Read 6. New Trends on Pesticide Residue Analysis text version

New Trends on Pesticide Residue Analysis in Foodstuffs and its Managements

Canping Pan China Agricultural University Email: [email protected]


· 1 Overview of Agriculture and Chemicals Application: Food Security and Safety · 2 MRL and Pesticide Residues in World Foodstuffs · 3 Pesticide Residue Management and Recent Analytical Methodologies : MRL harmonization, global data review, minor crop, crop classification, representative crop, MRL calculator, uncertainty in residue analysis, method of analysis, risk analysis principles, etc

Top Food Safety Hazards

from Larry D. Sanders

· Consumer perception:

pesticides & food-borne diseases


1. 2. 3. 4. 5. 6. Food-borne diseases Malnutrition Environmental contaminants (lead/mercury) Naturally occurring toxins Pesticide residue Deliberate food additives

Countries by USD value of their agricultural output, as of 2006.

Modern Agriculture Faces Challenges

· Challenges Population increase Arable Land area Drought Energy crisis (bio-energy produce like maize and agric land use) · Strategies: Fertilizer pesticide is essential material for agric GMO crops and other technical etc

World Population and Food Security

Food production must double by 2050 to meet the demand of the world's growing population and innovative strategies are needed to help combat hunger, which already affects more than 1 billion people in the world... 2009, a panel discussion on "New cooperation for global food security".

From FAO website

Number and percentage of World undernourished persons

· · · · · · 2005-2007:848million (13%) 2000-2002:833million (14%) 1995-1997:788million (14%) 1990-1992:843million (16%) 1979-1981:945million (21%) 1969-1971:958million (26%)


World foodgrains production likely to dip by 2.5% in 2009-10

· In 2008-09, the global foodgrains production stood at 1,792 million tonnes and is likely to fall by 2.5% in 2009-10 · global consumption is forecast to rise by five million tonnes from last month to a record 1,741 MT, mainly because of increasing use of maize to produce ethanol in the US


· Worldwide, about 10,000 species of insects are important as pest, out of 750,000 identified species. · Over 50,000 species of fungi are responsible for some 1,500 plant diseases; · Over 1,800 species of weeds out of the known 30,000 cause serious economic loss. · About 15,000 species of nematodes produce more than 1,500 serious deleterious effects on plants. · 30 household pests are worthy of attention, like files, fleas, bedbugs, lice, cockroaches, mites, termites and moths · Every year pests destroy food which could be food for 135 million people.

Pesticides are effective tools for Agro-producing

Pest Weeds Diseases Insects Storage Rats Others

From An Indian statistic

Loss of Food Grains (%) 28 25 23 10 8 6

2001-2009 Pesticide sales Worldwide

2001-2009 sales sales (million dollar) 2001 2002 2003 2004 2005 2006 2007 2008 2009

data: Phillips McDougall

Change rate% -6.8 -5.0 -1.6 4.7 -2.5 -6.5 2.8 10.2 -0.4

25,760 25,150 26,710 30,725 31,190 30,425 33,390 40,475 37,880

Advantages of Pesticides

· · · · · Cost effectiveness. Timeliness and flexibility Quality, quantity and price of produce. Prevention of various problems. Protection of pets and humans, Enviroment

Potential adverse effects of pesticides

· Risk: Residues in food, possible health effects at high residue levels · Ground water, Air contamination · Drift of sprays and vapour · Reduction of beneficial species · Resistance development · Harm to farmer workers

Key: Proper application and good management of Pesticides

International and inter-regional Level: FAO pesticide specification, PIC, POPs, Codex MRL National levels: Pesticide quality control Pesticide registration (Efficacy, Residue, Metabolism, Toxicology, Eco-toxicology, Impurity Profile etc) MRL setting based on risk assessment Monitoring of market survey, Importing MRLs Total diet study Environment monitoring - Training

Risk assessment for pesticide residues

· establishment of the WTO on 1 January 1995 · Agreement on the Application of Sanitary and Phytosanitary Measures (SPS) · Codex Committee on Pesticide Residues (CCPR) is part of the Joint FAO/WHO Food Standards Programme. · Codex MRLs: facilitate international trade and protect the health of consumers. · Measures which might affect international trade must:

not be stricter than necessary to achieve objective not be maintained without sufficient scientific evidence be consistent and transparent be based on sound scientific risk assessment.

Pesticide risk assessment:

link the MRLwith ADI/ARfD

JMPR procedure for mrl setting

Residue Data

Market enforcement Residue definition and .. Metabolism study etc

Residue trials on GAP



Toxicological Data


Intake assessment Inter, national

Intake Data

Intake ADI; ARfD

intake > ADI; ARfD

recommend MRL

recommend MRL, exceeding ADI or ARfD ?

Importance of Residue Chemistry

Sample Integrity

Storage Stability

Sample Integrity


Method Suitability Residue Definitions

Tolerance/ MRL Field Trial

Analytical Method

Method Efficiency

Dietary Assessment Directions for Use

From Michael A. Doherty,a lecture on puzzle at residue chemistry

2 MRL and Residues in foodstuffs

· · · · · EU,(NL...) UK USA, FDA Canada China ...

· Are our foods safe ?

In the EU, as from 1 September 2008, a new legislative framework (Regulation (EC) No 396/2005 of the European Parliament and of the Council) on pesticide residues is applicable.

Others: · DG SANCO - Standing Committee on Food Chain & Animal Health · DG SANCO - Rapid Alert System for Food and Feed (RASFF) · DG SANCO - Environment: Endocrine Disruptors · DG SANCO - The Food and Veterinary Office (FVO)

· Regulation vs. Directive

­ Regulation: directly in force in member states ­ Directive: must be implemented in national legislation

· Scope

­ All food » fresh » processed » composite ­ Feed (new) ­ Products must be listed in Annex I ­ Pesticides according to 91/414 » some need no MRL -> in Annex IV

­ MRL setting under Regulation 396/2005

· · · · · · Data Requirements for Residue Studies Guidance documents Role Rapporteur Member State (RMS) Role European Food Safety Authority (EFSA) Role European Commission Role Standing Committee of the Food Chain and Animal Health (SCFCAH)

The Rapid Alert System for Food and Feed (RASFF) ­an important tool in the EU efforts to ensure food safety

· (EU-27, Commission, EFSA and Norway, Liechtenstein and Iceland) · notifications in 2008 : alert (528), information (1,138) and border rejection (1,377)

­ Data Requirements for Residue Studies (91/414 ­ OECD)

· · · · · · · · · · · Residue definition (Risk assessment and monitoring/enforcement) Chronic and acute exposure risk assessment endpoints Processing factors MRL proposals Stability of residues Metabolism, distribution and expression of residues (plants, animals) Residue trials (plant products, livestock feeding studies) Processing studies, incl. distribution peel/pulp Proposed residue definition for risk-assessment and MRL-setting Proposed pre-harvest intervals Estimation of exposure from diet and other sources

­ Guidance documents

­ Data Compiled in Dossier ­ EU regulation 396/2005 gives procedure to set MRLs

· Application of authorisation in a member state · Member state:

­ ­ ­ ­ ­ evaluates necessity of MRL requires applying for MRL notifies Commission and EFSA evaluates application (possibly done by RMS) reports to Commission and EFSA


­ assesses » suitability proposed method of analysis for routine control » anticipated LOD » risks of exceeding ADI or ARfD ­ has three months

· Commission

­ Prepares Regulation ­ Decision to be made in the SCFCAH ­ has three months

­ EU regulation:

· Official control (monitoring & enforcement) obligatory

­ Directly linked to official controls of food and feed

· Official control: Regulation 882/2004

­ Community reference laboratories ­ Requires national reference laboratories


· 2005 for example: A total of 62,569 samples were analysed. 349 compounds analyzed · no residues were detected in 54.3 % of the samples, while a further 41.0 % of the samples contained residues that were below or equal to the maximum residue limits (MRL) laid down at EU or national level. In 4.7 % of all samples, residues above the MRL (national or EC-MRL) were found.

2009 EU monitoring plan

First 2009 Pesticide Residue Figures: UK

· 392 out of 570 samples of 16 different foods tested had no detectable residues. · 164 samples contained levels below the maximum residue level (MRL) · 15 incidences in 14 samples (2.6%) contained residues in excess of the legal levels. We have looked carefully at the findings and concluded that in all cases the residues found were unlikely to have resulted in any health effects for consumers." - Dr Ian Brown , Medical News Today, UK

USDA Pesticide Data Program ­ Imidacloprid :Anticipated Residues

Number of Commodity Samples Apple Juice Asparagus Blueberries Blueberries, Frozen Broccoli Celery Grape Juice Green Beans Green Onions (V1) Greens, Collard 372 108 726 18 554 741 745 741 186 240 Detects 0 1 79 2 372 205 0 6 1 56 % with Detects ­ 0.9 10.9 11.1 67.1 27.7 ­ 0.8 0.5 23.3 Range of Detected Values, ppm ­ 0.015 0.0005 - 0.074 0.001 - 0.015 0.0005 - 0.021 0.001 - 0.032 ­ 0.013 - 0.093 0.002 0.010 - 0.41 LODs, ppm 0.009 - 0.020 0.009 0.0003 - 0.009 0.0003 - 0.009 0.0003 0.001 - 0.009 0.009 - 0.021 0.009 - 0.010 0.001 0.009 - 0.010 Tolerance, ppm 0.5 4.0 3.5 3.5 3.5 6.0 1.5 4.0 NT 3.5

US FDA -1996

US FDA , 2007

US FDA 2007 report

FDA 2007 cont. report

Type of Feed

# of Sampl es

Samples with No Pesticid e Residue s # 99 57 34 17 10 6 223 % 86.1 71.3 57.6 89.5 76.9 100.0 76.4

Samples Exceedi ng Regulato ry Guidanc e # 3 4 0 0 0 0 7 % 2.6 5.0 0.0 0.0 0.0 0.0 2.4

% Whole/Ground Grains Plant By-products Mixed Feed Rations Supplements/Misc. Hay & Hay Products Animal By-products TOTALS 115 80 59 19 13 6 292

51 Domestic Surveillance and 18 Import Samples of Animal Feed


· most frequently found residues in the TDS foods other than infant and toddler foods (those found in 2% or more of the samples), the total number of findings, and the percent occurrence in the four market baskets analyzed in FY 2007 (916 total samples). · The five most frequently observed chemicals were: DDT, malathion, chlorpyrifos-methyl, endosulfan, and dieldrin, and are the same as those observed for the past several years.

Residues find in TDS 2007

Pesticide(2) DDT Malathion Endosulfan Dieldrin Chlorpyrifos Chlorpropham Permethrin Quintozene Thiabendazole(3) Hexachlorobenzene Phenylphenol, oCarbaryl(4) Lindane Heptachlor Total No. of Findings 229 146 129 120 67 53 53 53 51 36 34 27 25 23 Occurance % 25 16 15 14 13 7 6 6 6 6 4 4 3 3 3 Range, ppm 0.0001-0.0289 0.0004-0.054 0.0002-0.031 0.0001-0.034 0.0001-0.020 0.0001-0.173 0.0004-1.622 0.0002-0.480 0.0001-0.007 0.001-0.975 0.0001-0.0009 0.003-0.392 0.001-0.189 0.0001-0.002 0.0001-0.001

Chlorpyrifos methyl 133

Frequency of Occurrence of Pesticide Residues in the Total Diet Study for Infant and Toddler Foods in FY 2007 Pesticide(2) Thiabendazole(3) Carbaryl Endosulfan DDT Chlorpyrifos Chlorpropham Malathion Phenylphenol, oChlorpyrifos methyl Benomyl(3) Captan Permethrin Dieldrin Total No. of Findings 39 36 24 19 18 17 14 13 12 10 10 9 8 Occurence % 18 17 11 9 8 8 7 6 6 5 5 4 4 Range, ppm 0.001-0.314 0.001-0.070 0.0001-0.011 0.0001-0.002 0.0002-0.016 0.002-0.140 0.0006-0.017 0.005-0.058 0.0001-0.048 0.010-0.029 0.012-0.153 0.0005-0.007 0.0001-0.0007

Pesticides Residues and Metals in Processed Tomato Products, Juice products 2008-2009, CANADA · The Food Safety Action Plan (FSAP) aims to modernize and enhance Canada's food safety system. · 297 (290 imported, 7 domestic) processed tomato products collected and analyzed in the targeted survey. The samples included 10 different types of processed tomatoes from 13 different countries. The top import countries of processed tomato products were targeted which include the United States and Italy.

Residue and metal in Juice, 20082009 Canada

· The majority of the samples (78.5%) were found to contain no detectable pesticide residues and all 186 samples were in compliance with Canadian pesticide MRLs. · These results are expected for fruit juice concentrates as it is anticipated that fewer pesticides are used on fruit intended for juice. Furthermore, processing (washing, heating, etc) may also remove or deplete pesticide residues.

Residues in Canadian Baby foods

140 120 100 80 60 40 20 0 poul t r y, or gani c veget abl e, or gani c f r ui t m eat Tot al N of o. Sam es pl no det ect abl e r esi dues non- vi ol at i ve r esi dues Fr ui t / veg j ui ce, C ooki e, or gani c

Specific food fruit fruit, organic meat poultry poultry, organic vegetable vegetable, organic Fruit/veg juice Fruit/veg juice, organic Cookie Cookie,

sample positive s results1 34 10 10 14 2 20 10 132 18 94 6 4 1 0 0 1 0 10 3 16

Residues found bifenthrin, diphenylamine, thiabendazole, o-phenylphenol carbaryl, o-phenylphenol, thiabendazole chlorpropham no pesticide residues detected no pesticide residues detected bifenthrin no pesticide residues detected diphenylamine, thiabendazole, imazalil, carbaryl, amitraz, tebuconazole carbaryl, thiabendazole chlorpyrifos-methyl, diphenylamine, pirimiphos-methyl, thiabendazole

Canada COMPLIANCE SUMMARY FOR FRESH FRUIT AND VEGETABLE COMMODITIES 2004-2005 Import monitoring (2004-2005): 139 violations among 24840 samples, 2610 positive Domestic samples 11,050, positive:1,051, violation: 26

-Canadian Food Inspection Agency

Pesticide in Canadian processed tomato products

· The samples analysed in this targeted survey illustrated a 100% compliance rate with Canadian pesticide MRLs in processed tomato products. · This is similar to the compliance rates seen in most fresh and processed tomato products sampled under the regular monitoring program.

·Are our foods safe ?

· MRL set according to residue data at critical GAP (Max application rate, timing of application, maximum number of application, mininum spray interval, short PHI ) and dietary risk assessment · GAP: efficacy, low pressure for environment and beneficial organisms · Market survey, enforcement of MRLs; TDS study, Environmental monitoring MRL: regulation of violation GAP, facilitate trading , safe for consumer ADI/ARfD are reference endpoints for human, MRL level residue are of no health concern for consumer!

3 Pesticide Residue Management and Recent Analytical Methodologies

-MRL harmonization efforts - Revision on Principle of risk analysis - Work sharing, global data review, - OECD residue group and FAO manual on pesticide residue data submission - minor crop, crop classification, representative crop, - MRL calculator, - uncertainty in residue analysis, method of analysis, -others etc

3.1 MRL harmonization

· · · · · Different GAPs Crop group disharmony Residue definition Mrl recommendation method Policy and Consumer's evaluation MRLs are not a level for identifying safe, different risk assessment different MRLs

· Developed countries set more restricted MRLs · Importing MRLs · growing popularity of organic foods and the use of private standards by food retailers. · scientific advice developed in an open transparent manner

Trade Barriers among Countries

EU rejects Basmati shipments over pesticide residue Debadatta Das, June 29, 2010

In a blow to India's rice exports, Basmati, world's most famous rice, is now under the European Union's scanner. The EU claims that there is too much of the pesticide soprothiolane in the shipments.

CCPR 42th meeting and a Presymposium on minor crop/minor use

· Xi'an China2010,April

Definition of residue: Factors to consider

· Composition and levels found in metabolism studies (>10%) · Toxicological properties · Magnitude of the Residue · Metabolites/degradates common to other pesticides or natural compounds? · Availability of methods (economic methods) · Have other authorities established a definition? · No single approach applies to all situations ­ must be case by case. · Guidance document: Definition of Residue (series on Testing and Assessment, No.63)

MRL harmonization: A Pilot project

In this Pilot project, CCPR will develop a process for new chemicals that allows establishment of Codex MRLs (or at least allows JMPR recommendation of Codex MRLs) before national governments establish MRLs. · 42th CCPR:JMPR would conduct an independent, parallel review along with a global joint review team and recommend MRLs before national governments or other regional registration authorities establish MRLs on sulfoxaflor in 2011.

From Dr Brindle, BASF

FAO manual on data requirements of pesticide residues for the estimation of MRLs

Brief introduction of update FAO Manual on pesticide residues · The first version of this manual, published in 1997, presented the principles applied by the JMPR from 1963-1997 · The first official edition (2002) of the manual was published in 2002, which incorporated additional information from the JMPR reports of 1997­2001, in particular long-term dietary risk assessment placed formally in 1998 and the methods for short-term risk assessment developed in 1999, · The second edition (2009) describes the basic principles currently applied by the FAO Panel in the evaluation of pesticide residues for recommending MRLs. Some elements of the OECD documents have been incorporated in the Manual. GLs and Guidance documents have been listed under references.


FAO manual on data requirements of pesticide residues for the estimation of MRLs

Contents of the update FAO Manual: 9 Chapters,13 Appendix and 1 index In addition to general updating of the text, the second edition contains new information on:

Metabolism studies; Requirements regarding on environmental fate; Performance characteristics of analytical methods; Planning and implementing supervised residue trials; Use of residue monitoring data for estimation of maximum residue levels for spices; · Statistical evaluation of residue data; · Calculation of burden in animals, based on expanded feed consumption tables; · Estimation of dietary intake of residues.


· · · · ·

3.2 Revision on Principle of risk analysis

· 41st CCPR Session it established an Electronic Working Group led by Argentina to revise the Risk Analysis Principles Applied by the Committee on Pesticide Residues if the periodic evaluation (15 years) abolished and the CXLs maintained,


· complexity of the issues - to retain the periodic re-evaluation procedure and revocation of MRLs without a scientific basis?. - use conditions of the compounds may change with time, older existing Codex MRLs may not reflect current use patterns (GAPs) and that some of the old toxicological studies and residue trials may not meet contemporary standards?.

Priority Lists of Pesticides Tables

· Naming of manufacturers in the list of priorities · identification of the manufacturers improved transparency and significantly facilitated communication · CCPR Committee agreed to include the names of manufactures in the Priority List of Chemicals Scheduled for Evaluation and ReEvaluation by JMPR.

3.3 OECD Pesticides Programme: Structure

Helps OECD governments to co-operate in assessing and reducing the risks of agricultural pesticides -harmonizing policies -providing tools

What is work sharing?

· All types of sharing of work in pesticide review, from the ad-hoc exchange of existing reviews and other information, to well structured divisions of work such as parallel reviews and joint reviews. Beneficial: · Quality of decisions and public confidence enhanced · Scarce resources released for more refined assessment -> sounder scientific conclusions · Review time for new and existing registrations reduced ­> reduction in backlog · Reduced uncertainty for industry · Potential for broader labels and harmonisation of MRLs (via Codex) · Benefits for addressing minor use issues

Resolution of obstacles to work sharing

­ Publications « Overview of Country and Regional Review Procedures for Agricultural Pesticides and Relevant Documents » & « Frequently Asked Questions about Work Sharing on Pesticide Registration Reviews » ­ Future Guidance on planning joint reviews ­ Harmonisation of reporting formats: dossiers, mongraphs and templates

· Templates:

­ are tools for electronic data submission ­ are formats for reporting test study summaries ­ are not data entry screens

OECD is developing electronic "export formats"

64 "industry: dossiers" VS "government: monographs"

Sharing of national review reports and joint reviews

· Resolution of obstacles to work sharing · Harmonization of data requirements, test guidelines and hazard/risk assessment procedures

­ Inventory and harmonization of data requirements for registration (chemical pesticides and bio-pesticides) ­ OECD Test Guidelines and Guidance Documents (e.g. on Pesticide Residue Chemistry)

OECD Residue Chemistry activities: Outputs

· Establishment of the Residue Chemistry Expert Group (2003) · 9 Test Guidelines ­ TG 501: Metabolism in Crops TG 502: Metabolism in Rotational Crops TG 503: Metabolism in Livestock TG 504: Residues in Rotational Crops (Limited Field Studies) TG 505: Residues in Livestock TG 506: Stability of Pesticide Residues in Stored Commodities TG 507: Nature of Pesticide Residues in processed Commodities High Temperature-Hydrolysis TG 508: Magnitude of Pesticide Residues in Processed Commodities TG 509: Crop Field Trial · 4 Guidance Documents ­ Definition of Residue ­ Overview of Residue Chemistry Studies ­ Magnitude of Pesticide Residues in Processed Commodities ­ Pesticide Residue Analytical Methods

3.4 Goals of Joint Review Process for New Pesticide Active Ingredients

· Harmonize endpoints (ADIs; ecotox concerns) and MRLs to the greatest extent possible. · Maximizing resources · Broad scientific expertise and peer review · Global market access for reduced risk pesticides


· Joint Review:

Several authorities evaluate a pesticide active ingredient at the same time-- they receive the same submission at the same time, develop a joint schedule, and divide the work; at the conclusion each makes its own independent regulatory decision with the goal (but not requirement) of harmonization of endpoint selection and MRL establishment. One authority has completed work on a chemical and other authorities subsequently use the completed reviews in completing their own reviews on their own schedule.

· Work Sharing:

Roles in a Joint Review

· Roles Countries/Regional Authorities Can Perform in a Joint Review

­ Primary Review: Conduct initial review of assigned studies and write draft study evaluations; address peer review comments and write final study evaluations ­ Peer Review: Conduct secondary review of assigned studies and provide comments to the primary reviewer; excellent for capacity building ­ Observer: Access to all data and information; full participant in meetings and full understanding of reviews; no work assignments; excellent for capacity building

· Different countries play different roles at different times and for different chemicals

Examples of Work Splits on Recent Joint Reviews

Chemical Pyrasulfatole Pyroxsulam Chlorantraniliprole Spirotetramat

Thiencarbazone/ Cyprosulfamide

Toxicology Australia United States United States United States United Kingdom Canada

Residue Chemistry Canada Australia Australia Canada United Kingdom Canada

Ecotoxicology United States Australia United Kingdom Austria Canada United States United States United States

Environmental Fate United States Canada Ireland Austria United States United States Canada

Product Chemistry Australia United States Canada Canada United Kingdom United States Germany

Saflufenacil *Australia peer reviewer Fluopyram *Japan peer reviewer Penthiopyrad


United States Canada

United States

United Kingdom

United Kingdom

Results-- Completed and Current Joint Reviews (At Least Trilateral)

· PROGRESS TO DATE: ­ Completed: 6 ­ In Progress: 6 ­ 2010-2012: 9 (planned submissions) · POWER OF "Global" PROCESS ­ Chlorantraniliprole: Australia, Canada, Ireland, United Kingdom, U.S., New Zealand. ­ Submitted 2007 ­ Registered in joint review countries 2008 ­ Currently Registered in at least 36 countries and has Codex MRLs established 2009

Global Joint Reviews Summary

· Global Joint Reviews are fast becoming the standard way of doing business · Harmonization issues still challenging · Many advantages are evident · All authorities are invited and welcomed to participate (in whatever capacity they desire) · Important to ensure that International Standard Setting Bodies are not "left behind"

3.5 Minor crop/specialty crop/minor use

· Registration based on benefits · Responsibilities of registrant products

· -2007 12 Rome Global Minor Crop Summit

Crop Grouping

Regulators: accelerate MRLs system, Less redundant data to review Industry: More crops with fewer trials Minor Crop Farmers: Pest-management tools, Reduced trade barriers

-----------------------------------------------------------------------------Possible challenges: · Crop grouping internationally · Efficacy tests, · Extrapolation risk and Restrictions (use pattern, representative crop residue) · Risk cup capacity VS analytical method, resistance, drift

Minor Crops

· minor crops: minor uses, specialty crops · Definition needed

-EU Regulation 1107/2009 -41th CCPR · Guidance and Principles on the Selection of Representative Commodities for the Extrapolation of MRLs to Commodity Groups · revision of the Classification of Foods and Feeds with the inclusion of minor crops

EWG Tasks on minor crops

· to continue to identify priority minor uses and specialty crops for MRL setting, · and to facilitate data submissions to JMPR, · and to prepare proposals for definitions of minor use and specialty crops for use by CCPR and JMPR.

Example Pome fruits MRL

· Summary of residue data selected for STMR, HR and maximum residue level estimation (rank order, median underlined): · Apples: 0.049, 0.058, 0.15, 0.16, 0.17, 0.18, 0.18, 0.19, 0.20, 0.22, 0.37, 0.38, 0.58 mg/kg. · Pears: 0.094, 0.097, 0.10, 0.14, 0.24, 0.13 0.16, 0.29 mg/kg · Pome fruits: 0.049, 0.058, 0.094, 0.097, 0.10, 0.13, 0.14, 0.15, 0.16, 0.16, 0.17, 0.18, 0.18, 0.19, 0.20, 0.22, 0.24, 0.29, 0.37, 0.38, 0.58 mg/kg


Residue Extrapolation

· · · · · · · · · · · · · · · FC 0001 Citrus fruits FP 0009 Pome fruits FS 0012 Stone fruits FB 0018 Berries and other small fruits FI 0030 Assorted tropical and sub-tropical fruits - inedible peel VB 0040 Brassica (cole or cabbage) vegetables, Head cabbages, Flowerhead brassicas , , VC 0045 Fruiting vegetables, Cucurbits( ) VO 0050 Fruiting vegetables, other than Cucurbits VL 0053 Leafy vegetables VP 0060 Legume vegetables VD 0070 Pulses VR 0075 Root and tuber vegetables GC 0080 Cereal grains TN 0085 Tree nuts


· Pesticide Initiative Program (PIP): Cooperation program between the EU and the ACP countries under the umbrella of the COLEACP. Developed at the request of the ACP/EU Council of Ministers at Cotonou in April 2000 the PIP to provide a response to the critical situation growers are facing as a consequence of

­ the European review for the re-registration of existing substances and ­ the harmonisation of the European regulations setting Maximum Residue Levels (MRL) for pesticides in fresh produce.



EU Import Tolerances - PROCESS

Within EU

Focal point National Taskforce on Horticulture

Within country

Priorities identified Crop/pesticide

** Approved ITs

Approval process


Trials sites


Data generated

EU-IT requested

EU IMPORT TOLERANCES Successes relevant to symposium


· · · · · · · · · · Beans with pods Mango Okra Pineapple Papaya Passion fruit Snow peas Yams Cassava Sweet potatoes

· · · · · · · · · · · · · · Chlorothalonil Abamectin Acetamiprid Cyromazine Difenoconazole Thiametoxam Methoxyfenozide Myclobutanil Spinosad Tebuconazole Trifloxystrobin Bifenthrin Thiophanate methyl Spiromesifen


· · · · · · · Syngenta Bayer Nisso Dow Bayer FMC Arysta


3.6 MRL calculator: transparency and precise science in mrl recommendation

· 2009, NAFTA calculator method was evaluated, (2004 · Review on OECD MRL calculator · JMPR 2009 report: ".... evaluation of residue data is a complex task that requires the consideration of factors and parameters additional to the numerical residue values. Consequently, MRL estimates cannot be based solely on automatic calculation using any currently available "statistical" methods." ·

Goal: Find The ,Best` MRL

· Statistical goal of the OECD MRL calculator: · to produce an MRL proposal in the region of the 95th percentile (`p95') of the underlying residue distribution, which is conservative in the sense that it will tend `to make errors' by overestimating the p95 rather than by underestimating it for most datasets.

0.7 Primary samples 0.6 Relative frequency 0.5 0.4 0.3 0.2 0.1 0 0.0 0.5 0.9 1.4 1.8 2.3 2.7 3.2 3.6 4.1 4.5 Midpoint [mg/kg] 95% 97.5% Composite samples

NAFATA MRL Calculator

Review/inspect field trial data

More than 10% nondetects?


Enter data into MRL spreadsheet

Yes Examine probability plot and lognormal test statistic Enter data into MLE spreadsheet Copy MLE-based fill-in values

Yes More than 15 samples? Yes No Use minimum of UCLmedian95th and 95/99 Rule as MRL

Data lognormal?



Use 95/99 Rule as MRL



Use Mean+3SD as MRL

Maximum Residue Levels

Lognormal Probability Plot FAO Carbaryl Eggplant



y = 0.5944x - 2.1369 R


= 0.7547

0.2500 Concentrations



0.0313 0.1 1 2 5 10 20 30 50 70 80 90 95 98 99 99.9


General guiding principles of OECD MRL calculator project

· The procedure must be a practical implementation of sound statistical methods. · It must be simple to use without requiring extensive statistical knowledge on the part of the user.

· It should produce a clear and unambiguous MRL proposal for most residue datasets produced by field trials. · It should harmonize existing procedures in OECD member countries as much as possible and provide a basis to to foster MRL harmonization for interested parties (CCPR, JMPR, EFSA)

Residue Residue DATA DATA

n3 n ?3 Yes




Distributional tests:



No. of Values >LOQ

medium large

Lognormal Normal Weibull


Does (any) distribution pass the fit test?


Determine best distribution distribution (best cc) (best cc)

Calculate 95UCL95th & 99th percentile

Less than regulatory regulatory limits? limit?




Greater than HR?


Calculate Calculate Mean + 4SD Mean + 3SD & UCLMed95 Mean + MaxLOQ Minimum of 95UCL95th & 99th percentile

Less than regulatory regulatory limits? limit?

Greater than HR?


Minimum of Nonparametric methods

2009 Draft OECD Calculator version 2.5


Regulatory limit


Workflow Of The New Version Of the Calculator 2010

1. The mean and the standard deviation values of the dataset are computed: 2. The calculated MRL is the maximum taken from 3 calculations:

­ ­ the "mean + 4 times the standard deviation" value is evaluated as the default proposal which will be most often used; the "the triple of the mean" value is also computed to provide a "floor" to the calculation; that is to guarantee that the sample coefficient of variance (CV = standard deviation / mean) used in the calculation is at least 0.5. A correction factor for censored data (=data less than LOQ) has been added. The factor depends on the the percentage of censored data in the data set. the HR value is also used as a "floor" to guarantee that the MRL proposal is always greater than or equal to the highest residue.


· MRL= Maximum (mean + 4*standard deviation, 3*mean*CF, HR). · Finally the calculated MRL is rounded as necessary


Comparison with JMPR decisions

1000.00 100.00 MRLs produced by draft calculator

Equality line MRL Calc = MRL JMPR


1.00 0.01 0.1 1 10 100 1000


0.01 MRLs proposed by JMPR

The graphs shows MRLs produced by the draft calculator (Y-axis) with the MRLs proposed by JMPR experts (X-axis). Both axes are represented using a logarithmic scale. The points on the blue line correspond to datasets for which the draft calculator yields an MRL-estimate that is equal to the MRL proposed by experts. Points above (below) the line correspond to datasets for which the draft calculator yields an MRL-estimate that is higher (lower) than the MRL proposed by JMPR.

3.7 pesticides analytical methods and uncertainty

Uncertainty and MRL compliance limits

Interpretation with expanded uncertainty 2007:v1


· the evaluation of the recent EC PT schemes demonstrates that a FFP variability of 25% can be accepted as a sound representation of performance under these circumstances. As a consequence, accepting 25% variability as a standard deviation would lead to a generalized assumption of ±50% MU.

· Accepting such a generalized approximation for pesticide multi-residue analysis methods, a generalized top-down approach might result in larger MU values than such derived for each individual pesticide/commodity combination by systematic bottom-up calculations. · However, the application of generic MU is considerably more practical and easier to obtain. Generalized values, like ±50% MU, mostly would expand safety margins around MRLs.


empirical top-down estimation of ±50% MU could complement a mathematically stringent bottom-up calculation model if the respective empirical quality criteria are met. Alternatively the Horwitz formula approach of estimating concentration-dependent MU based on the evaluation of results of interlaboratory collaborative tests could be applied as well. · It is proposed to further develop a specific guidance for the application of empirical MU concepts applicable particularly in the field of pesticide residue analysis of foodstuffs.

EWG on uncertainties of pesticide residue analysis at CCPR


Analytical Methods

Analytical Methods and Residues of Concern

Data Collection

· Risk assessment residues · Enforcement residues


· Enforcement residues

Data collection methods are often the same as enforcement methods

· ANALYSIS OF PESTICIDE RESIDUES: RECOMMENDED METHODS · CODEX STAN 229-1993, REV.1-2003 · 3940th CCPR : IAEA leading EWG · 41th CCPR: informative

· working group on method of analysis to prepare a discussion paper for the next session, addressing the issues raised in CX/PR 10/42/15 in relation to the status of the repository list of analytical methods · to discuss the implications of maintaining the list as either a resource list or as preferred/obligatory methods.

4 Conclusion and Discussions

· Email: [email protected]


6. New Trends on Pesticide Residue Analysis

101 pages

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