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
DG SANCOMrs. Almut Bitterhof
ORGANISING GROUPDr. Amadeo R. Fernández-AlbaDr. Milagros MezcuaMr. Octavio MalatoMrs. Carmen Ferrer
QUALITY CONTROL GROUPDr. Antonio ValverdeMr. Stewart Reynolds
STATISTICAL GROUPDr. Carmelo Rodríguez
ADVISORY GROUPDr. Michelangelo AnastassiadesMr. Richard FussellDr. Miguel GamónDr. Magnus JezussekDr. André de KokMr. Ralf Lippold Dr. Sonja MasselterDr. Tuija Pihlström Dr. Mette Erecius PoulsenDr. Darinka Stajnbaher
EUPT-Panel
Mrs. Veerle Vanheusden
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Participation
No.
Of L
abs
Participation
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Country No. of Labs Country No. of Labs Country No. of Labs
Austria 3 (-1) Greece 10 Portugal 3
Belgium 8 (+4) Hungary 4 Romania 3
Brazil 1 (-1) Iceland 1 Saudi Arabia 1 New
Bulgaria 2 (+1) India 1 Serbia 1
China 2 New Ireland 1 Slovakia 2
Cyprus 1 Israel 1 Slovenia 3
Croatia 3 Italy 24 Spain 28 (+3)
Czech Republic 3 (+1) Latvia 1 Sweden 2
Denmark 2 Lithuania 1 Switzerland 3 (-1)
Estonia 2 Luxembourg 2 (+1) The Netherlands 2
Finland 2 Malta 2 (-1) Turkey 1
France 10 (+1) Morocco 1 New United Kingdom 4
Norway 1 Uruguay 1
Germany 25 (+2) Poland 11 (+2)Total No. of Labs = 175Total No. of non EU/EFTA Labs = 13Total No. of Countries = 40
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Total No. of Labs = 175
EU/EFTA Labs = 162
Other countries Labs = 13
Participation
(27 EU + 3 EFTA + 1 acceding country* + 2 Candidate countries + 7 other countries)
*Although it is now an EU member state, Croatia was acceding country when the exercise took place
Total No. of Countries = 40
EU/EFTA countries = 30
Other countries = 10
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
3-hydroxy-carbofuranAcephateAcetamipridAcrinathrinAldicarbAldicarb SulfoneAldicarb SulfoxideAmitrazAzinphos-methylAzoxystrobinBenfuracarbBifenthrinBitertanolBoscalidBromopropylateBromuconazoleBupirimateBuprofezinCadusafos*CaptanCarbarylCarbendazim CarbofuranCarbosulfanChlorfenapyrChlorfenvinphosChlorobenzilate*ChlorothalonilChlorpropham ChlorpyrifosChlorpyrifos-methyl
ClofentezineClothianidinCyfluthrinCypermethrin Cyproconazole CyprodinilDeltamethrinDemeton-S-methylsulfoneDesmethyl-pirimicarbDiazinonDichlofluanidDichlorvosDicloranDicofolDifenoconazoleDiflubenzuronDimethoateDimethomorphDMSTDiphenylamineDMF DMPFEndosulfan alphaEndosulfan betaEndosulfan sulfateEPNEpoxiconazoleEthionEthoprophosEtofenproxFenamiphosFenamiphos sulfoneFenamiphos sulfoxide
FenarimolFenazaquinFenbuconazoleFenhexamidFenitrothionFenoxycarbFenpropathrinFenpropimorphFenthionFenthion oxonFenthion oxon sulfoneFenthion oxon sulfoxideFenthion sulfoneFenthion sulfoxideFipronilFludioxonilFlufenoxuronFluopicolide* FluquinconazoleFlusilazoleFlutolanil* FlutriafolFolpetFosthiazateHexaconazoleHexythiazoxImazalilImidaclopridIndoxacarb IprodioneIprovalicarbIsofenphos-methylKresoxim-methyl
Lambda-CyhalothrinLinuronLufenuronMalaoxonMalathionMepanipyrimMetaflumizone*Metalaxyl and metalaxyl-MMetconazoleMethamidophosMethidathionMethiocarbMethiocarb sulfoneMethiocarb sulfoxideMethomylMethoxyfenozideMonocrotophosMyclobutanilOmethoateOrthophenylphenolOxadixylOxamylOxydemeton-methylPaclobutrazoleParaoxon-methylParathion-ethylParathion-methyl PenconazolePencycuronPendimethalinPhenthoatePhosalonePhosmet
Phosmet oxonPhoximPirimicarbPirimiphos-methylProchlorazProcymidoneProfenofosPropargitePropiconazolePropyzamideProthioconazoleProthiofosPyraclostrobinPyridabenPyrimethanilPyriproxyfenQuinoxyfenSpinosad
SpirodiclofenSpiroxamineTau-FluvalinateTebuconazoleTebufenozideTebufenpyradTeflubenzuronTefluthrinTetraconazoleTetradifonThiabendazoleThiaclopridThiamethoxamThiodicarb
Tolclofos-methylTolylfluanidTriadimefonTriadimenolTriazophosTrichlorfon TrifloxystrobinTriflumuronTrifluralinTriticonazoleVinclozolin Zoxamide
Thiophanate-me
175 pesticides
*Not in the coordinated multiannual control programme
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Pesticides used for thetreatment
Acephate Linuron
Azoxystrobin Methiocarb
Chlorpropham Pencycuron
Chlorothalonil Prochloraz
Cypermethrin Procymidone
Diazinon Spirodiclofen
Fluopicolide* Thiabendazole
Flutolanil* Thiacloprid
FosthiazateTotal: 18
Iprovalicarb
* Not in the coordinated
multiannual control programme
New in the target list
* COMMISSION IMPLEMENTING REGULATION (EU) No 788/2012 of 31 August 2012
concerning a coordinated multiannual controlprogramme of the Union for 2013, 2014 and 2015 toensure compliance with maximum residue levels ofpesticides and to assess the consumer exposureto pesticide residues in and on food of plant andanimal origin .
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
ACTIVITY DATE
- Publishing the Target Pesticide List, Calendar on the Web page 22nd October 2012
- Receiving Application Form from invited laboratories. 3rd Dec 2012 - 7th Jan 2013
- Specific Protocol published on the Web site 7th Jan 2013 at the latest
- Filling in the Laboratory Scope from the Participants: Form 0 8th-18th January 2013
- Sample distribution. 21st January 2013
- Deadline for receiving sample acceptance: Form 1 25th January 2013
- Deadline for receiving results: Form 2, Form 3 and Form 4 13th February 2013
- Filling in Form 5 20th-27th February 2013
- Preliminary Report: provisional results, medians and z-scores. April 2013
- Final Report to the Laboratories December 2013
CALENDARCALENDAR
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
WEB PAGE: Forms
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
Potato
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Organic Potatoes were grown in Almería, Spain
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Post harvest treatment with commercial formulation and with standard solution
EURL-FVEUPT-FV15 Results
4th Joint Workshop of the European Union Reference Laboratories Commercial products used to treat the sample
Pesticide Concentration(mg/kg)
MRRL Type Commercial Product
Acephate <0.1 0.01 Standard Dr.Ehrenstorfer
Azoxystrobin 0.1-0.2 0.01 Commercial Ortiva 25% P/V
Chlorpropham >1 0.01 Standard Sigma-Aldrich
Chlorothalonil 0.1-0.5 0.01 Commercial Bravo 50
Cypermethrin <0.1 0.01 Commercial Citron 10%
Diazinon 0.1-1 0.01 Commercial Fegazinongole 60%
Fluopicolide <0.1 0.01 Standard Sigma-Aldrich
Flutolanil 0.1-0.5 0.01 Standard ChemService
Fosthiazate <0.1 0.01 Commercial Nemathorin 10 G
Iprovalicarb <0.1 0.01 Standard Sigma-Aldrich
Linuron <0.1 0.01 Standard Sigma-Aldrich
Methiocarb 0.1-0.2 0.01 Standard Dr.Ehrenstorfer
Pencycuron 0.1-1.0 0.01 Commercial Trotis 25 sc
Prochloraz <0.1 0.01 Standard Sigma-Aldrich
Procymidone <0.1 0.01 Commercial Driza 50%
Spirodiclofen 0.1-1.0 0.01 Standard Sigma-Aldrich
Thiabendazole >1 0.01 Commercial Textar 60T
Thiacloprid 0.1-0.5 0.01 Commercial Calypso 48% P/V
EURL-FVEUPT-FV15 Results
4th Joint Workshop of the European Union Reference Laboratories Commercial products used to treat the sample
Pesticide Concentration(mg/kg)
MRRL Type Commercial Product
Acephate <0.1 0.01 Standard Dr.Ehrenstorfer
Azoxystrobin 0.1-0.2 0.01 Commercial Ortiva 25% P/V
Chlorpropham >1 0.01 Standard Sigma-Aldrich
Chlorthalonil 0.1-0.5 0.01 Commercial Bravo 50
Cypermethrin <0.1 0.01 Commercial Citron 10%
Diazinon 0.1-1 0.01 Commercial Fegazinongole 60%
Fluopicolide <0.1 0.01 Standard Sigma-Aldrich
Flutolanil 0.1-0.5 0.01 Standard ChemService
Fosthiazate <0.1 0.01 Commercial Nemathorin 10 G
Iprovalicarb <0.1 0.01 Standard Sigma-Aldrich
Linuron <0.1 0.01 Standard Sigma-Aldrich
Methiocarb 0.1-0.2 0.01 Standard Dr.Ehrenstorfer
Pencycuron 0.1-1.0 0.01 Commercial Trotis 25 sc
Prochloraz <0.1 0.01 Standard Sigma-Aldrich
Procymidone <0.1 0.01 Commercial Driza 50%
Spirodiclofen 0.1-1.0 0.01 Standard Sigma-Aldrich
Thiabendazole >1 0.01 Commercial Textar 60T
Thiacloprid 0.1-0.5 0.01 Commercial Calypso 48% P/V
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 homogeneity in the treated sample was studied using the 2006 Harmonised Protocol.
-The sampling standard deviation of all the pesticides must be lower than the critical value.
Ssample2 < c
Homogeneity
20 extracts
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Homogeneity
All the pesticides passed the homogeneity test
Pesticide Mean Conc.(mg/Kg) Ss2 c Ss2 < c
Pass/FailAcephate 0.066 3.06 x 10-6 4.72 x 10-5 PassAzoxystrobin 0.181 9.94 x 10-6 3.60 x 10-4 PassChlorothalonil 0.211 -2.41 x 10-5 5.60 x 10-4 PassChlorpropham 1.453 1.40 x 10-4 2.85 x 10-2 PassCypermethrin 0.114 -3.46 x 10-6 1.68 x 10-4 PassDiazinon 0.181 -2.31 x 10-6 4.44 x 10-4 PassFluopicolide 0.123 5.06 x 10-6 1.70 x 10-4 PassFlutolanil 0.336 -4.22 x 10-5 1.47 x 10-3 PassFosthiazate 0.076 9.30 x 10-6 6.46 x 10-5 PassIprovalicarb 0.084 5.95 x 10-6 7.77 x 10-5 PassLinuron 0.107 1.74 x 10-5 1.43 x 10-4 PassMethiocarb 0.139 2.54 x 10-5 2.60 x 10-4 PassPencycuron 0.332 9.54 x 10-6 1.21 x 10-3 PassProchloraz 0.048 4.22 x 10-7 2.61 x 10-5 PassProcymidone 0.120 5.34 x 10-6 1.93 x 10-4 PassSpirodiclofen 0.411 1.45 x 10-4 2.22 x 10-3 PassThiabendazole 1.456 1.24 x 10-3 2.30 x 10-2 PassThiacloprid 0.364 4.98 x 10-5 1.57 x 10-3 Pass
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
HomogeneityPesticide Mean Conc. Homogeneity
(mg/Kg)Assigned value
(mg/Kg) Difference (%)
Acephate 0.066 0.083 20.5Azoxystrobin 0.181 0.203 10.8Chlorothalonil 0.211 0.160 -31.9Chlorpropham 1.453 1.700 14.5Cypermethrin 0.114 0.100 -14.0Diazinon 0.181 0.195 7.2Fluopicolide 0.123 0.099 -24.2Flutolanil 0.336 0.410 18.0Fosthiazate 0.076 0.080 5.0Iprovalicarb 0.084 0.090 6.7Linuron 0.107 0.098 -9.2Methiocarb 0.139 0.136 -2.2Pencycuron 0.332 0.269 -23,4Prochloraz 0.048 0.058 17,2Procymidone 0.120 0.110 -9,1Spirodiclofen 0.411 0.444 7,4Thiabendazole 1.456 1.710 14,9Thiacloprid 0.364 0.338 -7,7
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Stability
1st Analysis - prior to the sample shipment
2nd Analysis - after the deadline for reporting results
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Stability
PesticideConcentration (mg/kg)
Day 1(1st analysis)
Day 1(2nd analysis)
Mean 1
Day 2(1st analysis)
Day 2(2nd analysis)
Mean2
(M2-M1)M1 %
Acephate 0.051 0.069 0.060 0.061 0.067 0.064 0.067 7Azoxystrobin 0.159 0.158 0.159 0.171 0.176 0.174 0.095 9Chlorothalonil 0.214 0.218 0.216 0.221 0.235 0.228 0.056 6Chlorpropham 1.344 1.495 1.420 1.468 1.398 1.433 0.010 1Cypermethrin 0.113 0.116 0.115 0.115 0.111 0.113 -0.013 -1Diazinon 0.166 0.183 0.175 0.180 0.178 0.179 0.026 3Fluopicolide 0.127 0.127 0.127 0.126 0.129 0.128 0.004 0Flutolanil 0.321 0.331 0.326 0.325 0.323 0.324 -0.006 -1Fosthiazate 0.061 0.059 0.060 0.061 0.065 0.063 0.050 5Iprovalicarb 0.081 0.079 0.080 0.092 0.091 0.092 0.144 14Linuron 0.093 0.087 0.090 0.088 0.086 0.087 -0.033 -3Methiocarb 0.137 0.148 0.143 0.136 0.135 0.136 -0.049 -5Pencycuron 0.327 0.321 0.324 0.370 0.369 0.370 0.140 14Prochloraz 0.049 0.049 0.049 0.050 0.051 0.051 0.031 3Procymidone 0.120 0.124 0.122 0.127 0.126 0.127 0.037 4Spirodiclofen 0.443 0.451 0.447 0.438 0.441 0.440 -0.017 -2Thiabendazole 1.245 1.259 1.252 1.375 1.385 1.380 0.102 10Thiacloprid 0.295 0.292 0.294 0.306 0.310 0.308 0.049 5
All the pesticides passed the stability test
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Stability
Additionally: 3rd Analysis - reproducing the delivery conditions that the samples experienced during 48 hours
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Stability
PesticideConcentration (mg/kg)
Day 1(1st analysis)
Day 1(2nd analysis)
Mean 1
48h(1st analysis)
48h(2nd analysis)
Mean2
(M2-M1)M1 %
Acephate 0.051 0.069 0.060 0.062 0.057 0.060 -0.008 -1Azoxystrobin 0.159 0.158 0.159 0.169 0.164 0.167 0.050 5Chlorothalonil 0.214 0.218 0.216 0.201 0.219 0.210 -0.028 -3Chlorpropham 1.344 1.495 1.420 1.507 1.403 1.455 0.025 3Cypermethrin 0.113 0.116 0.115 0.107 0.104 0.106 -0.079 -8Diazinon 0.166 0.183 0.175 0.180 0.171 0.176 0.006 1Fluopicolide 0.127 0.127 0.127 0.130 0.127 0.129 0.012 1Flutolanil 0.321 0.331 0.326 0.323 0.309 0.316 -0.031 -3Fosthiazate 0.061 0.059 0.060 0.065 0.063 0.064 0.067 7Iprovalicarb 0.081 0.079 0.080 0.086 0.082 0.084 0.050 5Linuron 0.093 0.087 0.090 0.084 0.085 0.085 -0.061 -6Methiocarb 0.137 0.148 0.143 0.144 0.135 0.140 -0.021 -2Pencycuron 0.327 0.321 0.324 0.347 0.328 0.338 0.042 4Prochloraz 0.049 0.049 0.049 0.053 0.050 0.052 0.051 5Procymidone 0.120 0.124 0.122 0.123 0.117 0.120 -0.016 -2Spirodiclofen 0.443 0.451 0.447 0.431 0.410 0.421 -0.059 -6Thiabendazole 1.245 1.259 1.252 1.355 1.328 1.342 0.071 7Thiacloprid 0.295 0.292 0.294 0.323 0.311 0.317 0.080 8
All the pesticides passed the stability test
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Spirodiclofen[M+H]+: 411.1124C21H24Cl2O4
100ppb_Mix FV15_Potato
400ppb_Spirodiclofen_Potato
400ppb_Spirodiclofen_Solvent
Sample_189_FV15
100ppb_Mix FV15_Potato
Sample_189_FV15
Spirodiclofen “correct” storage conditions
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
SpirodiclofenC21H24Cl2O4
[M+H]+: 411.1124
Spirodiclofen-enolC15H14Cl2O3
[M+H]+: 313.0393 Sample_189
3-OH-Spirodiclofen-enolC15H14Cl2O4
[M+H]+: 329.0342
SpirodiclofenC21H24Cl2O4
[M+H]+: 411.1124
Spirodiclofen –sample after 4 days at room temperature
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Spirodiclofen Spirodiclofen-enol
3-hydroxy-spirodiclofen-enol
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
ProchlorazC15H17N3O2Cl3
[M+H]+: 376.0381
Sample 189 Day 1
Sample 189 Day 4 room temp.
Sample 189 Day 1
Sample 189 Day 4 room temp.
PROCHLORAZ- Potato sample at room temperature during 4 days
Prochloraz metaboliteC11H14NOCl3
[M+H]+: 282.0213
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
Azoxystrobin
mg/kg
Freq
uenc
y
0 0.1 0.2 0.3 0.40
20
40
60
80
Chlorothalonil
mg/kg
Freq
uenc
y
0 0.1 0.2 0.3 0.40
10
20
30
40
50
60
Acephate
mg/Kg
Freq
uenc
y
0 0,03 0,06 0,09 0,12 0,150
10
20
30
40
50
60
Chlorpropham
mg/Kg
Freq
uenc
y
0 1 2 3 40
20
40
60
80
Median: 0.083 mg/kg Median: 0.203 mg/kg
Median: 0.160 mg/kg Median: 1.700 mg/kg
Distribution of data-Histograms
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Diazinon
mg/kg
Freq
uenc
y
0 0.1 0.2 0.3 0.40
20
40
60
80
Flutolanil
mg/kg
Freq
uenc
y
0 0.2 0.4 0.6 0.80
10
20
30
40
50
60
Cypermethrin
mg/kg
Freq
uenc
y
-0,02 0,08 0,18 0,28 0,380
20
40
60
80
Fluopicolide
mg/Kg
Freq
uenc
y
0 0,03 0,06 0,09 0,12 0,15 0,180
10
20
30
40
50
Median: 0.100 mg/kg Median: 0.195 mg/kg
Median: 0.099 mg/kg Median: 0.410 mg/kg
Distribution of data-Histograms
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Iprovalicarb
mg/kg
Freq
uenc
y
0 0.03 0.06 0.09 0.12 0.150
10
20
30
40
50
60
Methiocarb
mg/kg
Freq
uenc
y
0 0.04 0.08 0.12 0.16 0.2 0.240
10
20
30
40
50
60
Pencycuron
mg/kg
Freq
uenc
y
0 0.1 0.2 0.3 0.4 0.5 0.60
10
20
30
40
50
Linuron
mg/Kg
Freq
uenc
y
0 0,03 0,06 0,09 0,12 0,15 0,180
10
20
30
40
50
60
Median: 0.090 mg/kg Median: 0.098 mg/kg
Median: 0.136 mg/kg Median: 0.269 mg/kg
Distribution of data-Histograms
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Spirodiclofen
mg/kg
Freq
uenc
y
0 0.2 0.4 0.6 0.8 10
10
20
30
40
50
60
Prochloraz
mg/Kg
Freq
uenc
y
0 0,02 0,04 0,06 0,08 0,10
10
20
30
40
Procymidone
mg/Kg
Freq
uenc
y
0 0,04 0,08 0,12 0,16 0,2 0,240
20
40
60
80
Thiabendazole
mg/Kg
Freq
uenc
y
0 1 2 3 40
10
20
30
40
50
60
Median: 0.058 mg/kg Median: 0.110 mg/kg
Median: 0.444 mg/kg Median: 1.710 mg/kg
Distribution of data-Histograms
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Thiacloprid
mg/Kg
Freq
uenc
y
0 0,2 0,4 0,6 0,80
10
20
30
40
50
60
Fosthiazate
mg/kg
Freq
uenc
y
0 0.03 0.06 0.09 0.12 0.150
10
20
30
40
50
Median: 0.080 mg/kg
Median: 0.338 mg/kg
Distribution of data-Histograms
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Pesticides Median (mg/kg)
Prochloraz 0.058
Fosthiazate 0.080
Acephate 0.083
Iprovalicarb 0.090
Linuron 0.098
Fluopicolide 0.099
Cypermethrin 0.100
Procymidone 0.110
Methiocarb 0.136
Chlorothalonil 0.160
Diazinon 0.195
Azoxystrobin 0.203
Pencycuron 0.269
Thiacloprid 0.338
Flutolanil 0.410
Spirodiclofen 0.444
Chlorpropham 1.700
Thiabendazole 1.710
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Pesticides Median (mg/kg)
Prochloraz 0.058
Fosthiazate 0.080
Acephate 0.083
Iprovalicarb 0.090
Linuron 0.098
Fluopicolide 0.099
Cypermethrin 0.100
Procymidone 0.110
Methiocarb 0.136
Chlorothalonil 0.160
Diazinon 0.195
Azoxystrobin 0.203
Pencycuron 0.269
Thiacloprid 0.338
Flutolanil 0.410
Spirodiclofen 0.444
Chlorpropham 1.700
Thiabendazole 1.710
0.058-0.100 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Pesticides Median (mg/kg)
Prochloraz 0.058
Fosthiazate 0.080
Acephate 0.083
Iprovalicarb 0.090
Linuron 0.098
Fluopicolide 0.099
Cypermethrin 0.100
Procymidone 0.110
Methiocarb 0.136
Chlorothalonil 0.160
Diazinon 0.195
Azoxystrobin 0.203
Pencycuron 0.269
Thiacloprid 0.338
Flutolanil 0.410
Spirodiclofen 0.444
Chlorpropham 1.700
Thiabendazole 1.710
0.100-0.500 mg/kg
0.058-0.100 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Pesticides Median (mg/kg)
Prochloraz 0.058
Fosthiazate 0.080
Acephate 0.083
Iprovalicarb 0.090
Linuron 0.098
Fluopicolide 0.099
Cypermethrin 0.100
Procymidone 0.110
Methiocarb 0.136
Chlorothalonil 0.160
Diazinon 0.195
Azoxystrobin 0.203
Pencycuron 0.269
Thiacloprid 0.338
Flutolanil 0.410
Spirodiclofen 0.444
Chlorpropham 1.700
Thiabendazole 1.710
0.058-0.100 mg/kg
0.100-0.500 mg/kg
0.500-2.000 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Pesticides MRRL (mg/kg) Median (mg/kg) FFP RSD (%) Qn RSD (%)Acephate 0.01 0.083 25 21.3
Azoxystrobin 0.01 0.203 25 15.3
Chlorothalonil 0.01 0.160 25 26.4
Chlorpropham 0.01 1.700 25 19.9
Cypermethrin 0.01 0.100 25 26.6
Diazinon 0.01 0.195 25 20.4
Fluopicolide 0.01 0.099 25 15.7
Flutolanil 0.01 0.410 25 14.1
Fosthiazate 0.01 0.080 25 19.4
Iprovalicarb 0.01 0.090 25 17.3
Linuron 0.01 0.098 25 20.4
Methiocarb 0.01 0.136 25 21.2
Pencycuron 0.01 0.269 25 16.5
Prochloraz 0.01 0.058 25 26.8
Procymidone 0.01 0.110 25 19.9
Spirodiclofen 0.01 0.444 25 20.0
Thiabendazole 0.01 1.710 25 22.1
Thiacloprid 0.01 0.338 25 18.4
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013%
Robust standard deviations
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Pesticides
No. of Reported
Results
No. of False Negative
Results
No. of Not Analysed
Results
Percentage of Reported Results
(out of 160)
Acephate 124 8 28 78Azoxystrobin 151 1 8 94Chlorothalonil 134 5 21 84Chlorpropham 134 3 23 84Cypermethrin 146 6 8 91
Diazinon 159 0 1 99Fluopicolide 95 0 65 59
Flutolanil 99 1 60 62Fosthiazate 101 1 58 63Iprovalicarb 124 0 36 78
Linuron 126 1 33 79Methiocarb 128 4 28 80Pencycuron 113 0 47 71Prochloraz 134 3 23 84
Procymidone 153 1 6 96Spirodiclofen 105 2 53 66
Thiabendazole 134 1 25 84Thiachloprid 121 2 37 76
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
z-Scores
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Acceptable Questionable Unacceptable
z-Scores classification
%
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Pesticides Median(mg/kg)
Acceptable (%)
Questionable(%)
Unacceptable (%)
Acephate 0.083 90.1 3.8 6.1
Azoxystrobin 0.203 98.0 0.7 1.3
Chlorothalonil 0.160 83.5 7.2 9.3
Chlorpropham 1.700 93.4 3.0 3.6
Cypermethrin 0.100 89.4 6.0 4.6
Diazinon 0.195 95.0 3.1 1.9
Fluopicolide 0.099 95.7 4.3 0.0
Flutolanil 0.410 96.0 2.0 2.0
Fosthiazate 0.080 96.0 2.0 2.0
Iprovalicarb 0.090 97.6 1.6 0.8
Linuron 0.098 95.2 4.0 0.8
Methiocarb 0.136 93.1 2.3 4.6
Pencycuron 0.269 97.3 1.8 0.9
Prochloraz 0.058 89.7 8.1 2.2
Procymidone 0.110 94.8 3.3 1.9
Spirodiclofen 0.444 90.6 4.7 4.7
Thiabendazole 1.710 95.6 3.0 1.4
Thiacloprid 0.338 95.0 2.5 2.5
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Pesticides Median(mg/kg)
Acceptable (%)
Questionable(%)
Unacceptable (%)
Acephate 0.083 90.1 3.8 6.1
Azoxystrobin 0.203 98.0 0.7 1.3
Chlorothalonil 0.160 83.5 7.2 9.3
Chlorpropham 1.700 93.4 3.0 3.6
Cypermethrin 0.100 89.4 6.0 4.6
Diazinon 0.195 95.0 3.1 1.9
Fluopicolide 0.099 95.7 4.3 0.0
Flutolanil 0.410 96.0 2.0 2.0
Fosthiazate 0.080 96.0 2.0 2.0
Iprovalicarb 0.090 97.6 1.6 0.8
Linuron 0.098 95.2 4.0 0.8
Methiocarb 0.136 93.1 2.3 4.6
Pencycuron 0.269 97.3 1.8 0.9
Prochloraz 0.058 89.7 8.1 2.2
Procymidone 0.110 94.8 3.3 1.9
Spirodiclofen 0.444 90.6 4.7 4.7
Thiabendazole 1.710 95.6 3.0 1.4
Thiacloprid 0.338 95.0 2.5 2.5
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab003Lab064Lab077Lab084Lab087Lab089Lab145Lab147Lab150Lab001Lab160Lab021Lab102Lab074Lab035Lab020Lab129Lab106Lab025Lab034Lab172Lab055Lab090Lab012Lab028Lab058Lab065Lab017Lab134Lab143Lab171Lab050Lab166Lab011Lab013Lab027Lab032Lab125Lab173Lab072Lab162Lab109Lab137Lab053Lab061Lab069Lab015Lab114Lab007Lab066Lab101Lab140Lab024Lab051Lab117Lab105Lab110Lab108Lab159Lab008Lab076Lab097Lab123Lab067Lab057Lab059Lab082Lab062Lab073Lab100Lab165Lab029Lab038Lab103Lab130Lab026Lab136Lab014Lab047Lab093Lab132Lab135Lab004Lab043Lab054Lab078Lab044Lab052Lab039Lab068Lab111Lab118Lab156Lab033Lab158Lab121Lab083Lab107Lab161Lab030Lab046Lab075Lab112Lab163Lab018Lab144Lab104Lab120Lab092Lab094Lab119Lab126Lab138Lab002Lab131Lab005Lab080Lab099Lab116Lab154Lab085Lab022Lab037Lab045Lab095Lab128Lab079Lab006Lab049Lab086Lab010Lab019
90%4%6%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both
L L L L L L L L L L L L
* False Negatives
** ******
AcephateMedian: 0.083 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013y
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Lab027Lab084Lab016Lab078Lab117Lab153Lab172Lab116Lab032Lab090Lab094Lab106Lab098Lab033Lab133Lab079Lab002Lab112Lab100Lab072Lab015Lab070Lab123Lab008Lab025Lab089Lab166Lab004Lab073Lab154Lab096Lab001Lab006Lab013Lab018Lab060Lab113Lab131Lab141Lab050Lab051Lab114Lab137Lab049Lab017Lab074Lab012Lab035Lab045Lab111Lab125Lab126Lab138Lab157Lab007Lab052Lab088Lab143Lab020Lab134Lab146Lab058Lab168Lab011Lab029Lab036Lab039Lab044Lab061Lab068Lab069Lab086Lab139Lab034Lab165Lab028Lab038Lab063Lab054Lab151Lab159Lab005Lab080Lab024Lab136Lab108Lab118Lab150Lab156Lab135Lab105Lab149Lab059Lab075Lab097Lab022Lab093Lab144Lab009Lab065Lab043Lab030Lab095Lab099Lab109Lab110Lab129Lab130Lab145Lab158Lab160Lab048Lab057Lab142Lab161Lab019Lab171Lab066Lab140Lab021Lab102Lab103Lab120Lab119Lab121Lab173Lab003Lab082Lab104Lab128Lab053Lab127Lab042Lab067Lab083Lab163Lab064Lab076Lab092Lab132Lab047Lab014Lab026Lab107Lab101Lab062Lab055Lab046Lab077Lab037Lab085Lab010
L LG L LGGLGGL LGG L L L L B
98%1%1%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
*
AzoxystrobinMedian: 0.203 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab006Lab027Lab083Lab134Lab153Lab084Lab149Lab159Lab136Lab053Lab013Lab051Lab106Lab068Lab125Lab137Lab165Lab015Lab090Lab025Lab114Lab118Lab085Lab172Lab116Lab032Lab062Lab002Lab008Lab007Lab112Lab147Lab050Lab054Lab097Lab016Lab044Lab121Lab123Lab005Lab117Lab078Lab012Lab009Lab099Lab115Lab077Lab094Lab133Lab160Lab034Lab120Lab039Lab132Lab011Lab035Lab060Lab064Lab069Lab119Lab138Lab150Lab152Lab063Lab065Lab018Lab070Lab079Lab093Lab107Lab145Lab022Lab082Lab163Lab059Lab042Lab058Lab037Lab086Lab110Lab111Lab113Lab151Lab154Lab156Lab017Lab055Lab046Lab066Lab080Lab131Lab101Lab104Lab146Lab096Lab166Lab021Lab061Lab095Lab143Lab003Lab048Lab020Lab030Lab105Lab067Lab103Lab074Lab087Lab092Lab139Lab024Lab038Lab049Lab109Lab144Lab028Lab142Lab173Lab033Lab161Lab140Lab073Lab098Lab029Lab171Lab052Lab019Lab031Lab135Lab088Lab026Lab158Lab102Lab108Lab004Lab043Lab075Lab129
GGGGGLGGGGGG
84%7%9%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
*****
Median: 0.160 mg/kgChlorothalonil
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab083Lab085Lab160Lab010Lab153Lab003Lab057Lab114Lab142Lab105Lab123Lab145Lab088Lab002Lab100Lab131Lab044Lab038Lab063Lab055Lab165Lab166Lab106Lab039Lab108Lab025Lab015Lab090Lab053Lab143Lab013Lab073Lab032Lab168Lab074Lab118Lab001Lab018Lab109Lab141Lab134Lab137Lab034Lab020Lab078Lab112Lab092Lab082Lab022Lab050Lab146Lab028Lab036Lab051Lab061Lab150Lab171Lab017Lab136Lab046Lab030Lab135Lab149Lab094Lab029Lab102Lab110Lab111Lab121Lab129Lab139Lab120Lab138Lab147Lab127Lab163Lab097Lab173Lab054Lab103Lab066Lab019Lab049Lab172Lab042Lab077Lab119Lab007Lab005Lab062Lab161Lab011Lab004Lab048Lab125Lab024Lab093Lab132Lab154Lab067Lab047Lab130Lab043Lab027Lab033Lab068Lab156Lab065Lab035Lab021Lab058Lab059Lab076Lab080Lab158Lab079Lab099Lab026Lab140Lab006Lab075Lab116Lab101Lab014Lab070Lab037Lab107Lab052Lab151Lab016Lab064Lab012Lab089Lab072Lab104Lab008Lab095
L GGGGGGGL GGG
93%3%4%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
** *
ChlorprophamMedian: 1.700 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab002Lab006Lab064Lab072Lab077Lab083Lab153Lab010Lab170Lab032Lab136Lab057Lab094Lab071Lab084Lab137Lab053Lab033Lab011Lab163Lab009Lab165Lab013Lab145Lab133Lab157Lab092Lab100Lab117Lab134Lab001Lab046Lab050Lab090Lab160Lab107Lab151Lab172Lab087Lab106Lab156Lab085Lab146Lab012Lab114Lab007Lab075Lab123Lab038Lab079Lab095Lab022Lab147Lab149Lab051Lab015Lab060Lab068Lab103Lab115Lab154Lab158Lab065Lab116Lab161Lab034Lab030Lab166Lab036Lab047Lab069Lab073Lab078Lab019Lab096Lab108Lab018Lab028Lab044Lab074Lab113Lab125Lab152Lab008Lab099Lab120Lab159Lab048Lab062Lab171Lab063Lab142Lab005Lab024Lab143Lab127Lab173Lab025Lab118Lab110Lab111Lab121Lab128Lab168Lab021Lab035Lab058Lab097Lab105Lab017Lab088Lab104Lab039Lab067Lab102Lab029Lab061Lab112Lab119Lab126Lab129Lab139Lab141Lab132Lab020Lab043Lab093Lab135Lab042Lab098Lab052Lab054Lab076Lab086Lab130Lab150Lab080Lab066Lab055Lab109Lab140Lab004Lab049Lab101Lab144Lab037Lab070Lab059Lab089Lab138Lab026Lab027
GGGGL LGGGGG
89%6%5%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
******
CypermethrinMedian: 0.100 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab114Lab170Lab153Lab077Lab003Lab053Lab057Lab013Lab087Lab136Lab157Lab133Lab090Lab100Lab032Lab061Lab084Lab159Lab025Lab165Lab050Lab112Lab123Lab046Lab151Lab137Lab072Lab049Lab039Lab009Lab134Lab001Lab015Lab044Lab070Lab073Lab126Lab145Lab152Lab008Lab034Lab012Lab131Lab172Lab028Lab085Lab146Lab017Lab166Lab011Lab018Lab027Lab094Lab150Lab160Lab019Lab048Lab036Lab005Lab079Lab118Lab002Lab149Lab033Lab060Lab064Lab069Lab138Lab141Lab171Lab047Lab062Lab092Lab007Lab051Lab030Lab054Lab117Lab143Lab067Lab042Lab082Lab055Lab074Lab111Lab113Lab121Lab139Lab144Lab156Lab158Lab058Lab106Lab063Lab168Lab097Lab089Lab115Lab135Lab029Lab068Lab110Lab125Lab129Lab142Lab078Lab088Lab093Lab147Lab173Lab022Lab116Lab128Lab065Lab086Lab108Lab119Lab038Lab099Lab120Lab059Lab066Lab105Lab080Lab075Lab083Lab102Lab107Lab127Lab130Lab101Lab103Lab020Lab104Lab024Lab076Lab162Lab163Lab132Lab010Lab154Lab035Lab004Lab026Lab140Lab096Lab043Lab014Lab161Lab016Lab031Lab037Lab052Lab021Lab045Lab006Lab095Lab109Lab098
GGGLGGGGLG
95%3%2%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
DiazinonMedian: 0.195 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab084Lab078Lab090Lab137Lab013Lab039Lab051Lab050Lab166Lab161Lab015Lab173Lab002Lab123Lab112Lab129Lab008Lab018Lab100Lab105Lab025Lab061Lab022Lab029Lab106Lab011Lab017Lab099Lab118Lab150Lab024Lab068Lab046Lab093Lab103Lab042Lab066Lab120Lab007Lab012Lab044Lab074Lab108Lab136Lab143Lab163Lab038Lab067Lab028Lab035Lab064Lab086Lab111Lab119Lab121Lab020Lab075Lab097Lab034Lab052Lab102Lab030Lab079Lab165Lab049Lab059Lab149Lab171Lab043Lab045Lab156Lab065Lab083Lab131Lab132Lab054Lab073Lab005Lab048Lab055Lab047Lab104Lab004Lab092Lab107Lab062Lab057Lab037Lab145Lab109Lab138Lab080Lab010Lab026Lab110
G G L L G L G G G G L G L L G L L
96%4%0%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
FluopicolideMedian: 0.099 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab083Lab084Lab123Lab090Lab039Lab161Lab165Lab072Lab008Lab015Lab025Lab137Lab051Lab096Lab166Lab012Lab001Lab074Lab086Lab108Lab050Lab112Lab054Lab018Lab022Lab105Lab062Lab094Lab099Lab011Lab052Lab118Lab024Lab028Lab013Lab002Lab106Lab030Lab100Lab017Lab068Lab067Lab173Lab004Lab035Lab103Lab078Lab093Lab104Lab029Lab061Lab066Lab129Lab044Lab111Lab121Lab042Lab120Lab102Lab007Lab058Lab059Lab109Lab138Lab145Lab020Lab021Lab034Lab097Lab075Lab149Lab064Lab119Lab171Lab132Lab107Lab005Lab110Lab065Lab057Lab043Lab046Lab049Lab006Lab095Lab156Lab143Lab079Lab038Lab092Lab073Lab055Lab136Lab033Lab163Lab026Lab080Lab037Lab045Lab010
G L G G G L G L L L L L L G
96%2%2%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
*
FlutolanilMedian: 0.410 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab058Lab053Lab156Lab002Lab082Lab025Lab029Lab008Lab106Lab130Lab046Lab100Lab129Lab050Lab051Lab028Lab105Lab011Lab062Lab001Lab035Lab090Lab112Lab086Lab012Lab049Lab015Lab054Lab166Lab007Lab102Lab123Lab061Lab173Lab024Lab043Lab068Lab137Lab018Lab055Lab065Lab079Lab093Lab132Lab034Lab066Lab172Lab009Lab075Lab097Lab013Lab067Lab074Lab103Lab111Lab171Lab020Lab101Lab108Lab059Lab080Lab145Lab165Lab039Lab095Lab017Lab033Lab083Lab004Lab044Lab057Lab136Lab119Lab121Lab022Lab076Lab078Lab099Lab006Lab104Lab120Lab161Lab163Lab005Lab030Lab073Lab038Lab052Lab026Lab109Lab064Lab107Lab092Lab037Lab110Lab021Lab118Lab010Lab045Lab077Lab084Lab027
G G G G G L L L G L L L G L L L L G L
96%2%2%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
*
FosthiazateMedian: 0.080 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab084Lab008Lab095Lab072Lab162Lab025Lab135Lab112Lab078Lab010Lab051Lab123Lab028Lab001Lab090Lab166Lab114Lab015Lab029Lab054Lab129Lab161Lab017Lab035Lab131Lab039Lab073Lab024Lab074Lab105Lab106Lab145Lab171Lab173Lab011Lab018Lab137Lab004Lab013Lab007Lab050Lab143Lab034Lab043Lab044Lab049Lab102Lab108Lab165Lab093Lab111Lab150Lab002Lab066Lab069Lab100Lab062Lab151Lab006Lab020Lab032Lab068Lab075Lab097Lab146Lab061Lab065Lab099Lab120Lab160Lab058Lab157Lab138Lab012Lab045Lab059Lab103Lab067Lab127Lab019Lab080Lab132Lab046Lab064Lab101Lab110Lab119Lab126Lab130Lab156Lab158Lab052Lab092Lab048Lab082Lab083Lab104Lab163Lab030Lab159Lab063Lab038Lab079Lab055Lab057Lab033Lab076Lab107Lab121Lab022Lab047Lab136Lab005Lab021Lab118Lab109Lab140Lab053Lab096Lab026Lab037Lab085Lab086Lab027
L L L L L L L L L L L L G L L L G L
97.6%1.6%0.8%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
IprovalicarbMedian: 0.090 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab085Lab156Lab084Lab011Lab066Lab008Lab092Lab007Lab012Lab096Lab123Lab161Lab090Lab153Lab050Lab025Lab061Lab028Lab063Lab094Lab051Lab088Lab112Lab015Lab039Lab172Lab166Lab114Lab160Lab100Lab117Lab043Lab054Lab086Lab106Lab017Lab020Lab137Lab013Lab032Lab073Lab102Lab136Lab162Lab035Lab045Lab048Lab118Lab024Lab058Lab173Lab111Lab129Lab135Lab033Lab046Lab171Lab151Lab034Lab163Lab029Lab105Lab004Lab044Lab075Lab110Lab159Lab095Lab150Lab157Lab018Lab022Lab074Lab093Lab099Lab108Lab119Lab139Lab078Lab053Lab097Lab005Lab026Lab059Lab132Lab065Lab072Lab068Lab104Lab121Lab130Lab141Lab145Lab158Lab030Lab038Lab049Lab165Lab103Lab047Lab079Lab083Lab120Lab001Lab076Lab107Lab138Lab140Lab144Lab067Lab154Lab128Lab019Lab057Lab055Lab064Lab062Lab002Lab006Lab037Lab109Lab080Lab010Lab021Lab101Lab052Lab098
L L L L L L L L L L L L L L L L L L L L GG
95%4%1%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
*
LinuronMedian: 0.098 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab010Lab060Lab094Lab138Lab084Lab160Lab153Lab008Lab078Lab067Lab031Lab007Lab053Lab027Lab090Lab151Lab134Lab086Lab131Lab146Lab161Lab051Lab135Lab011Lab015Lab069Lab166Lab025Lab102Lab100Lab054Lab114Lab032Lab123Lab150Lab092Lab112Lab106Lab093Lab024Lab074Lab159Lab049Lab171Lab019Lab149Lab172Lab017Lab012Lab118Lab018Lab028Lab029Lab066Lab068Lab095Lab111Lab126Lab145Lab158Lab173Lab050Lab020Lab154Lab022Lab120Lab075Lab137Lab034Lab039Lab073Lab001Lab005Lab043Lab044Lab045Lab070Lab108Lab109Lab121Lab129Lab079Lab099Lab055Lab004Lab082Lab058Lab059Lab132Lab165Lab061Lab110Lab119Lab038Lab035Lab026Lab046Lab083Lab065Lab006Lab014Lab076Lab101Lab107Lab002Lab047Lab097Lab128Lab021Lab037Lab104Lab130Lab136Lab072Lab103Lab052Lab030Lab048Lab163Lab080Lab096Lab105Lab057Lab033Lab064Lab156Lab062Lab085Lab140Lab098Lab013Lab077
L L L L L L L L L L L L B L L L G
93%2%5%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
****
MethiocarbMedian: 0.136 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab172Lab039Lab084Lab053Lab007Lab032Lab157Lab090Lab100Lab079Lab161Lab051Lab106Lab050Lab015Lab018Lab078Lab123Lab008Lab058Lab094Lab112Lab049Lab028Lab011Lab014Lab025Lab166Lab002Lab165Lab137Lab045Lab066Lab109Lab102Lab017Lab105Lab022Lab005Lab140Lab149Lab114Lab082Lab143Lab092Lab001Lab013Lab024Lab074Lab110Lab145Lab136Lab088Lab063Lab019Lab020Lab068Lab086Lab095Lab103Lab108Lab111Lab138Lab156Lab173Lab065Lab093Lab097Lab135Lab012Lab034Lab075Lab054Lab163Lab038Lab035Lab044Lab107Lab129Lab073Lab099Lab026Lab059Lab064Lab067Lab046Lab057Lab083Lab006Lab029Lab076Lab132Lab004Lab043Lab085Lab119Lab120Lab033Lab121Lab130Lab030Lab055Lab037Lab080Lab104Lab052Lab062Lab101Lab118Lab061Lab021Lab158Lab010
L GG G L L L L L G L G L L L L L L
97%2%1%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
PencycuronMedian: 0.269 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab012Lab053Lab133Lab078Lab156Lab153Lab009Lab079Lab032Lab151Lab113Lab134Lab013Lab096Lab067Lab090Lab069Lab150Lab051Lab050Lab008Lab159Lab018Lab145Lab065Lab165Lab046Lab123Lab160Lab100Lab172Lab015Lab103Lab007Lab166Lab075Lab098Lab137Lab006Lab019Lab064Lab068Lab107Lab114Lab152Lab052Lab038Lab095Lab157Lab005Lab033Lab034Lab022Lab024Lab057Lab072Lab025Lab111Lab161Lab059Lab062Lab073Lab082Lab112Lab143Lab094Lab108Lab044Lab158Lab102Lab105Lab131Lab043Lab045Lab086Lab163Lab017Lab011Lab036Lab049Lab074Lab093Lab106Lab063Lab021Lab120Lab129Lab136Lab173Lab121Lab154Lab002Lab039Lab028Lab119Lab135Lab001Lab004Lab054Lab099Lab140Lab142Lab061Lab076Lab083Lab010Lab030Lab058Lab088Lab138Lab168Lab097Lab026Lab066Lab130Lab047Lab104Lab132Lab029Lab092Lab171Lab128Lab014Lab020Lab055Lab101Lab037Lab118Lab141Lab048Lab085Lab109Lab070Lab077Lab110Lab035Lab080
L L GL L L L L L G L L L L L LG L G
90%8%2%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
** *
ProchlorazMedian: 0.058 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab083Lab153Lab170Lab012Lab084Lab133Lab131Lab151Lab022Lab090Lab032Lab156Lab116Lab165Lab114Lab166Lab082Lab069Lab100Lab009Lab015Lab070Lab077Lab087Lab157Lab085Lab137Lab050Lab073Lab172Lab117Lab001Lab057Lab123Lab146Lab160Lab002Lab008Lab018Lab060Lab094Lab113Lab134Lab145Lab150Lab152Lab054Lab099Lab028Lab046Lab120Lab025Lab036Lab051Lab092Lab112Lab097Lab039Lab106Lab127Lab034Lab140Lab017Lab161Lab010Lab011Lab027Lab044Lab047Lab061Lab068Lab074Lab107Lab108Lab109Lab110Lab111Lab138Lab139Lab141Lab171Lab049Lab142Lab042Lab065Lab066Lab067Lab093Lab143Lab159Lab136Lab005Lab072Lab007Lab088Lab149Lab030Lab102Lab016Lab029Lab031Lab033Lab075Lab076Lab119Lab121Lab125Lab129Lab158Lab163Lab168Lab173Lab004Lab038Lab078Lab058Lab118Lab144Lab026Lab020Lab021Lab063Lab104Lab103Lab132Lab006Lab079Lab080Lab095Lab055Lab062Lab105Lab147Lab024Lab003Lab128Lab059Lab035Lab043Lab019Lab052Lab048Lab130Lab101Lab154Lab089Lab037Lab053Lab135Lab096Lab064Lab098Lab086Lab013
GGGGGGG L GGGG GGGGGGGGGGGGGG
95%3%2%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
*
ProcymidoneMedian: 0.110 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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Lab058Lab083Lab053Lab084Lab156Lab149Lab038Lab050Lab039Lab085Lab078Lab096Lab118Lab090Lab161Lab013Lab106Lab015Lab020Lab046Lab086Lab123Lab035Lab006Lab079Lab051Lab165Lab082Lab120Lab025Lab008Lab114Lab066Lab012Lab044Lab074Lab121Lab145Lab166Lab068Lab108Lab110Lab005Lab065Lab017Lab095Lab022Lab054Lab002Lab100Lab028Lab111Lab173Lab055Lab007Lab067Lab119Lab150Lab034Lab045Lab107Lab011Lab099Lab102Lab018Lab061Lab097Lab158Lab093Lab112Lab075Lab059Lab103Lab138Lab171Lab048Lab064Lab049Lab073Lab033Lab129Lab092Lab021Lab143Lab109Lab137Lab132Lab163Lab076Lab080Lab024Lab030Lab136Lab026Lab029Lab052Lab130Lab037Lab010Lab043Lab004Lab104Lab057Lab062Lab098Lab088Lab105
L L L L L L G GG L L L L L L L
91%5%5%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
* *
SpirodiclofenMedian: 0.444 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
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4
5
Lab172Lab048Lab073Lab132Lab020Lab022Lab106Lab004Lab094Lab154Lab069Lab160Lab096Lab134Lab011Lab074Lab035Lab108Lab028Lab001Lab084Lab032Lab050Lab085Lab002Lab171Lab125Lab131Lab112Lab161Lab025Lab063Lab143Lab052Lab015Lab107Lab066Lab092Lab043Lab166Lab057Lab051Lab053Lab118Lab044Lab078Lab034Lab114Lab137Lab039Lab049Lab012Lab047Lab102Lab159Lab054Lab018Lab061Lab077Lab086Lab090Lab111Lab119Lab129Lab138Lab146Lab150Lab024Lab072Lab120Lab017Lab013Lab128Lab097Lab135Lab082Lab029Lab045Lab121Lab158Lab153Lab010Lab058Lab060Lab008Lab065Lab093Lab007Lab104Lab142Lab145Lab062Lab005Lab157Lab019Lab130Lab059Lab030Lab075Lab038Lab026Lab064Lab109Lab110Lab123Lab156Lab165Lab067Lab100Lab036Lab151Lab144Lab099Lab014Lab033Lab055Lab163Lab101Lab080Lab140Lab068Lab076Lab083Lab079Lab173Lab027Lab098Lab021Lab037Lab103Lab006Lab046Lab136Lab105Lab095
L L L L L L L L L L L L L L L G L L G L L L
96%3%1%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
*
ThiabendazoleMedian: 1.710 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
-5
-4
-3
-2
-1
0
1
2
3
4
5
Lab063Lab160Lab162Lab019Lab150Lab053Lab078Lab027Lab069Lab050Lab095Lab106Lab011Lab172Lab025Lab074Lab154Lab049Lab161Lab123Lab135Lab151Lab001Lab029Lab032Lab129Lab158Lab100Lab092Lab105Lab028Lab012Lab166Lab114Lab173Lab015Lab137Lab034Lab118Lab102Lab035Lab060Lab090Lab112Lab051Lab061Lab134Lab017Lab024Lab020Lab082Lab004Lab054Lab062Lab066Lab085Lab013Lab044Lab111Lab138Lab165Lab103Lab136Lab045Lab110Lab093Lab097Lab073Lab033Lab153Lab065Lab094Lab008Lab067Lab120Lab132Lab022Lab157Lab072Lab075Lab130Lab021Lab057Lab068Lab099Lab014Lab018Lab076Lab086Lab108Lab109Lab119Lab121Lab058Lab043Lab059Lab046Lab101Lab163Lab006Lab007Lab145Lab005Lab143Lab079Lab047Lab002Lab026Lab080Lab104Lab038Lab083Lab055Lab064Lab128Lab156Lab030Lab107Lab140Lab010Lab037Lab052Lab039
L L L L L L L L L L L L L
95.0%2.5%2.5%
AcceptableQuestionableUnacceptable
or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives
**
ThiaclopridMedian: 0.338 mg/kg
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Combined z-ScoresCombined z-Scores
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Average of Squared z-ScoresAverage of Squared z-Scores
AZ2AZ2 2 Good2 Good
3 Satisfactory3 Satisfactory3 Unsatisfactory3 Unsatisfactory
22AZ2
n
ZZn
1iii
n
ZZ2
n
1iii
AZ
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
AZ2 Representation92 % Good 7 % Satisfactory 1 % Unsatisfactory
Category A: 54 % of the EU/EFTA Laboratories
(87 Laboratories out of 160)
EU Laboratories
EUPT-FV14: 91 % Good 2 % Satisfactory 7 % Unsatisfactory
NRLs OfLs
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
False Positives
6 different laboratories from EU/EFTA countries reported 6 pesticides as false
positives
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)
Lab038 Captan 0.131 GC-MSD (EI) 0.01 0,01
Lab060 Dimethomorph 0.110 LC-MS/MS (QQQ) (ESI+) 0.01 0.01
Lab077Carbendazim (sum of benomyland carbendazim expressed as
carbendazim)0.040
HPLC-FDConfirmation: GC-MS/MS (QQQ) (EI+)
0.01 0.01
Lab114 Methiocarb sulfone 0.612 LC-MS/MS (QQQ) (ESI+) 0.01 0.01
Lab128 Fludioxonil 0.123 LC-MS/MS (QQQ) 0.01 0.01
Lab160 Tebuconazole 0.011 LC-MS/MS (QQQ)(ESI+) 0.01 0.01
False Positives
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Captan
Carbendazim
False Positives
LC-MS/MS or LC-FD
Carbendazim
Dimethomorph
Fludioxonil
Methiocarb sulfone
Tebuconazole
GC-MS or GC-MS/MS
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Other detected pesticides
Methiocarb sulfoxide
Metabolites
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Methiocarb sulfoxide
Spiked with methiocarb
0.136 mg/kg 0.013 mg/kg
Methiocarb
Other detected pesticides
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Methiocarb sulfoxide0.013 mg/kg
Not used for the evaluation of the laboratories for statistical reasons
Other detected pesticides
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Impurities of commercial formulations
Other detected pesticides
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Diazinon Sulfotep
Spiked with diazinon
0.195 mg/kg Aprox. 0.040 mg/kg(NOT included in the
target list)
Other detected pesticides
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
50ppb_Sulfotep_Solvent
Sample_189_FV15
Sample_60_SM05
Sulfotep[M+H]+: 323.0300C8H20O5P2S2
LC-QTOF-MS
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
0.05 mg/kg Sulfotep in Potato matrix Sample EUPT-
FV15_189A
LC-QQQ-MS/MS
323.1>97.0
323.1>115.0
323.1>97.0
323.1>115.0
Ratio: 62 % Ratio: 63 %
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Contamination of comercial formulations
Other detected pesticides
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
BLANK POTATO Std. 10 µg/kg POTATO SAMPLE 79A FV15
DIMETHOATE (Found in the sample at approx. 3 µg/kg)
SRM1 230>125.1
SRM2 230>199.1 SRM2
230>199.1
SRM1 230>125.1
SRM1 230>125.1
SRM2 230>199.1
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
BLANK POTATO Std. 10 µg/kg POTATO SAMPLE 79A FV15
DIMETHOATE (Found in the sample at approx. 3 µg/kg)
SRM1 230>125.1
SRM2 230>199.1 SRM2
230>199.1
SRM1 230>125.1
SRM1 230>125.1
SRM2 230>199.1
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
BLANK POTATO Std. 10 µg/kg POTATO SAMPLE 79A FV15
DIMETHOATE (Found in the sample at approx. 3 µg/kg)
SRM1 230>125.1
SRM2 230>199.1 SRM2
230>199.1
SRM1 230>125.1
SRM1 230>125.1
SRM2 230>199.1
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
BLANK POTATO Std. 10 µg/kg POTATO SAMPLE 79A FV15
DIMETHOATE (Found in the sample at approx. 3 µg/kg)
SRM1 230>125.1
SRM2 230>199.1 SRM2
230>199.1
SRM1 230>125.1
SRM1 230>125.1
SRM2 230>199.1
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Endosulfan Alpha (concentration < 10 µg/kg)
238.8>204 Std. 5 µg/kg Potato FV15 189A
194.9>158
241>206
194.9>160
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013Endosulfan Beta (concentration < 10 µg/kg)241>206 Std. 5 µg/kg Potato FV15 189A
238.8>204
206.9>172
194.9>158.9
EURL-FVEUPT-FV15 Results
4th Joint Workshop of the European Union Reference Laboratories
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Evolution of the laboratories performance throughout the yearsDispersion of results
No.
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
False Negatives
Evolution of the laboratories performance throughout the years
%
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Labs in Category A
No. of Pesticides in Target List
% of Labs in Cat.A
Evolution of the laboratories performance throughout the years
71 %
51 % 51 % 51 % 45 %56 % 52 % 52 %68
82
113
128
144 144
175 175
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Labs in Category A
Evolution of the laboratories performance throughout the years
EUPT-FV-07 EUPT-FV-13
EUPT-FV-14 EUPT-FV-15
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
National Reference Laboratories
Evolution of the laboratories performance throughout the years
No. Of NRLs with AZ2 > 2
No. Of NRLs in Cat.B
No.
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Common PesticidesSpirodiclofen
New in EUPT-FV14Target List
Present in EUPT-FV14and EUPT-FV15
Test Item
% of Reported Results % of False Negative results
EUPT‐FV‐14 58 3
EUPT‐FV‐15 66 1
% of z‐scores
Acceptable Questionable Unacceptable EUPT‐FV‐14 89 2.0 9.0EUPT‐FV‐15 91 4.5 4.5
Evolution of the laboratories performance throughout the years
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Common PesticidesThiabendazole
% of z‐scores
Acceptable Questionable Unacceptable
EUPT‐FV‐13 83 8 8
EUPT‐FV‐14 97 1 2
EUPT‐FV‐15 95 3 1
Evolution of the laboratories performance throughout the years
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Common PesticidesIprodione
% of z‐scores
Acceptable Questionable Unacceptable
EUPT‐FV‐07 85 3 11
EUPT‐FV‐09 86 4 10
EUPT‐FV‐14 93 2 5
Evolution of the laboratories performance throughout the years
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Conclusions
• Proficiency Tests are an efficient evaluation system, as they allow to
follow the performance of the laboratories network.
• Throughout the years the results of the PTs have improved, although the
laboratories should put their efforts into increasing the number of
pesticides in their scope.
• The introduction of new pesticides in the target list provides an incentive for
the laboratories to expand their scope.
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
• At least one laboratory from each Member State participated in EUPT-FV-15.
• No differences between the results obtained by different methods of
analysis were observed.
• The concentration of the pesticides did not affect the results within the
range of concentrations of this PT.
• Overall, the results were very good. Laboratories generally achieved
accurate results for all the pesticides present in the test item.
Conclusions
4th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides
Almería 23rd-25th October 2013
Thank you foryour AttentionThank you foryour Attention