almería 23 -25 october 2013 - eurl | pesticides · almería 23rd-25th october 2013 dg sanco mrs....

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



Participation

No.

Of L

abs

Participation


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



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



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



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 .



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



WEB PAGE: Forms



Potato



Organic Potatoes were grown in Almería, Spain



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


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



- 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



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



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



Stability

1st Analysis - prior to the sample shipment

2nd Analysis - after the deadline for reporting results



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



Stability

Additionally: 3rd Analysis - reproducing the delivery conditions that the samples experienced during 48 hours



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



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



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



Spirodiclofen Spirodiclofen-enol

3-hydroxy-spirodiclofen-enol



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



RESULTS



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


Distribution of data-Histograms



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






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






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






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



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



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


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



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


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



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


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


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


Almería 23rd-25th October 2013%

Robust standard deviations


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



z-Scores



Acceptable Questionable Unacceptable

z-Scores classification

%


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



-5

-4

-3

-2

-1

0

1

2

3

4

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


Almería 23rd-25th October 2013y

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Lab027Lab084Lab016Lab078Lab117Lab153Lab172Lab116Lab032Lab090Lab094Lab106Lab098Lab033Lab133Lab079Lab002Lab112Lab100Lab072Lab015Lab070Lab123Lab008Lab025Lab089Lab166Lab004Lab073Lab154Lab096Lab001Lab006Lab013Lab018Lab060Lab113Lab131Lab141Lab050Lab051Lab114Lab137Lab049Lab017Lab074Lab012Lab035Lab045Lab111Lab125Lab126Lab138Lab157Lab007Lab052Lab088Lab143Lab020Lab134Lab146Lab058Lab168Lab011Lab029Lab036Lab039Lab044Lab061Lab068Lab069Lab086Lab139Lab034Lab165Lab028Lab038Lab063Lab054Lab151Lab159Lab005Lab080Lab024Lab136Lab108Lab118Lab150Lab156Lab135Lab105Lab149Lab059Lab075Lab097Lab022Lab093Lab144Lab009Lab065Lab043Lab030Lab095Lab099Lab109Lab110Lab129Lab130Lab145Lab158Lab160Lab048Lab057Lab142Lab161Lab019Lab171Lab066Lab140Lab021Lab102Lab103Lab120Lab119Lab121Lab173Lab003Lab082Lab104Lab128Lab053Lab127Lab042Lab067Lab083Lab163Lab064Lab076Lab092Lab132Lab047Lab014Lab026Lab107Lab101Lab062Lab055Lab046Lab077Lab037Lab085Lab010

L LG L LGGLGGL LGG L L L L B

98%1%1%


or L ≡ LCor G ≡ GCor B ≡ Both* False Negatives

*

AzoxystrobinMedian: 0.203 mg/kg



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Lab006Lab027Lab083Lab134Lab153Lab084Lab149Lab159Lab136Lab053Lab013Lab051Lab106Lab068Lab125Lab137Lab165Lab015Lab090Lab025Lab114Lab118Lab085Lab172Lab116Lab032Lab062Lab002Lab008Lab007Lab112Lab147Lab050Lab054Lab097Lab016Lab044Lab121Lab123Lab005Lab117Lab078Lab012Lab009Lab099Lab115Lab077Lab094Lab133Lab160Lab034Lab120Lab039Lab132Lab011Lab035Lab060Lab064Lab069Lab119Lab138Lab150Lab152Lab063Lab065Lab018Lab070Lab079Lab093Lab107Lab145Lab022Lab082Lab163Lab059Lab042Lab058Lab037Lab086Lab110Lab111Lab113Lab151Lab154Lab156Lab017Lab055Lab046Lab066Lab080Lab131Lab101Lab104Lab146Lab096Lab166Lab021Lab061Lab095Lab143Lab003Lab048Lab020Lab030Lab105Lab067Lab103Lab074Lab087Lab092Lab139Lab024Lab038Lab049Lab109Lab144Lab028Lab142Lab173Lab033Lab161Lab140Lab073Lab098Lab029Lab171Lab052Lab019Lab031Lab135Lab088Lab026Lab158Lab102Lab108Lab004Lab043Lab075Lab129

GGGGGLGGGGGG

84%7%9%



*****

Median: 0.160 mg/kgChlorothalonil



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Lab083Lab085Lab160Lab010Lab153Lab003Lab057Lab114Lab142Lab105Lab123Lab145Lab088Lab002Lab100Lab131Lab044Lab038Lab063Lab055Lab165Lab166Lab106Lab039Lab108Lab025Lab015Lab090Lab053Lab143Lab013Lab073Lab032Lab168Lab074Lab118Lab001Lab018Lab109Lab141Lab134Lab137Lab034Lab020Lab078Lab112Lab092Lab082Lab022Lab050Lab146Lab028Lab036Lab051Lab061Lab150Lab171Lab017Lab136Lab046Lab030Lab135Lab149Lab094Lab029Lab102Lab110Lab111Lab121Lab129Lab139Lab120Lab138Lab147Lab127Lab163Lab097Lab173Lab054Lab103Lab066Lab019Lab049Lab172Lab042Lab077Lab119Lab007Lab005Lab062Lab161Lab011Lab004Lab048Lab125Lab024Lab093Lab132Lab154Lab067Lab047Lab130Lab043Lab027Lab033Lab068Lab156Lab065Lab035Lab021Lab058Lab059Lab076Lab080Lab158Lab079Lab099Lab026Lab140Lab006Lab075Lab116Lab101Lab014Lab070Lab037Lab107Lab052Lab151Lab016Lab064Lab012Lab089Lab072Lab104Lab008Lab095

L GGGGGGGL GGG

93%3%4%



** *

ChlorprophamMedian: 1.700 mg/kg



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Lab002Lab006Lab064Lab072Lab077Lab083Lab153Lab010Lab170Lab032Lab136Lab057Lab094Lab071Lab084Lab137Lab053Lab033Lab011Lab163Lab009Lab165Lab013Lab145Lab133Lab157Lab092Lab100Lab117Lab134Lab001Lab046Lab050Lab090Lab160Lab107Lab151Lab172Lab087Lab106Lab156Lab085Lab146Lab012Lab114Lab007Lab075Lab123Lab038Lab079Lab095Lab022Lab147Lab149Lab051Lab015Lab060Lab068Lab103Lab115Lab154Lab158Lab065Lab116Lab161Lab034Lab030Lab166Lab036Lab047Lab069Lab073Lab078Lab019Lab096Lab108Lab018Lab028Lab044Lab074Lab113Lab125Lab152Lab008Lab099Lab120Lab159Lab048Lab062Lab171Lab063Lab142Lab005Lab024Lab143Lab127Lab173Lab025Lab118Lab110Lab111Lab121Lab128Lab168Lab021Lab035Lab058Lab097Lab105Lab017Lab088Lab104Lab039Lab067Lab102Lab029Lab061Lab112Lab119Lab126Lab129Lab139Lab141Lab132Lab020Lab043Lab093Lab135Lab042Lab098Lab052Lab054Lab076Lab086Lab130Lab150Lab080Lab066Lab055Lab109Lab140Lab004Lab049Lab101Lab144Lab037Lab070Lab059Lab089Lab138Lab026Lab027

GGGGL LGGGGG

89%6%5%



******

CypermethrinMedian: 0.100 mg/kg



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Lab114Lab170Lab153Lab077Lab003Lab053Lab057Lab013Lab087Lab136Lab157Lab133Lab090Lab100Lab032Lab061Lab084Lab159Lab025Lab165Lab050Lab112Lab123Lab046Lab151Lab137Lab072Lab049Lab039Lab009Lab134Lab001Lab015Lab044Lab070Lab073Lab126Lab145Lab152Lab008Lab034Lab012Lab131Lab172Lab028Lab085Lab146Lab017Lab166Lab011Lab018Lab027Lab094Lab150Lab160Lab019Lab048Lab036Lab005Lab079Lab118Lab002Lab149Lab033Lab060Lab064Lab069Lab138Lab141Lab171Lab047Lab062Lab092Lab007Lab051Lab030Lab054Lab117Lab143Lab067Lab042Lab082Lab055Lab074Lab111Lab113Lab121Lab139Lab144Lab156Lab158Lab058Lab106Lab063Lab168Lab097Lab089Lab115Lab135Lab029Lab068Lab110Lab125Lab129Lab142Lab078Lab088Lab093Lab147Lab173Lab022Lab116Lab128Lab065Lab086Lab108Lab119Lab038Lab099Lab120Lab059Lab066Lab105Lab080Lab075Lab083Lab102Lab107Lab127Lab130Lab101Lab103Lab020Lab104Lab024Lab076Lab162Lab163Lab132Lab010Lab154Lab035Lab004Lab026Lab140Lab096Lab043Lab014Lab161Lab016Lab031Lab037Lab052Lab021Lab045Lab006Lab095Lab109Lab098

GGGLGGGGLG

95%3%2%



DiazinonMedian: 0.195 mg/kg



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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%



FluopicolideMedian: 0.099 mg/kg



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Lab083Lab084Lab123Lab090Lab039Lab161Lab165Lab072Lab008Lab015Lab025Lab137Lab051Lab096Lab166Lab012Lab001Lab074Lab086Lab108Lab050Lab112Lab054Lab018Lab022Lab105Lab062Lab094Lab099Lab011Lab052Lab118Lab024Lab028Lab013Lab002Lab106Lab030Lab100Lab017Lab068Lab067Lab173Lab004Lab035Lab103Lab078Lab093Lab104Lab029Lab061Lab066Lab129Lab044Lab111Lab121Lab042Lab120Lab102Lab007Lab058Lab059Lab109Lab138Lab145Lab020Lab021Lab034Lab097Lab075Lab149Lab064Lab119Lab171Lab132Lab107Lab005Lab110Lab065Lab057Lab043Lab046Lab049Lab006Lab095Lab156Lab143Lab079Lab038Lab092Lab073Lab055Lab136Lab033Lab163Lab026Lab080Lab037Lab045Lab010

G L G G G L G L L L L L L G

96%2%2%



*

FlutolanilMedian: 0.410 mg/kg



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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%



*

FosthiazateMedian: 0.080 mg/kg



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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%



IprovalicarbMedian: 0.090 mg/kg



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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%



*

LinuronMedian: 0.098 mg/kg



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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%



****

MethiocarbMedian: 0.136 mg/kg



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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%



PencycuronMedian: 0.269 mg/kg



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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%



** *

ProchlorazMedian: 0.058 mg/kg



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Lab083Lab153Lab170Lab012Lab084Lab133Lab131Lab151Lab022Lab090Lab032Lab156Lab116Lab165Lab114Lab166Lab082Lab069Lab100Lab009Lab015Lab070Lab077Lab087Lab157Lab085Lab137Lab050Lab073Lab172Lab117Lab001Lab057Lab123Lab146Lab160Lab002Lab008Lab018Lab060Lab094Lab113Lab134Lab145Lab150Lab152Lab054Lab099Lab028Lab046Lab120Lab025Lab036Lab051Lab092Lab112Lab097Lab039Lab106Lab127Lab034Lab140Lab017Lab161Lab010Lab011Lab027Lab044Lab047Lab061Lab068Lab074Lab107Lab108Lab109Lab110Lab111Lab138Lab139Lab141Lab171Lab049Lab142Lab042Lab065Lab066Lab067Lab093Lab143Lab159Lab136Lab005Lab072Lab007Lab088Lab149Lab030Lab102Lab016Lab029Lab031Lab033Lab075Lab076Lab119Lab121Lab125Lab129Lab158Lab163Lab168Lab173Lab004Lab038Lab078Lab058Lab118Lab144Lab026Lab020Lab021Lab063Lab104Lab103Lab132Lab006Lab079Lab080Lab095Lab055Lab062Lab105Lab147Lab024Lab003Lab128Lab059Lab035Lab043Lab019Lab052Lab048Lab130Lab101Lab154Lab089Lab037Lab053Lab135Lab096Lab064Lab098Lab086Lab013

GGGGGGG L GGGG GGGGGGGGGGGGGG

95%3%2%



*

ProcymidoneMedian: 0.110 mg/kg



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Lab058Lab083Lab053Lab084Lab156Lab149Lab038Lab050Lab039Lab085Lab078Lab096Lab118Lab090Lab161Lab013Lab106Lab015Lab020Lab046Lab086Lab123Lab035Lab006Lab079Lab051Lab165Lab082Lab120Lab025Lab008Lab114Lab066Lab012Lab044Lab074Lab121Lab145Lab166Lab068Lab108Lab110Lab005Lab065Lab017Lab095Lab022Lab054Lab002Lab100Lab028Lab111Lab173Lab055Lab007Lab067Lab119Lab150Lab034Lab045Lab107Lab011Lab099Lab102Lab018Lab061Lab097Lab158Lab093Lab112Lab075Lab059Lab103Lab138Lab171Lab048Lab064Lab049Lab073Lab033Lab129Lab092Lab021Lab143Lab109Lab137Lab132Lab163Lab076Lab080Lab024Lab030Lab136Lab026Lab029Lab052Lab130Lab037Lab010Lab043Lab004Lab104Lab057Lab062Lab098Lab088Lab105

L L L L L L G GG L L L L L L L

91%5%5%



* *

SpirodiclofenMedian: 0.444 mg/kg



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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%



*

ThiabendazoleMedian: 1.710 mg/kg



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Lab063Lab160Lab162Lab019Lab150Lab053Lab078Lab027Lab069Lab050Lab095Lab106Lab011Lab172Lab025Lab074Lab154Lab049Lab161Lab123Lab135Lab151Lab001Lab029Lab032Lab129Lab158Lab100Lab092Lab105Lab028Lab012Lab166Lab114Lab173Lab015Lab137Lab034Lab118Lab102Lab035Lab060Lab090Lab112Lab051Lab061Lab134Lab017Lab024Lab020Lab082Lab004Lab054Lab062Lab066Lab085Lab013Lab044Lab111Lab138Lab165Lab103Lab136Lab045Lab110Lab093Lab097Lab073Lab033Lab153Lab065Lab094Lab008Lab067Lab120Lab132Lab022Lab157Lab072Lab075Lab130Lab021Lab057Lab068Lab099Lab014Lab018Lab076Lab086Lab108Lab109Lab119Lab121Lab058Lab043Lab059Lab046Lab101Lab163Lab006Lab007Lab145Lab005Lab143Lab079Lab047Lab002Lab026Lab080Lab104Lab038Lab083Lab055Lab064Lab128Lab156Lab030Lab107Lab140Lab010Lab037Lab052Lab039

L L L L L L L L L L L L L

95.0%2.5%2.5%



**

ThiaclopridMedian: 0.338 mg/kg



Combined z-ScoresCombined z-Scores



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



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



False Positives

6 different laboratories from EU/EFTA countries reported 6 pesticides as false

positives



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



Captan

Carbendazim

False Positives

LC-MS/MS or LC-FD

Carbendazim

Dimethomorph

Fludioxonil

Methiocarb sulfone

Tebuconazole

GC-MS or GC-MS/MS



Other detected pesticides

Methiocarb sulfoxide

Metabolites



Methiocarb sulfoxide

Spiked with methiocarb

0.136 mg/kg 0.013 mg/kg

Methiocarb




Methiocarb sulfoxide0.013 mg/kg

Not used for the evaluation of the laboratories for statistical reasons




Impurities of commercial formulations




Diazinon Sulfotep

Spiked with diazinon

0.195 mg/kg Aprox. 0.040 mg/kg(NOT included in the

target list)




50ppb_Sulfotep_Solvent

Sample_189_FV15

Sample_60_SM05

Sulfotep[M+H]+: 323.0300C8H20O5P2S2

LC-QTOF-MS



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 %



Contamination of comercial formulations




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


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


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


4th Joint Workshop of the European Union Reference Laboratories



Evolution of the laboratories performance throughout the yearsDispersion of results

No.



False Negatives

Evolution of the laboratories performance throughout the years

%



Labs in Category A

No. of Pesticides in Target List

% of Labs in Cat.A


71 %

51 % 51 % 51 % 45 %56 % 52 % 52 %68

82

113

128

144 144

175 175



Labs in Category A


EUPT-FV-07 EUPT-FV-13

EUPT-FV-14 EUPT-FV-15



National Reference Laboratories


No. Of NRLs with AZ2 > 2

No. Of NRLs in Cat.B

No.



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




Common PesticidesThiabendazole

% of z‐scores


EUPT‐FV‐13 83 8 8

EUPT‐FV‐14 97 1 2

EUPT‐FV‐15 95 3 1




Common PesticidesIprodione

% of z‐scores


EUPT‐FV‐07 85 3 11

EUPT‐FV‐09 86 4 10

EUPT‐FV‐14 93 2 5




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.



• 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



Thank you foryour AttentionThank you foryour Attention

almería 23 -25 october 2013 - eurl | pesticides · almería 23rd-25th october 2013 dg sanco mrs....

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