EUPT-CF8 Incurred and spiked pesticides in wheat · EUPT-CF8 Incurred and spiked pesticides in...
Transcript of EUPT-CF8 Incurred and spiked pesticides in wheat · EUPT-CF8 Incurred and spiked pesticides in...
EUPT-CF8 Incurred and spiked pesticides in wheat
Mette Erecius Poulsen, Gitte Andersen and Susan Strange Herrmann Copenhagen, 18 December 2014
National Food Institute, Technical University of Denmark
PTs on cereals/feed – overview
2007 2008 2009 2010 2011 2012 2013 2014EUPT-C1 /SRM2
EUPT-C2 EUPT-C3 /SRM4
EUPT-C4 EUPT-C5 /SRM6
EUPT-C6 EUPT-CF7 EUPT-CF8
Test material Wheat flourWheat flour Oat flour Rye flour Rice flour Barley Feed Wheat flour
no. of participants 64 74 111 118 155 (133) 149 (127) 120 (106) 160 (141)
No. of target pesticides 37 55 60 72 104 107 116 111MRM no. of incurred pesticides 3 9 14 13 10 8 19 14
no. of spiked pesticides 4 4 3 7 10 4 5SRM no. of incurred pesticides 2 2 2 2
no. of spiked pesticides 1 2 1 7
Total no. of pesticides in test item 10 15 18 19 24 18 23 19
National Food Institute, Technical University of Denmark
Organising team at EURL
•Mette Erecius Poulsen, Senior Chemist •Anne Kruse Lykkeberg, Senior Chemist •Gitte Andersen, Chemist •Merete B. Ludwigsen, Chemical Technician •Inge Schröder, Chemical Technician •Lisbet Pilhkjær, Chemical Technician •Jens-Ole Frimann, System Developer
3
National Food Institute, Technical University of Denmark
Scientific Group
Advisory Group
Amadeo R. Fernández-Alba
André de Kok
Antonio Valverde
Darinka Štajnbaher
Magnus Jezussek
Michelangelo Anastassiades
Miguel Gamón
Ralf Lippold
Dr. Sonja Masselter
Stewart Reynolds
Tuija Pihlström
Quality Group
Antonio Valverde
Stewart Reynolds
National Food Institute, Technical University of Denmark
Participation Country # labs Country # labs Country # labsArgentina 3 Germany 23 Poland 15Austria 2 Greece 3 Portugal 2Belgium 3 Hungary 4 Republic of Belarus 1Brasil 5 Iceland 1 Romania 8Bulgaria 3 India 2 Serbia 2Burkina Faso 1 Indonesia 1 Singapore 1Croatia 5 Ireland 1 Slovakia 2Cyprus 2 Italy 20 Slovenia 3Czech Republic 3 Kenya 2 Spain 18Denmark 1 Lithuania 1 Sweden 2Egypt 1 Luxembourg 1 Tanzania 1Estonia 1 Netherlands 6 Thailand 1Finland 1 New Zealand 1 United Kingdom 3France 6 Norway 1 Total 163
National Food Institute, Technical University of Denmark
Participation Country # labs Country # labs Country # labsArgentina 3 Germany 23 Poland 15Austria 2 Greece 3 Portugal 2Belgium 3 Hungary 4 Republic of Belarus 1Brasil 5 Iceland 1 Romania 8Bulgaria 3 India 2 Serbia 2Burkina Faso 1 Indonesia 1 Singapore 1Croatia 5 Ireland 1 Slovakia 2Cyprus 2 Italy 20 Slovenia 3Czech Republic 3 Kenya 2 Spain 18Denmark 1 Lithuania 1 Sweden 2Egypt 1 Luxembourg 1 Tanzania 1Estonia 1 Netherlands 6 Thailand 1Finland 1 New Zealand 1 United Kingdom 3France 6 Norway 1 Total 163
National Food Institute, Technical University of Denmark
Target Pesticide List • 111 pesticides • 4 new
– Bixafen – Flonicamid – Fluxapyroxad – Metrafenone
• 9 deleted – Aldrin – Chlordane, cis- – Chlordane, oxy – Chlordane, trans- – Dieldrin – Endrin – Heptachlor – Heptachlorepoxid-cis – Heptachlorepoxid-trans
National Food Institute, Technical University of Denmark
• Grown in Denmark in 2013
• Field treated by Aarhus University, Research Department
Flakkebjerg
Wheat
National Food Institute, Technical University of Denmark
Incurred and spiked pesticides Pesticide
Application on cereals in the field Spike in laboratory
Azoxystrobin xBixafen xBoscalid xCarbendazim xChlorothalonil x xCypermethrin x xDeltamethrin-cis x xEndosulfan-sulfate xEpoxiconazole xFlonicamid xFluxapyroxad xLindane xLinuron xMetconazole xMetrafenone x xProthioconazole xPyraclostrobin xSpiroxamine x xTrifluralin x
National Food Institute, Technical University of Denmark
• Samples were distributed on Monday 19 May 2014 (13 May to Third
Countries
• Most samples were delivered to EU laboratories on 20 or 21 May 2014
Sample shipment
National Food Institute, Technical University of Denmark
Homogeniety test
Mean, mg/kg Ss2 c Ss
2 < c Azoxystrobin 0.211 0.00000 0.0033 PassBixafen 0.082 0.00005 0.0001 PassBoscalid 0.324 0 0.0063 PassCarbendazim 0.055 0.00001 0.0001 PassChlorthalonil 0.029 0.00001 0.0001 PassCypermethrin 0.891 0 0.0482 PassDeltamethrin 0.053 0 0.0002 PassEndosulfan-sulfate 0.057 0 0.0002 PassEpoxiconazole 0.122 0 0.0008 PassFlonicamid 0.102 0 0.0003 PassFluxapyroxade 0.179 0.00017 0.0004 PassLindane 0.035 0 0.0000 PassLinuron 0.069 0.00002 0.0003 PassMetconazole 0.110 0.00014 0.0001 PassMetrafenone 0.381 0 0.0081 PassProthioconazole desthio 0.179 0.00040 0.0004 PassPyraclostrobin 0.070 0.00004 0.0001 PassSpiroxamin 0.064 0.00006 0.0001 PassTrifluralin 0.058 0 0.0001 Pass
National Food Institute, Technical University of Denmark
Stability test
Mean, mg/kgFreezer| x1 - yi | 0.3×σ
| x1 - yi | ≤ 0.3×σ
Azoxystrobin 0.243 0.017 0.017 PassBixafen 0.071 0.001 0.006 PassBoscalid 0.305 0.015 0.025 PassCarbendazim 0.058 0.000 0.000 PassChlorothalonil 0.027 0.003 0.003 PassCypermethrin 0.908 0.053 0.057 PassDeltamethrin 0.042 0.003 0.003 PassEndosulfan-sulfate 0.034 0.000 0.003 PassEpoxiconazole 0.118 0.005 0.009 PassFlonicamid 0.088 0.004 0.008 PassFluxapyroxade 0.150 0.012 0.012 PassLindane 0.038 0.003 0.003 PassLinuron 0.065 0.004 0.006 PassMetconazole 0.098 0.005 0.008 PassMetrafenone 0.362 0.015 0.028 PassProthioconazole-desthio 0.159 0.005 0.015 PassPyraclostrobin 0.061 0.004 0.006 PassSpiroxamin 0.057 0.003 0.005 PassTrifluralin 0.034 0.002 0.003 Pass
National Food Institute, Technical University of Denmark
Calculation of assigned values and uncertainty of assigned values
• Algoritm A mean of the results from EU laboratories (and EFTA) – Only result from participant that
• Reported to add water to the samples before extration or • used mixture of solvent and water or • used ASE
• Outliers • Only obvious uncorrect results
• Uncertainty • 𝑢=1.25 *(𝑠∗ /√𝑛) • s* is robust standard deviation (Alg A standard deviation) • N is the number of participants
National Food Institute, Technical University of Denmark
Assigned values
PESTICIDES
Assigned values only water addition,
mg/kgAzoxystrobin 0.228Bixafen 0.079Boscalid 0.328Carbendazim 0.073Chlorothalonil 0.042Cypermethrin 0.766Deltamethrin-cis 0.040Endosulfan-sulfate 0.040Epoxiconazole 0.117Flonicamid 0.104Fluxapyroxad 0.165Lindane 0.038Linuron 0.074Metconazole 0.101Metrafenone 0.376Prothioconazole-desthio 0.201Pyraclostrobin 0.074Spiroxamine 0.060Trifluralin 0.040
0.00
0.10
0.20
0.30
0.40
0.50
0.60
0.70
0.80
0.90
Lin
dan
eEn
do
sulf
an-s
ulf
ate
Del
tam
eth
rin
-cis
Trif
lura
lin
Ch
loro
thal
onil
Sp
irox
amin
eC
arb
end
azim
Pyr
aclo
stro
bin
Lin
uro
nB
ixaf
enM
etco
naz
ole
Flo
nic
amid
Epox
icon
azol
eFl
uxa
pyr
oxad
Pro
thio
con
azol
e-…
Azo
xyst
rob
inB
osca
lid
Met
rafe
non
eC
yper
met
hri
n
mg/kg
Assigned values
National Food Institute, Technical University of Denmark
Reported results and false negatives Pesticide
No. of reported
results No. of NAFalse
negatives % resultsAzoxystrobin 116 19 2 85Bixafen 67 68 0 49Boscalid 117 18 1 86Carbendazim 97 38 1 71Chlorothalonil 90 45 22 66Cypermethrin 125 10 1 92Deltamethrin-cis 123 12 10 90Endosulfan-sulfate 126 9 7 93Epoxiconazole 110 25 1 81Flonicamid 79 56 0 58Fluxapyroxad 60 75 3 44Lindane 126 10 5 93Linuron 95 40 2 70Metconazole 87 48 2 64Metrafenone 83 52 1 61Prothioconazole-desthio 86 49 3 63Pyraclostrobin 97 38 2 71Spiroxamine 97 38 4 71Trifluralin 106 29 2 78
National Food Institute, Technical University of Denmark
Reported results and false negatives Pesticide
No. of reported
results No. of NAFalse
negatives % resultsAzoxystrobin 116 19 2 85Bixafen 67 68 0 49Boscalid 117 18 1 86Carbendazim 97 38 1 71Chlorothalonil 90 45 22 66Cypermethrin 125 10 1 92Deltamethrin-cis 123 12 10 90Endosulfan-sulfate 126 9 7 93Epoxiconazole 110 25 1 81Flonicamid 79 56 0 58Fluxapyroxad 60 75 3 44Lindane 126 10 5 93Linuron 95 40 2 70Metconazole 87 48 2 64Metrafenone 83 52 1 61Prothioconazole-desthio 86 49 3 63Pyraclostrobin 97 38 2 71Spiroxamine 97 38 4 71Trifluralin 106 29 2 78
National Food Institute, Technical University of Denmark
Reported results and false negatives Pesticide
No. of reported
results No. of NAFalse
negatives % resultsAzoxystrobin 116 19 2 85Bixafen 67 68 0 49Boscalid 117 18 1 86Carbendazim 97 38 1 71Chlorothalonil 90 45 22 66Cypermethrin 125 10 1 92Deltamethrin-cis 123 12 10 90Endosulfan-sulfate 126 9 7 93Epoxiconazole 110 25 1 81Flonicamid 79 56 0 58Fluxapyroxad 60 75 3 44Lindane 126 10 5 93Linuron 95 40 2 70Metconazole 87 48 2 64Metrafenone 83 52 1 61Prothioconazole-desthio 86 49 3 63Pyraclostrobin 97 38 2 71Spiroxamine 97 38 4 71Trifluralin 106 29 2 78
National Food Institute, Technical University of Denmark
Reported results and false negatives Pesticide
No. of reported
results No. of NAFalse
negatives % resultsAzoxystrobin 116 19 2 85Bixafen 67 68 0 49Boscalid 117 18 1 86Carbendazim 97 38 1 71Chlorothalonil 90 45 22 66Cypermethrin 125 10 1 92Deltamethrin-cis 123 12 10 90Endosulfan-sulfate 126 9 7 93Epoxiconazole 110 25 1 81Flonicamid 79 56 0 58Fluxapyroxad 60 75 3 44Lindane 126 10 5 93Linuron 95 40 2 70Metconazole 87 48 2 64Metrafenone 83 52 1 61Prothioconazole-desthio 86 49 3 63Pyraclostrobin 97 38 2 71Spiroxamine 97 38 4 71Trifluralin 106 29 2 78
National Food Institute, Technical University of Denmark
Reported results and false negatives Pesticide
No. of reported
results No. of NAFalse
negatives % resultsAzoxystrobin 116 19 2 85Bixafen 67 68 0 49Boscalid 117 18 1 86Carbendazim 97 38 1 71Chlorothalonil 90 45 22 66Cypermethrin 125 10 1 92Deltamethrin-cis 123 12 10 90Endosulfan-sulfate 126 9 7 93Epoxiconazole 110 25 1 81Flonicamid 79 56 0 58Fluxapyroxad 60 75 3 44Lindane 126 10 5 93Linuron 95 40 2 70Metconazole 87 48 2 64Metrafenone 83 52 1 61Prothioconazole-desthio 86 49 3 63Pyraclostrobin 97 38 2 71Spiroxamine 97 38 4 71Trifluralin 106 29 2 78
National Food Institute, Technical University of Denmark
False positive results
Lab code Pesticide Concentration
mg/kg Determination
technique RL,
mg/kg 104 Captan 0.209 LC-MS/MS QQQ 0.06
1 Fenvalerate and Esfenvalerate 0.01 GC-Ion Trap 0.01 147 HCH-beta 0.0294 GC-MS/MS (QQQ) 0.01 111 Quinoxyfen 0.01 75 * Permethrin 0.0946 GC- (µ) ECD 0.005 69 * Tebuconazole 0.057 LC-MS/MS QQQ 0.01
National Food Institute, Technical University of Denmark
28
Calculations of z-scores • For each laboratory/pesticide combination :
z = (x-X) / σ
– x is the result reported by the participant or the specific reporting limit of the lab for those labs not having detected the pesticide present in the test material
– X is the assigned value, Alg A mean without outliers – σ is the target standard deviation obtained by multiplying the
median by the FFP RSD of 25%
• |z| ≤ 2 Acceptable • 2 < |z| < 3 Questionable • |z| > 3 Unacceptable
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
13 28 35 41 42 45 46 53 56 71 78 86 89 91 97 99 106
111
118
140
150
156
119
143 96 108 55 19 147 36 159 47 161 4
107 50 64 110
134 59 124 18 114 73 126
121
109
163 21 38 72 76 74 16 120 40 17 70 82 20 5 14 84 34 29 26 3 33 67 141 66 87 31 95 112 58 61 2 49 30 48 65 43 63 122 11 83 104 15 92
z-sc
ores
Chlorothalonil Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.042 Assigned value: mg/kg
51 (56%)
* * * * * * * * * * * * * * * * * * * * * * * False negatives
30 (34%) 9 (10%)
90
Alg. A RSD = 49%
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
56 86 127
147 85 99 50 46 18 41 163 39 22 36 55 92 122
107 64 35 160
140 8
106 74 59 84 44 72 32 57 108
136
134 89 126 82 135 21 83 132
161 80 138 7 76 10 40 96 23 114 70 34 24 111 4 66 63 20 43 51 65 17 31 68 15 104 1
141 5 25 77 128
112
148
117 11 52 58 120
123
159 37 13 38 71 73 142 2 88 14 30 45 47 87 48 124 19 9 98 109
150 61 49 53 78 119
144 16 67 79 97 121 3 6 91 33 95 110 26 118
145
133
146 27
z-sc
ores
Lindane Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.038 Assigned value: mg/kg
112 (90%)
****** False negatives
9 (7%) 4 (3%)
125
Alg. A RSD = 16%
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
56 55 140 99 95 97 33 81 104
136 38 74 40 35 110
145
123 28 83 7 44 17 105
143
107 30 32 4
141 87 161 53 29 147 26 156 91 122 19 160 13 11 82 16 126 3 43 109
157 59 65 84 5 42 49 111 70 14 47 88 121 80 27 64 120
124 18 48 2 67 76 45 92 98 21 63 20 61 112 89 159 34 31 66 150
134
142 8 78 22 106 36 39 73 46 96 71
z-sc
ores
Carbendazim Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.073 Assigned value: mg/kg
81 (84%)
* False negatives
5 (4%) 11 (12%)
97
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
054
002
120
056
032
126
128
068
037
107
014
034
036
060
074
020
028
007
105
009
087
063
050
125
071
127
101
064
092
043
121
059
061
094
132
029
076
051
016
086
025
075
093
083
065
017
005
096
039
023
067
027
033
124
069
123
030
035
070
021
113
026
015
073
019
085
006
122
055
z-sc
ores
Carbendazim Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.252 Assigned value: mg/kg
59 4 6
69 EUPT-CF7
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
56 55 140 99 95 97 33 81 104
136 38 74 40 35 110
145
123 28 83 7 44 17 105
143
107 30 32 4
141 87 161 53 29 147 26 156 91 122 19 160 13 11 82 16 126 3 43 109
157 59 65 84 5 42 49 111 70 14 47 88 121 80 27 64 120
124 18 48 2 67 76 45 92 98 21 63 20 61 112 89 159 34 31 66 150
134
142 8 78 22 106 36 39 73 46 96 71
z-sc
ores
Carbendazim Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.073 Assigned value: mg/kg
81 (84%)
* False negatives
5 (4%) 11 (12%)
97
Low solubility,
In ethyl acetate 0.135 mg/ml
check if standard is dissolved
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
38 140 74 107 73 63 17 111 80 150 99 27 84 11 58 76 4 30 10 44 89 87 142
126 20 59 71 64 65 57 32 53 109 14 2 51 106 48 49 77 39 66 34
z-sc
ores
Prothioconazole-desthio Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.201 Assigned value: mg/kg
78 (91%)
* * * False negatives
4 (5%) 4 (5%)
86
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
56 95 97 55 35 23 74 147
111 24 17 51 92 25 4 52 134
163
136
143 76 140 8
120
142
122 54 77 64 107 27 36 37 3 47 21 91 80 141
132 31 44 63 159 84 13 40 5
104 58 71 99 157 34 67 145 89 100
112
124
110
123 70 126 29 38 43 121 72 150 1 20 98 26 50 109 45 160 30 73 49 53 61 83 57 105
161 78 82 87 19 96 16 14 11 2 66 10 65 59 46 88 106 79 133 7 15 81 33 32 18 42 39 48 156
127
z-sc
ores
Azoxystrobin Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.228 Assigned value: mg/kg
113 (97%)
* * False negatives
1 (1%) 2 (2%)
116
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
56 55 97 35 95 58 10 74 108 21 80 136 17 92 76 3
119 54 27 51 36 122
132 25 37 73 84 24 141
111 34 134 47 77 159 64 66 23 104 52 143
145
107 13 89 91 1 63 140 19 96 5
109
126 29 71 161 43 163 59 4 30 40 105 31 99 147 20 123
150 38 120 61 72 78 82 133 70 98 121 16 87 156 7 46 53 44 142 49 26 57 67 124 2 65 88 160 14 157
100 11 83 106 18 110 32 81 39 45 33 8 42 48 15 50 112
127
z-sc
ores
Boscalid Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.328 Assigned value: mg/kg
112 (97%)
* False negatives
3 (1%) 2 (2%)
117
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
56 55 95 35 36 46 97 73 58 84 29 134
107
111 23 92 147 21 27 140 80 63 156 1 17 91 124
112 11 13 38 40 47 96 141 3 70 76 25 126
132
159 4 43 72 89 161 51 34 150 61 77 120
133
142 32 59 66 31 67 74 123 15 24 44 121
145 14 37 78 7 30 98 82 64 5 52 19 109
110 26 2 16 143 10 20 57 79 157
160 49 83 71 53 99 105
122
106 88 48 65 87 33 81 18 39 45 8 42 22
z-sc
ores
Epoxiconazole Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.117 Assigned value: mg/kg
104 (95%)
* False negatives
3 (3%) 3 (2%)
110
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
120 95 99 18 74 35 122
145 91 160
126 40 3 83 161
159
107 58 92 5 44 38 141 30 121
110 70 53 71 13 43 96 143 14 134 63 67 119 17 32 57 76 147 66 109 19 88 1 65 87 89 112
124 4 34 21 80 82 106
111 49 2 59 150 11 20 16 26 33 42 61 98 48 73 64 45 84 97 47
z-sc
ores
Flonicamid Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.104 Assigned value: mg/kg
75 (96%)
1 (0%) 3 (4%)
79
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
23 56 55 97 95 73 119 35 120
140
111 80 107 29 76 27 67 105
134
141 13 92 31 72 147 91 7
145 8
124
104 44 3 84 99 121 46 63 47 64 150
161
112 70 58 71 98 143 11 5
142 10 21 2 96 14 53 88 59 4
126 49 30 106 19 40 81 100 48 136 38 26 82 109 43 89 45 65 17 20 16 83 160 32 159
110
157 61 87 39 34 18 74 33 66 42 122
127
z-sc
ores
Pyraclostrobin Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.074 Assigned value: mg/kg
89 (92%)
* * False negatives
4 (4%) 4 (4%)
97
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
55 97 35 96 74 34 111
120
107 73 76 1 67 124 13 134 87 99 161 91 84 43 47 70 38 44 63 150 11 4 17 20 53 160 3 5 71 66 14 30 110
145 21 98 106 82 83 2
126 59 49 121 46 89 112
159 61 78 19 64 48 65 122 18 80 109 16
z-sc
ores
Bixafen Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.079 Assigned value: mg/kg
65 (97%)
2 (3%) 0 (0%)
67
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
33 111 96 35 97 17 34 64 120
134
124 63 67 107 84 13 112 87 30 66 150 1 5 44 141 43 126 91 70 89 121 11 21 71 16 76 4 80 19 73 122
145 61 47 159 49 106 98 2 38 160 83 53 109 65 14 59 110 18 48
z-sc
ores
Fluxapyroxad Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.165 Assigned value: mg/kg
57 (95%)
* * * False negatives
0 (0%) 3 (5%)
60
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
85 163
142
147 97 89 119 46 134
135 55 99 18 59 33 41 108 76 7
146 1 65 64 29 19 136 91 112
143 35 107 74 10 156 16 83 63 160 44 122 66 92 32 54 5 4 24 72 161
123 34 57 51 56 84 109
110 14 100 43 47 53 11 37 13 77 21 138 48 105 25 73 17 49 106
132
104 58 157 52 114 38 23 26 87 121 40 159 96 70 45 82 150
133 20 126
141
111 2
145 88 42 80 61 71 3 98 118 67 95 36 140
124 30 79 39 78 120 50 144 22 127 8 27 15
z-sc
ores
Cypermethrin Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.766 Assigned value: mg/kg
106 (84%)
* False negatives
11 (10%) 8 (6%)
125
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
85 56 79 99 104
122
133
150
156
163
147
118 29 97 50 46 72 43 119
161 40 15 112 38 92 8 91 36 11 143 96 21 53 23 74 111
142 1 70 18 141 89 59 134 35 84 157 76 34 3 24 63 160 51 108
123
136
146 13 159 41 82 66 138 37 19 25 107 54 32 45 71 77 140 4 64 65 73 121
114 52 132 61 88 98 144 55 10 16 67 80 14 87 110 30 135 2
106 5 47 49 48 58 126 20 83 109 57 26 120 17 7 33 124 44 100
145 39 95 22 42 78 27
z-sc
ores
Deltamethrin-cis Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.040 Assigned value: mg/kg
102 (83%)
*********** False negatives
14 (11%) 7 (6%)
123
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
56 71 78 86 127
133 85 54 111
146 33 30 96 50 41 156
142
147 92 119
140 74 11 99 7 89 55 35 135 18 64 17 8 21 29 159
160 32 47 76 84 136
150
161 34 63 80 4
109
106 13 16 77 108 91 107 72 3 5 65 82 126 14 20 24 38 45 52 141 22 1 10 25 70 134 26 36 43 51 66 97 98 123 19 61 53 57 144 67 112 2 9
122
118
163 37 49 44 6
138 87 59 58 83 132 40 68 117 39 42 120
110
128
114
145
124 48 46 79 148
121 95 73 157
105 27
z-sc
ores
Endosulfan-sulfate Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.040 Assigned value: mg/kg
110 (87%)
******** False negatives
15 (13%) 1 (1%)
126
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
30 56 46 59 84 18 160 10 11 147 64 92 140 8 35 99 40 74 21 143 82 70 20 111 96 32 110 13 55 91 122 76 112 72 161 66 36 80 19 63 106 5 29 38 65 78 1
134 4
109
107 2 48 61 57 58 87 157
141 89 45 83 150
159 47 79 121
123 95 49 14 105 16 44 71 98 142
145
144 34 67 24 26 42 43 53 3
120 17 7 73 124
126
132
156 77 86 39 51 23 104 33 133 52 97 27 136
z-sc
ores
Trifluralin Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.040 Assigned value: mg/kg
102 (96%)
* * False negatives
1 (1%) 3 (3%)
106
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
56 120
104 92 97 55 95 35 82 15 27 107 7 19 74 159 4
143 8 64 141 99 91 134
122 38 80 17 147 42 40 145 13 83 84 88 111
142 76 44 73 140
157 30 70 26 32 53 109
161 96 63 5 71 87 59 61 3
160 21 43 49 98 29 124 14 47 65 81 89 106 58 136 46 67 11 110 2 57 10 150
121 66 16 123 20 78 34 18 39 126 33 48 112 45
z-sc
ores
Linuron Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.074 Assigned value: mg/kg
91 (97%)
* * False negatives
2 (1%) 2 (2%)
95
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
21 56 157 35 97 92 107
126 4 74 19 17 156 84 121
111 96 13 159 27 134 73 38 64 47 88 63 3 67 161 76 30 34 40 141 99 80 124 87 26 89 91 5 43 58 110
120 14 32 70 98 123
133
143 7 44 150 46 71 11 65 78 142 42 106
145 59 2 10 49 66 160 16 109 20 57 83 82 18 112 39 33 53 61 122 48 31
z-sc
ores
Metconazole Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.101 Assigned value: mg/kg
82 (94%)
* * False negatives
2 (1%) 3 (2%)
87
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
142 42 97 99 80 96 92 76 35 107
143
104
111
147
145 19 161 10 91 58 21 134 84 141 55 159 73 122 32 38 13 43 17 5 14 1 57 109 87 26 70 63 150 95 110
123 47 49 106
124 67 82 4 11 53 71 74 16 20 30 112 66 65 98 160 3
121 83 34 61 64 89 44 88 2 45 18 59 126
120 48 33 31
z-sc
ores
Metrafenone Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.376 Assigned value: mg/kg
79 (95%)
* False negatives
1 (1%) 3 (4%)
83
National Food Institute, Technical University of Denmark
-5.0
-4.0
-3.0
-2.0
-1.0
0.0
1.0
2.0
3.0
4.0
5.0
23 56 95 119 97 92 15 147
156
121 27 99 40 134 38 21 81 120
141 20 53 8 73 91 72 111
140
161
106 43 17 124
107 47 80 89 71 143 44 19 11 35 126 5 32 49 70 42 87 88 13 3
142 59 160 76 10 145 61 2 14 4 16 39 83 109 7 26 84 98 150 64 45 122 65 46 30 67 82 74 96 36 57 18 78 31 157 48 110 66 34 63 123
159
112 33 133
z-sc
ores
Spiroxamine Acceptable Questionable Unacceptable Number of labs
Water added No water added Not specified ASE
0.060 Assigned value: mg/kg
89 (92%)
* * * * False negatives
2 (2%) 6 (6%)
97
National Food Institute, Technical University of Denmark
Alg. A RSD
0
0.25
Azo
xyst
robi
n
Bix
afen
Bos
calid
Car
bend
azim
Chl
orot
halo
nil
Cyp
erm
ethr
in
Del
tam
ethr
in-c
is
Endo
sulfa
n-su
lfate
Epox
icon
azol
e
Flon
icam
id
Flux
apyr
oxad
Lind
ane
Linu
ron
Met
cona
zole
Met
rafe
none
Prot
hioc
onaz
ole-
dest
hio
Pyra
clos
trob
in
Spi
roxa
min
e
Trifl
ural
in
National Food Institute, Technical University of Denmark
No. of reported results Assigned values Acceptable Questionable Unacceptable False negatives
Azoxystrobin 117 0.228 114 1 2 2Bixafen 67 0.079 65 2 0 0Bosca l id 117 0.328 112 3 2 1Carbendazim 98 0.073 81 5 12 1Chlorothalonil 91 0.042 51 31 9 23Cypermethrin 126 0.766 106 12 8 1Deltamethrin-cis 124 0.040 102 14 8 11Endosul fan-sul fate 127 0.040 110 16 1 8Epoxiconazole 110 0.117 104 3 3 1Flonicamid 79 0.104 75 1 3 0Fluxapyroxad 60 0.165 57 0 3 3Lindane 126 0.038 112 10 4 6Linuron 95 0.074 91 2 2 2Metconazole 87 0.101 82 2 3 2Metrafenone 83 0.376 79 1 3 1Prothioconazole-desthio 86 0.201 78 4 4 3Pyraclostrobin 97 0.074 89 4 4 2Spiroxamine 97 0.060 89 2 6 4Tri flura l in 106 0.040 102 1 3 2
Acceptable, questionable and unacceptable results
National Food Institute, Technical University of Denmark
No. of reported results Assigned values Acceptable Questionable Unacceptable False negatives
Azoxystrobin 117 0.228 114 1 2 2Bixafen 67 0.079 65 2 0 0Bosca l id 117 0.328 112 3 2 1Carbendazim 98 0.073 81 5 12 1Chlorothalonil 91 0.042 51 31 9 23Cypermethrin 126 0.766 106 12 8 1Deltamethrin-cis 124 0.040 102 14 8 11Endosul fan-sul fate 127 0.040 110 16 1 8Epoxiconazole 110 0.117 104 3 3 1Flonicamid 79 0.104 75 1 3 0Fluxapyroxad 60 0.165 57 0 3 3Lindane 126 0.038 112 10 4 6Linuron 95 0.074 91 2 2 2Metconazole 87 0.101 82 2 3 2Metrafenone 83 0.376 79 1 3 1Prothioconazole-desthio 86 0.201 78 4 4 3Pyraclostrobin 97 0.074 89 4 4 2Spiroxamine 97 0.060 89 2 6 4Tri flura l in 106 0.040 102 1 3 2
Acceptable, questionable and unacceptable results
National Food Institute, Technical University of Denmark
No. of reported results Assigned values Acceptable Questionable Unacceptable False negatives
Azoxystrobin 117 0.228 114 1 2 2Bixafen 67 0.079 65 2 0 0Bosca l id 117 0.328 112 3 2 1Carbendazim 98 0.073 81 5 12 1Chlorothalonil 91 0.042 51 31 9 23Cypermethrin 126 0.766 106 12 8 1Deltamethrin-cis 124 0.040 102 14 8 11Endosul fan-sul fate 127 0.040 110 16 1 8Epoxiconazole 110 0.117 104 3 3 1Flonicamid 79 0.104 75 1 3 0Fluxapyroxad 60 0.165 57 0 3 3Lindane 126 0.038 112 10 4 6Linuron 95 0.074 91 2 2 2Metconazole 87 0.101 82 2 3 2Metrafenone 83 0.376 79 1 3 1Prothioconazole-desthio 86 0.201 78 4 4 3Pyraclostrobin 97 0.074 89 4 4 2Spiroxamine 97 0.060 89 2 6 4Tri flura l in 106 0.040 102 1 3 2
Acceptable, questionable and unacceptable results
National Food Institute, Technical University of Denmark
• To be classified as Category A laboratory the labs had to report at least 90% of the pesticide present in the test material (≥17 pesticide residues) and report no false positive.
• Evaluation of the overall performance, the Average of the Squared z-Score (AZ2) are calculated:
• z ≤ 2 Good • 2 < z < 3 Satisfactory • z > 3 Unsatisfactory
Catagory A laboratories and combined z-scores
n
ZAZ
n
ii∑
== 1
2
2
National Food Institute, Technical University of Denmark
0.0
1.0
2.0
3.0
4.0
5.05 70 14 98 13 4 3 19 2 49 32 26 43 67 141 82 65 160 87 11 109 76 91 161 89 63 64 20 121 53 80 59 126 44 83 84 159 61 16 110 17 107
124
134
150 34 145 66 21 30 74 18 38 106 35 112 47 99 71 122 92 73 48 120 96 42 33 97
OFL
NRL AZ2 Catagory A: 67 labs (50%)
Good: 85%
Satisfactory: 10 %
Unsatisfactory: 4%
National Food Institute, Technical University of Denmark
• Test Item
– Maize. Kernels from a fodder variety
• Planned shipment date – 13 April 2015
EUPT-CF9