L. Roberts. Department of Geography and Environmental Engineering, Johns Hopkins Univeristy, Baltimore, MD, United States Dichloroacetamide safeners of the form Cl2CHC(=O)NR2 are neutral organic compounds commonly included in herbicide formulations to protect crop plants from the toxic effects of herbicides. We examined the reactivity of three safeners and ten structural analogs in suspensions of Fe(II) and goethite. Analysis of reaction products indicates each safener can undergo stepwise hydrogenolysis (replacement of chlorine with hydrogen) in suspensions at near-neutral pH. Product formation rates were monitored and several structure-reactivity trends are evident: (1) the R=phenyl analog is 3x more reactive than R=cyclohexyl; (2) the R=allyl analog is 10x more reactive than R=propyl; and (3) hydrogenolysis rates increased with the length of the R=alkyl analogs (ethyl < n-propyl < n-butyl < n-pentyl < n-hexyl) and spans over two orders of magnitude. Noting that the redox-active center (a dichloro-carbon) is uniform for all compounds, we posit that R-groups strongly influence reaction rates by promoting sorption interactions near reactive surface sites. ENVR 411 Electrochemical production, fate and transport, and relative toxicity or dioxins and furans: A case study from Midland, Michigan

K. Ritter, [email protected], D. Allen, and M. Carney. Stratus Consulting, Boulder, Colorado, United States Polychlorinated dibenzodioxins and dibenzofurans, dioxins and furans, accumulate in the environment and are toxic at low concentrations. Effects in animals and humans include weight loss, skin lesions, immunotoxicity, reproductive effects, and death. Specific dioxin and furan congeners have different relative toxicities, reflected by the World Health Organization (WHO) toxicity equivalent factors (TEFs). Dioxins and furans have been released as inadvertent by-products of industrial processes, including incineration, pulp and paper production, and electrochemical production of organochlorine chemicals. Least is known about the latter process. Their fate and transport in the environment is often assumed to be controlled by preferential association with organic-rich clay grain size fractions. Here we present emerging results from a case study, a chemical manufacturing facility in Midland, Michigan. The electrochemical processes involved in their production; grain size distribution and their fate and transport; and findings that may question their WHO-assigned relative toxicities are discussed. ENVR 412 Polymerization studies of metallic solutions O. Coskuner1,2, and J. Cavazos1, [email protected] 1Department of Chemistry, The University of Texas at San Antonio, San Antonio, Texas, United States, 2Computational Chemistry Group, National Institute of Standards and Technology, Gaithersburg, Maryland, United States Aqueous transition metal ions play important roles in diverse areas, such as environmental chemistry, geochemistry, nanotechnology, and medicinal chemistry. One of the important aspects in these solutions is the water dissociation mechanism, which is a rare event and impacts the hydration structure of metal ions. In addition, polymetallic structure studies in aqueous solution are more challenging. Here, we present the hydration structure of trivalent aluminum (Al) and its molecular mechanism in the formation of polyaluminum species in aqueous solution for various pH values. In fact, the structure of Al3+ for low and high pH values is known to be octahedron and tetrahedron structures, respectively. However, its structure for environmentally relevant pH values has been debated. We demonstrate our studies on single Al3+ ion and polyaluminum species in aqueous solution performed using CarParrinello molecular dynamics simulations with transition path sampling calculations. ENVR 413 Effects of hydrology and macrophytes on iron cycling in an intertidal Georgia salt marsh

C. J. Dean, [email protected], J. S. Beckler, and M. Taillefert. Department of Earth and Atmospheric Sciences, The Georgia Institute of Technology, Atlanta, GA, United States The flux of nutrients in intertidal salt marsh sediments can control primary productivity, carbon remineralization, and coastal processes on a larger scale. While iron oxides scavenge phosphate near the sediment surface, reducing conditions regulated by microbial sulfate reduction can redissolve oxides and release phosphate. This study investigates iron/phosphate interactions based on different hydrologically mediated redox environments and compares them with the effects of radial oxygenation by vascular macrophytes. Results illustrate that macrophytes have a small influence on redox conditions compared to controls exerted by hydrodynamic gradients and tidal cycling. Flat marsh areas are subjected to low hydrodynamic gradients that facilitate formation of reduced environments dominated by sulfate reduction and the release of iron and phosphate into surface waters. Tidal creeks are subjected to higher hydrodynamic gradients, are more oxidized, and tend to accumulate phosphate and iron. These findings suggest that a holistic approach encompassing hydrological factors is necessary to study redox processes in salt marsh sediments. ENVR 414 Rates and mechanisms of iron(II) sulfides oxidation by dissolved oxygen Y. Bi, [email protected], S. P. Hyun, and K. Hayes. Department of Civil and Environmental Engineering, University of Michigan, Ann Arbor, Michigan, United States Redox conditions have a strong impact on the mobility of a redox-sensitive nuclide uranium. Field-scale remediation studies at uranium contaminated Department of Energy sites have focused on biological reduction of uranium to its tetravalent oxidation state so as to precipitate as sparingly soluble solids under reducing environments. However, from a long term perspective, the U(IV) solids so formed may eventually be exposed to oxidizing environments. In this work, the impact of iron(II) sulfide minerals on the oxidation kinetics of U(IV) solid uraninite was experimentally studied to investigate their role in slowing the oxidation of uraninite when exposed to oxidizing environments. Oxidation kinetics of iron(II) sulfides synthesized under simulated sulfate reducing conditions were measured in a batch reactor under controlled atmospheric conditions as a function of pH and dissolved oxygen concentration. Both the aqueous and solid phase oxidation products were analyzed over time to assess the oxidation rates for different types of iron sulfides. The results indicate that the relative oxidation rates and oxidation products are highly dependent on the solution conditions. The results are also expected to contribute to a better understanding of S and Fe cycling under fluctuating redox conditions, as well as the fate and transport of U in natural and engineered environments.

ENVR 415 Arsenic partitioning in redox gradients: TXRF study of diffusion-limited columns with controlled boundary conditions A. S. Vega, S. E. Acevedo, E. Leiva, G. E. Pizarro, and P. A. Pasten, [email protected] Department of Hydraulic and Environmental Engineering, Pontificia Universidad Catolica de Chile, Santiago, Chile The fate of arsenic in aqueous systems is controlled by its interactions with the redox chemistry of iron and sulfur species. Where redox gradients occur, sorption/desorption and precipitation/dissolution reactions involving iron and sulfur minerals determine the fate of arsenic. Since many arsenic-rich environments are characterized by sharp chemical gradients (e.g., oxic-anoxic interfaces in water and sediment columns), it has been challenging to characterize the interaction between the kinetics of chemical reactions of the AsFe-S system and diffusion-limited mass transport. We used TXRF (total reflection x-ray fluorescence), image analysis, and traditional wet chemistry techniques to characterize the fate of arsenic in a set of diffusion-limited laboratory columns filled with porous media and controlled boundary conditions. These techniques allowed us to provide a multi-element characterization of the aqueous and solid phase and to contrast it with the results of a thermodynamic equilibrium model. ENVR 416 Seasonal anoxia in an arsenic contaminated lake: Biological and chemical controls on arsenic release from sediments A. R. Keimowitz1, [email protected], B. J. Mailloux2, K. Wovkulich3, S. N. Chillrud3, J. Ross3, and J. Harkness1. 1Department of Chemistry, Vassar College, Poughkeepsie, NY, United States, 2Department of Earth and Environmental Sciences, Barnard College, New York, NY, United States, 3Department of Geochemistry, Lamont-Doherty Earth Observatory of Columbia University, Palisades, NY, United States Previous releases of arsenic from the Vineland Chemical Company Superfund site have contaminated the sediments of Union Lake (NJ). Monitoring during two summers indicates that anoxia in Union Lake is often transitory, possibly due to frequent overturning of the large, shallow lake. Therefore arsenic releases from the sediments are relatively minor: bottom water arsenic concentrations were <30 ppb, representing <5% of the dissolved arsenic content of the lake. Manganese concentrations increase prior to, and more appreciably than, increases in arsenic and iron concentrations, consistent with manganese acting as a redox buffer preventing large arsenic releases during transient anoxia. Putative microbial arsenic reductase genes (ArrA) were detected in water samples from before, during, and after anoxia and arsenic release. No statistical differences were observed between genes observed at 7.5 m depth but different times; the genes

observed at 4 m depth were significantly different than those observed at 7.5 m depth. ENVR 417 Quantum mechanical prediction of contaminant reactivity in groundwater: An example for hexamethylphosphoramide (HMPA) J. Blotevogel1, [email protected], T. Borch1, A. Mayeno2, and T. C. Sale3. 1Department of Soil and Crop Sciences, Colorado State University, Fort Collins, CO, United States, 2Department of Environmental & Radiological Health Sciences, Colorado State University, Fort Collins, CO, United States, 3 Department of Civil and Environmental Engineering, Colorado State University, Fort Collins, CO, United States For many groundwater contaminants, key properties that govern their fate in both natural environments and engineered remediation systems are often unknown. Thus, we have developed a predictive methodology based on density functional theory (DFT) that can be used to screen new and emerging contaminants such that natural attenuation processes, remediation approaches, degradation kinetics, and persistent intermediates can be identified. Redox mapping revealed that strong oxidants are needed to degrade the model contaminant HMPA, a mutagenic and possibly carcinogenic solvent which has been detected in groundwater in the US. The prediction of potential degradation pathways based on free energies of reaction showed that several competing degradation pathways can occur. Free energies of activation were determined to identify both the primary degradation pathway and persistent reaction products. The developed predictive methodology can be used to assess the environmental fate for any new and emerging contaminant and its transformation products. ENVR 418 Quantum-chemical simulation of the formation of As (IV) during the oxidation of arsenite G. V. Korshin1, [email protected], A. M. Kuznetsov2, and A. N. Maslii2. 1Civil and Environmental Engineering, University of Washington, Seattle, WA, United States, 2Technology, Division of Inorganic Chemistry, Kazan State Technological University, Kazan, Russian Federation Quantum-chemical (QC) modeling of the formation of carbonate complexes of As(III) and their interactions with hydroxyl radical were carried out using the GAUSSIAN 98 program package within the density functional theory (DFT). In agreement with the data of prior electrochemical experiments, QC modeling indicated the prevalence of relatively weak mono-carbonate complex of As(III) and its enhanced reactivity in interactions with hydroxyl-radical. These interaction cause the bound carbonate to exit the inner complexation shell (as carbon

dioxide leaving group) with simultaneous formation of As(IV) intermediates. These transient species readily undergo oxidation and/or disproportionation to form As(V) species. QC modeling also allows examining and comparing the activation energies and geometries of As(III) transformations that correspond to different pathways of its oxidation. ENVR 419 Acid mine drainage at two sites in Floyd County, Kentucky P. D. Thompson, [email protected], and T. L. Vierheller, [email protected] Department of Chemistry, Big Sandy Community and Technical College, Prestonsburg, Kentucky, United States Water samples were collected from two focus streams in Floyd County that have been impacted by acid mine drainage. Samples were also collected from two reference streams that have little or no current impact from acid mine drainage. Samples were sent to the Kentucky Geological Survey Laboratory and analyzed for thirty elements, of which twenty-two were detected. The focus streams were found to have high concentrations of aluminum, iron, manganese, and sulfur relative to the reference streams for most sampling events. The focus streams were also found to have low pH, high acidity, and the presence of sediments derived from acid mine drainage. ENVR 420 Redox/acid-base conditions and iron chemistry in marsh wetland soils, northeast China Y. Zou, [email protected], M. Jiang, X. Lu, and X. Yu. Northeast Institute of Geography and Agroecology, Chinese Academy of Sciences, Changchun, Jilin, China The Eh/pH conditions, dissolved Fe(II), Fe(III), and organic carbon (DOC) were examined through in-situ sampling of three typical marsh wetlands. The results showed that the Eh varied from -30 mV to 280 mV and pH from 6.0 to 8.5, with the greater Eh and smaller pH in the upper soil layers (0-20 cm) than that in the deeper layers (40-60 cm). The vertical distribution trend of dissolved Fe was the same with pH, because the negative effect of pH increment on Fe solubility was greater than the positive effect of Eh decrement with soil depth. Except abiotic conditions, microbial activities indirectly affect the redox status of dissolved Fe. The rich carbon content (DOC > 20 mg/L) in the upper layers enhanced the bioreduction of Fe(III) species, because the ratios of Fe(III)/Fe(II) did not decrease with soil depth, and there were significant positive correlations between DOC and dissolved Fe(II). ENVR 421

Discussing the role of natural organic matter as electron shuttle in the process of contaminant removal by metallic iron C. Noubactep, [email protected] Angewandte Geologie, Universität Göttingen, Goettingen, Lower Saxony, Germany The literature contains many contradictory findings regarding the aqueous behaviour of natural organic matter (NOM) in the presence of metallic iron (Fe0). NOM is independently considered as (i) a target contaminant or (ii) a ubiquitous species promoting or inhibiting the process of contaminant removal in Fe0/H2O systems. However, given that NOM serves as "electron mediator" or "electron shuttle", its promoting impacts should be evidenced in the process of contaminant reductive transformation, this has not been always the case. The objective of the present contribution is three fold: (i) theoretically analyse the Fe0/H2O system and discuss the impact of NOM on it, (ii) identify experimental conditions which are likely to enable reliable results, and (iii) review available results to identify bias that might have enabled contradiction of the hart fact, that NOM is an electron shuttle. ENVR 422 Occurrence and fate of human-used macrolide antibiotics in a small Mediterranean river (Arc River, Southern France) S. Chiron1, [email protected], J. Feirtosa-Felizzola1, and D. Vione2. 1Laboratoire Chimie Provence, Aix-Marseille Universities, Marseille, France, 2Analytical Chemistry Department, Torino University, Torino, Italy Monitoring of the macrolide antibiotics (MLs) clarithromycin (CLA) and roxithromycin (ROX) in the Arc River (Southern France) showed that these compounds are present in both water and sediment. Degradation in water would occur via the direct photolysis of the Fe(III)-MLs complexes. A photolysis model applied to the Fe(III)-clarithromycin complex in river water showed that a half-life of 10 days was predicted in May. Photoinduced degradation of MLs mainly implied changes in the structure of the aglycone, probably leading to their detoxification. The adsorption/transformation of CLA and ROX on the surface of three environmental subsurface sorbents (clay, iron (III) and manganese (IV) oxy-hydroxides) was also investigated. Adsorption probably occurred through a surface complexation mechanism and was accompanied by slow degradation of the selected MLs. Transformation proceeded through two parallel pathways: A major pathway was the hydrolysis of the cladinose sugar and a minor pathway was the N-dealkylation of the amino sugar. ENVR 423 Influence of redox conditions on DDE dechlorination in Palos Verdes Shelf, CA sediments

S. Qin1, [email protected], M. Reinhard1, G. Hopkins1, and R. P. Eganhouse2. 1 Stanford University, Department of Chemical and Environmental Engineering, Stanford, CA, United States, 2USGS, Reston, VA, United States Although DDT has been banned in the US since 1972, metabolites of DDT still contaminate sediments and biota in many places and remain an environmental concern. Recent studies on the Palos Verdes Shelf, CA have shown that under field conditions, parent DDT transformed rapidly (;0.5/yr) into DDE. DDE, in turn, is reductively dechlorinated more slowly (0.05/yr) into DDMU (1-chloro-2-[2chloro-1-(4-chlorophenyl)ethenyl]benzene). The environmental factors that control the rate of DDE dechlorination are poorly understood. To evaluate the impact of redox conditions on DDE dechlorination rates, we developed sulfate reducing and methanogenic microcosms using sediments from two contaminated sites at PVS. During four months of incubation, we observed DDE transformation into DDMU (18.4-46.2% of DDE) and further into DDNU (2.2-4.1% of DDE). Adding electron donor (a mixture of fatty acids) promoted sulfate reduction, hydrogen production and DDE transformation suggesting that hydrogen plays a key role in the dechlorination of DDE and its metabolites. ENVR 424 Cathodic Fenton degradation of 4,6-dinitro-o-cresol with nano-magnetite X. Zeng1, [email protected], K. Hanna2, and A. T. Lemley1. 1Graduate Field of Environmental Toxicology, Department of Fiber Science & Apparel Design, Cornell University, Ithaca, New York, United States, 2Laboratoire de Chimie Physique et Microbiologie pour l'Environnement, Université Henri Poincaré, Villers-les-Nancy, Lorraine, France The successful removal of 4,6-dinitro-o-cresol (DNOC) was reported using nanomagnetite as the iron source and cathodic Fenton treatment as the source of hydrogen peroxide. Operating conditions were optimized for DNOC initial concentrations, pH values and nano-magnetite quantities. The results showed that smaller DNOC initial concentration and lower pH led to faster degradation of DNOC. It was also observed that the amount of nano-magnetite affected the degradation rate at lower pH, while it had no influence at neutral pH. The results showed that homogeneous reactions dominated at lower pH and some direct electrolysis takes place at neutral pH, while contributions from heterogeneous reactions were not obvious under these experimental conditions. A model was developed to describe the degradation mechanism at the low pH, with an excellent fit to the experimental data. This is the first time that nano-magnetite was combined with cathodic Fenton, and it shows promise for the future. ENVR 425 Mössbauer study of Fe(II) sorbed on clay minerals

M. V. Schaefer, [email protected], C. A. Gorski, and M. M. Scherer. Department of Civil and Environmental Engineering, The University of Iowa, Iowa City, IA, United States Our group, as well as others, have shown that electron transfer occurs between sorbed Fe(II) and structural Fe(III) in Fe oxides and magnetite. It is unclear, however, whether a similar Fe(II)-Fe(III) electron transfer takes place for clay minerals. It is well known that structurally-bound Fe(II) in clay minerals can reduce many environmentally important contaminants, such as nitrobenzene, carbon tetrachloride, and polychlorinated alkanes, but little is known about the electron transfer process between the structural Fe(II) and contaminants. Some have suggested that structural Fe(II) electron transfer occurs via the clay basal surface, yet contaminants are not readily reduced by Fe(II) sorbed at basal surfaces. Here, we use the isotope selectivity of 57Fe Mössbauer spectroscopy to investigate the ability of aqueous or sorbed Fe(II) to reduce structural Fe(III) in oxidized clays. ENVR 426 Influence of magnetite stoichiometry on rates of microbial iron respiration T. Pasakarnis1, [email protected], M. McCormick2, G. Parkin1, and M. Scherer1. 1Department of Civil and Environmental Engineering, University of Iowa, Iowa City, Iowa, United States, 2Department of Biology, Hamilton College, Clinton, New York, United States Magnetite (Fe3O4) is a common form of iron in the environment, arising from biotic and abiotic reduction of iron oxides, and from oxidation of ferrous minerals and iron metal from natural and anthropogenic sources. We have recently shown that magnetite stoichiometry, as defined by the ratio of FeII to FeIII, controls both the extent of FeII uptake from solution and rates of nitrobenzene reduction. Dissimilatory iron reducing bacteria (DIRB) have been shown to reduce magnetite to ferrous hydroxyl carbonate, soluble FeII, and siderite, however, it is unclear whether or how magnetite stoichiometry will influence the rate of magnetite reduction by DIRB. Here we explore how magnetite stoichiometry influences the ability of DIRB to utilize magnetite as an electron acceptor, and whether electron transfer between DIRB and magnetite alters the stoichiometry of the magnetite particles. ENVR 427 Photo-Fenton reaction at neutral pH A. W. Vermilyea, and B. M. Voelker, [email protected] Department of Chemistry and Geochemistry, Colorado School of Mines, Golden, CO, United States

The photo-Fenton reaction, the oxidation of photoproduced Fe(II) by hydrogen peroxide, yields reactive oxidants that may degrade recalcitrant organic compounds in natural surface waters. In this work, we measured the rates of both the photo-Fenton reaction and OH production during irradiations of model Fe-DOM systems at pH 7.0. Use of benzene as a OH probe and nitrate photolysis as the OH source indicated that the yield of phenol from the reaction of benzene with OH was reduced in the presence of iron and DOM. Even when this reduction in yield was accounted for, the rate of OH production was much smaller than the rate of the photo-Fenton reaction, indicating that OH was not the only oxidant produced. However, the photo-Fenton reaction is still likely to be significant for contaminant degradation in circumneutral surface waters. ENVR 428 Effects of fluorescence quenching by iron and zinc on the colored dissolved organic matter pool in an urban watershed J. H. Goldman1,2, [email protected], J. A. Needoba1, and S. Rounds2. 1 Environmental and Biomolecular Systems, OHSU, Beaverton, OR, United States, 2Water Science Center, USGS, Portland, OR, United States Dissolved organic carbon (DOC) represents a significant carbon reservoir in all ecosystems, and recent advances in fluorescence spectroscopy can be used to quantify and characterize the colored dissolved organic matter (CDOM), a subset of the DOC pool. Organic matter can interact with metal ions to form organometal complexes, which can have a quenching effect on the fluorescence signature, causing uncertainties in interpreting the complex three-dimensional excitationemission matrices (EEMs). In the Portland, Oregon urban watershed zinc and iron are found in variable concentrations, 100nM to 5000nM, amongst the differing river basins due to groundwater and anthropogenic influences. This study identifies the impact of zinc and iron on the CDOM pool and its quenching capabilities on a range of samples with varying quantities and qualities of DOC. Quantification of changes in peak intensities and excitation/emission pairs, represented in the EEMs, demonstrates the quenching abilities of these metals on the natural organic matter. ENVR 429 Freeze-thaw effects on redox potential and dissolved iron in wetland soil solutions X. Yu1,2, [email protected], G. Wang1,2, [email protected], X. Lu1,2, [email protected], Y. Zou1, [email protected], and M. Jiang1, [email protected] 1Key Lab of Wetland Ecology and Environment, Northeast Institute of Geography and Agroecology, Chinese Academy of Sciences, Changchun, Jilin, China, 2Graduate University of Chinese Academy of Sciences, Beijing, China

The redox potential and dissolved iron responding to five freeze-thaw cycles in three typical wetland soil solutions (humus marsh soil, meadow marsh soil and meadow albic soil) of Sanjiang Plain, Northeast China, were studied throng insitu soil column simulation. Freeze-thaw treatments were performed by incubated the soil columns at -10 °C for 1 d and at 5 °C for 7 d. The results showed that 82.2% of the Eh values of freeze-thaw treated soil columns were greater than that of controls, which resulted from the inhibited reduction of Fe3+ species. The concentrations of Fe2+, Fe3+, and total dissolved iron (TFe) of the treatment soil columns were all smaller than that of controls. The concentrations of TFe were decreased from (0.62±0.08) mg·L-1 to (1.25±0.16) mg·L-1. And the freeze-thaw effects on redox potential and dissolved iron were more significant in the upper annular wetland soil layers than in the lower layers. ENVR 430 Characteristics and reactivity of atmospherically stable nanoscale zerovalent iron particles H.-S. Kim, [email protected], J.-Y. Ahn, K.-Y. Hwnag, and I. Hwang. School of Civil and Environmental Engineering, Pusan National University, Busan, Republic of Korea Shell layers of FeH2 NZVI (Nanoscale Zero-Valent Iron) particles (RNIP) were modified by a controlled air contact procedure to produce atmospherically stable NZVI particles. The shell-modified NZVI particles were resistant to rapid aerial oxidation when they were expose to air and were observed to have degradation efficiencies for TCE that were equivalent to about 80% of those of the pristine NZVI particles. The aging experiments for the shell-modified particles in the water and the air were conducted to investigate the role of the modified shell in the passivation/depassivation processes and in the NZVI reactivity. Instrumental analyses using TEM, XRD, XPS, and XANES showed that the predominant iron oxide on the shells of the modified NZVI particles was magnetite. NZVI particles aged in various conditions showed different mineralogical characteristics. Core/shell models of the shell-modified NZVI particles were proposed. ENVR 431 Use of organic redox mediators in the electrochemical characterization of the redox properties of natural organic matter and mineral phases M. Aeschbacher, [email protected], T. B. Hofstetter, R. P. Schwarzenbach, and M. Sander, [email protected] Department of Environmental Sciences, ETH Zurich, Zurich, Zurich, Switzerland Direct electrochemical characterization of the redox properties of `bulky' environmental phases such as natural organic matter and Fe-containing clay minerals is impeded by limited accessibility of the redox sites in these phases to working and redox electrodes. This study demonstrates how redox-active organic

compounds can be used as mediators between environmental phases and electrodes. Suitable mediators were identified by spectrophotometic assays and by catalytic peaks in cyclic voltammetry and chronocoulometry. The mediators presented span a wide range in standard reduction potential Eh0 and include the radicals diquat (Eh0= -0.36 V) and 2,2'-azino-bis[3-ethylbenzthiazoline-6sulphonic acid] (Eh0= +0.68 V) with pH-independent reduction potentials, and the redox dye dichlorophenol-indophenol (Eh0= +0.22 V at pH 7). Applications are presented including the chronocoulometric quantification of electron accepting and donating capacities of humic substances and iron-containing clays, and the determination of Eh-pH diagrams of oxidized and reduced humic acids by acidbase titration in the presence of small mediator concentrations. ENVR 432 Magnetite redox properties: Implications for biogeochemical reactivity C. A. Gorski1, [email protected], J. T. Nurmi2, P. G. Tratnyek2, T. B. Hofstetter3, M. Aeschbacher3, M. Sander3, and M. M. Scherer1. 1Department of Environmental Engineering and Science, University of Iowa, Iowa City, IA, United States, 2Division of Environmental and Biomolecular Systems, Oregon Health & Science University, Beaverton, OR, United States, 3Institute of Biogeochemistry and Pollutant Dynamics, Swiss Federal Institute of Technology (ETH), Zurich, Switzerland Magnetite (Fe3O4) is commonly found in the environment, and laboratory studies have shown it to be capable of reducing several environmental contaminants. Recent work by our group has demonstrated that the reactivity of magnetite with dissolved Fe2+ and nitroaromatics is strongly dependent upon particle stoichiometry (x = Fe2+/Fe3+). Here, we present measurements characterizing the magnetite redox potential (Eh) as a function of stoichiometry using two techniques: a powder disk electrode (PDE), where magnetite is packed into a junction between the electrode and the solution, and mediated electrochemical reduction and oxidation (MER and MEO, respectively), which utilizes soluble electron mediators that allow for electron transfer between suspended solids (magnetite) and the electrode. Electrochemical data indicates that Eh is related to the stoichiometry, with lower potentials observed for more reduced magnetites (higher x). Using the measured Eh values, we developed a quantitative structureactivity relationship (QSAR) to help predict nitroaromatic degradation rates by magnetite. ENVR 433 Photochemical phenol oxidation by humic substances K. S. Golanoski1, [email protected], Y. Zhang1, [email protected], R. DelVecchio2, [email protected], and N. V. Blough1, [email protected] 1Department of Chemistry and Biochemistry, University

of Maryland, College Park, MD, United States, 2Department of Earth System Science Interdisciplinary Center, University of Maryland, College Park, MD, United States The photochemical oxidation of phenols by humic substances has long been recognized and is now attributed primarily to their reaction with excited triplet states of the humic substances (eg, aromatic ketones). To test this idea, we have examined for a series of phenols the dependence of their initial rates of oxidation on phenol and dioxygen concentration for both unaltered and borohydride reduced Suwanee River Fulvic Acid (SRFA). A comparison between the initial rates of phenol oxidation and hydrogen peroxide production will also be presented. The results will be discussed within the context of a triplet versus charge transfer model. ENVR 434 Effect of phenols on the photochemical production of hydrogen peroxide from Suwannee River fulvic acid Y. Zhang1, [email protected], K. S. Golanoski1, R. DelVecchio2, and N. V. Blough1. 1Department of Chemistry, University of Maryland, College Park, Maryland, United States, 2Earth System Science Interdisciplinary, University of Maryland, College Park, Maryland, United States Hydrogen peroxide is found ubiquitously in the aquatic environment, where it is primarily formed via dismutation of O2- produced photochemically by a reductant within chromophoric dissolved organic matter. We have found that in the presence of Suwannee River Fulvic Acid (SRFA), the addition of phenol donors enhances the initial rate of the photochemical formation of H2O2 ,with the rate increasing linearly with donor concentration and following the order DMOP > TMP > 4MP. These results can be interpreted as due to the reduction of excited triplet states (e.g., aromatic ketones, quinones) by the phenol donor followed by electron transfer to O2, or alternatively to the reaction of the phenol donor with a excited donor acceptor pair (D+A-) to form DA-, thus preventing recombination and allowing A- to react with O2 to form O2- .The effect of SRFA reduction with sodium borohydride on the rate of H2O2 production will also be presented. ENVR 435 Coupled arsenotrophy in a photosynthetic hot spring biofilm from Mono Lake, California S. E. Hoeft1, [email protected], T. R. Kulp1, S. Han2, B. Lanoil2, J. F. Stolz3, R. S. Oremland1, and F. Wolfe-Simon4. 1Water Resources Division, U.S. Geological Survey, Menlo Park, CA, United States, 2Department of Biological Sciences, University of Alberta, Edmonton, AB, Canada, 3Department of Biological Sciences, Duquesne University, Pittsburgh, PA, United States, 4Department of

Earth and Planetary Sciences, Harvard University, Cambridge, MA, United States Arsenic is toxic to humans and most other forms of life. Despite its toxicity, certain microbes have evolved that can utilize arsenic oxyanions for energy generation. This can be achieved either by employing arsenite (As(III)) as an autotrophic electron donor or by using arsenate (As(V)) as a respiratory electron acceptor. We recently discovered light-dependent oxidation of As(III) to As(V) in naturally-occurring microbial biofilms in Mono Lake, California (1). Redpigmented biofilms grew prolifically on rock and cobble surfaces present under anoxic hot spring waters (;45oC) located on Paoha Island. Clonal libraries based on 16S rRNA gene sequences of these biofilms indicated a community dominated (;85%) by sequences from the Ectothiorhodospira genus that is comprised of photosynthetic bacteria. Functional genes for arsenate respiration (arrA), arsenic resistance (arsC) were detected in sequenced amplicons of extracted DNA. Scraped biofilm materials incubated under anaerobic conditions rapidly oxidized As(III) to As(V) in the light via anoxygenic photosynthesis, but could also readily reduce As(V) to As(III) in the dark at equivalent rates. Back labeling experiments with 73As(V) conducted in the presence of 1 mM As(III) showed that reduction to 73As(III) could also occur in the light, thereby demonstrating the co-occurrence of these two processes as an example of coupled arsenotrophy. Aerobic incubations of biofilm materials in the dark oxidized As(III) to As(V), although it was not clear if genes for arsenite oxidase (aoxB) were present. These results demonstrate a close linkage of these arsenic redox processes within these biofilms. (1) Kulp et al. 2008. Science. 321, 967970. ENVR 436 Oxidation of elemental mercury by Fenton reagent T. Liu1, [email protected], H. Zhang1, [email protected], and B. Gu2, [email protected] 1Department of Chemistry, Tennessee Tech University, Cookeville, TN, United States, 2Environmental Sciences, Oak Ridge National Laboratory, Oak Ridge, TN, United States Oxidation of elemental Hg(0) affects the fate of Hg in the environment. Hydroxyl free radical (·OH) is one of the most reactive environmental oxidants, whereas Fenton's reagent is an important source of ·OH in natural waters. We studied the oxidation of dissolved Hg(0) by the Fenton reagent (Fe(II) + H2O2) and found that Hg(0) can undergo rapid oxidation under dark conditions. We further studied the effects of pH, amount of the Fenton reagent, and the ratio of Fe(II):H2O2 on the oxidation. The reaction kinetics appeared to depend on pH with the highest oxidation rate occurring at pH about 2.7. The rate also depended on the ratio of Fe(II):H2O2 and concentrations of Fe(II) and H2O2 with an apparent zero-order kinetics observed at relatively high initial concentrations of Fe(II) and H2O2.

However, at relatively low concentrations, the oxidation was first-order followed by zero-order kinetics. ENVR 437 Bioreduction of poorly crystalline Fe(III)/Al(III)-hydroxide coprecipitates Y. T. Liu, [email protected], and D. Hesterberg. Department of Soil Science, North Carolina State University, Raleigh, NC, United States Natural Fe (hydr)oxides are usually substituted or coprecipitated with other cations, particularly Al, which is ubiquitous in soils and sediments. The objectives of this study were: (i) to quantify bioreducibility of Fe(III) from Al/Fe hydroxide coprecipitates (Al-FH) as affected by Al(III), and (ii) to depict local structure transformation during Al-FH bioreduction. Al-FHs with 0 to 75% Al/(Al+Fe) mole ratios were reduced using Shewanella putrefaciens CN32 with formate as the electron donor. Local coordination structures around central Fe in bioreduced solids were examined using x-ray absorption spectroscopy (XAS). During 36 dbioreduction, the HCl-extractable Fe(II) concentration and spectroscopic evidence suggested that the presence of Al would enhance the long-term reducibility of Fe(III) from Al-FHs due to the heterogenous surface sites provided by Al coprecipitates to retard Fe2+(aq) accumulation associated with Fe atoms. In other words, Al rendered particles more accessible to reactants and facilitated direct electron transitions between mineral surfaces and microbes. ENVR 438 Biochars from fast pyrolysis and gasification of switchgrass and corn stover C. E. Brewer1, [email protected], R. Unger2, and R. C. Brown1. 1Center for Sustainable Environmental Technologies, Iowa State University, Ames, IA, United States, 2Department of Agronomy, Iowa State University, Ames, IA, United States Seventeen chars with known production conditions were selected for chemical and physical characterization from fast pyrolysis and gasification of switchgrass and corn stover. Slow pyrolysis chars of the same feedstocks, as well as several hardwood chars, were included for comparison. The methods used to characterize the chars included proximate analysis, CHNS elemental analysis, BET surface area, higher heating value (HHV), particle density, photo-acoustic Fourier transform infrared spectroscopy (FTIR-PAS), cation exchange capacity (CEC), and quantitative 13C solid-state nuclear magnetic resonance (NMR) spectroscopy. Special attention was paid to the types of carbon and degree of aromaticity present in the char in relation to pyrolysis temperature. A follow-on soil incubation study was also conducted to relate char properties to soil fertility (plant-available nutrients, CEC, etc) responses.

ENVR 439 Biochars and soil humic surfactancy M. A. Chappell1, [email protected], J.-D. Mao2, L. S. Ford3, and C. L. Price1. 1U.S. Army Engineer Research & Development Center, Vicksburg, MS, United States, 2Dep. Chemistry, Old Dominion University, Norfolk, VA, United States, 3SpecPro, Inc., Huntsville, AL, United States Biochar amendments can impart favorable structural and fertility characteristics to soil, but can also be useful for studying some of the more esoteric properties of humics, such as solubility, chelation, and surfactancy. Previous studies showed that aromatic-rich humics stabilize nanoparticle dispersions, while more recently, we presented evidence suggesting that aromatic-rich humics showed diminished surfactancy with increased O-alkyl and O-alkyl C-O functional group content. Thus, we present detailed structural studies on the surfactive ability of low quality biochars, which in addition to aromatics, are expected to contain fatty acid groups, but limited in glycosidic-type groups. In particular, we characterize the size and shape of the aromatic clusters using solid-state 13C NMR techniques, including a long-range C-H dipolar dephasing method. Theoretical calculations of aromatic cluster size and geometry will be compared to experimental data collected from condensed standards. Aromatic descriptions will be compared to biochar dissolution and potential to stabilize nanosilver dispersions. ENVR 440 Overview of the pyrolysis platform for producing bio-oil and biochar D. A. Laird, [email protected] National Laboratory for Agriculture and the Environment, USDA, Agricultural Research Service, Ames, Iowa, United States Pyrolysis is a simple, inexpensive, and robust technology for transforming biomass into bio-oil, biochar, and syngas. Bio-oil can be used as a fuel in existing industrial boilers. Biochar can be used with existing infrastructure as a replacement for pulverized coal; however, use of biochar as a soil amendment results in significant environmental and agronomic benefits. Soil biochar applications have been shown to increase soil productivity by increasing nutrient and water use efficiency. Application of biochar to soils is a highly effective means of sequestering carbon because of the high stability of biochar carbon. Biochar adsorbs both nutrients and organic contaminants; hence the presence of biochar in soils is hypothesized to improve water quality. The robust nature of the pyrolysis combined with a distributed network of small pyrolysis plants is compatible with existing agriculture and forestry infrastructure. ENVR 441

Electricity generation using iron-reducing, haloalkaliphilic bacteria V. G. Paul1, [email protected], and M. R. Mormile1. 1Department of Biological Science, Missouri University of Science and Technology, Rolla, Missouri, United States, 2Department of Chemistry, Saint Louis University, St. Louis, Missouri, United States, 3Material Research Center, Missouri University of Science and Technology, Rolla, Missouri, United States Anaerobic, metal-reducing bacteria have been shown to transfer electrons obtained from organic compound oxidation to the surface of electrodes in a microbial fuel cell (MFC), thereby producing current. Such electron shunting ability has been identified in several species of bacteria. The present study used bacteria isolated from a saline, alkaline environment, Soap Lake, Washington, in an MFC. These samples were initially enriched for iron (III) reduction in batch cultures and the enrichments were used to inoculate the anode chamber of the MFC. Scanning electron microscopy showed the bacteria attached to a carbon cloth electrode. Current densities up to 12.5 mA/m2 were shown to be produced. The open circuit voltage was constant over several days, reaching up to ;1V. The MFC that was run with uninoculated media showed very little current which dropped within one day. Cyclic voltammetry experiments demonstrated that the bacteria made use of an electron mediator, methylene blue to enhance the transfer of electrons to the anode. Molecular characterization of the partial 16S rRNA gene and RFLP analysis showed that the bacterium responsible was a single species with a 97% similarity to the 16S rRNA gene of Halanaerobium sp. ENVR 442 Highly conductive textile electrodes for microbial fuel cells X. Xie1, [email protected], L. Hu2, M. Pasta2, C. S. Criddle1, and Y. Cui2. 1 Department of Civil and Environmental Engineering, Stanford University, Stanford, CA, United States, 2Department of Materials Science and Engineering, Stanford University, Stanford, CA, United States High performance microbial fuel cells (MFCs) require effective mechanical and electrical interaction between electrode surfaces and attached microbial biofilms. Three-dimensional porous electrodes with large-surface area offer an attractive means of achieving this objective. Here we report a novel porous electrode in which a conductive carbon nanotube (CNT) coating is applied to a commercial textile. The CNT-textile composite was evaluated as an anode in a MFC. The macroporous structure of textile allowed growth of biofilm inside the anode, increasing the active surface area for electron transfer. The CNT-textile composite outperformed a normal carbon cloth electrode, and appears promising for MFC applications. ENVR 443

OmcZ, a mobile, extracellular, c-type cytochrome that accumulates at the anode in current-producing biofilms of Geobacter sulfurreducens K. Inoue, [email protected], A. E. Franks, [email protected], K. P. Nevin, [email protected], and D. R. Lovley, [email protected] Microbiology, University of Massachusetts, Amherst, MA, United States The c-type cytochrome OmcZ is essential for optimal current production in Geobacter sulfurreducens. When cells grow with fumarate as the electron acceptor were treated with an antibody to OmcZ and a secondary gold-labeled antibody it was apparent with transmission electron microscopy that OmcZ was secreted outside of the cells. Immunogold labeling of ultrathin sections of currentproducing biofilms revealed that OmcZ was localized in the extracellular matrix and that OmcZ specifically accumulated at the graphite anode surface forming a dense layer of the cytochrome. A similar accumulation of OmcZ was not observed in biofilms grown on the same graphite material, but with fumarate as the electron acceptor. These results, coupled with the previously published finding that deleting the gene for OmcZ dramatically limits electron exchange with the anode, suggest that OmcZ plays an important role in facilitating electron transfer between the biofilm and the anode surface. ENVR 444 Various strategies to enhance electrical power production of a microbial fuel cell running on swine liquid manure D. Y. Martin1, [email protected], R. Hogue1, P. Dube1, R. Theriault2, S. Kaliaguine3, S. Garnier3, A. Levesque1, and T. Jeanne1. 1Research and Development Institute for the Agri-Environment (IRDA), Quebec, Quebec, Canada, 2Department of Soils and Agrifood Engineering, Laval University, Quebec, Quebec, Canada, 3Department of Chemical Engineering, Laval University, Quebec, Quebec, Canada This project is devoted to producing a microbial fuel cell running on swine liquid manure (MFClm) as fuel. To prevent clogging in tubing and cells, liquid fraction coming from centrifuged liquid manure is used. Four strategies have been investigated to enhance electrical power production. The first one involved the use of various support media to optimize surface area on which bacteria may develop. The second one implied the use of electrophylic bacteria species already identified in literature to inoculate MFC-lm. The third one was to enhance cathodic yield by coating nafion on cathode. The fourth one was to create a more efficient electrolytic bridge in using a cations exchange membrane and a light acid electrolyte between anode and cathode. Once integrated, these innovations have permitted to double MFClm open circuit voltage (OCV) from 495 mV to 1042 mV and to increase by an order of magnitude power output from 85 to 928 mW m-2.

ENVR 445 Air-cathode microbial fuel cell array for electrochemically active microbe screening H. Hou1, [email protected], L. Li2, P. de Figueiredo2,3, and A. Han1,4. 1 Department of Electrical and Computer Engineering, Texas A&M University, College Station, TX, United States, 2Department of Plant Pathology and Microbiology, Texas A&M University, College Station, TX, United States, 3 Department of Veterinary Pathobiology, Texas A&M University, College Station, TX, United States, 4Department of Biomedical Engineering, Texas A&M University, College Station, TX, United States Microbial fuel cells (MFCs) have recently generated great interests in the bioenergy community because of their potentials in powering varieties of devices and for wastewater treatment. Optimization of MFC designs, exploring more electrochemically active microbes (`electricigens'), and examining their optimum operating conditions are attractive ways to increase power generation and efficiencies of MFCs. High throughput parallel analysis will greatly accelerate these studies. Here we describe an air-cathode MFC array that consist of 24 miniaturized air-cathode MFC systems on a chip format. The 5 x 7.5 cm chip use oxygen in ambient air as electron acceptor and was used to conduct parallel screening of environmental microbes to find those with high electricity generation abilities. A screening of ;2,000 species from Summerville Lake (TX) and Brazos River (TX) successfully discovered three electricigen species that generated higher power than the reference strain Shewanella oneidensis MR-1. The screening result was confirmed with a conventional H-type MFC. ENVR 446 Determination of the internal energy of wastewater E. S. Henderson, [email protected], T. P. Curtis, and J. Dolfing. Department of Civil Engineering and Geosciences, Newcastle University, Newcastle-Upon Tyne, United Kingdom The wastewater industry is facing a paradigm shift, learning to view wastewater not as a waste stream which we need to dispose of, but as a resource from which to generate energy. It has long been assumed that the amount of energy in the wastewater relates directly to COD, being roughly equal to the amount of energy if the COD was all glucose or acetate, around 14kJ/gCOD . The industrial wastewater examined in this study, using an improved methodology of freeze drying samples to eliminate loss of volatiles, has around 22kJ/gCOD, far higher than previously estimated, or determined, whilst domestic wastewater tested has slightely below that expected. The size of the resource that wastewater presents is clearly both complex and variable, it is not necessarily well characterised by

the use of a COD measurement and glucose or acetate substitutions, a systematic evaluation into the energy contained in wastewaters is needed. ENVR 447 Comparison of C, Pt/C, Pd/C as cathodic oxygen reduction catalysts in microbial fuel cells Y. Feng, [email protected], X. Shi, [email protected], X. Wang, H. Lee, Q. Yang, and J. Liu. Department of Environment Engineering, State Key Laboratory of Urban Water Resource and Environment of Harbin University of Technology, Harbin, Heilongjiang, China C, Pt/C, Pd/C powders were used as cathodic catalysts for oxygen reduction in air cathode microbial fuel cells (MFCs). Pd/C catalyst got the better performance than Pt/C and C catalysts in alkaline conditions. Several pretreatments were tested and were proven that oxygen reduction efficiency can be further improved by simple pretreatment. After applying all those catalysts on air-cathodes with Nifion bonder, the maximum current density of Pd/C was 7.96A/m2 (-0.3V, Ag/AgCl reference), which was slightly higher than that of C catalyst (6.85 A/m2) and Pt/C catalyst (6.34 A/m2). X-ray photoelecton spectroscopy (XPS), X-ray diffration (XRD) and Scanning electron microscope (SEM) tests for the catalysts before and after treatment showed that the atomic ratio of N, O, C on the catalyst surface was changed and may provide the reasons for the reduction activity. ENVR 448 Solar power assisted biohydrogen evolution in microbial electrolysis cells M.-J. Choi, [email protected], K.-J. Chae, K.-Y. Kim, F. F. Ajayi, and I. S. Kim. Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology, Gwangju, Jeollannam-do, Republic of Korea Photo-induced biohydrogen (PIB) production is one of the most promising biotechnology for green house gas-free and most potential energy. In this study, a two-chambered microbial electrolysis cell (MEC) was evaluated, which consists of a phototrophic anode and a platinum coated cathode. The phototrophic anode inoculated with Rhodobacter sphaeroides and heterotrophs. Photosynthetic microorganism, R. sphaeroides, converts solar energy from carbon dioxide and water into chemical energy, which is then converted into electric energy by heterotrophic bacteria such as electricigens. Then, H+ and e- were transferred to the cathode and produced hydrogen. Thermodynamic barrier between the anode and the cathode in MEC generally was controlled with an external power source dependant on fossil fuel, however, it was overcome with a dye sensitized solar cell. Therefore, PIB system can produce environmental friendly hydrogen without any substrate injection and external power source.

ENVR 449 Increase of current generation using three electrodes microbial fuel cell (TE-MFC): Floating-type MFC (FT-MFC) combined with sediment MFC (SMFC) I. S. Chang, [email protected], and J. An. Department of Environmental Science and Engineering, Gwangju Institute of Science and Technology, Gwangju, Republic of Korea The objective of this study is to examine the possibility of the higher current generation using TE-MFC; one of the electrodes was embedded in sediment; two electrodes were placed on the water surface layer and at 14 cm below from the water surface, respectively, configuring SMFC and FT-MFC by vertically positioning the three electrodes. When 5 mM acetate was applied to the TE-MFC system, the current production pattern (ranging from 0.08 to 0.1 mA) was similar with that of FT-MFC (0.1 mA). While acetate concentration applied was converted from 3 to 1 mM, the maximum current (0.28 mA) produced by TE-MFC was higher than those generated individually by SMFC and FT-MFC (0.15 and 0.15 mA, respectively). This result implies that TE-MFC could produce more current as well as higher power output as compared with individual operation of FT-MFC and SMFC. ENVR 450 Effect of temperature on the performance of air-cathode single chamber microbial fuel cells (MFCs) S. Cheng1,2, [email protected], B. Logan2, and D. Xing2,3. 1State Key Laboratory of Clean Energy Utilization, Department of Energy Engineering, Zhejiang University, Hangzhou, Zhejiang, China, 2Department of Civil and Environmental Engineering, Penn State University, University Park, Pennsylvania, United States, 3State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, Heilongjiang, China Effect of temperature on the performance of microbial fuel cells was studied using 4-cm cubic MFCs with air-cathodes and carbon brush anodes. At temperatures below 15° C, the MFC could not be started up following inoculation with either effluent of an old MFC or domestic wastewater, while at the temperature over 15° C, the MFC easily started up and produced power. The higher the temperature, the shorter the start-up time in the studied temperature region of 15° to 30° C. Once started up at 30° C, the reactors could sustainably generate electricity over the complete temperature range of 4° C to 30° C. For reactors initially run at 30° C, the maximum power densities were nearly a linear function of the temperature, increasing from 425 mW/m2 at 4° C to 1260 mW/m2 at 30° C. These findings demonstrate that the MFC can work over large temperature ranges, but that they must initially be started at 30° C to be effective at power generation.

ENVR 451 Stimulating the anaerobic degradation of aromatic hydrocarbons in contaminated sediments by providing an electrode as the electron acceptor T. Zhang, [email protected], S. M. FitzPatrick, [email protected], K. P. Nevin, [email protected], A. E. Franks, [email protected], and D. R. Lovley, [email protected] Department of Microbiology, University of Massachusetts, Amherst, Massachusetts, United States Initial laboratory studies demonstrated that although toluene was rapidly adsorbed onto graphite electrodes Geobacter metallireducens rapidly oxidized the adsorbed toluene to carbon dioxide with the electrodes serving as the sole electron acceptor. Providing graphite electrodes as an electron acceptor in anoxic hydrocarbon-contaminated marine sediments significantly stimulated the removal of added toluene and benzene. Rates of toluene and benzene removal accelerated with continued additions of toluene and benzene. [14C]-toluene and [14C]-benzene were quantitatively recovered as [14C]-CO2. Naphthalene degradation in sediments was also accelerated with electrodes and [14C]naphthalene was converted to [14C]-CO2. The results suggest that graphite electrodes can serve as a permanent, low-maintenance source of electron acceptor for the degradation of aromatic hydrocarbon contaminants in sediments, co-localizing the contaminants, the degradative organisms, and the electron acceptor. Thus, graphite electrodes may offer an attractive alternative for enhancing contaminant oxidation in anoxic environments. ENVR 452 Impact of oxygen crossover on layered electrode assembly, air cathode MFCs C. S. Butler, [email protected], and R. Nerenberg. Department of Civil Engineering and Geological Sciences, University of Notre Dame, Notre Dame, IN, United States Microbial fuel cells (MFCs) can be built with layered electrode assemblies, where the anode, proton exchange membrane (PEM), and cathode are pressed into a single unit. We studied the effect of materials and oxygen crossover on the microbial community and performance of MFCs with layered assemblies. Four MFCs were constructed using Nafion or Ultrex PEMs, and a plain carbon cloth electrode or a cathode with an oxygen-resistant diffusion layer. The MFC with a Nafion PEM and cathode diffusion layer achieved the highest power, 381 mW/m2 (20 W/m3). Microsensors revealed little accumulation of oxygen within the anode biofilm. However the diffusion rates into the anode were three times higher in MFCs with plain cathodes than those with a diffusion layer. Our results show oxygen crossover can significantly decrease performance and abundance of

exoelectrogens in MFCs with layered assemblies, therefore limiting crossover is of particular importance for these types of MFCs. ENVR 453 Electricity production in single-chamber microbial fuel cells using carbon source mixtures and evaluation of anodic biofilms T. Catal1,2,3, [email protected], P. Kavanagh1, H. Liu3, K. Katuri1,2, V. O'Flaherty2, and D. Leech1. 1School of Chemistry, National University of Ireland, Galway, Galway, Ireland, 2Microbiology, National University of Ireland, Galway, Galway, Ireland, 3Biological and Ecological Engineering, Oregon State University, Corvallis, Oregon, United States Microorganisms encounter complex mixtures of carbon sources if lignocellulosic materials, or even wastewaters are used as substrates in order to produce electricity in microbial fuel cells (MFCs). Various carbon sources including monosaccharides, acetate and glucuronic acid were tested in different combinations for electricity production in single chamber air-cathode MFCs. Anodic biofilms enriched at different temperatures using carbon source mixtures were examined using epi-fluorescent, scanning and transmission electron microscopy, and cyclic voltammetry for electrochemical evaluation. Regardless of the mixture composition, all sugars were preferentially/simultaneously utilized to produce electricity during operation. Volatile fatty acid production was observed in all experiments, and varied depending on the sugar combination during MFC operation. Anodic biofilms showed different morphological and electrochemical features depending on the carbon source and MFC conditions. Our results demonstrate that using carbon source mixtures might be advantageous against environmental stress conditions for electricity production in MFCs. ENVR 454 Bio-augmentation of anodic consortia with electrochemically active strain to improve the performance of microbial fuel cell S. Veer Raghavulu, [email protected], R. Kannaiah Goud, P. N. Sarma, and S. Venkata Mohan. Bioengineering and Environmental Centre, Indian Institute of Chemical Technology, HYDERABAD, Andhrapradesh, India Despite positive feedback on the application of microbial fuel cell (MFC) application, power output is still a major limitation for it economic feasibility. Bioaugmentation is one of the important strategies which can be positively used to augment the anodic microflora to improve the overall performance of MFC. In this communication, we present experimental data pertaining to the performance of MFC prior and after augmenting anodic microflora with Aeromonas hydrophila ATCC 7966, reported electrochemically active bacteria. Experiments were performed in single chambered MFC (air-cathode; non-catalyzed graphites as electrodes; Nafion 117 as PEM; anaerobic mixed culture as anodic biocatalyst)

which was in operation for 6 months to evaluate the performance of various wastewaters. Log phase Aeromonas culture (18 h) was augmented through designed synthetic wastewater and MFC was operated at pH 6 in batch mode accounting for loading rate of 0.40 kg COD/m3-day. The MFC after augmentation showed marked improvement in performance (after augmentation- 297 mV, 1.83 mA (100 ), 4.62 mW/m2; prior to augmentation- 173 mV, 1.04 mA (100 ), and 3.01 mW/m2). In spite of insignificant improvement in substrate degradation after augmentation, power yield showed improvement of several folds (0.01 to 0.12 W/kg CODR). ENVR 455 Carbon nanofiber modified air cathodes for improving electricity production in microbial fuel cells H. Wang1, [email protected], Z. Wu3, A. Plaseied2, P. Jenkins2, L. Simpson3, C. Engtrakul3, and Z. Ren1, [email protected] 1 Department of Civil Engineering, University of Colorado Denver, Denver, CO, United States, 2Department of Mechanical Engineering, University of Colorado Denver, Denver, CO, United States, 3Carbon Nanoscience Division, National Renewable Energy Laboratory, Golden, CO, United States Microbial fuel cells (MFCs) provide direct and efficient electricity generation from organic matters. The use of air-cathodes in MFCs is considered viable for practical systems, but the performance of the current design is limited due to the low efficiency of three phases (air-liquid-solid) reaction on the cathode surface. This limitation becomes more apparent when the high surface area brush anode is used in the system. Compared with traditional single chamber carbon cloth aircathode microbial fuel cells, highly conductive carbon nanofibers and single walled carbon nanotubes were coated with Pt nanoparticles on the air-cathodes to create a 3-D web structure for increasing surface area, supporting more efficient catalytic reaction, and reducing the kinetic resistance. Preliminary data showed a stable increase in voltage output, and further analysis will include electrochemical characterization and electrode configuration modifications will be presented. ENVR 456 Power generation by microbial fuel cells from sunlight S. Strycharz, [email protected], R. Snider, L. M. Tender, G. J. Vora, and N. Lebedev. Center for Bio/Molecular Science and Engineering, Naval Research Laboratory, Washington, DC, United States Photosynthetic processes may be harnessed in a microbial fuel cell to continuously re-generate the anode and cathode reactants from their products. Here we report our latest results in which the cathode half-cell of a sediment

microbial fuel cell was enriched with photosynthetic organisms resulting in enhanced catalytic activity at the cathode surface. Slow scan voltammetry revealed the development of a catalytic cathode biofilm over time resulting in 100-fold greater power density compared to an identical cell unexposed to light. Catalytic activity at the cathode surface could be linked to a diel light cycle (12 h light:12 h dark), that also contributed to a flux of O2, CO2, and nitrogen in the cathode compartment; as well as sustained power during darkness. Here we report our findings from our initial phylogenetic analysis of the cathode community and its potential relationship to the cathode catalytic activity. ENVR 457 Glycerol utilization and performance of microbial fuel cells J. Chignell, [email protected], and H. Liu. Biological and Ecological Engineering, Oregon State University, Corvallis, OR, United States Biodiesel production processes generate large amount of glycerol as a waste coproduct. In microbial fuel cells (MFCs), glycerol, as a fermentable substrate, is subject to competitive dynamics between fermentative bacteria and anodereducers species in a mixed anode community that can decrease energyconversion efficiencies of. To investigate the dynamics of glycerol use by pure and mixed cultures of anode bacteria, pure glycerol and biodiesel waste glycerin were used as substrat in MFCs in both single step and two-step (fermentation followed by MFC) processes. Current, biomass, and competing electron sinks are quantified and changes in community structure are determined. ENVR 458 Novel electrochemically active bacterium phylogenetically related to Arcobacter butzleri isolated from a microbial fuel cell V. Viatcheslav Fedorovich1, M. Knighton2, U. Pagaling1, B. Ward2, A. Free2, [email protected], and I. Goryanin1. 1School of Informatics, University of Edinburgh, Edinburgh, United Kingdom, 2Institute of Evolutionary Biology, University of Edinburgh, Edinburgh, United Kingdom Exoelectrogenic bacteria are organisms which can transfer electrons to extracellular insoluble electron acceptors, and have the potential to be used in devices such as microbial fuel cells (MFCs). Currently, exoelectrogens have been identified among the -, - - and d-Proteobacteria, as well as among the Firmicutes and Acidobacteria. Here, we use culture-independent methods to identify two members of the genus Arcobacter, within the -Proteobacteria, which are selectively enriched within an acetate-fed MFC. One of these, Arcobacter butzleri strain ED-1, associates with the electrode and rapidly generates a strong electronegative potential as a pure culture when supplied with acetate. The mixed-community MFC in which ;90% of the population is comprised of the two

Arcobacter species generates a maximal power density of 296 mW/l. The demonstration of exoelectrogenesis by strain ED-1 is the first time this property has been shown for members of this genus. Our ongoing genomic analysis of the novel Arcobacter strains suggests a basis for their occupation of distinct ecological niches within the mature MFC. ENVR 459 Effect of ultrasound pre-treatment to inoculum and electrode surface area on performance of microbial fuel cell T. T. More1,2, [email protected], and M. M. Ghangrekar1, [email protected] 1Civil Engineering, Indian Institute of Technology Kharagpur, Kharagpur, West Bengal, India, 2Institute national de la recherche scientifique, Québec, Québec, Canada Effect of ultrasound pre-treatment to mixed anaerobic inoculum sludge and electrode surface area on performance of dual chambered microbial fuel cells (MFCs) is studied. Two identical MFCs were used in the study, MFC-1 inoculated with ultra-sonication and MFC-2 with heating-pretreatment. By increasing cathode surface area by 98.6% over a period of about two months, power was increased by 175.3% in MFC-1 and by 123.3% in MFC-2. When graphite granule anode surface area was gradually reduced afterwards from 1543 cm2 to 63.75 cm2, the overall power output was increased from 2.35 mW to 4.46 mW (by factor 1.9) in MFC-1, and from 2.05 mW to 4.99 mW (by factor 2.43) in MFC-2. The higher power output was observed with increased bacterial activities with relatively smaller anode surface and higher cathode surface area; hence, it is a critical parameter in MFC design. Ultra-sonication pretreatment has shown potential to improve the MFC performance in terms of power production and organic matter removal. ENVR 460 Study of adsorption phenomena in photocatalytic reaction of several indoor VOCs A. Maudhuit1, [email protected], C. Raillard1, [email protected], V. Hequet1, [email protected], L. Le-Coq1, [email protected], J. Sablayrolles2, [email protected], and L. Molins3, [email protected] 1GEPEA, UMR CNRS, Ecole de Mines de Nantes, Nantes, Cedex, France, 2Saint-Gobain Recherche, Aubervilliers, France, 3Saint-Gobain Quartz, St. Pierre les Nemours, France It is now well-known that Indoor Air Quality (IAQ) is deteriorated, particularly because of the presence of volatile organic compounds. To improve IAQ, a photocatalytic process can be used. Photocatalytic reactions can be decomposed into three steps: pollutants adsorption, chemical reaction and products desorption. In this work, the accessibility of pollutants to the reactive

sites of a TiO2 photocatalyst is studied. Firstly, adsorption mechanisms are approached through toluene adsorption isotherms. A model, called "Langmuirmulti" is built and allows a good fitting with obtained experimental data. To better understand adsorption mechanisms on TiO2 and to explore the role of water vapor, adsorption isotherms are also performed in dry air conditions with toluene and in humid air with acetone and heptane. Secondly, photocatalytic reactions are carried out for toluene, acetone and heptane. The Langmuir-Hinshelwood adsorption equilibrium constants are calculated and compared with those obtained with the "Langmuir-multi" model in dark conditions. ENVR 461 Understanding photocatalytic oxidation mechanisms of indoor VOCs using a QSAR approach C. Raillard, [email protected], B. F. Gao, [email protected], and V. Hequet, [email protected] GEPEA, UMR CNRS, Ecole de Mines de Nantes, Nantes, France In order to use heterogeneous photocatalysis as an effective indoor air treatment technique, the mechanism of the photocatalytic reaction of the pollutant under consideration should be known. The reactivities of individual molecules are needed. This study aims to investigate the photocatalytic oxidation mechanisms of several VOCs. This can be achieved by the combination of an experimental work together with theoretical calculations. The experimental results are modelled by the Langmuir-Hinshelwood relation at the initial time t0 of the photocatalytic reaction. The equilibrium and the kinetic constants are then calculated by linear regressions. In the same time, with the intention of determining the physical and chemical properties of the reactants, geometry optimizations of the compounds are performed with the B3LYP/6-31+G** hybrid density functional method. Then some molecular descriptors are calculated. Finally, correlations between the Langmuir-Hinshelwood constants and the molecular descriptors are examined using the QSAR methodology. ENVR 462 Nanostructure formation by chlorinated hydrocarbons on carbonate minerals: Overlooked surface chemistry regulating the vapor intrusion pathway C. Na, [email protected] Department of Civil Engineering and Geological Sciences, University of Notre Dame, Notre Dame, IN, United States Chlorinated hydrocarbons are prevalent contaminants in soils and sediments due to improper disposal and accidental spillage. An important pathway for human exposure of these contaminants is the intrusion of their vapors into occupied buildings through the unsaturated vadose zone. Using chloroform, trichloroethylene, and tetrachloroethane as representative CHC compounds, we

have discovered that their condensed vapors form nanostructure thin films on common carbonate minerals calcite (CaCO3) and rhodochrosite (MnCO3), as observed by using atomic force microscopy (AFM) (cf. Figure 1).

Further analyses using X-ray photoelectron spectrometry (XPS) have shown that at least the nanostructures induced by tetrachloroethane contain chlorine and carbon originating from the CHC compound. To our knowledge, the formation of CHC-induced nanostructures on mineral surfaces is a new type of nanoscale environmental surface chemistry that has not been either reported in the literature or incorporated in the modeling of vapor intrusion. ENVR 463 Probing pathogenic prion protein interactions with humic acid and mineral surfaces using the quartz crystal microbalance with dissipation K. H. Jacobson1, [email protected], K. Kumar3, and J. A. Pedersen1,2,3. 1 Department of Civil and Environmental Engineering, University of Wisconsin Madison, Madison, WI, United States, 2Department of Soil Science, University of Wisconsin - Madison, Madison, WI, United States, 3Molecular and Environmental Toxicology Center, University of Wisconsin - Madison, Madison, WI, United States Transmissible spongiform encephalopathies (TSEs), or prion diseases, are a family of neurodegenerative disorders caused by the misfolded version of the mammalian prion protein (PrP). Due to the extreme stability of these misfolded proteins, their release into the environment through shedding or carcass decomposition has been implicated in the spread of TSEs in some wild and domestic animal species. Current understanding of PrP attachment to environmental surfaces is limited. Using the quartz crystal microbalance with

dissipation monitoring, we studied PrP interactions with humic acid- and mineralcoated surfaces that prions are likely to encounter ex vivo as a function of solution composition. PrP interaction with humic acid exhibits pronounced pH dependency. The influence of humic acid composition and protein structure on PrP attachment to humic acid-coated and mineral surfaces will be discussed. ENVR 464 Influence of natural organic matter on the stability of Bacteriophage MS2 C. I. Rinciog1, [email protected], S. E. Mylon1, [email protected], N. Schmidt2, L. Gutierrez3, G. C. L Wong2, and T. H. Nguyen3. 1Department of Chemistry, Lafayette College, Easton, PA, United States, 2Department of Material Science, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 3University of Illinois at Urbana-Champaign, Department of Civil and Environmental Engineering, Urbana, IL, United States The stability of functionalized nanoparticles generally results from both steric and electrostatic interactions. Naturally occurring nanoparticles such as viruses are known to exploit this strategy for stability against aggregation. In natural systems, naturally organic matter (NOM) can adsorb to and effectively functionalize nanoparticle surfaces, affecting the fate and transport of these nanoparticles. This study reports the results of time resolved dynamic light scattering experiments used to measure the aggregation kinetics of a model virus, the bacteriophage MS2, across a range of solution chemistries both with and without NOM in order to understand what factors might destabilize viruses in aquatic systems. Results from were confirmed by small angle X-ray scattering experiments, which indicate a transition from repulsive to attractive interactions between MS2 virus particles as monovalent salts are replaced by divalent salts. ENVR 465 Effects of humic acid on the fate of heavy metals and TPHs in a wetland microcosm planted with Phragmites communis K. Sung1, [email protected], K. S. Kim1, S. Park2, D. Kang1, and Y. Chung1. 1 Department of Ecological Engineering, Pukyong National University, Busan, Republic of Korea, 2Department of Ocean Engineering, Pukyong National University, Busan, Republic of Korea This study investigated the effects of humic acid on the fate of heavy metals (Pb, Cu, Cd, and Ni) and total petroleum hydrocarbons (TPHs) in a wetland microcosm planted with Phragmites communis. The changes in soluble and exchangeable forms and in plant-available forms of heavy metals were monitored under artificially contaminated conditions, along with the TPH concentration and dehydrogenase activity (DHA). A control microcosm without humic acid and a microcosm planted with terrestrial plant species were also used in the study to investigate the effects of humic acid and soil moisture content. In comparison

with the control microcosm, the soluble and exchangeable forms of Pb in the wetland microcosm decreased while those of Cd and Ni increased by the addition of humic acid. The plant-available forms of Pb, Cu, Cd, and Ni increased up to 6.5, 159.3, 32.6 and 144.3%, respectively, with the addition of humic acid. Humic acid addition also resulted in high metal accumulation in the shoot and root of P. communis in the range of 4.9­105.1% and 3.7­46.8%, respectively. The results revealed that TPH degradation was slower in the wetland microcosm planted with P. communis than in the microcosm planted with the terrestrial plant, but the addition of humic acid increased the TPH degradation and microbial activities in the wetland microcosm. ENVR 466 Investigation of the protonation behavior of natural organic matter from the Rio Negro region by in situ spectroscopic methods G. V. Korshin1, [email protected], M. F. Benedetti2, M. Fabbricino3, and D. Dryer1, [email protected] 1Department of Civil and Environmental Engineering, University of Washington, Seattle, WA, United States, 2Laboratoire de Géochimie des Eaux, Université de Paris Diderot - Paris7 - IPGP, Paris, France, 3Department of Hydraulic and Environmental Engineering Girolamo Ippolito, University of Naples Federico II, Naples, Italy Protonation behavior of NOM originating from a creek (the Jau River) entering the Rio Negro in the Amazon basin was explored using potentiometric titrations, examination of the changes of absorbance and fluorescence spectra of NOM and their modeling using the NICA-Donnan theory. The deprotonation of NOM was accompanied by the emergence of distinct features in its differential absorbance and emission spectra. These changes were shown to be associated with the engagement of diverse carboxylic and phenolic chromophores, other relatively minor functionalities and also inter-chromophores interactions. The spectroscopic response of NOM to changes of its protonation status was especially notable for colloidal fractions. The evolution of the fluorescence and differential absorbance spectra of Rio Negro NOM indicates the presence of both uniformly observed and site-specific features of NOM associated with the biogeochemical processes contributing to its generation. ENVR 467 Role of morphology and natural organic matter in the aggregation kinetics of ZnO nanoparticles D. Zhou1,2, [email protected], and A. A. Keller1,2, [email protected] 1 Bren School of Environmental Science and Management, University of California, Santa Barbara, Santa Barbara, CA, United States, 2UC Center for Environmental Implications of Nanotechnology, United States

The aggregation kinetics of two types of ZnO nanoparticles was investigated. Distinct differences in aggregation kinetics were observed between the two ZnO particles. The aggregation of the nearly spherical ZnO (Me ZnO) exhibited strong dependence on the ionic strength (IS) of the solution; while minimal influence of IS was seen on the irregularly shaped ZnO (Mk ZnO). The CCC of ZnO was found to be a function of pH; the CCC increased significantly as the pH was further away from the point of zero charge. Natural organic matter (NOM) was found to substantially hinder the aggregation of ZnO particles (above 10 mg/L for the Me ZnO and above 1 mg/L for the Mk ZnO). A Langmuir adsorption model was used to describe the NOM to ZnO nanoparticle adsorption isotherms. To our knowledge, this is the first study to report the effect of particle morphology on nanoparticle aggregation. ENVR 468 Photoactivated behavior of metal oxide nanoparticles in natural waters S. Bennett, [email protected], and A. Keller, [email protected] School of Environmental Science and Management, Univeristy of California at Santa Barbara, United States The generation of ROS and the quenching of ROS are two important reactions in natural aqueous systems that may be mediated by nanomaterials (NMs). Upon entering aqueous media, NMs rapidly aggregate and form particles larger than the initial primary particle size. Emerging research suggest the presence of natural organic matter can drastically reduce aggregation. Understanding that aggregation is strongly related to ionic strength, presence of natural organic matter, pH and other variables, the degree of aggregation may vary widely in different natural waters and thus greatly influence ROS kinetics. Previous research has investigated the kinetics of ROS production in deionized water and will serve as a baseline for comparison. The overarching objective is to investigate the ability of nano-sized metal oxides to increase or quench the generation of ROS in freshwater, seawater, groundwater and natural organic matter dominated systems using a light source that closely mirrors the sun's emission spectrum. ENVR 469 Effects of Fe3+ injection rate, cooling and drying method on particle size, morphology, and mineral phase or iron oxide nanoparticles J. R. Ray, [email protected], W. Wan, and Y.-S. Jun, [email protected] Department of Energy, Environmental & Chemical Engineering, Washington University in St. Louis, St. Louis, MO, United States Iron oxide nanoparticles possess strong potential in sequestering toxic metal ions and decomposing harmful organic compounds in groundwater. To unlock their

full potential, they need to be properly synthesized and characterized. Using the forced hydrolysis synthesis, we will determine the effect of Fe3+ injection rates, cooling and drying methods on final product phase and size of iron oxide nanoparticles, and their stability in aqueous environments. The mineral phase was determined using XRD, FTIR-DRIFT and Raman spectroscopy, and particle size and morphology were observed using TEM and AFM. Preliminary results indicate hematite and maghemite mixtures exist as a function of Fe3+ injection rates, and an optimal Fe3+ injection rate exists which produces the most hematite nanoparticles. XRD data also indicates that oven dried samples produced more hematite than freeze dried samples. These results will provide a well-controlled synthetic method of iron oxide nanoparticles for potential use in environmental and biomedical applications. ENVR 470 Influence of nano-particles on partition of hydrophobic pollutants in aquatic systems E. Sahle-Demessie1, [email protected], H. Tadesse1, Q. Zhao1, and G. Sorial2. 1Office of Research and Development/NRMRL, U.S. Environmental Protection Agency, Cincinnati, OH, United States, 2Department of Civil and Environmental Engineering, University of Cincinnati, Cincinnati, OH, United States ENVR 471 Effect of Daphnia magna on the aggregation of citrate-stabilized Au nanoparticles in hard water B.-T. Lee, [email protected], T. J. Gately, D. M. Mitrano, H. Pace, and J. F. Ranville. Department of Chemistry & Geochemistry, Colorado School of Mines, Golden, CO, United States Interest in the potential for environmental exposures to nanoparticles (NPs) is being driven by the rapid growth of nanotechnology. NPs can be dissolved, aggregated, and sedimented in surface water, their fate being affected by aquatic chemistry. We observed the effects of hardness on the aggregation and sedimentation of citrate-stabilized Au NPs using UV-Vis, DLS, zeta potential, and ICP-OES. Daphnia magna, a representative aquatic organism for toxicity testing, was introduced into Au-NP hard water dispersions to also investigate the role of biological activity. Hard water aggregated and sedimented the Au-NPs from solution more quickly than moderately hard or soft water. Compression of the diffuse double layer by counter ions decreased the electrostatic repulsion and resulted in aggregation. The presence of D. magna partially reduced the destabilization (aggregation and sedimentation) of the Au-NPs in hard water. Biological activity (for example, movement or ingestion) should therefore be considered when aquatic exposures are investigated.

ENVR 472 Effect of natural organic matter on transport and distribution of Cryptosporidium Parvum oocysts in subsurface environment: A real time microscopic study in micromodel Y. Liu1, [email protected], C. Zhang2, M. S. Kuhlenschmidt3, T. B. Kuhlenschmidt3, and T. H. Nguyen1. 1Department of Civil and Environmental Engineering, the Center of Advanced Materials for the Purification of Water with Systems (waterCAMPWS), University of Illinois at Urbana-Champaign, Urbana, Illinois, United States, 2Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington, United States, 3 Department of Pathology, University of Illinois at Urbana-Champaign, Urbana, Illinois, United States Transport of Cryptosporidium parvum oocysts in subsurface environment is of great concern for water resources protection or drinking water treatment. However predicting transport of C. parvum oocysts in the subsurface environment is far from satisfactory. Modeling efforts have been made for transport of C. parvum oocysts through short packed-columns based on the observed breakthrough curve. Predicting spatial distribution and long distance transport of C. parvum oocysts remains challenging, partially due to the lack of knowledge of how C. parvum oocysts transport in porous media. Recently developed Radial Stagnation Point Flow Cell studies showed the importance of reversible deposition of C. parvum oocysts in secondary minimum under natural conditions. In the presence of natural organic matter (NOM), C. parvum oocysts surface properties are expected to be significantly modified by adsorbed NOM. Specifically, C. parvum oocysts surface is expected to become more negatively charged in the presence of NOM that enhance reversible deposition of C. parvum oocysts in secondary minimum and consequently increase the mobility of C. parvum oocysts. We hypothesize that reversible deposition of C. parvum oocysts in the secondary minimum contributes to C. parvum oocysts transport in porous media and enhances C. parvum oocysts entrapment in backward stagnation point. As a result, we expect to observe more C. parvum oocysts entrapped in backward stagnation point in the presence of NOM. This hypothesis will be tested by real time observation of C. parvum oocysts transport in a micromodel, in which pore structures are etched into silicon wafer to simulate two-dimensional subsurface environment. An electronic inverted microscope assembled with phase filter at bright field will be used to record images of transport of C. parvum oocysts in porous media. Distribution of C. parvum oocysts in porous media will be interpreted from the images. ENVR 473 Environmental selenium availability is directly related to mercury retirement and inversely related to methylmercury bioaccumulation in freshwater fish

N. V. C. Ralston, [email protected] Energy & Environmental Research Center, University of North Dakota, Grand Forks, ND, United States Members of Group 6a; oxygen (O), sulfur (S), selenium (Se) exhibit mercury (Hg) binding affinities in the order; O<<S<Se. Sulfur's affinity for Hg (1039M) is famously high, but the best Hg ligand is Se since its binding affinity (1045M) is ;1 million times greater. Thus, it is not surprising that methyl-Hg has recently been shown to be an irreversible inhibitor of Se-dependent enzymes. Although methylHg is the form that is most readily absorbed, vertebrates have been shown to accumulate Hg as highly insoluble inorganic HgSe. Virtually all forms of animal life that possess a nervous system employ Se-dependent enzymes to protect their brains from oxidative damage. Therefore, aquatic animals are expected to retire portions of their internalized Methyl-Hg as HgSe. Since HgSe is poorly absorbed up the food chain, improved Se-status in aquatic biota is likely to retire Hg to the sediments as HgSe. ENVR 474 Surfactants interaction with soil organic matter: Estimation of long-term effects on pesticides and trace metals availability M. Hernandez-Soriano1,2, [email protected], F. Degryse2, A. Pena1, M. D. Mingorance1, and E. Smolders2. 1Environmental Geochemistry, Estacion Experimental del Zaidin (CSIC), Granada, Spain, 2 Division of Soil and Water Management, Katholieke Universiteit Leuven, Leuven, Belgium Interaction of several surfactants with soil organic matter was evaluated in two agricultural soils by long-term incubation and column experiments, simulating soil irrigation or washing with surfactants aqueous solutions. The effect in organophosphorous pesticides and trace metals availability was subsequently estimated. Surfactants are widely known as solubilising agents and commonly used in household and industrial applications. Compounds selected for this work are representative of surfactants used in agriculture or present in sludge and wastewater. Cationic surfactants decreased the concentrations of dissolved soil organic matter, likely by promoting sorption of the hydrophobic matter. In contrast, anionic surfactant increased the soil organic matter solubility by reducing soluble Ca2+ that acts as a coagulant for organic matter. Alteration of soil organic matter significantly explained surfactant effects on trace metal and pesticide solubility, which largely varied with surfactant type. Results achieved are relevant for risk assessment and progress of remediation techniques. ENVR 475 Copper speciation in highway stormwater runoff

J. A. Nason, [email protected], D. J. Bloomquist, and M. S. Sprick. School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, Oregon, United States Highway stormwater runoff is a primary source of copper to surface waters. In the Pacific NW, many surface waters are inhabited by threatened and endangered salmonid species and recent research has indicated that very low (g/L) concentrations of dissolved copper can inhibit the olfactory senses of these species. Unfortunately, little is known about the extent to which copper is complexed with organic and inorganic ligands in stormwater. Through a yearlong field-sampling campaign, we have collected flow-weighted composite samples from four geographically and ecologically diverse sites in Oregon State. At one site, we have collected first-flush samples and discrete samples throughout individual storms. Stormwaters are being characterized in terms of general water quality (pH, conductivity, cations, anions, and dissolved organic carbon) and copper complexation is being evaluated using competitive ligand exchange-adsorptive cathodic stripping voltammetry with salicylaldoxime as the competing ligand. Preliminary results indicate that copper is >99.9% complexed with organic matter. ENVR 476 Initial stages of biofilm formation on different substrata in the Flint River A. I. Omoike, [email protected], C. Burrell, and C. Michael. Chemistry and Biochemistry, University of Michigan-Flint, Flint, MI, United States Biofilm plays a vital role in nutrients and toxic contaminants cycling in aquatic environments. In order to evaluate the initial stages of biofilm formation on different substrata, iron oxide (goethite and hematite) coated slides and silica slides in a sampling device were lowered in the Flint River. Carbohydrate and protein, the predominant constituents of biofilm extracellular polymeric substances (EPS) were measured by spectrophotometry during the first 6h-14 days. Increasing amounts of carbohydrate and protein accumulated on all the surfaces during the period of immersion, however, hematite surfaces (days 6-14) showed decreasing values. The carbohydrate to protein ratio for water extractable biofilm EPS (free) and EPS extracted by sonication (surface bound) on 6h slides were highly variable. Scanning electron microscopy revealed initial patchiness structure of biofilm, and at day 14 surfaces colonized with bacteria cells and diatoms. Surface composition of substrata can impact polysaccharide to protein ratio during initial biofilm formation. ENVR 477 Stability of manufactured nanoparticles in natural systems

A. Gelabert1, [email protected], Y. Sivry1, V. Siron1, R. Ferrari1, F. Juillot2, N. Menguy2, and M. F. Benedetti1. 1LGE, IPGP -UMR 7154, Université Paris Diderot, Paris, France, 2UMR 7590, IMPMC, Paris, France Engineered nanoparticles (NPs) have become largely widespread in numerous industrial fields during the last decade. However, their increasing use could result in the release of high NPs amounts in environmental settings. Thus, an accurate understanding of their behaviour in natural systems is required. The present study focuses on dissolution rate estimations for commercial NPs ZnO and TiO2 in natural waters (i.e., filtered Seine river water and seawater). In particular, the influence of an organic polymer coating was investigated. NPs dissolution rates were determined using Donnan Membrane Technique (free metal concentration) and ultrafiltration (free metal and small organic complexes). After a fast dissolution step reaching 1% of total zinc within the first hour for uncoated ZnO NPs in Seine water, precipitation of new mineral phases occurred. Interestingly, the behaviour of the coated ZnO NPs is different since the initial dissolution step takes place during the first 72 hours, to reach up to 10% of the total zinc. However, despite this difference in dissolution kinetics, both systems evolve similarly after 3 days, and reach a steady state after approximatively 3 months of interaction. Moreover, a strong dependence on pH has been noticed, with the slower dissolution rates associated to the higher pH. XPS measurements performed on native uncoated ZnO NPs evidenced the presence of a layer of Zn(OH)2 which accounts for almost 20% of the total Zn in the NPs. This Zn(OH)2 phase, which is more soluble than ZnO, may control the early dissolution steps of the NPs in our systems. ENVR 478 Examination of NOM physicochemical properties on nanomaterial transport in porous media C. P. McNew1, E. J. LeBoeuf1, [email protected], Y. Li2, L. M. Shor3, and D. A. Markov4. 1Department of Civil and Environmental Engineering, Vanderbilt University, Nashville, Tennessee, United States, 2Civil Engineering, University of Nebraska - Lincoln, Lincoln, Nebraska, United States, 3Department of Chemical, Materials, and Biomolecular Engineering, University of Connecticut, Storrs, Connecticut, United States, 4Vanderbilt Institute for Integrative Biosystems Research and Education, Vanderbilt University, Nashville, Tennessee, United States Nanoparticle transport in porous media was observed directly using flow cells arrays cast in poly(dimethyl siloxane) (PDMS). The approach allows key parameters including nanoparticle size and surface characteristics, solution chemistry, and surface-sorbed NOM physicochemical characteristics to be varied systematically while holding other variables constant. The applicability of a classic filtration model, employing a first-order attachment process to describe particle deposition, was used to quantify the influence of the experimental matrix on nanoparticle transport. Particle attachment efficiency was interpreted based

on interaction energies between particles and surfaces in the presence of sorbed natural organic matter (NOM). Advancements to classic filtration models are made by explicitly considering the interaction between nanomaterials and NOM by accounting for (1) desorption of NOM from porous media surfaces, (ii) adsorption of NOM onto nanomaterial surfaces, and (iii) influence of the steric repulsion from adsorbed NOM on porous media surfaces. ENVR 479 Enhanced mobility of nano-titanium dioxide by natural organic matter X. Yang, [email protected], Y. Liu, and R. Lerner. Department of Civil and Environmental Engineering, University of Alberta, Edmonton, Alberta, Canada Nano-TiO2 has been used extensively by industry, and research into the fate is still in its infancy. It has been reported that sewage contained Ti upward of several mg/L, and particles < 0.7m cannot be effectively removed. Thus nanoTiO2 will inevitably enter the environment. In this research, the effect of NOM on nano-TiO2 transport was studied. TiO2 was injected into 25cm sand columns for 3 pore volumes, and DI water was then injected to elute the remaining TiO2. Effluent was sampled, and the columns were divided into 5 sections to test retained TiO2 afterwards by ICP/MS. Results showed that the mobility of TiO2, in the presence of NOM at 20mg/L, increased significantly. The TiO2 effluent concentration was greatly enhanced, and the shape and sizes of retention profiles also changed greatly. Without NOM, the majority of retained TiO2 was near the inlet region. In the presence of NOM however, the TiO2 retention profiles showed an increasing gradient along the flow direction, resulting in higher concentrations near the outlet. ENVR 480 Purification of silver nanoparticles using diafiltration membranes and its applications for testing the fate, transport and toxicity of silver A. El Badawy1, [email protected], T. Luxton2, R. Silva3, K. Schekel2, M. Suidan1, and T. Tolaymat2. 1Civil and Environmental Engineering, University of Cincinnati, Cincinnati, OH, United States, 2US Environmental Protection Agency, United States, 3Shaw Environmental Inc., United States Numerous applications have been reported for silver nanoparticles (AgNPs) as a result of their unique properties. Thus, there is a great concern regarding the negative impacts of AgNPs upon release to the environment. During synthesis of AgNPs, the efficiency in the reduction of silver ion to the metallic silver (Ag0) is usually not 100%. Therefore, Ag+ ions (toxic to organisms) may be present in the synthesized AgNPs suspensions in addition to other residuals from the salts used in the reduction or stabilization of AgNPs. The residual ions, especially silver (Ag+) may limit the ability to perform accurate testing for the fate, transport

and toxicity of the AgNPs to the ecosystem. There is no concrete method for purifying AgNPs. Thus, this study is aimed at utilizing a diafiltration membrane technique for the purification of AgNPs and comparing the aggregation kinetics, transport and toxicity for the purified versus the unpurified AgNPs suspensions. ENVR 481 Effect of organic matter on zinc oxide nanoparticle aqueous interactions E. R. McKenzie, [email protected], and T. M. Young. Civil and Environmental Engineering, University of California, Davis, Davis, CA, United States Nanoparticles (NPs), such as zinc oxide, are being used in consumer products are likely to end up in surface waters. Once in the aquatic environment, aggregation with naturally occurring particles, complexation with organic matter (OM), and/or dissolution of these particles will tend to obscure their "unique" properties of toxicity or reactivity. In this study, the fate of zinc oxide NPs and clay mineral colloidal material is investigated in a model surface water. Previous studies indicate that OM often stabilizes NPs, reducing aggregation; these studies are typically confined to dissolved OM. In this study, Suwannee River NOM is separated into dissolved and colloidal fraction via ultra-filtration and the effects of both dissolve and colloidal OM on colloid/NP aggregation, zeta potential, and dissolution are monitored. ENVR 482 Neptunium(V) complexation with Suwannee River humic acid: Determination of the conditional stability constant P. B. Moran1, [email protected], and J. Ranville2, [email protected] 1 Tetra Tech, Golden, CO, United States, 2Department of Chemistry and Geochemistry, Colorado School of Mines, Golden, CO, United States The complexation of Np(V) with Suwannee River humic acid was investigated using an ion exchange technique combined with a discrete ligand modeling approach. Conditional stability constants (log ß) were obtained at pH 7.0 and 8.0 in 0.1 M NaClO4 using 8.0x10-7 to 1.0x10-5 M Np(V) and 10 to 200 mg/L humic acid at atmospheric PCO2. At pH 7.0 the log ß = 4.28 ± 0.02 while at pH 8.0 the value increased to 4.49 ± 0.02. ENVR 483 Hematite nanoparticles: Size and reactivity with respect to Pb adsorption and siderophore-promoted dissolution

L. E. Barton, [email protected], A. N. Quicksall, K. E. Grant, and P. A. Maurice. Department of Civil Engineering and Geological Sciences, University of Notre Dame, Notre Dame, Indiana, United States This research probed changes in properties and reactivity of hematite (-Fe2O3) as a function of size in the nanometer range (from ;80 to <10nm). Following syntheses from solution, particles were characterized for phase, crystallinity, morphology, surface composition and surface area using TEM, XRD, XPS, TGA and BET surface area analysis. All samples are pure phase hematite with TEM lattice fringes. Aqueous experiments explored dissolution by the siderophore desferrioxamine-B (DFO-B), adsorption of Pb, and effects of DFO-B on Pb adsorption. Siderophores are natural, low molecular weight organic ligands released by aerobic microorganisms. Sorption data suggest differences in metal binding for the different nanoparticles across a range of pH values. Dissolution data from experiments normalized for surface area demonstrate that particles <10nm dissolve more rapidly than larger particles. Ongoing research includes XAS analysis at Fe and Pb edges, exploration of coupled adsorption/dissolution kinetics, and planned research on particle thermal stabilities. ENVR 484 Sorption of atrazine by ordered mesoporous carbons and activated carbons: A comparative study J. Zhu1, [email protected], B. Deng2, [email protected], C. H. Lin3, [email protected], and J. Yang1, [email protected] 1Department of Agriculture & Environmental Science, Lincoln University of Missour, Jefferson, Mo, United States, 2Department of Civil and Environmental Engineering, University of Missouri, Columbia, MO, United States, 3Center for Agroforestry, School of Natural Resources, University of Missouri, Columbia, MO, United States Atrazine [2-chloro-4-(N-ethylamino)-6-(N-isopropylamino)-1, 3, 5-s-triazine] is a synthetic herbicide that has been used worldwide to control broadleaf and grassy weeds. Residual atrazine in soil can result in water contamination owing to its relatively high solubility, weak adsorptivity, and long residence half-time, which causes health and environmental concerns. This study investigated the sorption of atrazine from water by an ordered mesoporous carbon (OMC) and a lignitebased activated carbon (AC) as well as an aminated ordered mesoporous carbon (AOMC) and an aminated activated carbon (AAC) through batch experiments. Physiochemical properties of the carbons were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform IR spectroscopy (FTIR), potentiometry, and N2-adsorption/desorption (BET). Atrazine concentration was determined by high performance liquid chromatography (HPLC) with a UV­Vis detector. Results indicated that the atrazine sorption by activated carbons has a higher capacity than the ordered mesoporous carbons (58.23 vs. 47.53 mg/g) and a lower sorptive rate (12 vs. 6

hr). Impregnation of amine groups to the carbon surface did not enhance the atrazine removal from aqueous phase (36.09mg/g for AAC and 23.36mg/g for AOMCs). The sorption equilibrium isotherms could be well fitted into the Freundlich models. Keywords: Nanotechnology; Ordered Mesoporous Carbons; Activated Carbons; Atrazine Sorption ENVR 485 Photocatalytic degradation of phenol by hydrothermally synthesized TiO2SiO2 mixed oxides H. Kibombo, [email protected], D. Zhao, S. Budhi, A. Gonshorowski, and R. T. Koodali. Department of Chemistry, University of South Dakota, Vermillion, SD, United States Recent research studies have indicated that TiO2 photocatalysts, irradiated by UV-light, exhibit great potential for oxidative treatment of water. This work examines the loading of TiO2 onto a silica matrix in a sol-gel mixture, prepared by the hydrolysis of titanium isopropoxide using different co-solvents to promote gelation. The hydrothermally synthesized supported TiO2 revealed more superior photocatalytic activity for the degradation of phenol than mixed oxides prepared at room temperature. This enhanced activity is attributed to the effective dispersion of TiO2 crystallite species on the silica surface, as well as the separation of the photogenerated electrons and holes in the framework. The characteristics of the materials were investigated by powder X-ray Diffraction (XRD), UV-visible Diffuse Reflectance (DRS), Fourier Transform Infrared (FT-IR) and Raman spectroscopic techniques. The results suggest that crystallinity of the titania phase plays a predominant role in the photocatalytic activity. ENVR 486 Oxidant effects on TiO2 photoderdation of azo dye A07 solution J.-H. Shen1, [email protected], C.-H. Hsiao2, [email protected], Y.-S. Wang3, [email protected], and J.-J. Horng4, [email protected] 1 Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology, Douliou, Taiwan Republic of China, 2 Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology, Douliou, Taiwan Republic of China, 3 Graduate School of Engineering Science and Technology, National Yunlin University of Science and Technology, Douliou, Taiwan Republic of China, 4 Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology, Douliou, Taiwan Republic of China

The presence of metals and oxidants could affect--increasing or decreasing-the UV photo-catalyzation of TiO2 to remove A07 azo dye in solution. This study experimented many oxidants (KMnO4, K2Cr2O7, NaClO, CuCl2, HgCl2) to degrade AO7 under 254nm UV and various visible lights (yellow 550670 nm and red 610750 nm) at different pHs. Using the Orthogonal Experimental Design (OED) and Analysis of Variance (ANOVA), four factors of TiO2(P25) dosage, pH value, wavelengths, oxidants and oxidant concentrations were tested. After 8 hour of UV, the degradation of AO7 under UV/TiO2/Oxidants(KMnO4, K2Cr2O7, NaClO, CuCl2, HgCl2) ternary system were 96, 98, 96, 76 and 88% at pH 4, respectively. For visual lights, test conditions by ANOVA found 0.1 g/L TiO2 , 100M NaClO under red light at pH 4 yielding 98% removal. The roles of oxidants, metal ions or ClO-, may be functioned as electron acceptors in the process and lower the band-gap to able the photo-degradation by visual red light. Key words: TiO2, photodegradation, oxidant, AO7 ENVR 487 Removing AO7,Pb+2 and HSeO3- by compositing nano Fe-Ni with CNTs C.-H. Lee1, [email protected], Y.-S. Wang2, [email protected], and J.-J. Horng3, [email protected] 1Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology, Douliou, Taiwan Republic of China, 2Graduate School of Engineering Science and Technology, National Yunlin University of Science and Technology, Douliou, Taiwan Republic of China, 3Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology, Douliou, Taiwan Republic of China By using the experiment design to find the relative importance and the interactions of operation parameters, this research studied competitive effects of anionic and cationic pollutants removing by depositing nano iron-nickel (Fe-Ni) on aluminum oxides and nano carbon tubes (CNTs). The Taguchi method of Orthogonal Experimental Design (OED) and Analysis of Variance (ANOVA) were used to design the experiments and to analyze experimental factors. The OED included eighteen test (L18) on three parameters levels for seven dependent factors of adsorbent type, amount of Fe-Ni, solution pH , AO7 concentration, Pb+2 concentration, HSeO3- concentration and reaction time. The best removals were obtained by 1.5 g/L nano Fe-Ni/CNTs at pH 5 for Pb+2, AO7 and HSeO3- of 99, 98 and 99% after 60 minutes and the effluent standards could be achieved. Then, the Response Surface Methods (RSM) and Combined Array (CA) were used to further identify the interactions among factors of pH, Pb+2 and HSeO3concentrations. Our results showed that 0.5g/L nano Fe-Ni/CNT could remove complex pollutants of Pb+2, AO7 and HSeO3- up to 85, 92 and 27% at pH 3.6. The ineffective removal of HSeO3- was due to the competitive adsorption between anionic AO7 and HSeO3-. Thus, those composite nano-materials could effective remove cationic and anionic pollutants simultaneously. Keywords: experimental design, nano-material, complex pollutants

ENVR 488 Study of relationship between surface hydroxyl site and liquid-phase photocatalytic activity of titanium dioxide W. Li, [email protected], D. Li, [email protected], X. Fu, [email protected], and W. Zhang, [email protected] Research Institute of Photocatalysis, Fuzhou University, Fuzhou, Fujian, China In the process of photocatalytic degradation of organic pollutants, there is a great handicap to unveil the different roles of radical species. Besides photoexcited electrons and holes, ·OH, O2·- mostly participate in the oxidation-reduction process. Both theory and experiment show that surface ·OH is the most important and strongest intermediate species in the photocatalytic process. As a source of ·OH, surface hydroxyl groups played an important role in the process. In the mass characterizations, the structure and distribution of hydroxyl groups are easily to detect as a surface functional group. It is a pity that the state and role of surface hydroxyl groups have not yet been recognized clearly. Here in this paper, the concentration of hydroxyl groups, its role in the ·OH production and its effect on the photocatalytic activity were discussed concretely.

ENVR 489 Modified embedded atoms method study of the mechanical properties of carbon nanotube reinforced nickel composites J. Uddin1,2, [email protected], M. I. Baskes3, S. G. Srinivasan2,4, T. R. Cundari1,2, and A. K. Wilson1,2. 1Department of Chemistry, University of North Texas, Denton, TX, United States, 2Center for Advanced Scientific Computing & Modeling (CASCaM), University of North Texas, Denton, TX, United States, 3 Materials Science and Technology Division, Los Alamos National Laboratory, Los Alamos, NM, United States, 4Department of Materials Science & Engineering, University of North Texas, Denton, TX, United States Carbon nanotubes (CNTs) are among the stiffest and the strongest materials ever developed. Their other outstanding properties, as well as extraordinary

structural and chemical stability make CNTs a leading candidate for reinforcement fillers in nano-composite materials. There has been an increasing scientific and technological interest in this area to develop nano-composites aiming at among other properties, low density with high strength and stiffness. These composite materials are particularly attractive for many aerospace and other transportation applications where there is a renewed emphasis on reducing fuel consumption and producing lighter and stronger vehicle systems. Nickel is the primary ingredient of most aerospace superalloys, and therefore, is an attractive target for fabrication of ultra-strength materials with CNTs. In this talk, a computational study of the behavior of nano-composite materials that are formed by incorporating aligned single-walled and multi-walled carbon nanotubes (CNTs) into a bulk nickel matrix will be presented. Mechanical properties of these novel materials are predicted and strain-stress relationships are investigated by atomistic calculations with interactions derived from the modified embeddedatom method (MEAM). Simulations predict that all Ni/CNT composites are mechanically stable. ENVR 490 Peculiarities of PSSD pits in space and observation of Erzions Tracks producing pits swarms in PSSD in space Y. N. Bazhutov1, [email protected], and C. A. Tretyakova2. 1Pushkov Terrestrial Magnetism, Russian Academy of Science, Troitsk, Moscow region, Russian Federation, 2Skobeltsyn Nuclear Physics Institute, Lomonosov Moscow State University, Leninskie Gory, Moscow, Moscow region, Russian Federation Oriani & SPAWAR results in CR-39 films and their interpretation in the framework of the Erzion model initiated us to carry out research on this topic to investigate these effects. Around 40 years ago such film piles of Plastic SolidState Detector (PSSD) were exposed in a free space on the satellite orbit for studies of cosmic nuclei fluxes. The pit density in such old films was some orders larger than its background at sea level. To explain these effects of such PSSD films surfaces intensive cover by pits (tracks with special pit form & small depth) after exposure in a free space on the satellite orbit, we focused our attention on the cosmic ray Erzion mechanism. Low energy cosmic Erzion (E;10-100keV) beams penetrate the organic film substance due to catalytic cyclic nuclear exchange reactions that creates the big quantity (;106) of recoil nuclei (H1,H3,He4,C12,C14,N15...) with energy of 0.1-5 MeV. All this research confirmed the truth of the Erzion hypothesis. Moreover, we discovered the tracks of stopping negative charged cosmic Erzions in PSSD film pile, finished by pits swarm. ENVR 491 Thought experiment on nuclear fusion

N. Yabuchi, [email protected] Department of Fusion Development, High Scientific Research Laboratory, Japan Nuclear fusion engineering describes distinctive pathways of fusion of two positively charged nuclei. According to the equation for the Coulomb barrier (U = ZZ + e + e / r), when the distance r becomes r 0, the barrier U becomes U , and fusion must be dependent on a low-probability tunnel effect. However, by applying Coulomb's law (F = +e - e / 4r2) through action of a negatively charged electron and the positive charge, then attraction F, not repulsion, becomes significant (F ). Fusion thus becomes possible. To explain Arata's experiments, the author describes fusion in a modest thought experiment in which negatively charged electrons and positively charged deuterons are located side by side in a cube. This may cause a sort of balance, so that attraction between the electrons and the deuteron nuclei becomes 0.84 times stronger than the repulsion between the deuteron nuclei, and this results in a condensation near the center of the cube and fusion of the deuteron nuclei. The equation that may describe this process is 2D + 2D + 2D + 2D 4H*e2 + 4H*e2 8Be*4 4He2 + 4He2 = 47.6 MeV (where "*" indicates compound nuclei). ENVR 492 Retention of viruses in biosand filters amended with iron oxides S. D. Markazi1,2,3, [email protected], I. M. Bradley1,2, K. J. Swanson1, P. A. Maraccini1,2, K. M. Parker1,2, and T. H. Nguyen1,2. 1Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois, United States, 2The Center of Advanced Materials for the Purification of Water with Systems (WaterCAMPWS), University of Illinois at UrbanaChampaign, Urbana, Illinois, United States, 3School of Molecular and Cellular Biology, University of Illinois at Urbana-Champaign, Urbana, Illinois, United States The purpose of this study is to determine whether iron-amended biosand filters can be used to remove human enteric viruses from drinking water. These 20 L filters have non-galvanized nails distributed throughout the sand medium. Oxidation of the nails creates positively-charged surfaces to which negativelycharged virion particles adsorb via electrostatic interactions. Two types of experiments are currently being run. 50 mL sand columns incorporated with different distribution styles of zero-valent iron particles (10% by volume) are being compared to sand-only columns to determine which style most effectively removes MS-2 bacteriophage. The columns are charged daily with aquifer water seeded with MS-2, and 2.5% pasteurized primary effluent is added in order to stimulate biofilm growth. The columns have been run for 65 days, and the ironamended columns show ;7 log removal, whereas the sand-only column shows ;1 log removal. The full-size filters were packed following the most effective column model. The filters are charged with aquifer water with pasteurized primary effluent and tested for the removal of MS-2 bacteriophage, rotavirus, and

Escherichia coli. This technology can be used to enhance potable water purification in point-of-use biosand filters by removing viruses without the use of chlorine, thereby delivering safe water more easily and sustainably. ENVR 493 Application of sustainable organic mulch for the bioremediation of trichloroethylene Z. Wei, [email protected] Department of Civil Engineering, University of Toledo, Toledo, OH, United States Soluble substrates (electron donors) have been commonly injected into chlorinated solvent contaminated plume to stimulate reductive dechlorination. Recently, different types of organic mulches have received much attention as new supporting materials with economic advantages and sustainable benefits for engineered biowall systems. Previous studied reported that mulch installed in biowall systems could provide long term sources of organic carbon and electron donors for chlorinated solvent bioremediation. However, sorption capacities of organic mulches for chlorinated solvents haven't been studied yet. In this study, the physicochemical properties of three commercially available mulches (hardwood, pine, cypress) were characterized and their sorption capacities were elucidated by single, binary and quaternary isotherm tests with trichloroethylene (TCE), tetrachloroethylene (PCE), trans-dichloroethylene (trans-DCE) and cisdichloroethylene (cis-DCE). Reductive declorination rate of TCE and PCE under the presence of organic mulches were also compared to those of other soluble substrates. ENVR 494 Simultaneous removal of chromium and arsenate by Fe(II) from contaminated groundwater X. Guan, [email protected], H. Dong, and J. Ma. State Key Lab of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, Heilongjiang, China In the absence of arsenate, chromium removal by Fe(II) increased to a maximum with increasing pH from 4 to 7 while decreased with a further increase in pH. Chromium removal by Fe(II) was limited by the slow reaction rate of Cr(VI) reduction by Fe(II) and the solubility of Fe0.75Cr0.25(OH)3 at pH7. However, chromium removal by Fe(II) was controlled by the fraction of Cr(VI) converted to Cr(III) at pH>7. The presence of arsenate resulted in a decrease in chromium removal by Fe(II) at pH7. The remarkable influence of chromate on arsenate removal by Fe(II) was associated with the oxidative property of chromate, which could oxidize Fe(II) to Fe(III) and thus facilitated the removal of arsenate. Arsenate was removed by both adsorption and co-precipitation with

Fe0.75Cr0.25(OH)3 and FeOOH precipitates. Arsenate formed monodentate complexes with Fe(III) at pH 4.5-7.6 and formed both monodentate and bidentate complexes with Fe(III) at pH above 7.6. ENVR 495 Photochemical fate of Atorvastatin in the aquatic environment B. Razavi, [email protected], and W. J. Cooper, [email protected] Department of Civil and Environmental Engineering, University of California, Irvine, Irvine, CA, United States The indirect aquatic photochemical degradation of a class of pharmaceuticals known as statins, atorvastatin, was investigated. Atorvastatin, also known as lipitor, is a lipid lowering agent and is widely used in the prevention of cardiovascular events. Atorvastatin was chosen as the focus of this study due to its large production volume and widespread use. Atorvastatin has been detected at ng/L levels in a surface water sample, wastewater influent and wastewater effluent. This experiment was performed using both solar simulator (=300 nm) and UV reactor (=350 nm) for atorvastatin having concentrations of 20 ppm and 20 ppb and the results were compared. The indirect photolysis reaction rate constants of atorvastatin with singlet oxygen (1O2) and hydroxyl radical (·OH) were calculated and the destruction mechanisms were elucidated. The results of this study indicate that photooxidation mediated by 1O2 is the likely degradation pathway for atorvastatin in most natural waters. ENVR 496 Development and application of carbon nanomaterials for environmental wastewater cleanup D. M. Burke, [email protected], Z. Li, J. P. O'Byrne, M. A. Morris, and J. D. Holmes. Chemistry, University College Cork, Cork, Co. Cork, Ireland A major problem remains in finding a cheap and effective means of removing metal ions from water. The most common method is to use adsorbent materials with active surfaces to adsorb metal ions. Carbon nanocages (CNCs) were synthesised using a supercritical CO2 method and have exceptionally high surface areas of approximately 1300 m2/g. The production process was optimized by varying catalyst type, temperature and reaction pressure to obtain maximum yields and surface areas. These materials were subsequently tested for their ability to absorb metal ions from simulated waste water. The effects of agitation time, adsorbent loading, initial concentration of metal ions and pH were investigated. CNCs have excellent dispersibility in aqueous solution and were tested for Pb2+ and Cr6+ removal which gave equilibrium adsorption of 11.1 mg/g and 2.0 mg/g respectively at fixed pH. The intrinsic mechanical strength of CNCs

makes them ideal candidates for regeneration and therefore several adsorption cycles. ENVR 497 Bioconversion optimization strategies for high organic load wastewater utilizing phototrophic purple bacterial under micro aerobic condition E. I. Madukasi, [email protected], H. Lu, and W. Zhao. State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin, Heilongjiang, China Optimal strategies for new strain of phototrophic bacteria named Rhodobacter spheroides Z08 in treating simulated brewery wastewater (10,000 mg/L COD) micro aerobically is presented. The results showed that the process, when operated at 20­30° C, influent supplement with urea resulting to C: N: P of 200: 5: 10, and iron (Fe2+) addition up to 50.97 mg/L removed ;65% of the organic pollutants at a low hydraulic retention time. Magnesium addition up to 492.5 mg/L removed the pollutants by ;40%, while addition of molybdenum up to 200 mg/L increased the cell growth with pollutants removal of ;43%. The best impact was the addition of iron either as a sole micronutrient or in combination with magnesium (;55%). Major inorganic constituents of the wastewater were assimilated thereby augmenting the uptake of minerals and eliminating the third stage treatment process for inorganic nutrients removal. The biomass crude protein content is 43% stipulating potential for resource recovery ENVR 498 Sampling and analysis of produced water from selected sources in the Illinois Basin Y. Yang, [email protected], C. Knutson, [email protected], and S. A. Dastgheib, [email protected] Institute of Natural Resource Sustainability, University of Illinois at Urbana-Champaign, Champaign, IL, United States A large volume of water produced from oil and gas recovery operations is usually reinjected into the subsurface through disposal wells. A portion of the produced water, after treatment, could be suitable for supplementing freshwater needs of power generation plants. Utilization and treatment requirements of produced water highly depend on water quality. This study investigates the feasibility of using produced water from Enhanced Oil Recovery (EOR), Coal-Bed Methane (CBM) operations, and coal mines located in the Illinois Basin as cooling/process water in the coal-based power generation industry. Water samples were collected from selected oilfields, CBM sites, and coal mines and analyzed for pH, TDS, TSS, alkalinity, turbidity, ammonia, TPH, TOC, and various cations and anions. Water quality parameters will be presented and their implications on the treatment requirements will be discussed.

ENVR 499 Solid-supported thiols for aqueous mercury removal P. Jana1, [email protected], C. C. Chusuei2, J. A. Sells2, and D. A. Atwood1. 1 Department of Chemistry, University of Kentucky-Lexington, Lexington, Kentucky, United States, 2Chemistry Department, Missouri University of Science & Technology, Rolla, MO, United States Mercury is a pervasive environmental contaminant and there is a significant need for reagents and technologies capable of removing the element from water through either precipitation or filtration. N,N'-bis(2-mercaptoethyl)isophthalamide) abbreviated, BDTH2, has emerged as the preeminent reagent for the complete precipitation of mercury and other heavy metals from water. Aqueous heavy metal concentrations in the ppm to ppb range can be reduced, by complete precipitation of the BDT-metal compound, to below instrumental detection limits (Water Res. 42 (2008) 2025). The compound is now being marketed as B9 ("benign") by Merloc, LLC ([email protected]). It would be ideal to have a solid-supported reagent having the metal capture ability of BDTH2. To achieve this the new dithiol compound, 2,2'-[benzene-1,3-diylbis(carbonylimino)]bis(3sulfanylpropanoic acid) (abbreviated BCSH2) was synthesized. It contains pendant carboxylate groups that were used to covalently attach the compound to silica beads. The new solid-supported reagent, abbreviated Si-BCSH2, completely removes Hg(II) from water. XPS analysis confirmed the presence of covalent Hg-S bonding in the resulting SiBCS-Hg material. Details on the synthesis, characterization, mercury-capture ability, leaching profile, and Hg uptake optimization, of the new material will be presented. ENVR 500 Mechanistic understanding of insecticide aldicarb adsorption onto soil during water reuse A. E. Timofte1, [email protected], H. Shao1, J. Y. Yang2, D. A. Schupp3, and Y.-S. Jun1, [email protected] 1Department of Energy, Environmental, and Chemical Engineering, Washington University in Saint Louis, Saint Louis, Missouri, United States, 2Office of Research and Development, United States Environmental Protection Agency, Cincinnati, Ohio, United States, 3Shaw Environmental and Infrastructure, Incorporated, Cincinnati, Ohio, United States In analyzing the possibility of using reclaimed water to recharge aquifers, a better understanding of the interactions between the reclaimed water (with its possible contaminants) and native soil is required. This study investigated the adsorption of aldicarb, a carbamate insecticide which can be present in groundwater and wastewater, on a sandy soil. Using FTIR spectroscopy and XRD analysis, the soil components most responsible for the binding of aldicarb were identified: quartz and calcite (preferred over iron oxide, aluminum oxide and manganese dioxide). Coating the soil components with a mixture of humic and fulvic acid was

considered, and an enhanced aldicarb adsorption onto coated calcite was observed. In addition, most of the aldicarb adsorption occurred within a day, with insignificant changes after the first three days. The results of this study will provide fundamental information about the physico-chemical mechanisms of the adsorption of insecticides onto soil at potential wastewater reuse sites. ENVR 501 Sonochemical degradation of perfluorooctanesulfonate (PFOS) in aqueous film-forming foams (AFFFs) C. D. Vecitis1, [email protected], B. T. Mader3, and M. R. Hoffmann2. 1 Department of Chemical Engineering, Environmental Engineering Program, Yale University, New Haven, CT, United States, 2Department of Environmental Science and Engineering, California Institute of Technology, Pasadena, CA, United States, 33M Environmental Laboratory, 3M Company, Maplewood, MN, United States Aqueous film-forming foams (AFFFs) are fire extinguishing agents developed by the Navy to quickly and effectively combat fires occurring near explosive materials. Fluorochemical (FC) surfactants represent 1-5% of the AFFF composition, imparting properties such as high spreadability, negligible fuel diffusion and thermal stability to the foam. FCs are oxidatively recalcitrant, persistent in the environment, and have been detected in groundwater at AFFF training sites. Ultrasonic irradiation of aqueous FCs has been reported to degrade FC surfactants. Here we present results of the sonochemical degradation of aqueous dilutions of FC-600. The primary FC surfactant in FC600, PFOS, was sonolytically degraded over a range of FC-600 aqueous dilutions. Sonochemical PFOS-AFFF decomposition rates are similar to PFOSMilliQ rates indicating that the AFFF matrix only had a minor effect on the sonochemical degradation rate even though the total organic concentration was 50 times of the PFOS concentration, consistent with the superior FC surfactant properties. ENVR 502 Role of coupled redox transformations in the mobilization and sequestration of arsenic J. G. Hering, [email protected] Eawag: Swiss Fedl. Inst. Aquatic Sci. Technol., Duebendorf, Switzerland The mobility of arsenic in surface- and groundwater is influenced not only by changes in its own oxidation state but also by redox transformations of other elements, particularly iron. The significance of iron redox chemistry and the consequent dissolution and precipitation of solids that can serve as carrier phases for arsenic is well known. The relative importance of arsenic and iron redox processes in governing arsenic mobility will depend on a variety of

parameters that will be specific for a given system. Examples will be discussed based on observations of arsenic occurrence and mobility in two systems where coupled behavior of iron and arsenic has been observed. ENVR 503 Arsenic redox transformation by the humic substance model quinone AQDS A. Kappler1, [email protected], J. Jiang1, I. Bauer1, and A. Paul2. 1Center for Applied Geosciences, University of Tuebingen, Tuebingen, Germany, 2BAM, Fed. Inst. for Materials Research, Berlin, Germany Arsenic toxicity and mobility in the environment depend on its interactions with iron minerals and humic substances via complexation and redox reactions. Arsenite [As(III)] is generally considered to be more toxic and mobile than arsenate [As(V)]. Understanding microbiological and chemical redox processes leading to As redox changes is necessary to predict the environmental behaviour of As. We therefore studied the reactions of arsenite and arsenate with reduced humic model quinones. In particular, we quantified As(III) oxidation and As(V) reduction by oxidized and reduced AQDS (anthraquinone-2,6-disulfonic acid). Speciation of dissolved arsenic was determined by IC-ICP-MS. Quinone radicals were quantified by ESR. Our results in combination with thermodynamic modelling show that reduced quinones (i.e., semiquinone radicals and hydroquinones) can lead to both As(III) oxidation and As(V) reduction. These results suggest that microbial transformation of humics can lead to arsenic redox changes and thus influence arsenic toxicity and mobility. ENVR 504 Role of structural aluminum on ferrihydrite reduction: Implication for reductive dissolution of arsenic Y. Masue-Slowey1, [email protected], R. H. Loeppert2, [email protected], and S. Fendorf1, [email protected] 1Environmental Earth System Science, Stanford University, Stanford, CA, United States, 2Soil and Crop Sciences, Texas A&M University, College Station, TX, United States Reductive transformation of ferrihydrite and its impact on As retention have been studied extensively; however, little is known about how structural Al within ferrihydrite, a common substitution in natural system, alters biotransformation and As retention. We examine the extent to which structural Al influences reductive transformations of ferrihydrite and resulting impacts on As retention. Iron(II) catalyzed transformation of Al-ferrihydrite was examined at 1:80 to 1:20 As:(Al+Fe) molar ratio in batch slurries. Aluminum limits reductive transformation of ferrihydrite due to impeded electron delocalization, and Al-ferrihydrite transformed to goethite only after the reaction with 2.0 mM FeCl2. In fact, Fe(II)

breakthrough from packed mineral columns illustrates that structural Al limits Fe(II) retention/incorporation. Reductive dissolution/transformation of Alsubstituted ferrihydrite by Shewanella sp. ANA-3 [Fe(III) and As(V) reducer] reveals that greater dissolution of Al-ferrihydrite relative to ferrihydrite in the absence of As. However, the difference in dissolution between Al-ferrihydrite and ferrihydrite is negligible in the presence of adsorbed As. In the long-term, incongruent (reductive) dissolution of Fe relative to Al results in increasing proportions of structural Al that may limit As(III) retention. ENVR 505 Redox transformation of arsenic by Fe(II)-activated goethite (-FeOOH) T. Borch1, [email protected], K. Amstaetter2, P. Larese-Casanova3, and A. Kappler4. 1Department of Soil and Crop Sciences, Colorado State University, Fort Collins, CO, United States, 2Department of Environmental Engineering, Norwegian Geotechnical Institute, Oslo, Norway, 3Department of Geology and Geophysics, Yale University, New Haven, CT, United States, 4Geomicrobiology, Center for Applied Geosciences, University of Tuebingen, Tuebingen, Germany The redox state and speciation of arsenic (As) determine its environmental fate and toxicity. Knowledge about biogeochemical processes influencing arsenic redox state is thus important. Here we quantified arsenic redox changes by pHneutral goethite mineral suspensions amended with Fe(II) using wet-chemical and synchrotron X-ray absorption analysis. Goethite itself did not oxidize As(III) and, in contrast to thermodynamic predictions, Fe(II)-goethite systems did not reduce As(V). However, we observed rapid oxidation of As(III) to As(V) in Fe(II)goethite systems. Mossbauer spectroscopy showed initial formation of 57Fegoethite after 57Fe(II) addition plus a so far unidentified additional Fe(II) phase. No other Fe(III) phase could be detected by Mossbauer, EXAFS, SEM, XRD, or HR-TEM. This suggests that reactive Fe(III) species form as an intermediate Fe(III) phase upon Fe(II) addition and electron transfer into bulk goethite but before crystallization of the newly formed Fe(III) as goethite. This potentially explains the presence of As(V) in reduced groundwater aquifers. ENVR 506 Reduction of uranium(VI) by iron(II) species and minerals: Reactivity and uranium(IV) products M. I. Boyanov1, [email protected], D. E. Latta2, E. J. O'Loughlin1, C. A. Gorski2, M. M. Scherer2, and K. M. Kemner1. 1Biosciences Division, Argonne National Laboratory, Argonne, IL, United States, 2Department of Civil and Environmental Engineering, University of Iowa, Iowa City, IA, United States The Fe(II) species produced under dissimilatory iron reducing conditions are potential reductants of soluble U(VI) and can lead to the immobilization of

uranium as U(IV) minerals. Using Fe K-edge and U L-edge EXAFS spectroscopy we examined the reduction of U(VI) by abiotic iron species spanning the formal valence between Fe(II) and Fe(III), including aqueous Fe(II), Fe(II) sorbed to carboxyl surfaces, siderite, synthetic green rusts with different interlayer anions, stoichiometric magnetite, and magnetite-structure minerals with decreasing Fe(II) content. Results show variable Fe(II)-U(VI) reactivity depending on Fe(II) speciation. Reduction to U(IV) was observed in systems where Fe(II)-O6 octahedra were connected, but no reduction was observed by monomeric aqueous or adsorbed Fe(II) species or by siderite. The U(IV) products also varied and ranged between nanoparticulate uraninite (UO2) and mononuclear U(IV) species. The mobility of these distinct U(IV) phases will need to be studied in order to assess their impact on uranium bioremediation efforts. ENVR 507 Facultative anoxygenic photosynthesis by cyanobacteria driven by arsenite F. Wolfe-Simon1,2, [email protected], S. E. Hoeft2, and R. S. Oremland2. 1 Department of Earth and Planetary Sciences, Harvard University, Cambridge, MA, United States, 2U.S. Geological Survey, Menlo Park, CA, United States Over geologic time, the rise in atmospheric oxygen (O2) is attributed to the evolution and widespread proliferation of oxygenic photosynthesis in cyanobacteria. However, cyanobacteria maintain a metabolic flexibility that may not always result in O2 release. Cyanobacteria may use a variety of alternative electron donors, rather than water such as sulfur, iron, nitrogen, and arsenic; in part due to their use by anoxygenic phototrophs but also recent evidence suggests cyanobacteria can actively take advantage of these alternatives as well. We used a classical Winogradsky approach to enrich for cyanobacteria from the high salinity, elevated pH and arsenic-enriched waters of Mono Lake (CA). Experiments, optimized for cyanobacteria, revealed light-dependent, anaerobic arsenite-oxidation in sub-cultured slurries dominated by a filamentous Oscillatoria-like cyanobacterium (likely a Lyngbya/Phormidium/Plectonema subgroup member). 1mM arsenite induced facultative anoxygenic photosynthesis under continuous and circadian light. Future characterization includes isolation and molecular identification of the cyanobacterium and the arsenite oxidase and photosystem required for light capture. ENVR 508 Kinetics of U(VI) reduction by nanoscale zero-valent iron S. Yan1,3, [email protected], Z. Bao1,2, [email protected], and B. Deng3, [email protected] 1Key Laboratory of Bio-geology and Environmental Geology of Ministry of Education, China University of Geosciences, Wuhan, Hubei, China, 2Faculty of Material Science & Chemical Engineering, China

University of Geosciences, Wuhan, Hubei, China, 3Dept. of Civil & Environmental Engineering, University of Missouri, Columbia, MO, United States U(VI) reduction is a primary approach for uranium immobilization in the aquatic system. This study investigated the kinetics of U(VI) reduction by nanoscale zero-valent iron under different conditions over the pH range from 6.92 to 9.03. The results showed complexing reagents (bicarbonate, phenanthroline and triethanolamine) and temperature had major impacts on U(VI) reduction. For instance, at pH 6.92, the observed pseudo-first order reduction rate constants were about 22, 5 and 5 times lower than the control system without complexing reagents, when 5 mM bicarbonate, 1.5 mM phenanthroline, or 1.5 mM triethanolamine were added individually. In the presence of 5 mM bicarbonate, the observed pseudo-first order rate constants increased from 0.0084 to 1.43 h-1 with a temperature increase from 5 to 35°. The impacts of nanoscale zero-valent iron types on U(VI) reduction were also evaluated. ENVR 509 Roles of Pb(III) intermediates and hydroxyl radicals in the formation of PbO2 in Pb(II) oxidation by chlorine H. Liu, [email protected], G. Korshin, [email protected], and J. Ferguson, [email protected] Department of Civil and Environmental Engineering, University of Washington, Seattle, WA, United States The mobility of lead, one of the most dangerous contaminants, is dramatically affected by its oxidation state (+2 or +4). In drinking water systems, lead dioxide PbO2 exists as a highly dispersed phase formed via the oxidation by chlorine of Pb(II) solids found in corrosion scales. This oxidation process is likely to be associated with the generation of unstable Pb(III) intermediates whose nature and formation remain largely unexplored. In this study, we employed electrochemical methods such the technique of rotating ring disk electrode (RRDE) to quantify the generation of Pb(III) intermediates during Pb(II) oxidation. Results show that EC generation of Pb(III) intermediates is controlled by the production of hydroxyl radicals whose yields increase as nano-nuclei of PbO2 are formed on the electrode surface. Similar processes were determined to occur in non-electrochemically controlled aquatic system where the oxidation of Pb(II) by chlorine was also observed to decrease in the presence of specific hydroxyl radical scavengers such as p-chlorobenzoic acid (pCBA). These new findings provide new insights into the nature of major mechanisms affecting the redox chemistry of lead in drinking water conditions. ENVR 510 Mechanistic insights to the influence of adsorbed organic macromolecules on nanoparticle reactivity, toxicity, and mobility in porous media

T. Phenrat1,2, J. E. Song1,2, C. M. Cisneros1, D. P. Schoenfelder1, S. Chaithiraphant1, R. D. Tilton1,2, and G. V. Lowry1,2,3, [email protected] 1Civil & Environemntal Engineering, Carnegie Mellon University, Pittsburgh, PA, United States, 2Center for Environmental Implications of Nanotechnology (CEINT), Pittsburgh, PA, United States, 3Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA, United States Most nanoparticles (colloids) used in consumer products are coated with engineered polymeric surface modifiers to provide functionality or enhance their dispersion stability. These materials will also encounter natural organic matter (NOM) once released into the environment. Adsorption of engineered and NOM alters NP surface properties and therefore the interfacial phenomena governing NP reactivity, toxicity, and mobility in porous media. Here we discuss an approach to characterize the adsorbed polymer layer properties to provide mechanistic understanding of how the coating properties affect reactivity, toxicity, and mobility of NPs. Adsorbed polymer and NOM decreases reactivity of Fe0 nanoparticles by site blocking coupled with the decrease in availability of pollutants (TCE) via the adsorption to the macromolecule layer. Adsorbed biopolymer decreases the neurotoxicity to mammalian cells and antimicrobial properties of Fe0 nanoparticles, presumably due to the decrease of particle-cell interaction coupled with the lower intrinsic reactivity. However, adsorbed engineered and natural macromolecules increase NP mobility in porous media via electrosteric repulsions. Regression analysis of published data on the collision efficiency of NOM-coated latex and hematite particles, and on new data collected for poly(styrene sulfonate)-, carboxy methyl cellulose, and polyaspartate-coated hematite and titanium dioxide nanoparticles was used to develop an empirical correlation for determining the collision efficiency of NOMand polymer-coated nanomaterials. This correlation required a new dimensionless parameter, NLEK, representing electrosteric repulsions and lubrication afforded by adsorbed NOM or polyelectrolyte. An empirical correlation with three dimensionless parameters can predict the measured collision efficiency on coated nanoparticles over a wide dynamic range in particle type, coating type, and solution conditions (;80 data points). This study emphasizes the necessary of including the adsorbed NOM and polymer layer properties of the properties for understanding reactivity, toxicity, and mobility of NOM- and polymer-coated natural and manufactured nanomaterials. ENVR 511 Stability and aggregation of metal oxide nanoparticles in natural aqueous matrices A. A. Keller1, [email protected], H. Lenihan1, B. Cardinale1, R. Miller1, H. Wang1, D. Zhou1, and G. Cherr2. 1UC Center for Environ. Implic. Nanotech., University of California, Santa Barbara, Santa Barbara, CA, United States, 2 Bodega Marine Laboratory, University of California, Davis, Bodega, CA, United States

There is a pressing need for information on the mobility of nanoparticles in the complex aqueous matrices found in realistic environmental conditions. We dispersed three different metal oxide nanoparticles (TiO2, ZnO and CeO2) in samples taken from eight different aqueous media associated with seawater, lagoon, river, and groundwater, and measured their electrophoretic mobility, state of aggregation, and rate of sedimentation. The electrophoretic mobility of the particles in a given aqueous media was dominated by the concentration of natural organic matter (NOM) and IS, and was functionally independent of pH. NOM adsorbed onto these nanoparticles significantly reduces their aggregation, stabilizing them under many conditions. The relative rate of sedimentation in the various waters followed DLVO theory when the actual zeta potential was considered in the calculation. The transition from reaction to diffusion limited aggregation for the nanoparticle-to-nanoparticle attachment coefficient can be predicted from their measured electrophoretic mobility. ENVR 512 Evaluating the stability of nano-sized hematite in the presence of dicarboxylic acids J. J. Lenhart1, [email protected], S. E. Mylon2, R. Heyler2, E. M. Walton2, and Y. S. Hwang3. 1Department of Civil and Environmental Engineering and Geodetic Science, The Ohio State University, Columbus, Ohio, United States, 2Department of Chemistry, Lafayette College, Easton, PA, United States, 3Department of Civil and Environmental Engineering, Rice University, Houston, TX, United States Low molecular weight organic acids are a ubiquitous component of aquatic systems. This important pool of reactive ligands binds to mineral surfaces and thus significantly influences their physicochemical behavior. Predicting the impact of the adsorbed organic acids on the properties of the underlying mineral hinges upon integrating molecular-level understanding of the controlling surface complexation mechanisms with macro-scale observations of mineral behavior. We are examining the aggregation kinetics of nano-sized hematite in the presence of a suite of dicarboxylic acids of similar size and structure. Results indicate the structure of the adsorbed acid as determined from attenuated total reflectance Fourier-transform infrared spectroscopy, not the mode of adsorption, defines the resulting effect. For example, maleic acid, which directs both carboxyl groups to the surface when it binds enhances stability as defined by the critical coagulation concentration, whereas fumaric acid which binds with just one group appears to only marginally influence particle stability. ENVR 513 Influence of natural organic matter on the dissolution and bioavailability of silver nanoparticles

J. Gao1,2, [email protected], D. Barber3, [email protected], Y. Wang2, [email protected], K. Powers1, [email protected], B. Koopman1,2, [email protected], and B. Moudgil1, [email protected] 1Particle Engineering Research Center, University of Florida, Gainesville, FL, United States, 2 Department of Environmental Engineering Sciences, University of Florida, Gainesville, FL, United States, 3Center for Environmental and Human Toxicology, University of Florida, Gainesville, FL, United States Adsorption of natural organic matter (NOM) on nanoparticles can have dramatic impacts on particle dispersion resulting in altered fate and transport as well as bioavailability and toxicity. In this study, the adsorption isotherm of Suwannee River Humic Acid on silver nanoparticles was determined and showed a Langmuir adsorption at pH 7. It was also revealed that addition of low NOM increased the Ag content remaining in the system following ultracentrifugation, likely due to increased dissolution or dispersion; however, silver content decreased with increasing amount of NOM. Treatment of Daphnia with Ag nanoparticles (50 µg/L and pH 7) produced a linear decrease in toxicity with increasing NOM. These results clearly indicate the importance of water chemistry on toxicity of nanoparticulates and stress the importance of determining responsible mechanisms. ENVR 514 Role of natural organic matter of different composition on quantum dots stability and transformations V. I. Slaveykova, [email protected] Environmental Biophysical Chemistry, Swiss Federal Institute of Technology Lausanne (EPFL), Lausanne, VD, Switzerland The present study examines the role of pH, ionic strength, presence of humic or alginic acids, extracellular polymeric substances (EPS), on the stability and transformation of carboxyl-PEG-CdSe/ZnS core/shell quantum dots (QDs) in terms of number, hydrodynamic size and fluorescence of individual particles. Obtained results demonstrated that QDs form stable dispersions at nanomolar concentrations under conditions typical for freshwaters. Five or 15 mg C L-1 of humic acid or 50 mg C L-1 EPS did not significantly affect these parameters. In contrast, 5 or 50 mg C L-1 alginate shifted the hydrodynamic radius toward larger values, suggesting a possible capture of QDs by the alginate chains. Characterization of the QDs size and stability, and nanoparticles in general, in the presence of different organic constituents found in the aquatic systems is of utmost importance for the elucidation of the fate and potential impact of NPs in the environment. ENVR 515

Growth and aggregation of ZnS nanoparticles during coprecipitation with aquatic humic substances A. Deonarine1, B. L. T. Lau1, H. Hsu-Kim1, [email protected], G. R. Aiken2, and J. N. Ryan3. 1Department of Civil & Environmental Engineering, Duke University, Durham, NC, United States, 2U.S. Geological Survey, Boulder, CO, United States, 3Department of Civil, Environmental, and Architechtural Engineering, University of Colorado, Boulder, CO, United States Nanoparticulate metal sulfides such as ZnS are important for the speciation of pollutant metals in sediments, wastewater effluent, and other sulfidic environments. The aim of this work was to investigate how the composition of dissolved natural organic matter (NOM) influences colloidal stability as these nanoparticles precipitate in natural waters. In our previous work, we showed that for low molecular weight organics, surface association by thiol groups was important for stabilizing ZnS nanoparticles in water. Humic substances, however, are complex molecules that can interact with nanoparticle urfaces through shortrange interactions (e.g., surface complexation) and long-range interactions (e.g., electrosteric effects) that will influence overall nanoparticle stability. n this study, we compared several NOM fractions that were isolated from several surface waters and represented a range of characteristics (molecular weight, type of carbon, sulfur content, etc.). Dynamic light scattering was employed to monitor the size of ZnS nanoparticles as they precipitated and aggregated in solution containing dissolved NOM isolates. Particle growth was measured over time scales of hours to ; 1 day. Overall, growth rates were slower as NOM concentration increased (from 1 to 10 mg-C/L) and faster as ionic strength increased (from 0.01 to 0.1 M NaNO3). For the same NOM concentration and ionic strength, particle growth rates varied for the different type of NOM isolates. Rates appeared to correlate with the specific UV absorbance (wavelength=280 nm) of the NOM (R2 =0.62), weakly correlate with aromatic C content (R2 = 0.45) and molecular weight (R2=0.24), and poorly correlate with reduced-S content (R2 =0.03). Moreover, humic acid fractions were more effective in preventing aggregation compared to the respective fulvic acid fractions isolated from the same water body. These results highlight the important molecular components of NOM that may be responsible for surface association with ZnS nanoparticles, and ultimately, colloidal stability and mobility. ENVR 516 Natural organic matter enhanced mobility of nano zero-valent iron R. L. Johnson, [email protected], G. O'Brien Johnson, J. T. Nurmi, and P. G. Tratnyek. Oregon Health & Science University, Beaverton, OR, United States Column studies showed that the mobility of nanometer-sized zero-valent iron (nZVI) through granular media is greatly increased in the presence of natural organic matter (NOM). At NOM concentrations of 20 mg/L or greater, the nZVI

was highly mobile during transport experiments in 0.15-meter long columns packed with medium sand. Below 20 mg/L NOM, mobility of the nZVI was less; however, even at 2 mg/L the nZVI showed significantly increased mobility compared to the no-NOM case. Spectrophotometric and aggregation studies of nZVI suspensions in the presence of NOM suggest that sorption of the NOM onto the nZVI, resulting in a reduced sticking coefficient, may be the primary mechanism of enhanced mobility. Modeling the mobility of nZVI in porous media with filtration theory is challenging, but calibration of a simple model with experimental results from the column experiments reported here allows simulation of transport distances during injection. The simulation results show that the increased mobility due to NOM combined with the decrease in mobility due to decreased velocity with distance from an injection well could produce an injection zone that is wide enough to be useful for remediation but small enough to avoid reaching unwanted receptors. ENVR 517 Transport of engineered iron oxide nanoparticles in porous media in water: Effects of pH and natural organic matter W. Wang, [email protected], L. Liang, and B. Gu. Environmental Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, United States Transport of engineered iron oxide nanoparticles in porous media (quartz sand) in aqueous system was studied. Hematite and magnetite nanoparticles with average sizes ;15±10 nm were synthesized and used for the batch and column flow experiments. Deposition of the iron oxide nanoparticles on quartz was observed by scanning electron microscope, and nanoparticle aggregation was monitored in situ by small angle neutron scattering (SANS) measurements. Zeta potential measurements showed that surface charges reverse from positive to negative at pH 7.8 and 6.7 for pure hematite and magnetite, respectively, indicating that the point of zero charge (pzc) of these particles is near neutral. Column experiments showed that negatively charged iron oxide particles at high pH (pH=9.5) are stable and could transport through the porous media due to electrostatic repulsive forces between the nanoparticles and quartz. At low pH (pH=4.5), the iron oxide nanoparticles strongly interact with quartz surface and deposit onto the porous quartz media. SANS measurements indicate that both hematite and magnetite nanoparticles extensively aggregate in water at pH near the pzc (pH 6;8). However, adsorption of natural organic matter (NOM) such as humic acid and fulvic acid on iron oxides can shift pzc of the nanoparticles to lower pH, and breakthrough curves of iron oxide nanoparticles showed enhanced colloid migration in the quartz sand column near neutral pH. This research provides additional insights on how engineered nanoparticles transport and deposit in aqueous environmental system. ENVR 518

Community analysis and long-term performance of microbial fuel cells fed individual fermentation endproducts P. D. Kiely, [email protected], G. Rader, J. M. Regan, and B. E. Logan. Department of Civil and Environmental Engineering, Penn State University, State College, PA, United States Microbial fuel cells were operated for more than one year with individual fermentation endproducts of lignocellulose fermentation. Reactors were fed acetic, formic, lactic or succinic acid, or ethanol. Successful colonizers of each reactor, characterized by 16S clone libraries, included Rhodobacteraceae (Paracoccus denitrificans), Geobacteraceae (Pelobacter propionicus), Bradyrhizobiaceae (Rhodopseudomonas palustris), and Peptococcaceae (Desulfitobacterium hafniense). Delta Proteobacteria dominated most reactors, with the microbe Pelobacter propionicus dominating reactors fed lactic or acetic acid and making up a substantial proportion of reactors fed ethanol or succinic acid. 16S sequence information identified strains with significant similarity to previously identified exoelectrogens including, various Geobacter species, Rhodopseudomonas palustris and Desulfitobacterium hafniense. There were large variations in reactor performance with the different substrates, with power densities ranging from 835 mW/m3 (acetic acid) to 62 mW/m3 (formic acid), and Coulombic efficiencies (CE) of 20.6 % (acetic acid) to 4.8 (formic acid). Cathode performance deteriorated over time, as demonstrated by increases of 4% (succinic acid) to 118% (ethanol) when new cathodes were used. These results provide valuable insights into the effects of long-term MFC operation on reactor performance, cathode deterioration, and anodic microbial diversity. ENVR 519 Miniature microbial fuel cells with air-exposed anodes B. R. Ringeisen1, [email protected], J. C. Biffinger1, L. A. Fitzgerald1, S. Lizewski1, R. Ray1, B. Little1, P. K. Wu2, and E. Howard1. 1U.S. Naval Research Laboratory, United States, 2Southern Oregon University, United States Some of the most promising applications for microbial fuel cell (MFC) technology involve function in anaerobic environments such as wastewater, industrial sludge or marine sediment. In the past several years, distributed autonomous sensor (DAS) networks have been hailed as a paradigm-shifting technology to achieve persistent surveillance. Due to sensing and communication requirements, many of the environments DAS networks operate in are either air-exposed or fully aerobic. In order to achieve true persistence in the field (years), energy harvesting must be used to achieve autonomous power generation. Aerobic or air-exposed MFCs offer the potential to act as energy harvesters, utilizing carbon sources found in natural environments such as the littorals, lakes and rivers. We have developed several small-scale aerobic MFCs including pumped, passive and high throughput devices. We will present recent results where novel

facultative anaerobes or mixed cultures were used to generate current in miniature MFCs operating in air-exposed environments. ENVR 520 Microfabricated microbial fuel cell array for screening of electrochemically active microbes H. Hou1, [email protected], L. Li2, Y. Cho3, P. de Figueiredo2,4, and A. Han1,5. 1Department of Electrical and Computer Engineering, Texas A&M University, College Station, TX, United States, 2Department of Plant Pathology and Microbiology, Texas A&M University, College Station, TX, United States, 3 School of Mechanical Design and Automation Engineering, Seoul National University of Technology, Seoul, Republic of Korea, 4Department of Veterinary Pathobiology, Texas A&M University, College Station, TX, United States, 5 Department of Biomedical Engineering, Texas A&M University, College Station, TX, United States Microbial fuel cells (MFCs) are devices that directly generate electricity from organic compounds. Development of efficient MFCs capable of producing high power requires not only optimization of MFC designs, but also exploring more electrochemically active microbes and finding optimum operating conditions. Devices capable of high throughput analysis can greatly accelerate these efforts. Here, we describe the development of an MFC array, a compact and userfriendly platform for direct characterization and comparison of electrochemically active microbes in parallel. The MFC array consists of 24 independent miniature MFCs on a single 5 x 7.5 cm chip format, capable of 24 parallel analyses. The electricity generation profiles of the spatially distinct MFC chambers on the array loaded with Shewanella oneidensis MR-1 differed by less than 8%. A screening of environmental microbes using the MFC array identified an isolate displaying 2.3-fold higher power than the S. oneidensis MR-1 reference strain, validated using a conventional MFC. ENVR 521 Anode potential regulates microbial competition between anode-respiring bacteria and methanogens in the biofilm anode H.-S. Lee, [email protected], and B. E. Rittmann, [email protected] The Biodesign Institute at Arizona State University, Center for Environmental Biotechnology, Tempe, AZ, United States Single-chamber microbial electrolysis cells (MECs) seem promising for renewable H2 generation, because they minimize the ohmic over-potential by eliminating the membrane. However, H2 produced at the cathode can be consumed by H2-oxidizing microorganisms in the single-chamber MECs, with CH4 being a significance H2 sink. Thus, suppressing methanogenesis is a key for

high-yield H2 production in single-chamber MECs. Anode-respiring bacteria gain energy from the potential difference between donor substrate and their terminal intracellular electron carrier. Anode potential (Eanode) should regulate the potential for the terminal carrier, and the carrier's potential must be more negative than the anode potential to allow electron flow. We evaluated CH4 formation in a singlechamber MEC at Eanode values from -0.03 to -0.23 V vs. SHE. Electron balances showed that CH4 was the largest electron sink, consuming from 11% to 28% of acetate electrons as Eanode was decreased from -0.03 V to -0.23 V. ENVR 522 Multi-anode/cathode granular activated carbon microbial fuel cells (MACGACMFC): A costeffective design for high power generation from wastewater treatment B. Li, [email protected], and D. Jiang, [email protected] Civil and Environmenal Engineering, University of Connecticut, Storrs, CT, United States A novel MFC configuration, multianode/cathode granular activated carbon MFC (MAC-GACMFC) was developed with multiple graphite rods inserted into the GAC bed as anodes and multiple pieces of carbon cloth as cathodes. The unique feature of the MAC-GACMFC was that it incorporated multiple MFCs into a single unit, which improved the power generation at low operational cost and space occupation. The lab-scale tests showed that the power density of the 4anode/cathode GACMFCs was four times that of single-electrode GACMFCs. Meanwhile, the 4-anode/cathode GACMFCs exhibited better abilities to operate at high COD concentrations. In addition, electrode distance was the main factor for internal resistance (Rin). The single-electrode GACMFCs with same electrode distance but different cathode areas had the similar Rin, while the Rin varied substantially along the depth of MAC-GACMFCs. Multiple electrodes efficiently increased the capability of organic substrate degradation and electron acceptance, and led to high power generation. ENVR 523 Microliter-scale microbial fuel cells for on-chip bioelectricity generation F. Qian1, [email protected], M. Baum1, [email protected], Q. Gu1, [email protected], and D. E. Morse1,2,3, [email protected] 1Institute for Collaborative Biotechnologies, University of California, Santa Barbara, California, United States, 2California NanoSystems Institute, University of California, Santa Barbara, California, United States, 3Materials Research Laboratory, University of California, Santa Barbara, California, United States Microbial fuel cells (MFC) offer the possibility of harvesting electricity from organic substrates and renewable biomass through catalytic conversion by microorganisms. Recently there has been a growing interest in small-scale devices for studying fundamental bacteria/anode coupling and electron transfer.

In this regard, we developed microliter-scale MFCs that allow on-chip bacterial culture and bioelectricity generation. The MFC contains a well-defined 1.5-L anode chamber and 4-L cathode chamber, capable of microfluidic deliveries of both growth medium and catholyte. Different anode materials including gold and carbon were incorporated for bacterial growth. After inoculation of Shewanella oneidensis MR-1, quick current response was observed on an external load, repeatable with replenishment of organic substrates, and sustained for up to two weeks. A maximum current density of 1300 A/m3 and power density of 15 W/m3 were achieved using a flat gold anode. Electron microscopic studies revealed large-scale, uniform biofilm growth on the anode, and suggested that the small chamber volume could lead to enhanced bacterial colonization. Our result represents a versatile platform for studying the electron transfer at the interface of electrogenic cells and a variety of anode materials in MFCs, and suggests the possibility of powering nanodevices using on-chip bioenergy. ENVR 524 Coupled system optimization and economic analysis for the design of microbial fuel cells treating wastewater M. Silver1,4, [email protected], J. Buck2,4, [email protected], and N. Taylor3,4, [email protected] 1Engineering Systems Division, Massachusetts Institute of Technology, Cambridge, MA, United States, 2Department of Biological Engineering, Massachusetts Institute of Technology, Cambridge, MA, United States, 3Department of Biological Engineering, Harvard University, Cambridge, MA, United States, 4IntAct Labs LLC, Cambridge, MA, United States Microbial fuel cells are increasingly investigated as a means for simultaneous energy production and water treatment. Few studies have coupled rigorous models of MFC systems to economic analysis. This paper presents simulation studies performed under a Phase I SBIR grant from the United States Department of Agriculture. A pareto-optimization model for MFCs treating wastewater is developed, incorporating key design variables and constraints. This model is coupled to a discounted net-present-value economic analysis of capital and operations costs. Real world data for likely materials cost, energy value, and wastewater treatment values are used. The analysis indicates that for likely values of Biological Oxygen Demand and depending on the performance and capital structure of the MFC design, current rate can be more valuable than power density. These results and related findings have implications for MFC design, scale-up, and operation in the context of wastewater treatment. ENVR 525 From an air-cathode microbial fuel cell (MFC) to an air-cathode microbial desalination cell (MDC)

M. A. Mehanna1, [email protected], T. Saito1,2, J. Yang2, M. Hickner2, X. Cao3, X. Huang3, and B. E. Logan1. 1Department of Civil and Environmental Engineering, The Pennsylvania State University, State College, PA, United States, 2Department of Materials Science and Engineering, The Pennsylvania State University, State College, PA, United States, 3Department of Environmental Science and Engineering, Tsinghua University, State Key Joint Laboratory of Environment Simulation and Pollution Control, Beijing, P.R., China An air-cathode MDC was built by modifying a MFC to include three compartments, with the middle desalination compartment separated from the anode by an anion exchange membrane, and the air-cathode by a cation exchange membrane. Bacteria oxidize organic matter on the anode and release electrons to the anode and protons into the water producing electrical current. In order to balance charges, sodium chloride ions are removed from the middle compartment. Thus water is desalinated by the electricity generated by the bacteria. Parameters that were investigated include the concentrations of the initial substrate and the salt water. To improve the extent of desalination, we examined the performance of two custom-made membranes having higher ion exchange capacities than the commercially available membranes. Desalination was improved by 26%. Using this air-cathode MDC we achieved up to 63% desalination and produced power densities as high as 480 mW/m2. Coulombic efficiencies reached 60%. ENVR 526 Total nitrogen removal in a single-chamber, plug-flow microbial fuel cell C. S. Butler, J. P. Pavissich, [email protected], and R. Nerenberg. Department of Civil Engineering and Geological Sciences, University of Notre Dame, Notre Dame, IN, United States Microbial fuel cells (MFCs) can produce energy while removing BOD from wastewater, and MFCs with a biocathode can additionally achieve denitrification. However, MFCs cannot achieve nitrification. We propose a novel plug-flow MFC for BOD and total nitrogen removal, where nitrifying hollow-fiber membranes (HFMs) are integrated into the cathode. The process consists of a plug-flow reactor receiving BOD and ammonium. BOD is oxidized at the anode. Protons from BOD oxidzation and the influent ammonium, are conveyed by the flow to the cathode. In the cathode, racks of nitrifying HFMs are alternated with denitrifying biocathodes, providing nitrification and denitrification. No proton exchange membrane (PEM) is required and pH shifts are minimized. This configuration obtained a power density of 296 mW/m3 (5 mW/m2 cathode) and a coulombic efficiency of 17%. Nitrification and denitrification fluxes were up to 1.7 g NH4+N/m2 HFM/d and 1.6 g NO3--N/m2 cathode/d, respectively. We currently are developing a mathematical model to identify optimal operating conditions and potential configurations for scale-up.

ENVR 527 Perchlorate degradation using divalent titanium: Equilibrium, kinetic, and spectrophotometric study with modeling S. Park1, [email protected], C. Lee2, and B. Batchelor1. 1Department of Civil Engineering, Texas A&M University, College Station, TX, United States, 2 Research and Development, Doosan Hydro Technology, Inc, Tampa, FL, United States Perchlorate (ClO4-) is reported to be reduced only very slowly by most chemical reductants. This study was undertaken to determine the feasibility of developing treatment processes to destroy perchlorate by reaction with Ti(II). UV-visible spectra were used to investigate the characteristics of Ti(II) solutions. Effects of concentrations of titanium metal, acid and fluoride on production of Ti(II) and its ability to reduce perchlorate were examined through numerous batch, kinetic experiments. To enhance the reaction, five potential metal catalysts (molybdenum, copper, nickel, rhenium, tungsten) were evaluated. Second-order rate constants for perchlorate reduction were obtained from results of kinetic experiments. The fastest perchlorate degradation occurred with higher Ti(0) concentration, higher hydrochloric acid concentration and lower fluoride concentration. (k=0.199 mM-1day-1, half life=0.03 day)

This treatment process is suitable for solutions with high concentration of perchlorate such as found in waste ion exchange regenerants. ENVR 528

Bicarbonate-form anion exchange: Efficacy for water treatment and innovative regeneration techniques C. Rokicki, [email protected], and T. H. Boyer, [email protected] Department of Environmental Engineering Sciences, University of Florida, Gainesville, FL, United States Anion exchange is an effective process for removing contaminants from water, whereby resin-phase chloride exchanges with aqueous contaminants. A major limitation of anion exchange treatment is the disposal of a sodium chloride waste solution from the regeneration process. The goal of this work is to evaluate the efficacy of anion exchange using bicarbonate-form resin, which would eliminate the high salinity waste stream. Preliminary results show that carbon dioxide gas can be used to regenerate anion exchange resin.

ENVR 529 Electrocoagulation pretreatment for microfiltration: A sustainable combination to enhance water quality and reduce fouling in integrated membrane systems S. Chellam, [email protected], A. Bagga, and D. Clifford. Civil and Environmental Engineering, University of Houston, Houston, Texas, United States Several factors including deteriorations in source water quality and population growth have spurred the implementation of membrane technologies for water and wastewater treatment. Coagulating the feed water prior to microfiltration often reduces fouling and simultaneously improves filtered water quality. Electrocoagulation is a more sustainable alternative to conventional chemical coagulation since it nearly eliminates the direct handling of corrosive chemicals, does not affect alkalinity and bulk pH, and consequently can be easily adapted for use in portable water treatment units. The principal objective of this study was to compare iron electrocoagulation and conventional iron chemical coagulation to treat natural surface water prior to microfiltration. Dominant fouling mechanisms

over various time scales during microfiltration of raw and coagulated waters were also delineated. Performance was evaluated using both natural organic matter removal and transient flux decline data in the dead-end filtration mode over a range of coagulant dosages, pH, and transmembrane pressures. ENVR 530 Waste byproduct materials for removal of phosphorus from organic-rich surface water T. H. Boyer, [email protected], A. Persaud, P. Banerjee, P. Palomino, M. T. Brown, S. Arden, and R. J. Sindelar. Department of Environmental Engineering Sciences, University of Florida, Gainesville, FL, United States The goal of this work is to improve surface water quality by removing phosphorus (P) from tributaries that drain into lakes. This will be accomplished by a floating island treatment system that combines biological and physical-chemical treatment. This presentation will focus on the results of laboratory- and pilot-scale physical-chemical treatment experiments. The specific objective of this work is to evaluate the effectiveness of waste byproduct materials, such as recycled concrete and water treatment residuals, for P removal (Figure 1).

ENVR 531 Photocatalytic destruction of methyl t-butyl ether (MTBE) and 1,4-Dioxane and other water soluble ethers using visible light R. D. Barreto, [email protected], and D. A. Wood. Department of Biology and Chemistry, Purdue University North Central, Westville, IN, United States Water soluble ethers such as methyl t-butyl ether (MTBE) and 1,4-dioxane are common gasoline additives and solvents. Other compounds such as ethyl t-butyl ether (ETBE), t-amyl methyl ether (TAME) and diisopropyl ether (DIPE) are also

water soluble ethers and potential sources of water contamination. Previous work showed that MTBE, ETBE and TAME can be degraded using TiO2 in a batch slurry process. The pseudo first-order rate constant for degradation of MTBE, 1.2 x 10-3 s-1, ETBE, 4.63 x 10-4 s-1 and TAME, 5.63 x 10-4 s-1 with the process being attributed to photocatalytically by ultra-violet (UV) light. This work shows that MTBE, ETBE and TAME along with 1,4-Dioxane and DIPE are actually undergoing a degradation process involving visible light. Using the a batch slurry process incorporating a borosilicate filter that eliminated UV light, rate constant for degradation for MTBE, 4.2 x 10-4 s-1, ETBE, 4.63 x 10-4 s-1 and TAME, 7.72 x 10-4 s-1 were observed, comparable with those seen previously, while 1,4Dioxane and DIPE showed rates of 1.1 x 10-3 s-1 and, 6.3 x 10-4 s-1 respectively. In all cases, over 80% of the initial substrate was destroyed in less than 150 min. ENVR 532 Bio-based arsenic sorbent S. M. Miller, [email protected], and J. B. Zimmerman. Department of Chemical Engineering, Yale University, New Haven, CT, United States Arsenic contamination of the groundwater in and around Bangladesh poses a significant human health crisis. We have synthesized a novel bio-based arsenic sorbent: TiO2-impregnated chitosan beads (TICB). TICB is capable of removing both predominant forms of arsenic in groundwater, arsenate (As(V)) and arsenite (As(III)), from solution. Furthermore, in the presence of UV light, TICB is capable of oxidizing arsenite, the species that is most toxic and most resistant to conventional water treatment technologies, to arsenate for enhanced removal. The effectiveness of this sorbent across water quality parameters and a proposed mechanism of sorption will be reported. ENVR 533 Effect of solar disinfection on viral consituents K. R. Wigginton, [email protected], B. M. Pecson, [email protected], and T. Kohn, [email protected] Environmental Engineering Institute, Ecole Polytechnique Federale de Lausanne, Lausanne, Vaud, Switzerland Despite the widespread use of sunlight as a natural water disinfectant, little is known about the specific photoxidative mechanisms involved in sunlightmediated virus inactivation. Here we examine the reactions that occur as MS2 viruses are treated with UV irradiation and singlet oxygen (1O2), a reactive oxygen species that plays an important role in virus inactivation in surface waters. Viral capsid protein integrety was monitored with Matrix Assisted Laser Desporption Ionization (MALDI) and LC-MS-MS and enzymatic digestions were carried out to identify the location of protein oxidation. Preliminary results have demonstrated that extensive oxidative damage occurs within the virus proteins

when treated with UV and singlet oxygen, that the oxidative products from UV treatment differ significantly from those detected during 1O2 treatment, and suggest that capsid protein oxidation may play significant a role in virus inactivation. ENVR 534 Role of one and two electron transfer reactions in forming thermodynamically unstable intermediates as barriers in multi-electron redox reactions G. W. Luther, [email protected] College of Earth, Ocean, and Environment, University of Delaware, Lewes, DE, United States Thermodynamic calculations are performed for one or two-electron transfer steps and compared with known reactivity to determine the rate controlling step in a multi-electron reaction. Calculations are presented for selected reactions for compounds of C, O, N, S, Fe, Mn and Cu. The first step in reducing oxygen and nitrate with Fe(II) and Mn(II) is rate limiting as is the first step in oxidizing H2S and NH4+ with oxygen. Sulfide oxidation by Cu(II), Fe(III) and Mn(III,IV) phases in two-electron transfer steps is favorable but not in one-electron steps indicating that (nano)particles with bands of orbitals are needed to accept two electrons from sulfide. Ammonium oxidation by Fe(III) and Mn(III,IV) phases is generally not favorable for both one and two-electron transfer steps. The anammox reaction using hydroxylamine via nitrite reduction is the most favorable for NH4+ oxidation. Other chemical processes including photosynthesis and chemosynthesis and possible catalysts are considered for these transformations. ENVR 535 Assessment of the voltammetric evidence for FeS(aq) in sulfidic waters G. R. Helz1, [email protected], E. Bura-Nakic2, I. Ciglenecki2, and D. Krznaric2. 1 Chemistry and Biochemistry, University of Maryland, College Park, MD, United States, 2Marine and Environmental Research, Rudjer Boskovic Institute, Zagreb, Croatia Voltammetric scans of sulfidic natural waters often reveal electrochemical reduction signals near -1.1 V, commonly attributed to a dissolved iron sulfide species, possibly an FenSn cluster (designated FeS(aq) generically). Ambiguities surround its reported chemical composition, its properties, and its role in transport and bioavailability of iron. Cyclic voltammetry at Hg electrodes shows that the FeS(aq) signal arises not from a dissolved species, but from reduction of Fe2+ ions on FeS adlayers. FeS adlayers form on Hg electrodes by three mechanisms: replacement of HgS adlayers, capture of FeS nanoparticles from solution, or oxidation of Fe(0) sorbed to FeS adlayers in the presence of free sulfide. Because Fe2+ reduction commences at -1.1 V in sulfidic solutions, rather

than at -1.4 V as usually assumed, this ion has probably been underdetermined in much previous work. ENVR 536 Investigation of the kinetics of Cr(VI) reduction in the presence of cationic polysulfides A. Ting, [email protected], and M. Chrysochoou. Department of Environmental Engineering, University of Connecticut, Storrs, CT, United States Chemically reducing the wide-spread industrial contaminant, hexavalent chromium (Cr(VI)), to its less toxic and less mobile form, trivalent chromium (Cr(III)), has become more feasible and cost effective than ex-situ treatment. Calcium polysulfide, (CPS), has been utilized extensively for reducing Cr(VI) within chromite ore processing residue (COPR) and for field tests focusing on water contamination. While CPS has been tried in the field, no literature exists that investigates the kinetic rate and mechanisms associated with Cr(VI) reduction with polysulfides within the soil/water environment. This study evaluates the kinetics of the reaction between Cr(VI) and polysulfides under varying pH, dissolved oxygen levels, and Cr speciations (aqueous/adsorbed to FeOOH) to simulate changing conditions in soil environments. Preliminary kinetic data show that the kinetic rate of aqueous Cr(VI) reduction by polysulfides is very quick even under oxygenated conditions and that pH has a significant effect on the reducing species and the associated kinetic rates. ENVR 537 Surface charge of aggregated iron-oxide nanoparticles in mininginfluenced waters J. F. Ranville1, [email protected], B. N. Gartman1, and K. S. Smith2. 1 Department of Chemistry & Geochemistry, Colorado School of Mines, Golden, CO, United States, 2U.S. Geological Survey, Denver, CO, United States Concern over environmental contamination by engineered nanoparticles (ENPs) has emerged with the rise of the nanotechnology industry. Lack of direct information on ENP stability is a major limitation for risk assessment. Surface charge, a key parameter controlling NP aggregation and stability, is related to water composition (pH, ionic strength, dissolved organic matter). In the absence of information on ENPs, natural NPs (NNPs) could provide analogs useful in estimating ENP aquatic stability. Mining-influenced waters (MIWs) are excellent systems for study due to high concentrations of nanoparticulate hydrous-iron oxides (HFO). We observed in several MIWs, temporal and spatial variations of HFO surface charge, ranging from slightly positive, a rarely seen result, to slightly more negative; HFO aggregation was consistent with these findings. Results suggest both that ENP stability could vary in space and time, and could provide

insight into the question "Do aggregated ENPs pose risks similar to fully dispersed ENPs?" ENVR 538 Redox chemistry of sulfur in an aquifer underneath an industrial site and its incidence on metal solubility M. A. M. Kedziorek1, and A. C. M. Bourg2, [email protected] 1Dept. of Hygiene, Security and Environment, Institute of Technology, University of Bordeaux 1, Gradignan, France, 2Environmental Hydro Geochemistry, Dept. Geociences, University of Pau, Pau, France We investigated a fill phreatic aquifer contaminated by sulfur, acidity and copper beneath an industrial site (manufacturer of "bouillie bordelaise", a Bordeaux mixture). The speciation of sulfur and total copper were investigated in the solids and in the aquifer water. In the top of the cores, total sulfur ranges from 1.5% in the contaminated part of the site to a background value of 0.2% in its periphery were observed. Sulfate is the predominant solid species in the upper layers, especially at the level of the water table. Elemental S is the next most abundant species. Reduced S (degree of oxidation of -II or ­I) is observed, as a minor contributor, mostly in the areas where pyrite used to manufacture sulfuric acid was stored on the ground. Dissolved sulfate is high (up to 44 g/L) in groundwater in the contaminated zone. It controls the solubility of Cu, Ca and Fe. ENVR 539 Influence of organic-matter fractionation by natural iron nanoparticles on copper speciation and aquatic copper toxicity K. S. Smith1, [email protected], J. F. Ranville2, D. J. Diedrich3, D. M. McKnight4, and R. M. Sofield5. 1U.S. Geological Survey, Denver, CO, United States, 2 Department of Chemistry and Geochemistry, Colorado School of Mines, Golden, CO, United States, 3Windward Environmental LLC, Seattle, WA, United States, 4 INSTAAR, University of Colorado, Boulder, CO, United States, 5Department of Environmental Sciences, Western Washington University, Bellingham, WA, United States Dissolved organic matter (DOM) is known to decrease copper toxicity in aquatic environments due to its ability to bind copper. In an iron-rich environment, in this case a mining-influenced water (MIW), we found the protective effect of DOM to be reduced. We propose this is due to preferential binding of a fraction of the DOM with iron-rich nanoparticles formed in the water column. We performed copper-speciation determinations using an ion-selective electrode in laboratoryprepared EPA moderately hard water amended with 6 mg/L DOM that was isolated from (1) a stream receiving acidic iron- and aluminum-rich drainage, (2) an adjacent unimpacted stream, and (3) Suwannee River fulvic acid. Laboratory toxicity tests with Ceriodaphnia dubia were also performed. The differences in

copper toxicity observed for the various DOMs compared well with free-copper measurements. Comparison of free-copper measurements with calculatedcopper speciation using various thermodynamic models produced mixed results depending upon the model used. ENVR 540 Rates and mechanisms of lead(IV) oxide formation and dissolution Y. Xie, [email protected], Y. Wang, and D. E. Giammar. Department of Energy, Environmental and Chemical Engineering, Washington University in St. Louis, St Louis, MO, United States Lead(IV) oxide (PbO2) can develop as a corrosion product in lead service lines through oxidation of lead(0) and lead(II) species by free chlorine, but in the absence of free chlorine PbO2 can reductively dissolve and cause elevated lead concentrations in tap water. Dissolution rates of plattnerite (-PbO2) were quantified as a function of pH and concentrations of dissolved inorganic carbon (DIC), orthophosphate, and monochloramine. The dissolution rate increased with increasing DIC and decreasing pH. Orthophosphate inhibited PbO2 dissolution, and monochloramine decreased the dissolution rate for short contact times. The impact of water chemistry on the formation of PbO2 was studied over a range of pH, lead precursors, free chlorine, DIC, and initial lead concentrations. A threshold ratio of Cl2 to lead(II) to form PbO2 from lead(II) precursors was determined. The identity of the PbO2 polymorph formed depended on the lead(II) precursor and concentrations of total lead and DIC. ENVR 541 Structure and association of bioimmobilized uranium in sediments J. O. Sharp1,2, [email protected], H. Veeramai2, P. Junier2, C. Roquier2, E. J. Schofield3, J. Lezama3, S. Webb3, K.-U. Ulrich4, L. Blue4, S. Chinni5, B. Tebo5, J. Bargar3, and R. Bernier-Latmani2. 1Colorado School of Mines, Golden, CO, United States, 2Ecole Polytechnique Federal de Lausanne, Switzerland, 3 Stanford Synchrotron Radiation Laboratory, Menlo Park, CA, United States, 4 Washington University, St. Louis, MO, United States, 5Oregon Health and Science University, Portland, OR, United States Microbial reduction of uranium is a promising technology for in situ immobilization in contaminated aquifers. While it is traditionally believed that an insoluble precipitate (UO2) dominates these systems, recent studies suggest that interactions with organic matter or iron minerals may lead to alternative forms of reduced uranium in the subsurface. To explore these interactions, bioaugmented soil columns were stimulated for reductive U(VI) immobilization for three months resulting in maximal concentrations in excess of 1mmol U / kg sediment. Structural bulk and microprobe x-ray absorption spectroscopy of harvested

sediments indicate that the majority of immobilized uranium is reduced to U(IV); however, spectra are not consistent with crystalline UO2. Microprobe analyses of heterogeneities yields further insights into the potential association of U(IV) with iron and organic matter. Phylogenetic analysis reveals that while the system was amended with Shewanella, Firmicutes dominated the columns throughout the immobilization process. ENVR 542 Effects of natural and contaminant dissolved organic carbon upon microbial transport through aquifer sediments R. W. Harvey, [email protected], D. W. Metge, L. B. Barber, and G. R. Aiken. National Research Program, U.S. Geological Survey, Boulder, CO, United States The effects of natural and contaminant dissolved organic carbon (DOC) upon microbial transport through aquifer sediments were assessed using flow-through and static columns. Sediments from two sites were used, one from a well-sorted, mildly acidic (pH 5-6) aquifer in Cape Cod, MA and one from a poorly sorted, slightly alkaline (pH 7-8) aquifer in Sonoma County, CA. Grain surfaces in both aquifers were characterized by patches of iron and aluminium oxides. For the Cape Cod sediments, bacterial transport was substantively enhanced in the presence of a C10-14 mixture of linear alkylbenzene surfactant homologs at 25 mg/L, but only under acidic conditions. Imbentin, a nonionic surfactant diminished bacterial transport up to 3-fold under alkaline conditions at only 0.2 mg/L. For the Sonoma County sediments, 2.2 mg/L of the hydrophobic acid fraction of DOC from the Russian River, increased transport of oocysts and carboxylated microspheres (2- and 3-microns) by more than 10-fold. ENVR 543 Effect of organic loading on the transport of Cryptosporidium parvum oocysts and oocysts-sized microspheres through three minerologically different granular porous media A. Mohanram1, [email protected], C. Ray2, R. W. Harvey3, D. W. Metge3, J. N. Ryan4, and J. Chorover5. 1Molecular Bioscience and Bioengineering, University of Hawaii, Manoa, Honolulu, HI, United States, 2Civil and Environmental Engineering, University of Hawaii, Manoa, Honolulu, HI, United States, 3U.S. Geological Survey, Boulder, CO, United States, 4Department of Civil, Environmental and Architectural Engineering, University of Colorado, Boulder, Boulder, CO, United States, 5Department of Soil, Water and Earth Science, University of Arizona, Tucson, Tucson, AZ, United States Flow-column studies were conducted to study effects of organic loading using anionic surfactant, sodium dodecyl sulfate (SDS), and Suwannee river humic acid (SRHA) upon transport of Cryptosporidium parvum oocysts and oocystssized microspheres through two tropical, volcanic (Poamoho and Lalamilo) soils

and one temperate, agricultural (Drummer) soil. Without SDS, 18% and 2% of microspheres and oocysts, respectively, were transported through Poamoho soil. However, in the presence of (0.1 mM) SDS, <1% recovery of oocysts and microspheres were transported in Poamoho soil and there was no breakthrough in Lalamilo soil. For Drummer soil, SDS caused an approximate 2-4- fold increase in transport of aforementioned colloids. In experiments with SRHA (50mg/L), humic acid altered the Poamoho soil causing reversible attachment of microspheres. Our data suggest the character of the organic affects oocyst transport and the presence of surfactant can either retard or enhance the mobility of colloids, depending on the soil type. ENVR 544 Interactions between natural organic matter and gold nanoparticles with different capping agents J. A. Nason, [email protected], and D. P. Stankus, [email protected] School of Chemical, Biological and Environmental Engineering, Oregon State University, Corvallis, Oregon, United States The adsorption of natural organic matter (NOM) to the surfaces of natural colloids and engineered nanoparticles is known to strongly influence, and in some cases control, their surface properties and aggregation behavior. As a result, the understanding of nanoparticle fate, transport and toxicity in natural systems must include a fundamental framework for predicting such behavior. Using a library of well-characterized gold nanoparticles with different capping agents (neutral, anionic, and cationic) and a range of NOM surrogates, we aim to develop a mechanistic understanding of how nanoparticle design (through the choice of stabilizing agent), the presence and nature of the NOM, and aqueous chemistry (pH, ionic strength) influence particle stability. UV-vis spectroscopy and timeresolved dynamic light scattering are being used to characterize nanoparticle aggregation in the presence of NOM surrogates and methods are under development to quantify adsorption through changes in particle electrophoretic mobility with respect to adsorbed NOM. ENVR 545 Influence of natural organic matter on the adhesion of Au nanoparticlescoated polystyrene latex beads to mica using "colloid" probe atomic force microscopy B. J. R. Thio1, [email protected], J. H. Lee2, C. Meredith2, and A. Keller1, [email protected] 1Bren School of Environmental Science and Management, University of California, Santa Barbara, Santa Barbara, CA, United States, 2School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, United States

The rapid growth in the nanomaterials manufacturing in recent years has raised concerns about potential adverse effects on organisms and ecosystems if such man-made nanoparticles are leached into natural aquatic systems during their life-cycle. Natural organic matter (NOM) exists in natural aquatic environments, and readily adsorbs to nanoparticles. However, much is still unknown about nanomaterials' adhesive properties to important biogeochemical surfaces such as mica. Direct adhesion force measurement of a nanoparticle to mica using AFM is difficult as the particle is of the same length scale as a typical curvature of a sharpened AFM tip. We present an alternative by attaching gold-nanoparticles coated micron-sized polystyrene (PS) latex beads onto tipless AFM cantilevers. This `colloid' probe technique is then used to measure the gold nanoparticle adhesion by comparing adhesion forces to a clean PS control bead under different pH and ionic strength conditions in the presence and absence of NOM. ENVR 546 Deposition and aggregation kinetics of rotavirus in the presence of divalent cations and natural organic matter L. A. Gutierrez1, [email protected], N. W. Schmidt2, [email protected], G. C. L. Wong3, [email protected], and T. H. Nguyen1, [email protected] 1 Department of Civil and Environmental Engineering, the Center of Advanced Materials for the Purification of Water with Systems (waterCAMPWS), University of Illinois at Urbana-Champaign, Urbana, Illinois, United States, 2Department of Physics, the Center of Advanced Materials for the Purification of Water with Systems (waterCAMPWS), University of Illinois at Urbana-Champaign, Urbana, Illinois, United States, 3Department of Material Science and Engineering, the Center of Advanced Materials for the Purification of Water with Systems (waterCAMPWS), University of Illinois at Urbana-Champaign, Urbana, Illinois, United States The present study investigated the aggregation kinetic of rotavirus (RV) in solution and its deposition on silica surface and natural organic matter (NOM) surface in the presence of monovalent (Na+) and divalent (Ca2+ and Mg2+) cations and NOM. Salt and NOM concentration were adjusted to mimic environmentally relevant conditions in groundwater. Time-resolved dynamic light scattering (DLS) was used to study aggregation kinetic of RV. Our results show that even at high concentrations of Na+ in solution (600 mM), RV does not aggregate at the timeframe used (4 hours) and at a NOM concentration of 10 mg/l TOC. Although divalent cations certainly caused aggregation of RV al lower concentrations (5 mM), Ca2+ had a more favorable effect that Mg2+ in the aggregation kinetics. Steric interactions would be responsible for this low aggregation rate. On the other hand, quartz crystal microbalance (QCM) coupled with a radial stagnation point flow (RSPF) system was used to study deposition kinetics of rotavirus on silica surface and NOM surface. A more efficient deposition was found when Ca2+ ions were present in solution than Mg2+ at all the concentrations tested (0.1 to 1 mM). Nevertheless, no noticeable deposition

was detected in the presence of Na+. However, classic DLVO theory failed to predict the aggregation behavior of RV as well as its deposition on silica surface. Experimental results in both studies suggest that steric repulsions and electrostatic interactions were the dominant mechanism in the deposition and aggregation kinetics of RV in solution as well as specific interaction with divalent cations. Furthermore, RV deposition on silica soil would behave more favorable in the presence of Ca2+ than Mg2+. ENVR 547 Role of divalent cations on deposition kinetics of Cryptosporidium parvum oocysts onto natural organic matter surfaces D. Janjaroen1, [email protected], Y. Liu1, M. S. Kuhlenschmidt2, T. B. Kuhlenschmidt2, and H. T. Nguyen1, [email protected] 1Department of Civil and Environmental Engineering, University of Illinois at Urbana-Champaign, Urbana, IL, United States, 2Department of Pathobiology, University of Illinois at UrbanaChampaign, Urbana, IL, United States A Radial Stagnation Point Flow (RSPF) system coupled with a microscope was used to study the influence of specific interaction on deposition kinetics of C.parvum oocysts onto quartz and Suwannee River Natural Organic Matter (SRNOM)-coated surface in solutions with different cation concentrations (Ca2+ or Mg2+). Deposition kinetics of viable oocysts were compared with those after treatment with Proteinase K. Inductive Coupled Plasma (ICP) was employed to measure percentage of free cation reduction in deposition solutions. Deposition of oocysts on SRNOM surface in Ca2+ was bserved higher than in Mg2+, even energy barriers calculated from Derjaguin-Landau-Verwey-Overbeek (DLVO) theory for Ca2+ were higher than for Mg2+. ICP data also showed that Ca2+ in solution bound to oocysts surface more than Mg2+. On the other hand, the attachment of oocysts on quartz surface was observed the same in both Ca2+ and Mg2+, which agreed with energy barriers calculated from DLVO and ICP data. The deposition results and ICP data suggested that Ca2+ enhance deposition of oocysts on SRNOM surface because of specific interaction of Ca2+ with carboxyl groups on both SRNOM and oocysts surfaces. ICP data further suggested that Ca2+ bind to treated oocysts less than to viable ones. The deposition of treated oocysts on SRNOM surface also decreased significantly when compared with non-treated oocysts. The result with treated oocysts showed that removal of carboxyl group on oocysts surface led to lower deposition on SRNOM surface. In addition, the maximum attachment efficiency was less than 1 at high cation concentration due to steric interaction. ENVR 548 Surfactant effects on pathogen attachment at the hematite (-Fe2O3)-water interface

X. Gao, [email protected], and J. Chorover, [email protected] Department of Soil, Water & Environmental Science, University of Arizona, Tucson, AZ, United States Prior studies have indicated that the subsurface transport of Cryptosporidium parvum is diminished in sediments containing iron oxides, but the molecular mechanisms are poorly known, as are the impacts thereon of natural organic matter (NOM). Using ATR-FTIR, we examined the molecular mechanisms of viable C. parvum öocyst adhesion at the hematite-water interface over a wide range in solution chemistry. The anionic surfactant sodium dodecylsulfate (SDS) was used as a surrogate for NOM to examine the impacts of surfactant-type components on öocyst adhesion mechanisms. Results indicate öocyst surface carboxylate groups form inner-sphere complexes with hematite Fe metal centres in the absence of SDS. Such direct chemical bonding is likely one mechanism whereby Fe oxides diminish öocyst transport. The presence of SDS significantly diminishes the Fe-carboxylate complexation, suggesting that the sulphate groups of SDS compete effectively for -Fe2O3 surface sites. Such surfactants may, therefore, increase the mobility of öocysts in the environment. ENVR 549 Engineering polymeric nanoparticle coatings for decreased toxicological impacts of nanoscale zero-valent iron K. B. Gregory1,3, [email protected], Z. Li1,3, K. Greden1, P. J. J. Alvarez2, and G. V. Lowry1,3. 1Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, PA, United States, 2Department of Civil and Environmental Engineering, Rice University, Houston, TX, United States, 3Center for Environmental Implications of Nanotechnology, CEINT, Carnegie Mellon University, Pittsburgh, PA, United States Nanoscale zero-valent iron (NZVI) particles that are used in aquifer remediation may come in contact with subsurface bacteria, and may adversely affect subsurface bacteria. Studies showed that NZVI is toxic toward E. coli at concentrations as low as a few mg/L. However, NZVI particles used in remediation are coated with polymers or natural organic matter (NOM). It is unclear how these surface coatings may affect the bactericidal properties of NZVI. The objectives of this study were to assess the effect that (i) coatings (both anthropogenic and natural) and (ii) particle oxidative state have on the bactericidal properties of NZVI on a gram-negative bacteria, Escherichia coli. Bacteria (106 cells/L) were exposed to 100 mg/L of bare or coated NZVI for 60 minutes under either aerobic or anaerobic conditions. Bacteria were plated at specified times over 60 minutes to determine the number of viable bacteria in the reactor. Bare NZVI was cytotoxic at only 100 mg/L NZVI with over 5 log kill after 60 minutes of exposure. Exposure under aerobic conditions resulted in less than 1 log kill. The lower bactericidal effects were due to rapid oxidation of the iron to Fe(II) and Fe(III) mineral phases that are not toxic. All organic coatings on NZVI

decreased or eliminated NZVI cytotoxicity when exposed at the same NZVI concentrations as in the bare case. The decrease in bactericidal effects of coated NZVI over bare NZVI was due to electrosteric repulsions afforded by the coatings that inhibited contact of NZVI with the bacteria. The inhibition of attachment to bacteria was confirmed with TEM and with NZVI sedimentation studies. These studies imply that surface coatings may engineered to minimize or eliminate the toxicological impacts of nanomaterials. ENVR 550 Sorption of genetically modified insecticidal Cry1Ab protein to soil organic matter J. E. Tomaszewski, [email protected], M. Madliger, [email protected], R. P. Schwarzenbach, [email protected], and M. Sander, [email protected] Department of Environmental Sciences, ETH Zurich, Zurich, Zurich, Switzerland Genetically modified Bt crops, which produce insecticidal Cry proteins for pest control, release Cry proteins to agricultural soils. The fate of these proteins in soils remains poorly understood, despite their potential adverse effects on nontarget soil-dwelling organisms. This study focuses on Cry1Ab sorption to and desorption from various humic substances (HS) and reference organic surfaces, at various pH (5 to 8) and ionic strength (10, 50mM), as measured by quartz crystal microbalance. From pH 5 to 7, sorption to HS decreased and desorption increased because of increasing electrostatic repulsion (IEPCry1Ab= 6). Also, at any given pH, sorption increased and sorption reversibility decreased with increasing HS aromaticity, demonstrating hydrophobic interactions. Consistent with these two interactions, sorption to HS at pH>IEPCry1Ab was less than to noncharged apolar polystyrene but greater than to highly negatively charged polyacrylic acid. The results show that both charge and polarity of HS affect the sorption of proteins and, likely, other bio-macromolecules, organic colloids, and nanoparticles. ENVR 551 Evaluation of MFC performances for the treatment of an urban wastewater: Comparison to aerobic treatment and direct electrolysis of biomass B. Erable, [email protected], L. Etcheverry, [email protected], and A. Bergel, [email protected] Bioprocesses, Laboratoire de Génie Chimique, Toulouse, France In collaboration with an international company expert in wastewater treatment, the aim of our work in France was to assess the potential of the MFC technology on the reduction of organic pollution of urban wastewater. Specifically, the treatment of the total organic load (COD) of urban wastewater was studied in MFC prototypes (1 and 25 liters). Aerobic treatment pilots of the same size were

also conducted in parallel. COD removal similar to those obtained in the aerobic reactor was achieved with the MFC technology optimizing the ratio between the electrode surface and the reactor volume. Throughout studies on COD oxidation, we followed the current generated on the bio-anodes in order to establish a correlation between the consumption of organic matter (biomass oxidized) and the production of electricity. The idea behind this monitoring of electrical current is to develop a biosensor for real time COD measurement. ENVR 552 Ionic liquid pretreatment of lignocellulosic materials for enhanced sustainable biogas and electricity generation C. Li1,2, [email protected], H. Hu3, [email protected], H. Liu3, K. P. Vogel4, B. Simmons1,2, and S. Singh1,2. 1Deconstruction, Joint Bioenergy Institute, Emeryville, CA, United States, 2Biomass Science and Conversion Technology Department, Sandia National Laboratories, Livermore, CA, United States, 3 Department of Biological and Ecological Engineering, Oregon State University, Corvallis, OR, United States, 4United States Department of Agriculutre, Grain, Forage and Bioenergy Research Unit, University of Nebraska, Lincoln, NE, United States Pretreatment of lignocellulosic biomass is an essential step for bioenergy production. Ionic liquids (ILs) have demonstrated promise for plant cell wall disruption and lignin rejection. Here, IL pretreatment is carried out on switchgrass to evaluate its effect on biomass conversion into biogas and electricity through anaerobic digestion. Results showed pretreated switchgrass exhibited reduced cellulose crystallinity, increased surface area and decreased lignin content. Microbial electrolysis cell (MEC) and microbial fuel cell (MFC) were used to directly convert switchgrass samples into biogas and electricity respectively. In the MEC system, biogas yield and current density were significantly enhanced by IL pretreatment three-fold. In the MFC system, power density from pretreated biomass was 38% higher than the untreated. These results showed that IL pretreatment has great potential for improving the conversion of lignocellulose into biogas and electricity and its application in the biomass utilization through anaerobic technology holds considerable promise in the near future. ENVR 553 Hydrolyzed sludge from a domestic WWTP as a feedstock for bioelectrochemical systems S. Brown, [email protected], A. Hervo, S. Pratt, and J. Keller. Advanced Water Management Centre, University of Queensland, Brisbane, Queensland, Australia Hydrolysed secondary sludge is a viable substrate for Anaerobic Digestion. The aim of this work was to evaluate the suitability of this material as a feedstock for

a BioElectrochemical System. A lab-scale system consisting of a fermenter in series with two granular-bed BESs was operated. BES performance on both the fermenter effluent and a synthetic feedstock was investigated. The synthetic influent work indicated that acetate and propionate were preferentially oxidised, whilst the key operating parameter was the ratio of the concentration of organic acids to alkalinity. The alkalinity of the fermenter effluent was optimised, firstly with the addition of synthetic phosphate buffer and secondly with anaerobic digester effluent. The optimised fermenter effluent consistently performed better than the equivalent synthetic influent, achieving Coulombic efficiencies > 85% and producing a higher current density. These results illustrate the suitability of hydrolysed biosolids, with future work focusing on reactor design and viable cathode options. ENVR 554 Bioelectrochemical perchlorate reduction in a microbial fuel cell C. Butler1, [email protected], P. Clauwaert2, S. Green3, W. Verstraete2, and R. Nerenberg1. 1Department of Civil Engineering and Geological Sciences, University of Notre Dame, Notre Dame, IN, United States, 2LabMET, Faculty of Bioscience Engineering, University of Ghent, Ghent, Belgium, 3Department of Oceanography, Florida State University, Tallahassee, FL, United States Perchlorate is an emerging surface and groundwater contaminant, and is of concern due to its mobility in the environment and its inhibitory effect on thyroid function. Microbial fuel cells (MFCs) may be a suitable method for its treatment. Perchlorate reduction in an MFC was established by increasing cathodic perchlorate loading, while decreasing nitrate loading. Perchlorate was removed without the need for electron shuttles or fixed electrode potentials, achieving a maximum perchlorate removal of 24 mg/L-d and 84% conversion to electricity. Reduction of perchlorate was pH and potential dependant, requiring pH between 8 and 8.5, and cathodic potential below -0.3 V vs. Ag/AgCl reference electrode to completely remove perchlorate. Additionally, the perchlorate-reducing biocathode community, which contained putative denitrifying Betaproteobacteria, shared little overlap with a purely denitrifying biocathode community from which it was adapted, which was comprised mostly of iron-oxiding genera. ENVR 555 Microbial electrolysis cell operation under thermophilic conditions B. Tartakovsky1, [email protected], P. Mehta1, M.-F. Manuel1, A. Lobato1,2, [email protected], A. Moran2, [email protected], and S. Guiot1. 1 Biotechnology Research Institute, National Research Council of Canada, Montreal, Quebec, Canada, 2Department of Chemical Engineering, University of Leon, Leon, Spain

Hydrogen production in a microbial electrolysis cell (MEC) continuously fed with either acetate or artificial wastewater was studied at mesophilic (30-40° C) and thermophilic (50-55° C) temperatures. Within the mesophilic range of temperatures each increase in MEC operating temperature resulted in an immediate increase in hydrogen production. At temperatures above 40° C each temperature increase was followed by a lag-phase. This lag phase was no longer than 24 h indicating a fast adaptation of the microbial community to thermophilic conditions. Hydrogen production rate reached a plateau at 50° C. When the carbon source was changed to artificial wastewater containing slowly hydrolysable organic matter, hydrogen production was also higher at thermophilic temperatures. Overall, the best volumetric performance was observed under thermophilic conditions, where at an applied voltage of 1 V a rate of 6 LH2/LR/day and a current density of 7 A/m2 were obtained for a MEC fed with acetate. ENVR 556 Hydrogen generation with hydrogenophilic dechlorinating bacteria in bioelectrochemical systems M. Villano1, F. Aulenta1, [email protected], L. De Bonis1, S. Rossetti2, and M. Majone1. 1Chemistry, Sapienza University of Rome, Rome, Italy, 2Water Research Institute, National Research Council, Monterotondo, Rome, Italy Hydrogenophilic dechlorinating bacteria are till now known for their ability to use hydrogen as electron donor to respire chlorinated solvents. Here we show that, in the absence of chlorinated compounds to be reduced, they can also carry the reverse reaction towards hydrogen generation (from water reduction), by using a graphite electrode as direct electron donor. With the electrode potential set at ­ 750 mV (vs. SHE), such bacteria promptly catalyzed the rate of hydrogen production, nearly 3 times more than in abiotic controls, in spite of no previous acclimation in electrochemical systems. Similar hydrogen production rates were obtained with the electrode potential set at -450 mV (vs. SHE), but in the presence of a low-potential redox mediator (methyl viologen). These results pinpoint the potential of dechlorinating bacteria as "novel" hydrogen catalysts for possible application in new energy technologies. ENVR 557 Water recycle and energy production in future biorefineries using MFC/MEC systems A. P. Borole, [email protected], and J. R. Mielenz. Oak Ridge National Laboratory, United States Future biorefineries are expected to require large amounts of water for production of biofuels and bioproducts. It has been reported that it takes 7-15

gallons of water to produce a gallon of ethanol (excluding water required for biomass production), so water recycle and reuse are important to biorefinery economics. This paper explores the synergy between microbial fuel/electrolysis cells (MFC/MECs) and biorefineries by investigating the potential for water recycle and determining the energy production potential of the recycle stream. Biorefinery process streams contain two substrates which are of interest: residual sugars and conversion byproducts. Current process diagrams remove water from residual organic streams to yield a syrup destined for use as fuel in boilers. Use of MFC/MECs can result in potential benefits to the biofuel production process. Effects of the proposed scheme on water recycle, conversion of biomass to biofuel, production of value-added byproducts, and the overall process will be discussed. Secondly, the development of MFCs for elimination of fermentation inhibitors such as phenolics which accumulate in the process stream will be presented. The inhibitors typically suppress ethanol yields if not removed from the recycle water. Conversion of sugar- and lignin- degradation products such as furfural, vanillic acid and 4-hydroxybenzaldehyde to electricity at power densities reaching 3700 mW/m2 will be presented, Potential for hydrogen production using microbial electrolysis cells (MFCs) from these substrates will also be presented. ENVR 558 Bioelectrochemical production of methane by a hydrogenophilic methanogenic culture M. Villano, [email protected], F. Aulenta, T. Ferri, and M. Majone. Chemistry Department, Sapienza University of Rome, Rome, Italy In this research, we investigated the bioelectrochemical production of methane gas from carbon dioxide reduction by using a microbial biocathode, based on a hydrogenophilic methanogenic culture, not previously acclimated in bioelectrochemical systems. Methane production was found to proceed on plain carbon cathodes, polarized at potentials more negative than -650 mV (vs. SHE), both via direct extracellular electron transfer and via abiotically produced hydrogen gas (i.e., via hydrogenophilic methanogenesis). The relative contribution of these routes to methane production was highly dependent on the cathode potential. The use of redox mediators (i.e.: Neutral Red, E°'= -325 mV vs. SHE) allowed to carry out the reaction at less reducing potentials (-450 mV vs. SHE), even thought methane production rates were remarkable lower than in the mediator-less systems. However, methane production could be increased through the formation of a biofilm on high specific surface electrodes.


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Abstract Title Page Anaheim 2011
Abstract Title Page Anaheim 2011
American Chemical Society