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<strong>Pesticides</strong>-<strong>Online</strong> <strong>and</strong><br />

<strong>Method</strong> <strong>Validation</strong> <strong>Database</strong><br />

Two <strong>Database</strong> Modules to Access Pesticide-Related Data via the Internet<br />

Dr. H. Zipper<br />

Chemisches und Veterinäruntersuchungsamt Stuttgart<br />

EU-CRL for Pesticide Residues using Single Residue <strong>Method</strong>s<br />

Test<br />

Version<br />

<strong>Online</strong>!


CIRCA<br />

Document<br />

Management<br />

System<br />

CRL-FV<br />

Fruits & Vegetables<br />

Member-<br />

Area<br />

[restricted<br />

access]<br />

CRL-CF<br />

Cereals & Feeding Stuff<br />

CRL-<strong>Pesticides</strong>-Website<br />

www.???.eu<br />

[= website for experts]<br />

CRL-FAO<br />

Food of Animal Origin<br />

→ www.pesticides-online.com<br />

→ <strong>Method</strong> <strong>Validation</strong> <strong>Database</strong><br />

CRL-SRM<br />

Single Residue <strong>Method</strong>s<br />

Two <strong>Database</strong> Modules to Access Pesticide-Related Data:<br />

2CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Targeted Sampling & Analysis<br />

High-Tech-Instrumentation & Fast Sample Preparation<br />

are Important, but...<br />

Important is not only<br />

How You Analyse<br />

but also…<br />

What You Analyse!<br />

Set priorities based on information...<br />

3CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Targeted Analysis<br />

Relevant spectrum<br />

Pome Fruit<br />

Relevant spectrum<br />

Berries<br />

… using SRM<br />

Laboratory spectrum<br />

using the MRM<br />

Entire spectrum<br />

of pesticides<br />

Potential Spectrum<br />

of the MRM<br />

4CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Targeted Analysis<br />

Relevant spectrum<br />

Pome Fruit<br />

Relevant spectrum<br />

Berries<br />

… using SRM<br />

Laboratory spectrum<br />

using the MRM<br />

Entire spectrum<br />

of pesticides<br />

Potential Spectrum<br />

of the MRM<br />

5CRL for<br />

Residues of <strong>Pesticides</strong> SRM


DATA-POOL: Collection/Distribution of Information<br />

Lab 3<br />

Lab 2<br />

Lab 4<br />

Lab 1<br />

Common<br />

Data-Pool<br />

Lab 5<br />

INTERNET<br />

Lab 7<br />

Lab 6<br />

6CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Aims:<br />

Discussion-Forum<br />

PESTICIDES-ONLINE<br />

- Information Exchange between Laboratories<br />

- Enable Targeted Pesticide-Analysis<br />

Pesticide-<br />

Data-Sheets<br />

Pesticide-Usage<br />

Data<br />

7CRL for<br />

Residues of <strong>Pesticides</strong> SRM<br />

Residue Findings


www.pesticides-online.com<br />

Navigation bar<br />

Navigation bar<br />

8CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Registration to <strong>Pesticides</strong>-<strong>Online</strong><br />

<strong>Online</strong>-Registration is necessary!<br />

After Registration only the Forum is can be used.<br />

Administrator will contact you by email <strong>and</strong> give you an access!<br />

The access is free of charge.<br />

Fill-in the requested<br />

information <strong>and</strong><br />

submit.<br />

Different access rights to <strong>Pesticides</strong>-<strong>Online</strong>:<br />

- Full access for official labs/organisations, labs/organisation that<br />

submit data (e.g. residue findings)<br />

- Limited access for labs/organisations that submit no data<br />

9CRL for<br />

- No access for NGO, journalists, private individuals, … SRM<br />

Residues of <strong>Pesticides</strong>


<strong>Pesticides</strong>-<strong>Online</strong> Users Around the World:<br />

10CRL for<br />

IS<br />

1<br />

UK<br />

14<br />

BE<br />

10<br />

NL D<br />

12 193<br />

LV<br />

DK SE PL FI EE<br />

1<br />

3 6 9 3 3<br />

CZ<br />

4<br />

SK<br />

6 HU<br />

3<br />

USA<br />

30<br />

IE<br />

2<br />

F<br />

13<br />

PT<br />

4<br />

ES<br />

29 MA<br />

3 CH<br />

29<br />

BR<br />

7<br />

UY<br />

AT IT<br />

7 31<br />

GH<br />

2<br />

SI<br />

3<br />

GR<br />

8<br />

RO<br />

1<br />

TR<br />

13<br />

RL<br />

1<br />

IL<br />

1<br />

SD CY<br />

1 1<br />

BG<br />

5<br />

KR<br />

3<br />

JP<br />

19<br />

CN<br />

2<br />

IN<br />

1<br />

CL<br />

3<br />

2<br />

AR<br />

3<br />

Residues of <strong>Pesticides</strong><br />

ZA<br />

1<br />

AU<br />

SRM<br />

2<br />

Currently 506 users from 53 countries


Various filter options<br />

for a targeted query<br />

View reference <strong>and</strong> contactinformation<br />

by clicking here<br />

Sorting<br />

options<br />

for the<br />

results<br />

11CRL for<br />

Residues of <strong>Pesticides</strong> SRM


<strong>Pesticides</strong>-<strong>Online</strong> - Statistics<br />

Residue Data<br />

>1 000 000 Entries<br />

(> 75 000 pos.)<br />

314 Different Commodities<br />

116 Countries of Origin<br />

678 Compounds Sought<br />

512 Compounds Found<br />

91 Info Sources (35 labs)<br />

12CRL for<br />

Residues of <strong>Pesticides</strong> SRM<br />

80000<br />

70000<br />

60000<br />

50000<br />

40000<br />

30000<br />

20000<br />

10000<br />

0<br />

4 5 6 7 8 9<br />

min


Results of Lab-Questionnaire 2006<br />

Website-section of lab-questionnaire:<br />

What types of data would you like to see in our common CRL website?<br />

Would you be willing to contribute data to such a database<br />

(= RESIDUE FINDINGS <strong>Database</strong>)?<br />

%<br />

70<br />

60<br />

50<br />

40<br />

30<br />

20<br />

10<br />

0<br />

61<br />

13CRL for<br />

Residues of <strong>Pesticides</strong> SRM<br />

1<br />

(71 answers<br />

to this questions)<br />

Yes No Don`t know yet<br />

38


Data Submission to <strong>Pesticides</strong>-<strong>Online</strong><br />

For more convenience, we try to<br />

use the data-formats (residue<br />

findings) that our users are<br />

already utilizing in their lab <strong>and</strong><br />

translate them into ours.<br />

Thus, please send us an example<br />

of your data so that we can look at<br />

it <strong>and</strong> see what we can do.<br />

If you don't have a LIMS in your lab,<br />

we can also offer you a tool based<br />

on Microsoft Access to easily collect<br />

your pesticides residue data.<br />

Which information do we need at<br />

least?<br />

- Commodity (+ Processing)<br />

- Pesticide sought for + value<br />

(negatives also interesting!!!)<br />

- Year of analysis<br />

- Country of origin<br />

14CRL for<br />

- (Other: organic, MRL-violation)<br />

SRM<br />

Residues of <strong>Pesticides</strong>


Various filter options<br />

for a targeted query<br />

Sorting options<br />

for the<br />

query results<br />

View reference <strong>and</strong> contactinformation<br />

by clicking here<br />

15CRL for<br />

Residues of <strong>Pesticides</strong> SRM


<strong>Pesticides</strong>-<strong>Online</strong> - Statistics<br />

Agricultural Usage Data<br />

>16 000 Entries<br />

194 Commodities<br />

473 <strong>Pesticides</strong><br />

35 Countries/Regions<br />

16CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Printing option<br />

Printing option<br />

Click here to see the<br />

„Pesticide Data Sheet“<br />

Physicochemical, Toxicological <strong>and</strong><br />

Analytical Information for<br />

795 <strong>Pesticides</strong> <strong>and</strong> Metabolites<br />

Sorting options<br />

for the<br />

results<br />

17CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Physicochemical <strong>and</strong><br />

Toxicological Data<br />

Analytical Data<br />

Analytical Data<br />

18CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Physicochemical data:<br />

- pKa<br />

- Water solubility<br />

- …<br />

Toxicological data:<br />

- ARfD<br />

- ADI<br />

19CRL for<br />

Residues of <strong>Pesticides</strong> SRM


LC-Behavior<br />

Typical recoveries<br />

with various<br />

multiresidue methods<br />

GC-Behavior<br />

20CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Unfortunately the Forum is not much used up to now.<br />

But ...<br />

21CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Results of Lab-Questionnaire 2006<br />

Would you like a discussion forum<br />

to be established?<br />

%<br />

100<br />

90<br />

80<br />

70<br />

60<br />

50<br />

40<br />

30<br />

20<br />

10<br />

0<br />

92<br />

(74 answers<br />

to this questions)<br />

Yes No<br />

Would you like the forum to be<br />

accessible also to colleagues outsite<br />

the CRL/NRL-Network (e.g.<br />

colleagues from countries outside<br />

the EU, from private labs...)?<br />

8<br />

Would you be willing to<br />

use such a forum?<br />

22CRL for<br />

0<br />

Residues of <strong>Pesticides</strong><br />

Yes No<br />

SRM<br />

Analytical labs Don`t know yet<br />

%<br />

%<br />

80<br />

70<br />

60<br />

50<br />

40<br />

30<br />

20<br />

10<br />

100,0<br />

90,0<br />

80,0<br />

70,0<br />

60,0<br />

50,0<br />

40,0<br />

30,0<br />

20,0<br />

10,0<br />

0,0<br />

72<br />

91,4<br />

7,1<br />

(70 answers<br />

to this questions)<br />

1,4<br />

Yes No No, due to lack of<br />

time, not lack of<br />

interest<br />

23<br />

1<br />

(69 answers<br />

to this questions)<br />

3


<strong>Method</strong> <strong>Validation</strong> <strong>Database</strong><br />

New project started this year:<br />

Test<br />

Version<br />

<strong>Online</strong>!<br />

→ <strong>Database</strong> for storage of data generated within<br />

the aim of method validation experiments in<br />

various laboratories.<br />

⇒ Enables the systematic collection <strong>and</strong><br />

customized retrieval of data produced during<br />

method validation in different laboratories.<br />

23CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Registration to <strong>Method</strong> <strong>Validation</strong> <strong>Database</strong><br />

<strong>Online</strong>-Registration will be necessary!<br />

Fill-in the requested<br />

information <strong>and</strong><br />

submit.<br />

24CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Query Section: Various filter options for a targeted query<br />

Filter options<br />

for commodity<br />

Filter options<br />

for extraction method,<br />

ISTD, Cleanup, …<br />

Filter options<br />

for compound<br />

Filter options<br />

for lab name, …<br />

25CRL for<br />

Residues of <strong>Pesticides</strong> SRM


1. Result list of individual recovery values<br />

Aggregation mode 1<br />

Aggregation mode 1<br />

N° of hits:<br />

N° of hits:<br />

All important experimental<br />

parameters are shown!<br />

Aggregation mode 2<br />

Aggregation mode 2<br />

26CRL for<br />

Residues of <strong>Pesticides</strong> SRM


2. List with aggregated recovery data<br />

Important experimental<br />

parameters are shown!<br />

Aggegation line for 2,4-D in Cucumber at Spiking level 0,01 mg/kg<br />

Aggegation line for 2,4-D in Raisin at Spiking level 0,01 mg/kg<br />

Aggegation line for all commodites at spiking level 0,01 mg/kg<br />

27CRL for<br />

Residues of <strong>Pesticides</strong> SRM


<strong>Method</strong> <strong>Validation</strong> <strong>Database</strong> - Statistics<br />

currently only data for QuEChERS-<strong>Method</strong>,<br />

but <strong>Method</strong> <strong>Validation</strong> <strong>Database</strong> is flexible to<br />

receive data from any other method!<br />

Recovery data for QuEChERS-<strong>Method</strong>:<br />

- 478 compounds<br />

- 44 commodities (apple, raisin, lemon, …)<br />

- 17 labs data submitted<br />

Recovery data of S19- <strong>and</strong> ChemElute will be<br />

submitted soon from different labs.<br />

You’re welcome to submit validation data from your lab!<br />

But how to submit?<br />

28CRL for<br />

Residues of <strong>Pesticides</strong> SRM


Data Submission to <strong>Method</strong> <strong>Validation</strong> <strong>Database</strong><br />

internet<br />

We offer a Data Submission-Format<br />

(→ Excel-file)<br />

If you are interested, please contact us!<br />

If you have huge amounts of recovery<br />

data, we will try to transform your data<br />

into our data-format.<br />

29CRL for<br />

Residues of <strong>Pesticides</strong> SRM


...our Pesticide Residue Team...<br />

Thank you very much<br />

for your Attention !<br />

30CRL for<br />

SRM<br />

Residues of <strong>Pesticides</strong>

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