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Milestone Microwave Solutions for Analytical Laboratories

Milestone Srl

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Milestone Mission

Milestone is an international company dedicated to providing the scientific community with the most technologically advanced microwave instrumentation for research and quality control applications

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Milestone Organization

· Established in 1989 · Organized in two operating units

­ Company headquarter based in Bergamo, Italy ­ Manufacture and R&D facility based in Germany

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Milestone Inc. in the USA Milestone General KK in Japan Direct representation in China and Korea A network of over 50 exclusive distributors worldwide

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Milestone Products

Digestion Clean Chemistry Extraction Synthesis Ashing Mercury Analysis

Ethos D DuoPUR Ethos TC DMA-80 Ethos PRO TraceCLEAN Ethos MOD Ethos SEL MicroSYNTH Pyro SAS Ethos E Start Pyro

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Microwave Sample Preparation for AA and ICP

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Summary

· · · · · Why microwaves? Theory of microwave heating Microwave instrumentation Applications "Clean Chemistry"

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The Bottleneck

· Analytical tools of the 21st century (AAS, ICP-AES, ICPMS) · Sample preparation tools of the 18th century (heating block, sand bath, Bunsen burner) · Sample preparation has become the bottle neck to higher productivity in the modern analytical laboratory

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Microwaves Save Sample Preparation Time

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Beef Liver Tuna Tissue PVC Margarine Sludge Heavy Oil Coal Blood Titanium Zirconium Oxide

Microwave

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Conventional

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Microwaves Improve Sample Preparation Quality

· No losses of volatile elements, complete recovery of Hg, Se, As etc. · Low blanks, minimum quantities of acids are used · No sample contamination from the environment or from other samples · Reproducible and fully documented sample preparation procedure · No acid fumes for improved laboratory personnel and working conditions

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Microwaves

· Microwaves are electromagnetic energy · Microwaves frequency ranges from 300 to 300.000 MHz · Microwaves wavelength ranges from 1 m to 1 mm · Frequencies for industrial, medical and scientific uses are 915 MHz, 2.450 MHz (12,25 cm wavelength), 5.800 MHz and 22.125 MHz

c H

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Materials Interaction with Microwaves

· Materials can be

­ Reflective (metals) ­ Absorptive (water) ­ Transparent (PTFE)

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Microwave Heating Mechanism

· Liquids rapidly absorb microwave energy by two mechanisms which take place simultaneously

­ Dipole rotation ­ Ionic conduction

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Conductive Heating

· Heat passes through the vessel walls prior reaching the reactants · Slow and inefficient method dependent from vessel material thermal conductivity · Vessel temperature in excess of reaction mixture temperature

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Microwave Heating

· Microwaves couple with reaction mixture molecules · Rapid temperature increase · Independent from vessel material thermal conductivity · Instantaneous localized superheating by ionic conduction and dipole rotation · No inertia (instant on-off) · Dependant from ionic conduction and dipolar polarization

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Multi-mode Microwave System

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Open vs. Closed Vessel Microwave Heating

250 Temperature (°C) 200 150 100 50 0 0 300 Time (sec) 600 0 900 20 Pressure (bar) 30

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10 ml of HNO3 are heated in Teflon open vessels at 300 W for 15' The highest temperature is just above the HNO3 boiling point (125°C) Heating rate doubles when double power is applied 10 ml of HNO3 are heated in Teflon closed vessels at 300 W for 15' The vapor pressure generated inside the vessels increases the boiling temperature of HNO3 At 25 bar the temperature is of 220°C

250 Temperature (°C) 200 150 100 50 0 0 300 Time (sec) 600

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Pressure (bar)

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0 900

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Pressure and Temperature

· Pressure is the mean and temperature is the goal · Increasing the temperature by 10°C doubles the rate of a reaction · Rapid microwave heating and the use of closed vessel allow for reducing the sample preparation time from hours to minutes

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Microwave Instrumentation

Sample preparation for AA and ICP

Closed vessel acid digestion

Open vessel acid digestion

Vacuum evaporation

Clean chemistry

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Microwave Instrumentation

· · · · Microwave oven Microwave control system Reaction monitoring and control Pressure vessels

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Microwave Oven

· Microwave cavity, structural frame of the system and door are the primary protective options · Modified kitchen type microwave systems are unsafe and do not permit controllable and reproducible operations

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Milestone Microwave Systems

· One microwave platform · Three different controllers to fit customer needs

­ Ethos D ­ Ethos TC ­ Ethos PRO

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Milestone Microwave Systems

· One microwave platform · Three different controllers to fit customer needs

­ Ethos D ­ Ethos TC ­ Ethos PRO

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Ethos features

· Built from the ground up for laboratory use, not a modified kitchen unit! · 1.600 W installed microwave power · 1.000 W delivered microwave power

­ Industry first dual magnetron system ­ Patented pre-mixing microwave cavity and pyramid shaped microwave diffuser for homogeneous microwave distribution

· · · · ·

Patented "pressure-responsive" door Corrosion resistant microwave cavity with PTFE coating Easy access to microwave cavity Microwave cavity of 35x35x35 cm (ca. 43 l) Acid resistant built-in exhaust system

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Ethos Video Presentation

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Ethos Terminal

· · · · · · · 12" large high resolution color screen controller "Touch control" display Supplied with keyboard and mouse "EasyControl" software for a complete control of all reaction parameters Optional "EasyDoc" software for data export on external computer Removable "Flash card" memory for data storing Interfaces for power, microwave unit, printer (parallel), external PC for data loading/unloading, balance (serial), keyboard and mouse

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EasyControl Software

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Program Editing

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Samples Data

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Program Run You draw it... and EasyCONTROL does it

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Reaction Monitoring and Control

· ATC-400/ATC-FO internal temperature control by thermocouple or fiber optic · IRTC-500 external temperature control by infrared sensor · APC-55 automatic pressure control · QP quality pressure sensor

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Reaction Monitoring and Control Benefits

· Acid digestion method development · Full control of reaction parameters · Full documentation of sample preparation procedure · Avoid vessel leakage, overheating and overpressurization

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ATC-400 Internal Temperature Control by Thermocouple

· Temperature sensor protected by a Teflon coated ceramic thermo-well · Easy and rapid insertion and removal of the sensor · No sensor bending · Fast response · Rugged construction · Works with any acid mixture · Temperature control up to 300°C for short time

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2 Hours at 240°C

300 250 Temperature (°C) 200 150 100 50 0 0 15 30 45 60 75 90 105 120 135 Time (minutes)

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IRT External Temperature Control by Infrared

· Non-contact sensor · All vessels are monitored · Prevents vessel shields overheating · Especially suitable for high boiling acids · Safety device

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Internal Temperature vs. External Temperature

300 Temperature (°C) 250 200 150 100 50 0 0 5 10 15 Time (minutes)

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APC-55 Automatic Pressure Control

· Pressure control up to 55 bar (800 psig) · Pressure monitor up to 100 bar (1.450 psig) · Solid state sensor with built-in electronics fully protected from acid vapors

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1,25 g BCR 185 Bovine Liver with 10 ml HNO3

250 Temperature (°C) 200 150 40 100 50 0 0.00 20 80 Pressure (bar) 60

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0.10 Time (hh.mm)

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QP Quality Pressure Sensor

· The QP sensor monitors the level of acid vapors in the Ethos microwave cavity · Microwave power is automatically adjusted once over a preset level · All vessels are monitored simultaneously and independently to effectively limit the pressure in each vessel · Over pressurization and venting are prevented

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When It Works

· Improper closing of all vessels · Vessel diffusion through walls or cover · Vessel venting, to control exothermic reactions or whenever the maximum pressure is reached in any of the vessels

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Milestone Vessels

Rotor MDR1000/6M HPR1000/10S MPR-300/12S PRO-16 PRO-24 Vessels 6 Material TFMTM Pressure 100 bar (1.450 psig) 100 bar (1.450 psig) 35 bar (500 psig) 30 bar (435 psig) 30 bar (435 psig) Temperature 260/300°C

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TFMTM

260/300°C

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TFMTM TFMTM TFMTM

260°C 250°C 250°C

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Milestone MDRTM Technology

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MDRTM Video Presentation

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TFMTM Features

· Hoechst trade name for chemically modified PTFE · Dense structure · Chemically inert · Thermal insulator · Microwave transparent · Melting range 320-340°C · Maximum working temperature for extended use 260°C, for short time 300°C

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Pressure Relief Mechanism

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PRO-16/PRO-24 Vessels

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Easy Handling

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Applications

Microwave Sample Preparation for AA and ICP

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Recommended Literature

· "Introduction to Microwave Sample Preparation" H.M. Kingston, Ed., ACS Professional Reference Book, Washington, DC, 1988 · "Microwave Enhanced Chemistry" H.M. Kingston and Stephen Haswell, Ed., ACS Professional Reference Book, Washington, DC, 1997

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Acid Classification in Closed Vessel Digestion

NONOXIDIZING · Hydrochloric acid · Hydrofluoric acid · Phosphoric acid · Diluted sulfuric acid · Diluted perchloric acid OXIDIZING · Nitric acid · Hot concentrated perchloric acid · Concentrated sulfuric acid · Hydrogen peroxide

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Organic Samples

· Food, feed, tissues, botanicals, biological samples etc.

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Nitric Acid

· Nitric acid is the most common oxidizing agent used to digest organic samples, according to the following reaction ORG + HNO3 = CO2 + H2O + NOX · Metals are converted into soluble nitrates, available for analysis

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· Based on sample decomposition with HNO3

­ 180°C for high fat samples (cheese, butter, vegetable oil etc.) ­ 160°C for high protein samples (bovine, serum, albumin) ­ 140°C for high carbohydrate samples (wheat, sugar etc.)

Target Digestion Temperature of Biological Samples

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Pressure during Microwave Digestion

· Temperature is key · Pressure is mean · Microwave heating raises acid temperature and vapor pressure · Gaseous products (CO2 and NOX) are formed from sample decomposition

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Nitric Acid Vapor Pressure

10 ml HNO3 250 Temperature (°C) 200 150 40 100 50 0 0.00 20 0 0.20 80 60 Pressure (bar)

Pressure (bar) Pressure (bar)

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0.10 Time (h.mm)

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0,25 g Organic Sample

0,25 g BCR 185 Bovine Liver with 10 ml HNO3 250 Temperature (°C) 200 150 40 100 50 0 0.00 20 0 0.20 80 60

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0.10 Time (h.mm)

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0,50 g Organic Sample

0,50 g BCR 185 Bovine Liver with 10 ml HNO3 250 Temperature (°C) 200 150 40 100 50 0 0.00 20 0 0.20 80 60

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0.10 Time (h.mm)

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0,75 g Organic Sample

0,75 g BCR 185 Bovine Liver with 10 ml HNO3 250 Temperature (°C) 200 150 40 100 50 0 0.00 20 0 0.20 80 60 Pressure (bar) Pressure (bar) Pressure (bar)

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0.10 Time (h.mm)

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1,00 g Organic Sample

1,00 g BCR 185 Bovine Liver with 10 ml HNO3 250 Temperature (°C) 200 150 40 100 50 0 0.00 20 0 0.20 80 60

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0.10 Time (h.mm)

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1,25 g Organic Sample

1,25 g BCR 185 Bovine Liver with 10 ml HNO3 250 Temperature (°C) 200 150 40 100 50 0 0.00 20 0 0.20 80 60

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0.10 Time (h.mm)

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Sample Weight Effect on Decomposition Pressure

80 70 Pressure (bar) 60 50 40 30 20 10 0 0.00 0.05 0.10 Time (h.mm) 0.15 0.20

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Effect of Sample Amount

· Higher pressure conditions · More exothermic reactions · Vessel and microwave system have to be capable of withstand or handle such over-pressurization · Vessel design and materials are key factors for safe microwave digestions

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Environmental Samples

· Soil, sediment, sludge, fly-ash, wastewater etc.

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· US-EPA 3015 SW-846 Update II Microwave-assisted acid digestion of acqueous samples and extracts · US-EPA 3051 SW-846 Update II Microwave-assisted acid digestion of sediments, sludges, soils and oils · US-EPA 3052 SW-846 Update III Microwave-assisted acid digestion of siliceous and organically based matrices

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US EPA 3015

· Sample amount 45 ml · Reagents 2,5 ml HNO3 65% and 2,5 ml HCl (37%) for FLAA and ICP), or 5 ml HNO3 65% only for FLAA, GFAA, ICP and ICP-MS · Microwave digestion time 20 minutes · Temperature to reach 160°C within 10 minutes and to remain between 165-170°C for other 10 minutes · Elements Al Sb As Ba Be Cd Ca Cr Co Cu Fe Pb Mg Mn Mo Ni K Se Na V Zn

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US EPA 3015

180 160 140 120 100 80 60 40 20 0 0 5 10 15 20 25 Time (minutes)

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Temperature (°C)

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Pressure (bar)

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US EPA 3051

· · · · · Sample amount 0,5 g Reagents 10 ml HNO3 65% Acid leaching method Microwave digestion time 10 minutes Temperature to reach 175°C within 5,5 minutes and to remain between 170-180°C for the balance of the 10 minutes · Elements Al Sb As B Ba Be Cd Ca Cr Co Cu Fe Pb Mg Mn Hg Mo Ni K Se Ag Na Sr V Zn

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US EPA 3051

200 180 160 140 120 100 80 60 40 20 0 0 3 6 9 12 15 Time (minutes) 20 18 16 14 12 10 8 6 4 2 0 Temperature (°C)

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US EPA 3052

· First US EPA-approved method to utilize the "Total microwave sample preparation" concept · Suitable for soil, sludge, sediment, fly-ash and oil-contaminated soil · Goal is a complete sample decomposition · Validated for Al Sb As B Ba Be Cd Ca Cr Co Cu Fe Pb Mg Mn Hg Mo Ni K Se Ag Na Sr Tl V Zn · Analyses by FL-AAS, CV-AAS, ICP-OES and ICP-MS

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Pressure (bar)

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US EPA 3052

· Temperature to reach 180°C within 5 minutes and to remain between 175-185°C for 10 minutes · Sample amount and reagents · From 0,5 g to 1,0 g · Basic acid mixture 9 ml HNO3 and 3 ml HF · Alternative combinations include HCl (Ag Ba Sb Fe Al determination), H2O2 (organic samples) and H2O (exothermal reactions)

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US EPA 3052

Microwave hardware requirements · Temperature control · Kitchen-type units not permitted · Possibly allowing acidic solution concentration and evaporation Pressure vessel requirements · Made of PFA or TFM · 50 ml volume or higher · 30 bar pressure or higher

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US EPA 3052

200 180 160 140 120 100 80 60 40 20 0 0 5 10 Time (minutes) 15 20 14 12 10 8 6 4 2 0 Pressure (bar) Temperature (°C)

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Inorganic Samples

· Metals, alloys, oxides, ores, rocks, slag, ceramics etc.

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Introduction, Chemistry

· Sample preparation procedures are strongly dependent on the chemical nature of the material to be digested and on the elements to be determined · The microwave acid(s) choice is often the same as used with "conventional" methods · Many geological samples may be digested according with the US EPA 3052 method

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Introduction, Microwave Profile

· Most inorganic samples show non-exothermal reactions and do not produce large amount of gases · The sample amount does not affect the ratio temperature/pressure as much as with organics · The digestion efficiency strongly depends on digestion temperature · The target is to bring the solution to the highest temperature in the shortest time (1st step) and to hold this temperature until the digestion is complete (2nd step) 03/04 75

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Iron Ore

· Acid digestion of 1,0 g with 6 ml HCl and 2 ml HNO3 · Microwave program 10 minutes @ 650 W (temperature 240°C, pressure 25 bar) · 6 vessels in a MDR1000/6M

250 Temperature (°C) 200 150 100 50 0 0 3 6 9 12 15 Time (minutes)

30 25 20 15 10 5 0 Pressure (bar)

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Our Experience at Your Service

· A library of nearly 400 sample preparation methods is available from Milestone

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TraceCLEAN

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DuoPUR

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Microwave Solvent Extraction

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ETHOS SEL Microwave Solvent Extraction Labstation

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Solvent extraction techniques

· · · · Soxhlet Sonication Supercritical Fluid Extraction Separatory Funnel Microwave heating

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Soxhlet

ADVANTAGES Standard method Large amount of sample Filtration not required Not matrix depending Unattended operation Low cost

DISADVANTAGES Long extraction time, up to 24-48 hours Large amount of solvent Elevated running costs

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1984 and 1986: the "pioneers"

· First papers on microwave solvent extraction by Ganzler, Bati and Valko "A new method for the extraction and high performance liquid chromatographic determination of vicine and convicine in favabeans" "Microwave extraction, a novel sample preparation method for chromatography"

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Time saving

Time (minutes) Compound Traditional Microwave Crude fat 180 5 Pesticides 90 1

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Milestone WeflonTM

· Chemically inert fluoropolymer · Absorbs microwave energy · Heats non-polar microwave transparent solvents · Allows reproducible heating conditions

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Accuracy and precision

Recovery % CV % Compound Traditional Microwave Traditional Microwave Crude fat 100 98 0,5 0,03 Pesticides 90 100 0,1 0,2

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ETHOS SEL Integrated Microwave Solvent Extraction System

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ETHOS SEL includes...

ETHOS microwave labstation ETHOS control terminal Built-in fiber optic temperature control QP "Quality Pressure" solvent sensor Magnetic stirring in all vessels easyWAVE software Choice of pressure rotors

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ATC-FO temperature control ATCby fiber optic

Microwave inert Easy handling Quick connection Teflon/ceramic protection Wide temperature measuring range, up 90 290°C to

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How the ATC-FO works

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QP "Quality Pressure" solvent sensor

· Monitors the level of solvent vapors in the ETHOS SEL cavity · Microwave power is automatically adjusted once over a preset level · All vessels are monitored simultaneously · Over pressurization and venting are prevented for safe operations

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ETHOS SEL magnetic stirrer

· Rotating magnetic field in the microwave cavity for stirring in each and every closed vessel Better extraction efficiency

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Effect of stirring during microwave extraction

"Stirring the sample during the extraction resulted in significant increase of the extraction yield for both pesticides in all samples"

No stirring Sample Lindane (as % Soxhlet) Aldrine (as % of Soxhlet) Soil 91,9 90,1 Sand 76,3 86,5 Stirring Sample Lindane (as % Soxhlet) Aldrine (as % of Soxhlet) Soil 92,8 102,1 Sand 89,6 102,3

F. Orsi and K. Ganzler "Determination of Lindane and Aldrine in Soils" report to Milestone, 1997

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WeflonTM inserts

WeflonTM stir bars for enhance extraction efficiency and improved heating rate of non polar solvents

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Milestone WeflonTM

· Chemically inert fluoropolymer · Absorbs microwave energy · Heats non-polar microwave transparent solvents · Allows reproducible heating conditions

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Applications

Microwave Solvent Extraction

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Microwave Ashing

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Pyro SAS

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Applications

Microwave Sulfate Ashing

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DMA-80 Direct Mercury Analyzer

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DMA-80 Advantages

· Direct Hg determination at trace level on solid and liquid samples · No sample digestion step · No wet chemistry pre-treatment step · Fast, approximately 6 minutes per sample · Eliminates waste disposal · Validated results (US EPA method 7473) for solid and liquid matrices

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DMA-80 Principle of operation

· Solid or liquid samples are weighed and introduced in the DMA-80 (quartz or metal sample boats are available) · The sample is initially dried and then thermally decomposed in a oxygen flow · Combustion products are carried off and further decomposed in a hot catalyst bed · Mercury vapors are trapped on a gold amalgamator and subsequently desorbed for quantitation · The mercury content is determined using atomic absorption spectrophotometry at 254 nm

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Applications

DMA80 Direct Mercury Analyzer

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Milestone Microwave Solutions for your Analytical Laboratory

Thank You and... Arrivederci!

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