Vom Erzeuger bis zur Ladentheke. Laboratory Performance Assessment Spring 2013 QS Fachgesellschaft Obst-Gemüse-Kartoffeln GmbH Report Test Material B Pesticide Residues in Basil Purée May 2013
Summary The Test Materials for the 2013 spring Laboratory Performance Assessment of QS Fachgesellschaft Obst-Gemüse-Kartoffeln GmbH were prepared by the GLP department of LUFA Speyer in March 2013 to provide individual Test Material tailored to QS needs. QS required two different materials in terms of spiked pesticides. Thus, both Test Materials were spiked with six different types of pesticides each and at different spike levels. Test Material B was distributed to thirty five (35) participants. This report refers to the performance assessment of laboratories which analysed Test Material B. Each laboratory received minimum 100 g Basil purée with six spiked pesticides. All 35 participants kept the term for the submission of results. The laboratories were requested to identify and quantify 6 pesticides. These were Biphenyl, Chlorfenapyr, Dichlorvos, Emamectin, Methomyl and Prochloraz. The performance assessment considers the following test criteria: - No false negative results have to be reported (thus identification of all six pesticides, see page 5 and tables 1 to 3, pp. 6-8), - No false positive results have to be reported (see page 5), - Correct quantification related to the 70-120% recovery criteria. The results for Prochloraz are withdrawn from the 70-120% assessment. They are presented in this report for information purposes only (see page 8). The assessment of Emamectin complies with the residue definition of Commission Regulation (EG) No. 396/2005: Emamectin benzoate B1a, expressed as emamectin. The overall performance assessment of the competence test (Material B) is summarised in the following table: QS criteria number of satisfactory participants total number of participants satisfactory (%) correctly identified all six pesticides > 20 µg/kg correctly identified AND reported satisfactory results for all five pesticides* * Prochloraz is not considered 25 35 71 14 35 40
Assessment of quantification: As announced in the letter of invitation, the assessment of quantification was exactly defined: Analytical results between 70 and 120% of the spiked levels have been considered satisfying. analyte spiked level number of satisfactory results (70-120% of the spiked level) total number of scores satisfactory (%) Biphenyl 45 27 27 100 Chlorfenapyr 80 29 35 83 Dichlorvos 35 20 32 63 Emamectin 167 30 34 88 Methomyl 450 31 34 91
Contents Page SUMMARY 2 1. TEST MATERIAL PREPARATION AND DESIGN 5 2. RESULTS 5 TABLE 1: RESULTS FOR BIPHENYL AND CHLORFENAPYR IN BASIL PURÉE TEST MATERIAL B 6 TABLE 2: RESULTS FOR DICHLORVOS AND EMAMECTIN IN BASIL PURÉE TEST MATERIAL B 7 TABLE 3: RESULTS FOR METHOMYL AND PROCHLORAZ IN BASIL PURÉE TEST MATERIAL B 8 FIGURE 1: ASSESSMENT OF BIPHENYL (SPIKED LEVEL: 45 µg/kg) IN BASIL PURÉE TEST MATERIAL B 9 FIGURE 2: ASSESSMENT OF CHLORFENAPYR (SPIKED LEVEL: 80 µg/kg) IN BASIL PURÉE TEST MATERIAL B 10 FIGURE 3: ASSESSMENT OF DICHLORVOS (SPIKED LEVEL: 35 µg/kg) IN BASIL PURÉE TEST MATERIAL B 11 FIGURE 5: ASSESSMENT OF METHOMYL (SPIKED LEVEL: 450 µg/kg) IN BASIL PURÉE TEST MATERIAL B 13 FIGURE 6: REPORTED LEVELS OF PROCHLORAZ (SPIKED LEVEL: 240 µg/kg) IN BASIL PURÉE TEST MATERIAL B 14 3. HOMOGENEITY TESTING 15 TABLE 5A: HOMOGENEITY DATA FOR BASIL HOMOGENATE SAMPLES (PROVIDED BY LAVES OLDENBURG) 15 TABLE 5B: HOMOGENEITY DATA FOR BASIL HOMOGENATE SAMPLES (PROVIDED BY LAVES OLDENBURG) 16
1. Test Material Preparation and Design The Test Material for this Performance Assessment was prepared by the GLP department of LUFA Speyer. The homogeneity tests were performed by the LAVES (Niedersächsisches Landesamt für Verbraucherschutz und Lebensmittelsicherheit) Oldenburg, Germany. The results of homogeneity testing are presented in table 5a and 5b (pp. 15-16). The following pesticides were spiked to give the approximate final concentrations: 45 µg/kg Biphenyl, 80 µg/kg Chlorfenapyr, 35 µg/kg Dichlorvos, 167 µg/kg Emamectin benzoate B1a expressed as Emamectin, 450 Methomyl and 240 µg/kg Prochloraz. The Test Material is based on Basil labelled as organic. Before using the Basil homogenate for spiking, it has been analysed and no levels of pesticides have been detected with a limit of detection at 10 µg/kg. The Basil purée was distributed into labelled bottles with at least 100 g in each. The bottles were stored at -20 C in the dark until distribution. 2. Results The participants were requested to report the pesticides the Basil purée had been analysed for. The results had to be reported without consideration of the recovery unless reported differently by the participants. The participants were asked to report also recovery rates for the quantified pesticides. The limit of quantification (LOQ) had to be specified for all sought and found pesticides. Each laboratory was given a number (laboratory code). The results of all participants analysing Test Material A are presented in tables 1 to 3 (pp. 6-8) and subsequently in figures 1 to 6 (pp. 9-14). Prochloraz is excluded from the 70-120% assessment since the homogeneity tests revealed low recoveries for Prochloraz in the Test Material. The results for Prochloraz are summarised in table 3 (p. 8) and figure 6 (p. 14). The results on Emamectin have been reported in several ways by the participats. Some of them reported it as Emamectin, some as Emamectin-benzoate, some differed between Emamectin(benzoate) B1a and B1b, some did not. All participants were therefore requested to report their results in accordance with the Commission Regulation (EG) No. 396/2005: Emamectin benzoate B1a, expressed as emamectin. One participant reported false positive results: laboratory code pesticide 34 Diflubenzuron, Isofenphosmethyl Ten participants reported false negative results: laboratory code pesticide 2 Biphenyl 5 Biphenyl 14 Biphenyl 36 Biphenyl 49 Biphenyl, Dichlorvos 52 Biphenyl 58 Methomyl 59 Emamectin 68 Biphenyl, Dichlorvos 69 Biphenyl, Dichlorvos Page 5 of 16
laboratory code result Biphenyl spiked level: 45 µg/kg recovery (%) LOQ accepted range : 31,5-54 result Chlorfenapyr spiked level: 80 µg/kg recovery (%) LOQ accepted range : 56-96 1 47 109 10 yes 83 108 10 yes 2 n.r. 86 85 5 yes 5 n.r. 51 120 10 no 6 50 70 10 yes 85 80 10 yes 11 35 91 10 yes 59 94 10 yes 13 43 88 10 yes 78 92 10 yes 14 n.r. 78 100 5 yes 16 51 89 10 yes 68 95 10 yes 17 38 100 10 yes 77 105 10 yes 20 46 90 10 yes 70 90 10 yes 22 37 96,7 5 yes 64 97,7 5 yes 23 42 70-120 10 yes 60 70-120 5 yes 26 36 5 yes 72 5 yes 27 46 72,7 10 yes 79 93,6 10 yes 33 40 104 10 yes 94 99 10 yes 34 32 70-120 10 yes 129 70-120 10 no 35 37 83 10 yes 69 90 10 yes 36 n.r. 94 99 10 yes 40 48 95 10 yes 88 97 10 yes 42 45 81 10 yes 89 100 10 yes 44 36 95 10 yes 80 95 10 yes 49 n.r. 45 98 10 no 52 n.r. 84 92 10 yes 54 35 77 5 yes 84 90,3 5 yes 56 36 89 10 yes 60 90 10 yes 57 34 100 10 yes 84 10 50 yes 58 43 100 10 yes 182 95 10 no 59 41 95 10 yes 67 97 10 yes 60 36 99,8 10 yes 78 97,5 10 yes 64 42 105 10 yes 85 114 10 yes 65 53 94 10 yes 90 80 10 yes 66 32 91 10 yes 72 91 10 yes 68 n.r. 98 87 10 no 69 n.r. 57 91 10 yes 71 41 98 10 yes 123 101 10 no n.r. = not reported Table 1: Results for Biphenyl and Chlorfenapyr in Basil Purée Test Material B Page 6 of 16
laboratory code result Dichlorvos spiked level: 35 µg/kg recovery (%) LOQ accepted range : 24,5-42 result Emamectin spiked level: 167 µg/kg recovery (%) LOQ accepted range : 117-200 1 31 105 10 yes 184 110 10 yes 2 20 90 10 no 174 95 5 yes 5 23 84,1 10 no 313 94 10 no 6 34 92 10 yes 162,6 110 10 yes 11 23 100 10 no 135 99 10 yes 13 22 89 10 no 178 99 10 yes 14 29 99 15 yes 140 91 10 yes 16 22 88 10 no 140 95 10 yes 17 26 92 10 yes 169 97 10 yes 20 28 90 10 yes 135 90 10 yes 22 26 103,6 5 yes 145 96 5 yes 23 25 70-120 5 yes 131 70-120 5 yes 26 23 10 no 189 10 yes 27 28 85,4 10 yes 126 65,4 10 yes 33 24 96 10 no 193 96 10 yes 34 23 70-120 10 no 40 70-120 10 no 35 20 84 10 no 153 87 10 yes 36 26 82,5 10 yes 136 98,6 10 yes 40 32 109 10 yes 145 101 10 yes 42 28 94 10 yes 171 86 10 yes 44 30 95 10 yes 167 95 10 yes 49 n.r. 129 110 10 yes 52 30 80 10 yes 143 96 10 yes 54 28 94,7 5 yes 150 98 5 yes 56 33 94 10 yes 160 83 10 yes 57 30 100 10 yes 145 100 10 yes 58 28 76 10 yes 252 90 10 no 59 21 140 10 no n.r. 60 30 104,2 10 yes 170 96,8 10 yes 64 21 86 10 no 185 98 10 yes 65 35 90 10 yes 179 83 10 yes 66 24 97 10 no 168 89 10 yes 68 n.r. 250 88 5 no 69 n.r. 199 105 10 yes 71 36 97 10 yes 150 93 10 yes n.r. = not reported Table 2: Results for Dichlorvos and Emamectin in Basil Purée Test Material B Page 7 of 16
laboratory code result Methomyl spiked level: 450 µg/kg recovery (%) LOQ accepted range : 315-540 result Prochloraz spiked level: 240 µg/kg recovery (%) LOQ 1 433 81 10 yes 161 96 10 2 510 80 5 yes 142 90 5 5 506 110 10 yes 112 112,7 10 6 450 90 10 yes 170 75 10 11 406 95 10 yes 70 99 10 13 371 93 10 yes 82 94 10 14 434 95 5 yes 72 83 5 16 405 94 10 yes 105 86 10 17 475 106 10 yes 118 105 10 20 460 90 10 yes 111 90 10 22 463 104 5 yes 100 85,2 5 23 392 70-120 10 yes 84 70-120 5 26 400 10 yes 78 5 27 435 88,2 10 yes 129 69,2 10 33 475 104 10 yes 97 93 10 34 650 70-120 10 no 108 70-120 10 35 433 90 10 yes 113 94 10 36 417 98,6 10 yes 87 98,6 10 40 420 103 10 yes 144 98 10 42 357 97 10 yes 183 85 10 44 480 95 10 yes 108 95 10 49 326 106 10 yes 44 80 10 52 356 98 10 yes 156 88 10 54 479 80 5 yes 95 89,5 5 56 420 93 10 yes 84 95 10 57 490 100 10 yes 95 100 10 58 n.r. 98 100 10 59 350 86 10 yes 160 92 10 60 572 94,2 10 no 119 85,4 10 64 500 86 10 yes 175 70 10 65 509 84 10 yes 84* 93 10 66 420 92 10 yes 120 96 10 68 679 91 10 no 105 90 10 69 402 102 10 yes 105 85 10 71 482 90 10 yes 88 98 10 n.r. = not reported * additionally reported: 12 µg/kg 2,4,6-Trichlorphenol (recovery 103%, LOQ: 5 µg/kg) Table 3: Results for Methomyl and Prochloraz in Basil Purée Test Material B Page 8 of 16
Biphenyl 60 120% spiked level 50 spiked level 40 result 30 70% spiked level 20 10 0 34 66 57 11 54 26 44 56 60 22 35 17 33 59 71 23 64 13 58 42 20 27 1 40 6 16 65 laboratory code Figure 1: Assessment of Biphenyl (spiked level: 45 µg/kg) in Basil Purée Test Material B Page 9 of 16
Chlorfenapyr 180 160 140 120 result 100 80 120% spiked level spiked level 60 70% spiked level 40 20 0 49 5 69 11 56 23 22 59 16 35 20 66 26 17 13 14 60 27 44 1 57 54 52 64 6 2 40 42 65 36 33 68 71 34 58 laboratory code Figure 2: Assessment of Chlorfenapyr (spiked level: 80 µg/kg) in Basil Purée Test Material B Page 10 of 16
Dichlorvos 120% spiked level 40 35 spiked level 30 result 25 20 15 70% spiked level 10 5 0 35 2 59 64 13 16 11 26 5 34 66 33 23 17 36 22 20 54 42 58 27 14 44 60 57 52 1 40 56 6 65 71 laboratory code Figure 3: Assessment of Dichlorvos (spiked level: 35 µg/kg) in Basil Purée Test Material B Page 11 of 16
Emamectin 300 275 250 result 225 200 175 150 125 100 120% spiked level spiked level 70% spiked level 75 50 25 0 34 27 49 23 11 20 36 14 16 52 22 40 57 54 71 35 56 6 44 66 17 60 42 2 13 65 1 64 26 33 69 68 58 5 laboratory code Figure 4: Assessment of Emamectin (spiked level: 167 µg/kg) in Basil Purée Test Material B Page 12 of 16
Methomyl 700 650 600 result 550 500 450 400 350 300 250 120% spiked level spiked level 70% spiked level 200 150 100 50 0 49 59 52 42 13 23 26 69 16 11 36 56 66 40 35 1 14 27 6 20 22 17 33 54 44 71 57 64 5 65 2 60 34 68 laboratory code Figure 5: Assessment of Methomyl (spiked level: 450 µg/kg) in Basil Purée Test Material B Page 13 of 16
Prochloraz result 250 240 230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 spiked level 49 11 14 26 13 56 23 65 36 71 57 54 33 58 22 68 69 16 44 34 20 5 35 17 60 66 27 2 40 52 59 1 6 64 42 laboratory code Figure 6: Reported levels of Prochloraz (spiked level: 240 µg/kg) in Basil Purée Test Material B Page 14 of 16
3. Homogeneity Testing The Homogeneity Testings were performed at the LAVES (Niedersächsisches Landesamt für Verbraucherschutz und Lebensmittelsicherheit) Oldenburg, Germany. Ten randomly chosen Test Material samples were analysed in duplicate to check the corresponding homogeneity of the six spiked pesticides. Biphenyl Test Material 1st extraction 2nd extraction Mean [mg/kg] [mg/kg] [mg/kg] Standard deviation TM B Nr.: 12 0.046 0.045 0.046 0.003 [mg/kg] TM B Nr.: 20 0.038 0.045 0.042 TM B Nr.: 35 0.037 0.046 0.041 Variation TM B Nr.: 42 0.048 0.051 0.049 7.5 % TM B Nr.: 50 0.041 0.038 0.040 TM B Nr.: 58 0.038 0.046 0.042 Recovery TM B Nr.: 70 0.050 0.049 0.049 99 % TM B Nr.: 78 0.049 0.041 0.045 TM B Nr.: 92 0.043 0.051 0.047 Spiked level TM B Nr.: 101 0.042 0.048 0.045 0.045 [mg/kg] Mean [mg/kg] 0.045 Chlorfenapyr Test Material 1st extraction 2nd extraction Mean Standard deviation TM B Nr.: 12 0.082 0.073 0.078 0.005 [mg/kg] TM B Nr.: 20 0.074 0.074 0.074 TM B Nr.: 35 0.079 0.074 0.077 Variation TM B Nr.: 42 0.071 0.071 0.071 6.5 % TM B Nr.: 50 0.082 0.087 0.085 TM B Nr.: 58 0.081 0.067 0.074 Recovery TM B Nr.: 70 0.085 0.082 0.083 99 % TM B Nr.: 78 0.085 0.085 0.085 TM B Nr.: 92 0.083 0.084 0.084 Spiked level TM B Nr.: 101 0.086 0.071 0.078 0.080 [mg/kg] Mean [mg/kg] 0.079 Dichlorvos Test Material 1st extraction 2nd extraction Mean [mg/kg] [mg/kg] [mg/kg] Standard deviation TM B Nr.: 12 0.036 0.031 0.034 0.002 mg/kg TM B Nr.: 20 0.034 0.029 0.032 TM B Nr.: 35 0.032 0.031 0.031 Variation TM B Nr.: 42 0.031 0.034 0.032 4.6 % TM B Nr.: 50 0.034 0.032 0.033 TM B Nr.: 58 0.036 0.032 0.034 Recovery TM B Nr.: 70 0.033 0.034 0.034 96 % TM B Nr.: 78 0.036 0.034 0.035 TM B Nr.: 92 0.035 0.037 0.036 Spiked level TM B Nr.: 101 0.037 0.033 0.035 0.035 mg/kg Mean [mg/kg] 0.035 Table 5a: Homogeneity Data for Basil Homogenate Samples (provided by LAVES Oldenburg) Page 15 of 16
Emamectin benzoate Test Material 1st extraction 2nd extraction Mean [mg/kg] [mg/kg] [mg/kg] Standard deviation TM B Nr.: 12 0.177 0.170 0.174 0.003 mg/kg TM B Nr.: 20 0.180 0.171 0.175 TM B Nr.: 35 0.182 0.168 0.175 Variation TM B Nr.: 42 0.168 0.178 0.173 1.8 % TM B Nr.: 50 0.182 0.183 0.182 TM B Nr.: 58 0.190 0.171 0.180 Recovery TM B Nr.: 70 0.173 0.182 0.177 93 % TM B Nr.: 78 0.187 0.173 0.180 TM B Nr.: 92 0.180 0.178 0.179 Spiked level TM B Nr.: 101 0.185 0.174 0.179 0.190 mg/kg Mean [mg/kg] 0.177 Methomyl Test Material 1st extraction 2nd extraction Mean [mg/kg] [mg/kg] [mg/kg] Standard deviation TM B Nr.: 12 0.431 0.413 0.422 0.017 [mg/kg] TM B Nr.: 20 0.425 0.406 0.415 TM B Nr.: 35 0.422 0.407 0.414 Variation TM B Nr.: 42 0.407 0.421 0.414 3.9 % TM B Nr.: 50 0.437 0.436 0.437 TM B Nr.: 58 0.467 0.439 0.453 Recovery TM B Nr.: 70 0.431 0.438 0.435 97 % TM B Nr.: 78 0.471 0.434 0.452 TM B Nr.: 92 0.438 0.452 0.445 Spiked level TM B Nr.: 101 0.454 0.461 0.458 0.450 [mg/kg] Mean [mg/kg] 0.434 Prochloraz Test Material 1st extraction 2nd extraction Mean [mg/kg] [mg/kg] [mg/kg] Standard deviation TM B Nr.: 12 0.158 0.151 0.154 0.009 [mg/kg] TM B Nr.: 20 0.143 0.133 0.138 TM B Nr.: 35 0.158 0.145 0.152 Variation TM B Nr.: 42 0.142 0.157 0.150 5.9 % TM B Nr.: 50 0.151 0.154 0.152 TM B Nr.: 58 0.162 0.153 0.158 Recovery TM B Nr.: 70 0.165 0.168 0.166 65 % TM B Nr.: 78 0.166 0.162 0.164 TM B Nr.: 92 0.167 0.169 0.168 Spiked level TM B Nr.: 101 0.166 0.159 0.162 0.240 [mg/kg] Mean [mg/kg] 0.156 Table 5b: Homogeneity Data for Basil Homogenate Samples (provided by LAVES Oldenburg) Page 16 of 16