Strategies for Improving Overall Efficiency in Pesticide ...

FPRW 2005 (42nd Annual Meeting)

Slide 1

Strategies for Improving Overall Efficiency

in Pesticide Residue Testing

Michelangelo AnastassiadesStuttgart Regional Chemical and Veterinary Control Laboratory


Slide 2

Increasing Expectations

by Authorities and/or Customers

� More Productivity (Higher Sample Throughput)

� Broader Analytical Scope (More Pesticides, Matrices)

� More Flexibility (Quicker Answers to Emerging Problems)

� Higher Impact (Effective Enforcement and Corrective Measures)� Requires Faster Analysis, Data Processing & Communic. of Results

by Consumers� More Transparency (Reporting Activities Including Websites with up-to-date Information, Statistical Evaluations of Results )

Limited Resources (Financial, Personnel)

Why is there more Efficiency Needed ?


Slide 3

Additional factors causing more lab-work

Regulatory Prescriptions

• Lower MRLs (Baby Food etc.)• Risk Assessment (ARfD, ADI) • Risk Communication (EU-RASFF)

More Anal. Instruments to be Operated

• GC: ECD, NPD, FPD, AEDMSD, MS/MS, ITD, TOF …

• LC: UV/DAD, FLDMS, MS/MS, TOF …

QA/QC

• (Re-) Accreditations, Audits• EU-Quality-Control Procedures• Method Validation• Proficiency Tests


Slide 4

29528

1200

256

950580

1600

3527

0

500

1000

1500

2000

2500

Number ofsamples

Positivesamples

Number offindings

MRLviolations

1992 2002

31%

75%

2.9%13%

CVUA Stuttgart

Increasin workloa

f 1,6 f 6

f 9

2.2/sample

Very laborious samples

0.6/sample

More pesticides sought and found...


Slide 5

What can be done to Improve Efficiency?(1) Simplify Organizational Structures� Create Potent Specialized & Centralized Laboratories� Take Advantage of Collaboration and Synergy Potentials

(2) Improve Laboratory Work� Fast and Effective Sample Preparation Methods� Sophisticated Instrumental Analysis and Data Processing

(3) Perform Targeted Sampling and Analysis� Collect Information; Set Priorities Considering Risks…

(4) Make the Best Out of Results (Enhance Impact)� Quick Evaluation and Communication of Results� Take Necessary Actions Quickly/Effectively (Traceability)� Use Results to Define New Priorities (Flexibility)


Slide 6

(1) Simplify Organizational StructuresFewer Big-Scale / Specialized Laboratories

are better than many small ones

Examples : England (CSL), The Netherlands, Private Sector

� Better Occupancy of Analytical Instruments

� Avoid Repetitive Work/Costs (Synergy)- Purchase, Maintenance (Instruments, Standards…)- QA/QC-Measures (Validation, Proficiency Tests) - Organization of Sampling- Documentation, Evaluation & Reporting of Results

ADVANTAGES:

� More Personnel , Specialization Possible - Sampling, Legal Issues, Reporting, Research …

� Bigger Budget


Slide 7

(2) More Efficiency in the Laboratory Use Simple and Fast Sample Prep. Methods

Fast (as Few Steps as Possible)Easy to PerformInexpensiveLow Solvent ConsumptionSafe for Personnel and EnvironmentSelective RuggedAchieve Good Recoveries for a Broad Analyte Spectrum�Thus Reducing the No. of Single (-Group) Residue Methods to Perform

Desirable Characteristics of a Multiresidue Method


Slide 8

Anastassiades et al. JAOAC Int. 86 (2003) 412-431

(Modified Version)

QuEChERS- Multiresidue-MethodWeigh 10 g of Frozen Sample

Shake

Shake & Centrifuge

Add ISTD-Solution

Shake & CentrifugeMix an Aliquot with MgSO 4 & SPE Sorbent

Add 10 mL Acetonitrile

Add 4 g MgSO 4 / 1 g NaCl / Buffered to pH 5-5.5 with Citrate Buffer

Acidify extract to pH ~5 to protect base-sensitive pesticides

Optionally: Add other “Analyte Protectants”Multiresidue Analysisby GC-MS, LC-MS ...

Optionally: Acidic Pesticides LC-MS


Slide 9

QuEChERS- Multiresidue-Method

Weigh 10 g of Frozen Sample

Add 10 mL Acetonitrile


Slide 10


Add ISTD-Solution

Shake Vigorously


Slide 11


Add 4 g MgSO4 , 1 g NaCl

Citrate Buffer Salts (pH 5-5.5)

Shake Vigorously


Slide 12


Following Phase Separation/Centrifugation -The Upper Phase is the Acetonitrile Extract

Centrifuge


Slide 13


Take an Aliquot and Mix it with MgSO4 & SPE Sorbent

(e.g. PSA, PSA/GCB, PSA/ODS)

Shake well and Centrifuge


Slide 14


Acidify Extract to pH ~5 to Protect Base-Sensitive Pesticides

Optionally: Add additional “Analyte Protectants”

Following Phase Separation/Centrifugation

Fill into Vials for GC- and LC-Based Analysis


Slide 15


Excellent Results in four EU-

Proficiency tests

Oranges 2002 Lettuce 2003

Tomatoes 2004 Grapes 2005


Slide 16

�Rapid (8 Samples in Less Than 30 min)

�Simple (No Laborious Steps, Minimal Sources of Errors)

�Cheap (~1 $ Sample Prep. Materials for 1 mL Extract)

� Low Solvent Consumption (10 mL Acetonitrile)

�Practically no Glassware Needed�Wide Pesticide Range (Polar, pH-Dependent Compounds)

�Extract in Acetonitrile (GC- and LC-Amenable)

Advantages



Slide 17

(3) Targeted Sampling & Analysis

Important is not only

How You Analysebut also…

What You Analyse!

High-Tech-Instrumentation & Fast Sample Preparationare Important, but...

Set priorities based on information...


Slide 18

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Slide 19

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Slide 20

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Thoughtfull development of instrumental analysismethods [MS (SIM), MS/MS (MRM) etc.]

Always considering the need to routinely fulfil the QA/QC requirements


Slide 21

More Questions Arising…

� Which Single-Residue Methodsshould be reasonably performed for which samples?

� For which compounds should my contract-lab look for? Duty of Care !


Slide 22

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% ��&#��

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Multi-Residue

Method(s)

Single-Residue

Method(s)

O

NH N

O

Cl C

CCl3

ClCl

H

C

F

F

O

NH C

O

NH OCF2CHF2

Cl

Cl

ARfDADI

MRL

'% #()�"# #


Slide 23

% ��&#��

�� % ��

O

NH N

O

Cl C

CCl3

ClCl

H

C

F

F

O

NH C

O

NH OCF2CHF2

Cl

Cl

ARfDADI

MRL

'% #()�"# #

��*��& ��& ��& ��

��Multi-Residue

Method(s)

Single-Residue

Method(s)


Slide 24

% ��&#��

�� % ��

Multi-Residue

Methods

Single-Residue

Methods

O

NH N

O

Cl C

CCl3

ClCl

H

C

F

F

O

NH C

O

NH OCF2CHF2

Cl

Cl

ARfDADI

MRL

'% #()�"# #

% ��#++��


Slide 25

Random Analysis

��

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There are>1200 pesticides

and…countless

commodity types worldwide

But…

The Aspirations of any

Newcomer…

This isn’t practicable


Slide 26

�*��& ��& ��

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The disillusionment:

Random Analysis


Slide 27

… using SRM

Potential Spectrumof the MRM

Entire spectrumof pesticides

Laboratory spectrumusing the MRM

Relevant spectrum

Pome Fruit

Relevant spectrum

Berries

Random Analysis


Slide 28

… using SRM

Potential Spectrumof the MRM

Entire spectrumof pesticides

Relevant spectrum

Pome Fruit

Relevant spectrum

Berries

Laboratory spectrumusing the MRM

Targeted Analysis

Non Optimized Spectrum


Slide 29

Targeted Sampling and Analysis

First Collect and Evaluate Information, then Design

a Targeted Analytical Scheme !

The Setting of Analytical Priorities (i.e. Profiling)

Requires Up-To-Date & Easily Accessible Information!


Slide 30

MRLs

Rapid AlertNotifications

Residue Datafrom other

Laboratories (Often Delayed)

Toxicological Data ADI, ARfD

Food Consumption

Data

Targeted Sampling and Analysis

Important Information for Decision Making

Information about the Analytical Behaviour of

Pesticides

Data on Pesticide Usage in Agriculture� Real Application Data (Usage Data, Surveys)� Recommendations to Farmers (from Authorities and Industry)� Pesticide Registration Data (Increasingly Important)

�Decreasing Information Availability


Slide 31

INTERNET

Currently, Information Flow Non-Systematic …

Lab 1

Lab 2

Lab 3

Lab 4 Lab 5

Lab 7

Lab 6


Slide 32

DATA-POOL: Collection/Distribution of Information

Common Data-Pool

Lab 1

Lab 2

Lab 3

Lab 4 Lab 5

Lab 7

Lab 6

INTERNET


Slide 33

www.Pesticides-Online.com


Slide 34

PESTICIDES-ONLINE

- Information Exchange between Laboratories- Enable Targeted Pesticide-AnalysisAims:

Re

sid

ue

Fin

din

gs

Pe

sticid

e-U

sa

ge

D

ata

Dis

cu

ssio

n-F

oru

m

Pe

sticid

e-

Data

-Sh

ee

ts


Slide 35

Sorting optionsfor theresults


Various filter options for a targeted query


Printing optionsfor query and result-list


View reference and contact-information by clicking hereView reference and contact-information by clicking here

View individual values by clicking here

View individual values by clicking here


Slide 36

Sorting optionsfor the

query results

Sorting optionsfor the

query results





View reference and contact-information by clicking hereView reference and contact-information by clicking here


Slide 37



Printing optionPrinting optionClick here to see the

„Pesticide Data Sheet“Click here to see the

„Pesticide Data Sheet“


Slide 38

View MS-SpectraView MS-Spectra

Typical recoveries

with various multiresidue

methods

Typical recoveries

with various multiresidue

methods

Chemical structureChemical structure

GC-behavior GC-behavior

Connection to our Forum to write or read messages on that specific pesticideConnection to our Forum to write or read messages on that specific pesticide

LC-behaviorLC-behavior

Physicochemical Data

Physicochemical Data


Slide 39


Slide 40

Residue Data

>480,000 Entries (36,000 pos.)

270 Different Commodities

112 Countries of Origin

523 Compounds Sought

374 Compounds Found

95 Info Sources

Data SubmissionData Submission

AdministratorAdministrator

Integration of the processed data into the database

Integration of the processed data into the database

Processing of submitted data by anautomatic system and/or manually

Processing of submitted data by anautomatic system and/or manually

Lab 1Lab 1 Lab 2Lab 2 Lab 3Lab 3

Lab 1 Lab 2Lab 2 Lab nLab 3Lab 3DatabaseDatabase

Access to the data viaPesticides-Online.comAccess to the data viaPesticides-Online.com

Lab nLab n

Pesticides-OnlineStatistics

min4 5 6 7 8 9

0

10000

20000

30000

40000

50000

60000

70000

80000


Slide 41

Agricultural Usage Data

>12,000 Entries

183 Commodities

456 Pesticides

16/30 Countries/Regions

Pesticide Data Sheets

Physicochemical, Toxicological and Analytical

Information for

701 Pesticides and Metabolites

C

CCl3

ClCl

H

Pesticides-OnlineStatistics


Slide 42

309 Members from 34 Countries

Pesticides-OnlineCurrent Users

D 143

CH 21

I 17

ES18

USA 15

UK 12

F 8

NL 8

TR7

JP6

SK4

SE 4

BE 4

BR2

EE 2

FI 2

IE 2

AT 3

DK 2

KR 1

RL1

MA 1

ZA1

PT1

IN 1

IL 1

PL 6

CZ1

HU1

SI 3

GR 5

RO 1

AU1

BG 2

46 %

July 2005


Slide 43

Researchers

Recognize Current

Problem Areas

Targeted Research

Residue-Analysts

Targeted Sampling and

Analysis

Monitoring-Coordinators

Recognize Problem Areas &

Set Priorities

Targeted Sampling &

Analysis Plans

Pesticides-OnlinePotential Users


Slide 44

Agric. AuthoritiesFarmers,

Pesticide Industry

Get ValuableFeedback

Take Early Measuresto Avoid

Future Problems

Organic Producers &

Control Bodies

Localize Risk Areas

Facilitate Judgement

of Residue Findings in Organic Food



Slide 45


Enforcement

„Duty of Care“Becomes

more Objective

Food Trader, Manufacturer,

Importer

Recognize Risks

Better Define the„Duty of Care“ and

Order Analyses Accordingly


Slide 46

Pesticides-OnlineCurrent Status (July 2005)

17

6

8

16

16

24

26

61

135

Other

Pesticide Industry

Organic Food Sector

Vendors of Analytical Equipment

Government Adminstration

Food Industry

Academia

Commercial Laboratories

Government Laboratories 46 %

20 %

9 %

8 %


Slide 47

� Access to Pesticides-Online:Currently Free of Charge (Non-Profit Initiative)

� Precondition for Permanent Access: Regular and Adequate Contribution of Data

� Aim:Ensure a Mutual Benefit from the Data-Pool for all Users

Possible future financing options

a) Access-fee for users not contributing data

b) Sponsoring

Pesticides-OnlineConditions of Access


Slide 48

You are all welcome to register and test Pesticides-Online !!


Slide 49

� Accept and Automatically Process more Data Formats

� Create a Glossary with Various LanguagesFor Commodities, Pesticides, Analytical Terminology

� Fill-in the Gaps in the Pesticide Data-Sheets

� Collect Data about Pesticide Stability (As Solids and in Solution)

� Create Data-Sheets for Commodities

� Enable Customized Query Reports to Assist Decision M aking

� Increase the Number of Users

The more Contributions the more Useful the Data Pool!

Pesticides-OnlineFuture Plans


Slide 50� More Findings

Using a Common Data-Pool Advantages

YES!!

� Helps to Elaborate Risk-Ranking (Priority) Lists

Make Information-based decision-making (meaningful testing programs )

Selectively expand the pesticide inventory and spectrum of target-pesticides

Thoughtful and more efficient use of programmable instruments

(e.g. MS-SIM, MS/MS of limited acquisition capacity)

Selection of methodologies to be used (sample preparation & measurement)

� More Clarity thus Care in Data EvaluationStimulates the detective-instinct of personnelHelps to reduce of Subjective (personal)“uncertainty”

by the “Confirmation” of findings (more confidence)


Slide 51

Samples become more transparent


Slide 52

Sweet Pepper CVUA Stuttgart 2000

German Monitoring 1999

Number of Samples

39

246

Positive Samples

39 (100%)

137 (56%)

Pesticides/sample on average

6,7

1,2

MRL-Violations

27

11

A real life example:

Information-Based AnalysisExample of Improved Efficiency

Using a targeted spectrum based on Pesticides-Online Information


Slide 53

Using the Spectrum of 2001 34 MRL-violations would have been missed in 2003 !

16.4 % of Samples54 Violations

5.8 % of Samples23 Violations

MRL-Violations

3.42.0Pesticides/Sample on average

271(Random Sampling)

291 (Random Sampling)

No. of Samples

German Monitoring 2003*

German Monitoring 2001Grapes

* The 2003 spectrum was chosen based on Pesticides-Online information

Information-Based AnalysisExample of Improved Efficiency


Slide 54

Efficiency in a General ContextAny Chain is

Only as Strong as its Weakest Link

Reporting of Resultsto the Responsible Bodies

Pesticide Analysis(Fast and targeted)

SamplingStrategy, Priorities, Locations

(Ports, Product Distribution Centers)

MeasuresEnforcement, Inspections,

Traceability, Education,Follow-up Controls


Slide 55

Conclusion


Slide 56

Thank you very much for your Attention !


Slide 57

The Rest of the CVUA StuttgartPesticide Residue Analysis Team

Hubert Zipper

Carmen Wauschkuhn

Eberhard Schüle

Nadja Looser

Diane Fügel

Dražen Kostelac

Ellen Scherbaum

Strategies for Improving Overall Efficiency in Pesticide ...

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