Almería 23 -25 October 2013 - EURL | Pesticides · 4th Joint Workshop of the European Union...

4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides

Almería 23rd-25th October 2013



Calendar

ACTIVITY DATE

Sending Application Form to laboratories 9th May 2013

Sending calendar and pesticides target list to participant laboratories. 14th May 2013

Deadline for receiving Application Form from laboratories. 17th May 2013

Sample distribution. 10th June 2013

Deadline for receiving results 28th June 2013

Preliminary Report: only results, no statistical treatment. July 2013

Final Report October 2013



Participants

1 Austria4 Belgium1 Denmark1 Finland3 France8 Germany2 Hungary1 Ireland8 Italy1 Norway*1 Poland1 Romania1 Slovakia8 Spain1 Sweden2 Switzerland*2 The Netherland

1 China1 Egypt1 Israel1 Saudi Arabia1 Serbia1 Uruguay

Non EU and EFTA countries

EU and EFTA countries

*EFTA countries

52 laboratories in total (16 of them NRLs)



Incurred Compounds20 LCa- and GCb- amenable pesticides

AcetamipridBuprofezin

CarbendazimChlorpyrifos

CypermethrinDifenoconazoleEndosulfan beta

EthofenproxFenpropathrinImidacloprid

Lambda cyhalothrinMethomyl

Parathion ethylPyridaben

Tebuconazole

BifenthrinEndosulfan alpha

Endosulfan sulphate Omethoate

Thiophanate methyl

Not evaluated (Median < 4MRRL)

Not evaluated (Homogeneity test fails)

15 pesticides evaluated



Preparation of the test item

Extend the tea on the crystallizer

Samples distributionSieving

Milling HomogenationReal sample

Sample packing



PesticidesHomogeneity median

concentration (mg/kg)

Assigned value(mg/kg)

Acetamiprid 0.148 0.108Buprofezin 0.213 0.180Carbendazim 0.271 0.250Chlorpyrifos 0.466 0.364Cypermethrin 0.145 0.112Difenoconazole 0.380 0.367Endosulfan beta 0.096 0.081Ethofenprox 0.234 0.170Fenpropathrin 0.258 0.188Imidacloprid 0.108 0.081Lambda cyhalothrin 0.175 0.141Methomyl 0.113 0.089Parathion ethyl 0.436 0.372Pyridaben 0.338 0.268Tebuconazole 0.423 0.338Thiophanate methyl* 0.259 0.190

Homogeneity

*Homogeneity test fails

4th Joint Workshop of the European Union Reference Laboratories for Residues of PesticidesAlmería 23rd-25th October 2013



Results



PesticidesNo. of

Reported Results

No. of False Negative

Results

No. of Not Analysed

Results

Percentage of Reported Results

(out of 46)*

Acetamiprid 36 4 6 78Bifenthrin* 19 22 5 41Buprofezin 41 3 2 89Carbendazim 42 0 4 91Chlorpyrifos 43 1 2 93Cypermethrin 31 6 9 67Difenoconazole 40 1 5 87Endosulfan alpha* 36 5 5 78Endosulfan beta 38 3 5 83Endosulfan sulfate* 39 2 5 85Ethofenprox 36 2 8 78Fenpropathrin 40 1 5 87Imidacloprid 33 7 6 72Lambda cyhalothrin 44 0 2 96Methomyl 29 9 8 63Omethoate* 20 19 7 43Parathion ethyl 40 2 4 87Pyridaben 44 1 1 96Tebuconazole 42 1 3 91Thiophanate methyl** 35 2 9 76

Sumary of reported results

*Median < 4 MRRL**Homogeneity test fails



Laboratory Code Pesticide Concentration

(mg/kg)Determination

Technique RL

(mg/Kg)MRRL

(mg/Kg) Extraction method used

Lab007 Orthophenylphenol 0.020 LC-MS/MS (QQQ) 0.01 0.02 QuEChERS

Lab009 Penconazole 0.071 LC-MS/MS (QQQ) 0.01 0.02 Modified QuEChERS withCaCl2

Lab011 Amitraz 0.126 LC-MS/MS (QQQ) 0.02 0.02 Modified QuEChERS withCaCl2

Lab012 Methidathion 0.041 GC-MS/MS (QQQ) 0.01 0.02 L-L extraction

Lab013 Carbaryl 0.042 Other 0.02 0.02 Modified QuEChERS withCaCl2

Lab034 Folpet 0.056 GC-MS/MS (QQQ), FPD, ECD 0.02 0.02 miniLuke

Lab035 Ethoprophos 0.155 LC and GC MS/MS (QQQ) 0.01 0.02 QuEChERS

Lab043 Ethoprophos 0.177 LC-MS/MS (QQQ) 0.01 0.02 QuEChERSLab043 Triazophos 0.196 LC-MS/MS (QQQ) 0.01 0.02 QuEChERS

False positives



Labo

rato

ryC

ode

Ace

tam

iprid

Bupr

ofez

in

Chl

orpy

rifos

Cyp

erm

ethr

in(c

yper

met

hrin

incl

.oth

er

mix

ture

s of

con

stitu

ent

isom

ers

(sum

of i

som

ers)

)

Dife

noco

nazo

le

Endo

sulfa

nbe

ta

Etof

enpr

ox

Fenp

ropa

thrin

Imid

aclo

prid

Met

hom

yl

Para

thio

n-et

hyl

Pyrid

aben

Tebu

cona

zole

Thio

phan

ate-

met

hyl

Lab003 ND NDLab006 NDLab007 ND ND NDLab010 NDLab011 ND NDLab013 NDLab016 ND ND ND NDLab018 NDLab020 NDLab022 ND ND NDLab025 ND NDLab026 NDLab027 ND ND ND NDLab033 NDLab034 ND NDLab035 NDLab039 NDLab043 ND ND NDLab047 NDLab050 NDLab051 ND ND NDLab054 ND ND ND ND

False negatives

QuEChERSCaCl2EtAcMiniLukeMeOHOther

False negatives (%) over the total number of

results per extraction method

QuEChERS: 6.9%CaCl2: 6.3%Ethyl Acetate method: 2.3%MeOH extraction: 6.7%miniLuke: 6.1%Other methods: 2.2%



Tea matrix compounds. QuEChERs_CaCl2 extraction method. Dilution:5 LC-TOF-MSAbsolute height ≥ 10000 counts

PT01_Green tea6659 compounds

Green tea3879

compounds



Pesticides MRRL(mg/Kg)

Median(mg/Kg)

u(mg/kg)

FFP RSD(%)

Qn RSD(%)

Acetamiprid 0.02 0.108 0.007 25 31

Buprofezin 0.02 0.180 0.014 25 39

Carbendazim 0.02 0.250 0.021 25 44

Chlorpyrifos 0.02 0.364 0.021 25 35

Cypermethrin 0.02 0.112 0.011 25 44

Difenoconazole 0.02 0.367 0.018 25 25

Endosulfan beta 0.02 0.081 0.007 25 44

Ethofenprox 0.01 0.170 0.012 25 34

Fenpropathrin 0.02 0.188 0.008 25 22

Imidacloprid 0.02 0.081 0.006 25 36

Lambda cyhalothrin 0.02 0.141 0.009 25 33

Methomyl 0.02 0.089 0.007 25 32

Parathion ethyl 0.02 0.372 0.021 25 29

Pyridaben 0.02 0.268 0.017 25 32

Tebuconazole 0.02 0.338 0.017 25 26

Median values, uncertainty and %RSDs for all pesticides present in the test item



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Acetamiprid72.5% Acceptable5.0% Questionable22.5% Unacceptable

*False Negatives

* ** *

Median: 0.108 mg/kg

or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ Other

Q Et

No water addition

Z-Scores

* * * *



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Buprofezin79.6% Acceptable6.8% Questionable13.6% Unacceptable

* * *

Median: 0.180 mg/kg

*False Negatives

Q mL

or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition

Z-Scores

** *



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Carbendazim57.1% Acceptable23.8% Questionable19.1% Unacceptable

Median: 0.250 mg/kg

O C mL


Z-Scores



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Chlorpyrifos88.6% Acceptable4.6% Questionable6.8% Unacceptable

*False Negatives

*

Median: 0.364 mg/kg

Q O mL


Z-Scores

*



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Cypermethrin62.2% Acceptable16.2% Questionable21.6% Unacceptable

*False Negatives

** * * * *

Median: 0.112 mg/kg

mL Q


Z-Scores

* * * * * *



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Difenoconazole90.2% Acceptable4.9% Questionable4.9% Unacceptable

*False Negatives

*

Median: 0.367 mg/kg

Q mL mL


Z-Scores

*



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Endosulfan beta70.7% Acceptable22.0% Questionable7.3% Unacceptable

Q Q

*False Negatives

*

* *

Median: 0.081 mg/kg


Z-Scores

***



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Etofenprox81.6% Acceptable7.9% Questionable10.5% Unacceptable

*False Negatives

* *

Median: 0.170 mg/kg

C Q C


Z-Scores

* *



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Fenpropathrin90.3% Acceptable2.4% Questionable7.3% Unacceptable

*False Negatives

*

Median: 0.188 mg/kg

Q Q Et


Z-Scores

*



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Imidacloprid72.5% Acceptable15.0% Questionable12.5% Unacceptable

* * * *

* * *

*False Negatives

Median: 0.081 mg/kg


Z-Scores

* * ** * * *



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Lambda cyhalothrin86.4% Acceptable9.1% Questionable4.5% Unacceptable

Median: 0.141 mg/kg

O O mL C Q


Z-Scores



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Methomyl65.8% Acceptable5.3% Questionable28.9% Unacceptable

*False Negatives

** * * *

* * * *

Median: 0.089 mg/kg

mL Q


Z-Scores

* * * * ** * * *



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Parathion-ethyl81.0% Acceptable14.2% Questionable4.8% Unacceptable

*False Negatives

* *

Median: 0.372 mg/kg


Z-Scores

* *



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Pyridaben84.4% Acceptable6.7% Questionable8.9% Unacceptable

*False Negatives

*

Median: 0.268 mg/kg

O M mL Q


Z-Scores

*



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Tebuconazole88.4% Acceptable2.3% Questionable9.3% Unacceptable

C Q

*False Negatives

*

Median: 0.338 mg/kg


Z-Scores

*



Classification of Z-scores for the pesticides reported

Pesticides Acceptable (%) Questionable (%) Unacceptable (%)

Acetamiprid 72.5 5.0 22.5Buprofezin 79.6 6.8 13.6Carbendazim 57.1 23.8 19.1Chlorpyrifos 88.6 4.6 6.8Cypermethrin 62.2 16.2 21.6Difenoconazole 90.2 4.9 4.9Endosulfan beta 70.7 22.0 7.3Ethofenprox 81.6 7.9 10.5Fenpropathrin 90.3 2.4 7.3Imidacloprid 72.5 15.0 12.5Lambda cyhalothrin 86.4 9.1 4.5Methomyl 65.8 5.3 28.9Parathion ethyl 81.0 14.2 4.8Pyridaben 84.4 6.7 8.9Tebuconazole 88.4 2.3 9.3



Category A and B

52%

48% Cat A

Cat B

24 LaboratoriesReported ≥ 90% analytes (14 pesticides)Without false positives

22 LaboratoriesReported < 90% analytes (14 pesticides)

and/or false positives

2 laboratories reported one falsepositive with ≥ 90% analytes




Special case



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033

Lab

007

Lab

018

Lab

039

Lab

054

Lab

008

Lab

017

Lab

034

Lab

052

Lab

030

Lab

025

Lab

004

Lab

005

Lab

006

Lab

032

Lab

001

Lab

012

Lab

021

Lab

046

Lab

002

Lab

009

Lab

023

Lab

035

Lab

014

Lab

050

Lab

029

Lab

019

Lab

024

Lab

047

Carbendazim57.1% Acceptable23.8% Questionable19.1% Unacceptable

Median: 0.250 mg/kg

O C mL


No water addition



-5,0

-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0

5,0La

b00

7

Lab

050

Lab

027

Lab

033

Lab

054

Lab

024

Lab

029

Lab

016

Lab

004

Lab

025

Lab

011

Lab

018

Lab

021

Lab

014

Lab

020

Lab

001

Lab

039

Lab

035

Lab

008

Lab

049

Lab

017

Lab

046

Lab

026

Lab

002

Lab

032

Lab

006

Lab

052

Lab

009

Lab

023

Lab

019

Lab

005

Lab

047

Lab

012

Lab

034

Lab

030

Lab

015

Lab

043

Thiophanate methyl59.5% Acceptable5.4% Questionable35.1% Unacceptable

*False Negatives

* *

Median: 0.190 mg/kg

Q Q Q




‐5,0

‐4,0

‐3,0

‐2,0

‐1,0

0,0

1,0

2,0

3,0

4,0

5,0Lab0

27

Lab0

16

Lab0

20

Lab0

11

Lab0

07

Lab0

33

Lab0

54

Lab0

49

Lab0

18

Lab0

26

Lab0

39

Lab0

04

Lab0

25

Lab0

08

Lab0

17

Lab0

52

Lab0

01

Lab0

06

Lab0

21

Lab0

32

Lab0

46

Lab0

02

Lab0

50

Lab0

09

Lab0

05

Lab0

15

Lab0

35

Lab0

14

Lab0

29

Lab0

34

Lab0

23

Lab0

12

Lab0

24

Lab0

30

Lab0

19

Lab0

47

Lab0

43

Carbendazim + Thiophanate methyl expressed as Carbendazim

No water addition


Q C

78.4% Acceptable8.1% Questionable13.5% Unacceptable

Median: 0.400 mg/kg



0

5

10

15

20

25

30

35

40

45

50

Carbendazim Thiophanate‐methyl Carb + TFM sum

Qn (%

)Qn (%)



Graph using individual values for Carbendazim and Thiophanate methyl

0,0

0,5

1,0

1,5

2,0

2,5

3,0

3,5

4,0

4,5

5,0La

b017

Lab0

01

Lab0

52

Lab0

08

Lab0

46

Lab0

04

Lab0

02

Lab0

32

Lab0

49

Lab0

23

Lab0

21

Lab0

26

Lab0

50

Lab0

05

Lab0

39

Lab0

06

Lab0

15

Lab0

18

Lab0

20

Lab0

33

Lab0

24

Lab0

47

Lab0

29

Lab0

30

EUPT-PT01 Graphical representation for laboratories in Category A

75.0% Acceptable 20.8% Questionable 4.2% Unacceptable

18 Laboratories 5 Laboratories 1 Laboratory





Conclusions



Conclusions• Fifty-two laboratories participated in EUPT-T01 (Six from no EU or EFTA countries, 16 NRLs).

• Pesticides considered as positives were those which were reported by both the Organiser and the majority of participants.

• A higher dispersion (Qn) than in most fruits and vegetables have been observed (As maximum 44%).

• For carbendazim and thiophanate methyl, the results were influenced by the different degrees of degradation obtained by participants during the sample handling.

• QuEChERS without calcium chloride addition modificcation, presented a higher dispersion accounted as Qn than for the whole data reported (average Qn for QuEChERS was 41% whereas for the combined data, it was 34%).

• One compound did not pass the homogeneity test (thiophanate methyl). This fact is clearly as a consequence of some degradation to carbendazim.

• Overall, the results can be considered to be good with regard to the z-scores for each pesticide present in the test item, except for some pesticides which obtained a value more than 20% of unacceptable results (3 of them).

• It would appear that multiresidue methods such as QuEChERS have improved following modification (CaCl2 addition).

• All of the laboratories applying the miniLuke method obtained acceptable results in terms of z-scores, except for carbendazim.



Data Analysis

1 2 3 4 5

EURL-FVScientific Group

ReportsSamples

andProtocol

INFORMATION

EUPT Web Page

General European Commission Proficiency Test Scheme



ACTIVITY DATEPublishing the Calendar and Matrix on the EURL-FV Web page. 23rd October 2012

Submission of Application Form by invited laboratories.3rd Dec. 2012

-7th Jan 2013

Sample distribution. 21st January 2012

Submission of sample receipt and acceptance - Form 0. As soon as sample is received

Deadline for receiving results - Form1 72 hours after receiving the sample

Preliminary Report. March 2013

Final Report distributed to the Laboratories. December 2013



EUROPEAN PROFICIENCY TEST - FRUITS AND VEGETABLES -MASS SCREENING 04- Participants

COUNTRY No. COUNTRY No.Austria 1* Italy 1*+5Belgium 1*+2 Latvia 1*China 2 Romania 2*Croatia 1 Serbia 1Czech Republic 1*+1 Slovenia 1*Denmark 1* Spain 6Estonia 1* Sweden 1*+1Finland 1* Switzerland 1*+1France 1*+7 The Netherlands 1*+1Germany 7 Turkey 1Greece 1 UK 1*+2

Hungary 1*+2

58

17 NRLs*17 NRLs*



EUPT-FV–SCREENING METHODS 5Participants with no results

COUNTRY No. of laboratory

Slovenia (results after the deadline) 3

58



10 No Participating

EU States

18 Participating

EU States

ChinaCroatiaSerbiaSwitzerlandTurkey

5 ParticipatingNon EU States

AustriaBelgiumCzech Republic DenmarkEstoniaFinlandFranceGermanyHungaryItalyLatviaNetherlandsRomaniaSloveniaSpainSwedenUnited Kingdom

BulgariaCyprusGreeceIrelandLithuaniaLuxembourgMaltaPolandPortugalSlovakia



Homogeneity testTest item No. 004

a004b

007a

007b

023a

023b

064a

064b

066a

066b

076a

076b

101a

101b

122a

122b

144a

144b

148a

148b

A. Cc*(mg/kg)

RSD(%)

Aldicarb sulfone D D D D D D D D D D D D D D D D D D D D 0.210 14.7Aldicarb Sulfoxide D D D D D D D D D D D D D D D D D D D D 0.426 9.0Atrazine D D D D D D D D D D D D D D D D D D D D 0.301 1.2Beta-Cyfluthrin D D D D D D D D D D D D D D D D D D D D 0.201 9.1Bromoxynil D D D D D D D D D D D D D D D D D D D D 0.386 7.8Clomazone D D D D D D D D D D D D D D D D D D D D 0.083 6.1Dieldrin D D D D D D D D D D D D D D D D D D D D 0.400 6.4Diuron D D D D D D D D D D D D D D D D D D D D 0.935 4.5Fluazinam D D D D D D D D D D D D D D D D D D D D 0.030 13.6Flufenacet D D D D D D D D D D D D D D D D D D D D 0.126 7.3Metamitron D D D D D D D D D D D D D D D D D D D D 0.184 6.8Methomyl# D D D D D D D D D D D D D D D D D D D D 0.037 9.4Metribuzin D D D D D D D D D D D D D D D D D D D D 0.225 4.4Molinate D D D D D D D D D D D D D D D D D D D D 0.060 12.3Oxamyl D D D D D D D D D D D D D D D D D D D D 0.092 7.4Picloram D D D D D D D D D D D D D D D D D D D D 0.098 13.1Picolinafen D D D D D D D D D D D D D D D D D D D D 0.488 13.7Propamocarb D D D D D D D D D D D D D D D D D D D D 0.082 7.7Prosulfocarb D D D D D D D D D D D D D D D D D D D D 0.247 9.3Quinoclamine D D D D D D D D D D D D D D D D D D D D 0.073 9.6Thiodicarb# D D D D D D D D D D D D D D D D D D D D 0.068 10.1Triflumizole D D D D D D D D D D D D D D D D D D D D 0.022 14.9

D: Detected A. Cc: Average Concentration RSD: Relative Standard Deviation (n=20) # Thiodicarb degradation product (not spiked)* Concentration evaluated by Organiser



The test material was spiked/treated with thiodicarb, which degrades to methomyl. The test material was not spiked/treated with methomyl.

Propazine, simazine and thiabendazole were not intentionally used to spike/treat the test material, but they were detected by the organisers at concentrations below 10 ppb due to impurities of the commercial formulations.

SN

OO

HN

SO

O

NO

ON

SNS

N

Thiodicarb Methomyl



Propazine (Q-TOF)

MS Spectra - 10ppb Propazine Potato

MS Spectra - Sample 107 SM05

Propazine[M+H]+: 230.1167

C9H16ClN5Therbuthylazine

10ppb Standard Potato

Sample 107 SM05

C ~ 1.3 ppb



Propazine (LC-QQQ)

Ratio SRM2/SRM1: 30%

SRM1: 230 / 146

SRM2: 230 / 188

SRM1: 230 / 146

SRM2: 230 / 188


Standard 10ppb Potato


Sample 1 SM05

Sample 1 SM05

C ~ 1.5 ppb



Simazine (Q-TOF)

Sample 107 SM05

20ppb Standard Potato Simazine

[M+H]+: 202.0853C7H12ClN5

MS Spectra - 20ppb Simazine Potato


C ~ 2.4 ppb



Simazine (LC-QQQ)

Ratio SRM2/SRM1: 57%Ratio SRM3/SRM1: 53%Ratio SRM3/SRM2: 94%

Ratio SRM2/SRM1: 63%Ratio SRM3/SRM1: 55%Ratio SRM3/SRM2: 88%

SRM2: 202 / 104

SRM3: 202 / 124

SRM1: 202 / 132

SRM2: 202 / 104

SRM3: 202 / 124

SRM1: 202 / 132

C ~ 2.3 ppb




Sample 1 SM05

Sample 1 SM05

Sample 1 SM05



Thiabendazole (Q-TOF)5x10

00.20.40.60.8

11.21.41.61.8

22.22.4

2.6+ESI EIC(202.0433) Scan Frag=90.0V 107A_SM05.d

5x10

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

5.5

+ESI EIC(202.0433) Scan Frag=90.0V 10ppb_SAS_Potato.d

Counts vs. Acquisition Time (min)3.6 3.65 3.7 3.75 3.8 3.85 3.9 3.95 4 4.05 4.1 4.15 4.2 4.25 4.3 4.35 4.4 4.45 4.5 4.55 4.6 4.65 4.7 4.75 4.8 4.85 4.9

Sample 107 SM05

10 ppb ThiabendazoleThiabendazole

[M+H]+: 202.0433C10H7N3S

5x10

0

0.5

1

1.5

2

2.5

+ESI Scan (4.076 min) Frag=90.0V 107A_SM05.d

202.1806([C11 H23 N O2]+H)+

125.9863

102.0341 167.0127121.0509

130.1588 158.0030141.9580 182.9853 194.1180151.0358110.0168 223.0638172.0944 214.9172

5x10

0

1

2

3

4

5

+ESI Scan (4.143 min) Frag=90.0V 10ppb_SAS_Potato.d

202.0434([C10 H7 N3 S]+H)+

125.9863102.0341 167.0132121.0509 130.1591 158.0033141.9586 182.9848 223.0687151.0357 194.1176110.0164 214.9171173.0298

Counts vs. Mass-to-Charge (m/z)90 95 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 205 210 215 220 225 230

MS Spectra - 10ppb Thiabendazole Potato


No formula match



Thiabendazole (LC-QQQ)

Sample 1 SM05

Sample 1 SM05


Standard 10ppb PotatoRatio SRM2/SRM1: 93%

SRM2: 202 / 131

SRM1: 202 / 175


SRM2: 202 / 131

SRM1: 202 / 175

C ~ 0.9 ppb



Ald

icar

bsu

lfone

Ald

icar

bsu

lfoxi

de

Atra

zine

Beta

-Cyf

luth

rin

Brom

oxyn

il

Clo

maz

one

Diel

drin

Diur

on

Flua

zinam

Fluf

enac

et

Met

amitr

on

Met

hom

yl#

Met

ribuz

in

Mol

inat

e

Oxa

myl

Picl

oram

Pico

linaf

en

Prop

amoc

arb

Pros

ulfo

carb

Qui

nocl

amin

e

Thio

dica

rb#

Trifl

umizo

le

Total Number of Reported Pesticides

50 50 53 51 40 49 53 46 31 45 39 50 51 37 52 10 39 47 46 22 50 42

% of Reported Pesticides 85 85 90 86 68 83 90 78 53 76 66 85 86 63 88 17 66 80 78 37 85 71

22 Evaluated Pesticides (21 added )1 Degradation product #

22 Pesticides= 2+5+15

(in green pesticides with concentration <100 ppb)



10

22

31

37 39 39 40 4245 46 46 47 49 50 50 50 50 51 51 52 53 53

0

10

20

30

40

50

60

Picloram

Quinoclam

ine

Fluazinam

Molinate

Metam

itron

Picolinafen

Bromoxynil

Triflumizole

Flufenacet

Diuron

Prosulfocarb

Propamocarb

Clomazone

Aldicarb sulfone

Aldicarb sulfoxide

Methom

yl (not spiked)

Thiodicarb

Beta‐Cyfluthrin

Metribuzin

Oxam

yl

Atrazine

Dieldrin

No

of R

epor

tsSM05 No of Reported Pesticides(57 Laboratories Reported Data)

* Concentration lower than 0.100 mg/kg

*

*

*

*

*

*

*

*

* *



18

39

54

65

68 68 70

74

79 81 81 82

86 88 88 88 88 89 89 91 93 93

0

10

20

30

40

50

60

70

80

90

100

Picloram

Quinoclam

ine

Fluazinam

Molinate

Metam

itron

Picolinafen

Bromoxynil

Triflumizole

Flufenacet

Diuron

Prosulfocarb

Propamocarb

Clom

azone

Aldicarb sulfone

Aldicarb sulfoxide

Methom

yl (not spiked)

Thiodicarb

Beta-Cyfluthrin

Metribuzin

Oxam

yl

Atrazine

Dieldrin%

of R

epor

tsSM05 % of Reported Data by Pesticide

(57 Laboratories Reported Data)

*

*

*

*

*

*

*

*

* *

* Concentration lower than 0.100 mg/kg



Preliminary Results

0

10

20

30

40

50

60

70

80

90

100

Fluopic

olide

Flut

olanil

Fosthi

azate

Spirod

iclofe

nPen

cycu

ronAce

phate

Iprov

alica

rbLin

uron

Methioc

arb

Chlorpr

opha

mChlo

rotha

lonil

Prochlo

raz

Thiabe

ndaz

ole

Cyperm

ethrin

Procym

idone

Azoxy

strob

inDiaz

inon

% o

f Rep

orts

Fv15 % of Reported Data by Pesticide



% of Reported Data by Laboratory(*NRL) (21+1 Pesticides Included)

09

1823

3241

50 5055 55 55

59 5964 64

68 68 68 68 6873 73 73

77 7782 82 82 82 82 82

86 86 86 86 86 86 86 86 8691 91 91 91

95 95 95 95 95 95 95 95 95 9510

010

010

010

0

0

20

40

60

80

100

120

Lab003*Lab032Lab028Lab051Lab050Lab060Lab015*Lab036Lab025*Lab048Lab054Lab012*Lab061Lab007Lab019Lab006*Lab009Lab010*Lab022Lab031Lab004*Lab008Lab040Lab018Lab044Lab001Lab020*Lab021Lab023Lab055*Lab057Lab014*Lab016*Lab024*Lab029Lab035Lab037Lab047Lab049Lab059Lab013Lab017Lab026Lab046*Lab005*Lab011Lab030Lab034*Lab038Lab039Lab041Lab043Lab056Lab058*Lab002Lab033*Lab042Lab053

% of R

eported Pe

sticides

90% 65% 24%



90 92 92 90

60

73 76

65

20 20 22 24

0

10

20

30

40

50

60

70

80

90

100

SM02 SM03 SM04 SM05

% laboratories with more than 50% of pesticides reported% laboratories with more than 70% of pesticides reported% laboratories with more than90% of pesticides reported



The test material was spiked/treated with thiodicarb, which degrades to methomyl. The test material was not spiked/treated with methomyl.

Propazine, simazine and thiabendazole were not intentionally used to spike/treat the test material, but they were detected by the organisers at concentrations below 10 ppb due to impurities of the commercial formulations.

Ethoxyquin has been reported by 3 laboratories but after the analysis by the organiser, it was not detected in the sample, all the other reported pesticides were detected only by one or two laboratories only.

Ethoxyquin

Other reported pesticides



MS Spectra - Sample 107 SM05Rt : 8.64 min

MS Spectra - 10ppb Ethoxyquin PotatoRt : 8.10 min

No formula match

Sample 107 SM05

10ppb Ethoxyquin PotatoEthoxyquin

[M+H]+: 218.1539C14H19NO

Ethoxyquin (Q-TOF)



Ethoxyquin (LC-QQQ)Standard 10ppb Potato

SRM2: 218 / 160

SRM1: 218 / 174

SRM2: 218 / 160

SRM1: 218 / 174


Sample 1 SM05

Sample 1 SM05





50

53

56 55

42

52

54

48

32

48

41

51

54

40

57

10

41

49 49

24

51

45

0 0

11

19

8

13

22

2 3

8

3

0

11

16

0 1

13

1

8

10

0

8

11 11 12

2

7 7

0

10

4

10

7

10 9

5

11

1

5

9 8

3

11

7

0

10

20

30

40

50

60

70

Aldicarb sulfone

Aldicarb sulfoxide

Atrazine

Beta-Cyfluthrin

Bromoxynil

Clom

azone

Dieldrin

Diuron

Fluazinam

Flufenacet

Metam

itron

Methom

yl*

Metribuzin

Molinate

Oxam

yl

Picloram

Picolinafen

Propamocarb

Prosulfocarb

Quinoclam

ine

Thiodicarb

Triflumizole

SM-05 Techniques (Full Scan) *not spiked

Total Number of Reported Detections (some laboratories apply more than one technique) Full Scan GC Full Scan LC



Full Scan Full Scan Full Scan



Thanks foryour Attention

Thanks foryour Attention



Method comparison



Median comparison

0,000

0,050

0,100

0,150

0,200

0,250

0,300

0,350

0,400

0,450

Med

ian (m

g/kg)

All

QuEChERS



Qn comparison

0

10

20

30

40

50

60

70

Qn (%

)

All

QuEChERS

Almería 23 -25 October 2013 - EURL | Pesticides · 4th Joint Workshop of the European Union...

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Transcript of Almería 23 -25 October 2013 - EURL | Pesticides · 4th Joint Workshop of the European Union...