Laboratory Performance Assessment Spring 2015 QS Fachgesellschaft Obst-Gemüse-Kartoffeln GmbH Report Test Material A Pesticide Residues in Red Pepper Purée June 2015
Index of contents Page 1. Scope of proficiency testing (PT) 3 2. Test items and homogeneity 3 2.1 Summary of results of homogeneity testing 4 3. Requested testing parameters 5 4. Criteria of assessment and test items 5 5. Demonstration of the results 5 6. Remarks and comments 6 7. Results, tables and graphics 7.1 Summary 7.2 Rating of performance 7.3 Results of Acetamiprid 7.4 Results of Bupirimate 7.5 Results of Cyprodinil 7.6 Results of Flutriafol 7.7 Results of Pirimicarb-desmethyl 7.8 Results of Propamocarb 7.9 Results of Triadimenol 6 6 7 9 11 13 15 17 19 21 page 2 of 23
1. Scope of proficiency testing (PT) This proficiency testing was run by QS Fachgesellschaft Obst-Gemüse-Kartoffeln GmbH. This proficiency testing represents an ability test. It is used to be an external quality assurance and shows on each testing field the performance/ability of the laboratory. This report refers to the performance assessment of laboratories which analysed test material A. Each laboratory received a sample of red pepper puree with seven spiked pesticides. 30 participants reported results and were evaluated. The evaluation and reporting was subcontracted to DRRR GmbH. 2. Test items and homogeneity QS required three different materials in terms of spiked pesticides. Thus, the three test materials partly differed in the type of spiked pesticides as well as in the levels of spiked pesticides. Test material A was distributed to thirty (30) participants. The test material for this Performance Assessment was prepared by the GLP department of LUFA Speyer. The homogeneity tests were performed by the LAVES Oldenburg, Germany. The material was distributed into labelled bottles with at least 100 g in each. The bottles were stored at - 20 C in the dark until distribution. The following pesticides were spiked to give the approximate final concentrations: 50 μg/kg Acetamiprid, 70 μg/kg Bupirimate, 280 μg/kg Cyprodinil, 80 μg/kg Flutriafol, 80 μg/kg Pirimicarb-desmethyl, 240 μg/kg Propamocarb and 90 μg/kg Triadimenol. page 3 of 23
2.1 Summary of results of homogeneity testing The homogeneity test was carried out at all requested parameters to get information about the principal suitability of the material for this proficiency testing. If the standard deviation (s material) of the material homogeneity is smaller than 30 % of a test statistic the samples are classified as homogenous. The test statistic is usually calculated of all previous proficiency testings with this material type determining the relative mean standard deviation as well as Uex of the relative mean standard deviation of all previous proficiency testings with this material type. The relative values are referred to absolute values related to the actual value of the material and are added to obtain the test statistic. When this rule could not be followed it will be proved if the higher variance is usual for this material type. The test statistic for the evaluation of the homogeneity test of test material A was calculated with the results from this proficiency testing round (), because no previous proficiency testing data is available for the requested parameter matrix combination. The homogeneity test was carried out at 10 representative random samples in double determination acc. to ISO 13528 (Intern. Harmonised Protocol). The homogeneity tests are subcontracted by: LAVES Oldenburg, Germany In the following table the evaluation of the homogeneity test is shown: parameter spiked level [µg/kg] mean (homogeneity test) [µg/kg] recovery (homogeneity test) [%] standard deviation of the material homogeneity (s material ) [µg/kg] test statistic [µg/kg] evaluation of the homogeneity test (s material < 30 % test statistic) Acetamiprid 50 51 102 1 6 homogenous Bupirimate 70 74 106 1 10 homogenous Cyprodinil 280 287 103 2 37 homogenous Flutriafol 80 76 95 1 11 homogenous Pirimicarbdesmethyl 80 82 103 1 11 homogenous Propamocarb 240 240 100 5 31 homogenous Triadimenol 90 89 99 0 15 homogenous page 4 of 23
3. Requested testing parameters The participants were requested to report which pesticides the red pepper puree had been analysed for. The results had to be reported without consideration of the recovery. 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. The laboratories were requested to identify and quantify the following seven pesticides. Acetamiprid Bupirimate Cyprodinil Flutriafol Pirimicarb-desmethyl Propamocarb Triadimenol. 4. Criteria of assessment and test items The test materials for the 2015 Spring Laboratory Performance Assessment of QS Fachgesellschaft Obst-Gemüse-Kartoffeln GmbH were prepared by the GLP department of LUFA Speyer to provide individual test material tailored to QS needs. The performance assessment considers the following test criteria: No false negative results are reported (thus identification of all seven pesticides) No false positive results are reported Correct quantification of at least 5 pesticides related to the 70 % 120 % recovery criteria. Analytical results between 70 % and 120% of the spiked levels have been considered satisfying. 5. Demonstration of the results Each laboratory was given a number (laboratory code). A summarized evaluation of the laboratory performance is shown in table 1 to 3 according to the test criteria. The results of all participants analysing Test Material A are presented in tables 4 to 11. Each table follows a diagram with the individual results in ascending order. The diagrams include the spiked level and the accepted range of the respective pesticide. page 5 of 23
6. Remarks and comments The performance of laboratory 30 is rated as failed, because the results were not submitted within the deadline. 7. Results, tables and graphics 7.1 Summary Table 1: Summarized laboratory rating in test material A QS criteria number of participants percent of participants passed 23 77 failed 7 23 total 30 100 Table 2: Number of satisfactory participants in test material A QS criteria number of satisfactory participants number of participants satisfactory % all analyts identified 25 30 83 all analyts identified and reported in acceptable results 18 30 30 no false positive results 30 30 100 page 6 of 23
7.2 Rating of performance Table 3: Rating laboratory code criterion 1 all analytes identified criterion 2 number of acceptable results criterion 3 number of false positive results rating 1 yes 7 0 passed 2 no 6 0 failed 3 yes 7 0 passed 4 no 4 0 failed 5 yes 3 0 failed 6 yes 5 0 passed 7 yes 7 0 passed 8 yes 7 0 passed 9 yes 7 0 passed 10 no 2 0 failed 11 yes 7 0 passed 12 yes 7 0 passed 13 yes 5 0 passed 14 no 6 0 failed 15 yes 7 0 passed 16 yes 7 0 passed 17 yes 6 0 passed 18 yes 7 0 passed 19 yes 6 0 passed 20 yes 7 0 passed 21 yes 7 0 passed 22 yes 7 0 passed 23 yes 7 0 passed 24 yes 7 0 passed 25 no 6 0 failed 26 yes 7 0 passed 27 yes 7 0 passed 28 yes 5 0 passed 29 yes 7 0 passed 30 yes 5 0 failed page 7 of 23
Table 4: Number of satisfactory results in test material A analyte number of satisfactory results total number of correct identification satisfactory (%) Acetamiprid 25 29 86 Bupirimate 29 30 97 Cyprodinil 30 30 100 Flutriafol 26 29 90 Pirimicarb-desmethyl 26 27 96 Propamocarb 24 28 86 Triadimenol 25 29 86 page 8 of 23
7.3 Results of Acetamiprid Table 5: Results for Acetamiprid in test material A Acetamiprid - spiked level: 50 µg/kg laboratory code result (µg/kg) recovery (%) LoQ (µg/kg) accepted range (µg/kg): 35-60 1 51 100 10 yes 2 58 110 10 yes 3 54 97 10 yes 4 46 104 10 yes 5 63 89 5 no 6 56,4 88 10 yes 7 55 100 10 yes 8 55 105 10 yes 9 50 100 10 yes 10 25,38 90 10 no 11 48 99 10 yes 12 49 80 10 yes 13 62 107 10 no 14 52 90,3 10 yes 15 54 89 10 yes 16 47 97 5 yes 17 48 97 10 yes 18 48 87 5 yes 19 42 91 10 yes 20 57 95 10 yes 21 44 85 10 yes 22 48 95 5 yes 23 55,2 95 10 yes 24 54 83 10 yes 25 no 26 48 93 10 yes 27 46 108 10 yes 28 66 97 10 no 29 53 103 10 yes 30 46 114 10 yes page 9 of 23
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7.4 Results of Bupirimate Table 6: Results for Bupirimate in test material A Bupirimate - spiked level: 70 µg/kg laboratory code result (µg/kg) recovery (%) LoQ (µg/kg) accepted range (µg/kg): 49-84 1 76 100 10 yes 2 50 87 10 yes 3 70 98 10 yes 4 54 102 10 yes 5 70 85 5 yes 6 82,2 79 10 yes 7 74 100 10 yes 8 59 100 10 yes 9 55 96 10 yes 10 64,97 90 50 yes 11 65 97 10 yes 12 55 92 10 yes 13 87 100 10 no 14 53 94,2 10 yes 15 59 105,9 10 yes 16 60 93 5 yes 17 65 98 10 yes 18 60 84 10 yes 19 52 99 10 yes 20 72 95 10 yes 21 62 98 10 yes 22 65 95 10 yes 23 60,2 85 10 yes 24 60 90 10 yes 25 63 96 10 yes 26 65 90 10 yes 27 60 77 10 yes 28 81 88,7 10 yes 29 62 96 10 yes 30 58 94 10 yes page 11 of 23
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7.5 Results of Cyprodinil Table 7: Results for Cyprodinil in test material A Cyprodinil - spiked level: 280 µg/kg laboratory code result (µg/kg) recovery (%) LoQ (µg/kg) accepted range (µg/kg): 196-336 1 265 120 10 yes 2 206 106 10 yes 3 232 98 10 yes 4 216 105 10 yes 5 300 75 5 yes 6 300 85 10 yes 7 265 100 10 yes 8 245 97 10 yes 9 289 110 10 yes 10 259,73 90 50 yes 11 259 96 10 yes 12 226 94 10 yes 13 276 106 10 yes 14 220 99,5 10 yes 15 231 117,1 10 yes 16 219 91 5 yes 17 250 98 10 yes 18 240 90 5 yes 19 212 96 10 yes 20 300 95 10 yes 21 270 118 10 yes 22 240 95 10 yes 23 228,1 85 10 yes 24 278 103 10 yes 25 210 104 10 yes 26 268 104 10 yes 27 226 71 10 yes 28 287 80,6 10 yes 29 249 94 10 yes 30 281 42 10 yes page 13 of 23
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7.6 Results of Flutriafol Table 8: Results for Flutriafol in test material A Flutriafol - spiked level: 80 µg/kg laboratory code result (µg/kg) recovery (%) LoQ (µg/kg) accepted range (µg/kg): 56-96 1 73 100 10 yes 2 71 107 10 yes 3 90 98 10 yes 4 52 98 10 no 5 100 87 5 no 6 97,2 79 10 no 7 80 100 10 yes 8 82 97 10 yes 9 71 89 10 yes 10 no 11 78 98 10 yes 12 81 105 10 yes 13 88 109 10 yes 14 72 94,9 10 yes 15 59 111 10 yes 16 70 101 5 yes 17 75 98 10 yes 18 78 98 10 yes 19 67 95 10 yes 20 90 95 10 yes 21 76 105 10 yes 22 75 95 10 yes 23 83,5 83 10 yes 24 86 105 10 yes 25 75 91 10 yes 26 82 103 10 yes 27 61 72 10 yes 28 92 83 10 yes 29 73 95 10 yes 30 60 71 10 yes page 15 of 23
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7.7 Results of Pirimicarb-desmethyl Table 9: Results for Primicarb-desmethyl in test material A Pirimicarb-desmethyl - spiked level: 80 µg/kg laboratory code result (µg/kg) recovery (%) LoQ (µg/kg) accepted range (µg/kg): 56-96 1 74 100 10 yes 2 81 107 10 yes 3 78 94 10 yes 4 no 5 91 77 5 yes 6 96,4 70 10 yes 7 70 100 10 yes 8 80 99 10 yes 9 73 94 10 yes 10 no 11 74 96 10 yes 12 85 96 10 yes 13 96 97 10 yes 14 no 15 64 77,9 10 yes 16 72 100 5 yes 17 71 94 10 yes 18 72 103 5 yes 19 103 95 10 no 20 84 95 10 yes 21 93 71 10 yes 22 75 90 10 yes 23 68,3 85 10 yes 24 83 82 10 yes 25 72 88 10 yes 26 82 99 10 yes 27 76 73 10 yes 28 92 89,9 10 yes 29 79 93 10 yes 30 63 63 10 yes page 17 of 23
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7.8 Results of Propamocarb Table 10: Results for Propamocarb in test material A Propamocarb - spiked level: 240 µg/kg laboratory code result (µg/kg) recovery (%) LoQ (µg/kg) accepted range (µg/kg): 168-288 1 218 80 10 yes 2 no 3 205 81 10 yes 4 237 93 10 yes 5 290 73 5 no 6 290 90 10 no 7 202 100 10 yes 8 271 110 10 yes 9 243 75 10 yes 10 no 11 228 94,7 10 yes 12 245 87 10 yes 13 220 108 10 yes 14 229 79,6 10 yes 15 243 50,4 10 yes 16 225 93 5 yes 17 293 81 10 no 18 239 77 10 yes 19 240 87 10 yes 20 280 95 10 yes 21 242 72 10 yes 22 231 80 5 yes 23 263,1 80 10 yes 24 263 83 10 yes 25 220 90 10 yes 26 199 79 10 yes 27 237 100 10 yes 28 246 81,4 10 yes 29 188 82 10 yes 30 86 113 10 no page 19 of 23
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7.9 Results of Triadimenol Table 11: Results for Triadimenol in test material A Triadimenol - spiked level: 90 µg/kg laboratory code result (µg/kg) recovery (%) LoQ (µg/kg) accepted range (µg/kg): 63-108 1 84 90 10 yes 2 84 83 10 yes 3 101 97 10 yes 4 53 99 10 no 5 110 93 5 no 6 103 88 10 yes 7 90 100 10 yes 8 93 100 10 yes 9 79 86 10 yes 10 no 11 88 99 10 yes 12 72 95 10 yes 13 92 103 10 yes 14 72 82,1 10 yes 15 71 84 10 yes 16 71 105 5 yes 17 90 97 10 yes 18 84 93 5 yes 19 88 92 10 yes 20 102 95 10 yes 21 102 119 10 yes 22 84 95 10 yes 23 81,8 90 10 yes 24 96 89 10 yes 25 73 89 10 yes 26 85 92 10 yes 27 78 86 10 yes 28 115 90,2 10 no 29 85 93 10 yes 30 45 115 10 no page 21 of 23
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QS Fachgesellschaft Obst-Gemüse-Kartoffeln GmbH GF: Dr. H.-J. Nienhoff Schedestraße 1-3 53113 Bonn Tel +49 228 35068-0 Fax +49 228 35068-10 info@q-s.de www.q-s.de page 23 of 23