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4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th 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)
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Preparation of the test item
Extend the tea on the crystallizer
Samples distributionSieving
Milling HomogenationReal sample
Sample packing
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Results
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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%
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Tea matrix compounds. QuEChERs_CaCl2 extraction method. Dilution:5 LC-TOF-MSAbsolute height ≥ 10000 counts
PT01_Green tea6659 compounds
Green tea3879
compounds
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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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
* * * *
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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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
** *
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Carbendazim57.1% Acceptable23.8% Questionable19.1% Unacceptable
Median: 0.250 mg/kg
O C mL
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Chlorpyrifos88.6% Acceptable4.6% Questionable6.8% Unacceptable
*False Negatives
*
Median: 0.364 mg/kg
Q O mL
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
*
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Cypermethrin62.2% Acceptable16.2% Questionable21.6% Unacceptable
*False Negatives
** * * * *
Median: 0.112 mg/kg
mL Q
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
* * * * * *
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Difenoconazole90.2% Acceptable4.9% Questionable4.9% Unacceptable
*False Negatives
*
Median: 0.367 mg/kg
Q mL mL
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ Other
Z-Scores
*
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Endosulfan beta70.7% Acceptable22.0% Questionable7.3% Unacceptable
Q Q
*False Negatives
*
* *
Median: 0.081 mg/kg
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
***
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Etofenprox81.6% Acceptable7.9% Questionable10.5% Unacceptable
*False Negatives
* *
Median: 0.170 mg/kg
C Q C
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
* *
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Fenpropathrin90.3% Acceptable2.4% Questionable7.3% Unacceptable
*False Negatives
*
Median: 0.188 mg/kg
Q Q Et
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
*
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Imidacloprid72.5% Acceptable15.0% Questionable12.5% Unacceptable
* * * *
* * *
*False Negatives
Median: 0.081 mg/kg
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
* * ** * * *
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lambda cyhalothrin86.4% Acceptable9.1% Questionable4.5% Unacceptable
Median: 0.141 mg/kg
O O mL C Q
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Methomyl65.8% Acceptable5.3% Questionable28.9% Unacceptable
*False Negatives
** * * *
* * * *
Median: 0.089 mg/kg
mL Q
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
* * * * ** * * *
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Parathion-ethyl81.0% Acceptable14.2% Questionable4.8% Unacceptable
*False Negatives
* *
Median: 0.372 mg/kg
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
* *
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
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5.0
Lab
022
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003
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010
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006
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035
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020
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033
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011
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052
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004
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039
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046
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001
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018
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041
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014
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050
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008
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023
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019
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015
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027
Lab
034
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012
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002
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026
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021
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030
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049
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009
Lab
032
Lab
043
Lab
025
Lab
029
Lab
047
Lab
005
Lab
024
Lab
013
Lab
042
Pyridaben84.4% Acceptable6.7% Questionable8.9% Unacceptable
*False Negatives
*
Median: 0.268 mg/kg
O M mL Q
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
*
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
-5.0
-4.0
-3.0
-2.0
-1.0
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004
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018
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007
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026
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035
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010
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041
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039
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046
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034
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015
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008
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024
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017
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052
Lab
001
Lab
019
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049
Lab
020
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002
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023
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050
Lab
032
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005
Lab
013
Lab
009
Lab
047
Lab
030
Lab
029
Lab
043
Lab
042
Tebuconazole88.4% Acceptable2.3% Questionable9.3% Unacceptable
C Q
*False Negatives
*
Median: 0.338 mg/kg
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
Z-Scores
*
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of PesticidesAlmería 23rd-25th October 2013
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Special case
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
-5,0
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6
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009
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050
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029
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019
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024
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047
Carbendazim57.1% Acceptable23.8% Questionable19.1% Unacceptable
Median: 0.250 mg/kg
O C mL
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ Other
No water addition
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
-5,0
-4,0
-3,0
-2,0
-1,0
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b00
7
Lab
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033
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016
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004
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025
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023
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005
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012
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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
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ OtherNo water addition
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
‐5,0
‐4,0
‐3,0
‐2,0
‐1,0
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1,0
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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
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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
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ Other
Q C
78.4% Acceptable8.1% Questionable13.5% Unacceptable
Median: 0.400 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
0
5
10
15
20
25
30
35
40
45
50
Carbendazim Thiophanate‐methyl Carb + TFM sum
Qn (%
)Qn (%)
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
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08
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46
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04
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02
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32
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49
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23
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21
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06
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15
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18
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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
or Q ≡ QuEChERSor C ≡ CaCl2or Et ≡ EtAcor mL ≡ MiniLukeor M ≡ MeOHor O ≡ Other
4th Joint Workshop of the European Union Reference Laboratories for Residues of PesticidesAlmería 23rd-25th October 2013
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Conclusions
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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.
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Data Analysis
1 2 3 4 5
EURL-FVScientific Group
ReportsSamples
andProtocol
INFORMATION
EUPT Web Page
General European Commission Proficiency Test Scheme
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 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*
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
EUPT-FV–SCREENING METHODS 5Participants with no results
COUNTRY No. of laboratory
Slovenia (results after the deadline) 3
58
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
10 No Participating
EU States
18 Participating
EU States
ChinaCroatiaSerbiaSwitzerlandTurkey
5 ParticipatingNon EU States
AustriaBelgiumCzech Republic DenmarkEstoniaFinlandFranceGermanyHungaryItalyLatviaNetherlandsRomaniaSloveniaSpainSwedenUnited Kingdom
BulgariaCyprusGreeceIrelandLithuaniaLuxembourgMaltaPolandPortugalSlovakia
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Propazine (LC-QQQ)
Ratio SRM2/SRM1: 30%
SRM1: 230 / 146
SRM2: 230 / 188
SRM1: 230 / 146
SRM2: 230 / 188
Ratio SRM2/SRM1: 29%
Standard 10ppb Potato
Standard 10ppb Potato
Sample 1 SM05
Sample 1 SM05
C ~ 1.5 ppb
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Simazine (Q-TOF)
Sample 107 SM05
20ppb Standard Potato Simazine
[M+H]+: 202.0853C7H12ClN5
MS Spectra - 20ppb Simazine Potato
MS Spectra - Sample 107 SM05
C ~ 2.4 ppb
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
Standard 10ppb Potato
Standard 10ppb Potato
Standard 10ppb Potato
Sample 1 SM05
Sample 1 SM05
Sample 1 SM05
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
MS Spectra - Sample 107 SM05
No formula match
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Thiabendazole (LC-QQQ)
Sample 1 SM05
Sample 1 SM05
Standard 10ppb Potato
Standard 10ppb PotatoRatio SRM2/SRM1: 93%
SRM2: 202 / 131
SRM1: 202 / 175
Ratio SRM2/SRM1: 95%
SRM2: 202 / 131
SRM1: 202 / 175
C ~ 0.9 ppb
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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)
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
*
*
*
*
*
*
*
*
* *
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
% 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%
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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)
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Ethoxyquin (LC-QQQ)Standard 10ppb Potato
SRM2: 218 / 160
SRM1: 218 / 174
SRM2: 218 / 160
SRM1: 218 / 174
Standard 10ppb Potato
Sample 1 SM05
Sample 1 SM05
Ratio SRM2/SRM1: 100%
Ratio SRM2/SRM1: 11%
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Full Scan Full Scan Full Scan
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Thanks foryour Attention
Thanks foryour Attention
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Thanks foryour Attention
Thanks foryour Attention
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Method comparison
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Qn comparison
0
10
20
30
40
50
60
70
Qn (%
)
All
QuEChERS