Laboratory Performance Assessment. Spring Report. Test Material B

Transcription

1 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

2 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 % recovery criteria. The results for Prochloraz are withdrawn from the % assessment.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

3 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 Chlorfenapyr Dichlorvos Emamectin Methomyl

4 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 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

5 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 ). 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 % 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

6 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 : yes yes 2 n.r yes 5 n.r no yes yes yes yes yes yes 14 n.r yes yes yes yes yes yes yes ,7 5 yes 64 97,7 5 yes yes yes yes 72 5 yes ,7 10 yes 79 93,6 10 yes yes yes yes no yes yes 36 n.r yes yes yes yes yes yes yes 49 n.r no 52 n.r yes yes 84 90,3 5 yes yes yes yes yes yes no yes yes ,8 10 yes 78 97,5 10 yes yes yes yes yes yes yes 68 n.r no 69 n.r yes yes no n.r. = not reported Table 1: Results for Biphenyl and Chlorfenapyr in Basil Purée Test Material B Page 6 of 16

7 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 : yes yes no yes ,1 10 no no yes 162, yes no yes no yes yes yes no yes yes yes yes yes ,6 5 yes yes yes yes no yes ,4 10 yes ,4 10 yes no yes no no no yes ,5 10 yes ,6 10 yes yes yes yes yes yes yes 49 n.r yes yes yes ,7 5 yes yes yes yes yes yes yes no no n.r ,2 10 yes ,8 10 yes no yes yes yes no yes 68 n.r no 69 n.r yes yes yes n.r. = not reported Table 2: Results for Dichlorvos and Emamectin in Basil Purée Test Material B Page 7 of 16

8 laboratory code result Methomyl spiked level: 450 µg/kg recovery (%) LOQ accepted range : result Prochloraz spiked level: 240 µg/kg recovery (%) LOQ yes yes yes , yes yes yes yes yes yes yes yes , yes yes ,2 10 yes , yes no yes ,6 10 yes 87 98, yes yes yes yes yes yes 95 89, yes yes n.r yes ,2 10 no , yes yes 84* yes no yes yes 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

9 Biphenyl % spiked level 50 spiked level 40 result 30 70% spiked level laboratory code Figure 1: Assessment of Biphenyl (spiked level: 45 µg/kg) in Basil Purée Test Material B Page 9 of 16

10 Chlorfenapyr result % spiked level spiked level 60 70% spiked level laboratory code Figure 2: Assessment of Chlorfenapyr (spiked level: 80 µg/kg) in Basil Purée Test Material B Page 10 of 16

11 Dichlorvos 120% spiked level spiked level 30 result % spiked level laboratory code Figure 3: Assessment of Dichlorvos (spiked level: 35 µg/kg) in Basil Purée Test Material B Page 11 of 16

12 Emamectin result % spiked level spiked level 70% spiked level laboratory code Figure 4: Assessment of Emamectin (spiked level: 167 µg/kg) in Basil Purée Test Material B Page 12 of 16

13 Methomyl result % spiked level spiked level 70% spiked level laboratory code Figure 5: Assessment of Methomyl (spiked level: 450 µg/kg) in Basil Purée Test Material B Page 13 of 16

14 Prochloraz result spiked level laboratory code Figure 6: Reported levels of Prochloraz (spiked level: 240 µg/kg) in Basil Purée Test Material B Page 14 of 16

15 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.: [mg/kg] TM B Nr.: TM B Nr.: Variation TM B Nr.: % TM B Nr.: TM B Nr.: Recovery TM B Nr.: % TM B Nr.: TM B Nr.: Spiked level TM B Nr.: [mg/kg] Mean [mg/kg] Chlorfenapyr Test Material 1st extraction 2nd extraction Mean Standard deviation TM B Nr.: [mg/kg] TM B Nr.: TM B Nr.: Variation TM B Nr.: % TM B Nr.: TM B Nr.: Recovery TM B Nr.: % TM B Nr.: TM B Nr.: Spiked level TM B Nr.: [mg/kg] Mean [mg/kg] Dichlorvos Test Material 1st extraction 2nd extraction Mean [mg/kg] [mg/kg] [mg/kg] Standard deviation TM B Nr.: mg/kg TM B Nr.: TM B Nr.: Variation TM B Nr.: % TM B Nr.: TM B Nr.: Recovery TM B Nr.: % TM B Nr.: TM B Nr.: Spiked level TM B Nr.: mg/kg Mean [mg/kg] Table 5a: Homogeneity Data for Basil Homogenate Samples (provided by LAVES Oldenburg) Page 15 of 16

16 Emamectin benzoate Test Material 1st extraction 2nd extraction Mean [mg/kg] [mg/kg] [mg/kg] Standard deviation TM B Nr.: mg/kg TM B Nr.: TM B Nr.: Variation TM B Nr.: % TM B Nr.: TM B Nr.: Recovery TM B Nr.: % TM B Nr.: TM B Nr.: Spiked level TM B Nr.: mg/kg Mean [mg/kg] Methomyl Test Material 1st extraction 2nd extraction Mean [mg/kg] [mg/kg] [mg/kg] Standard deviation TM B Nr.: [mg/kg] TM B Nr.: TM B Nr.: Variation TM B Nr.: % TM B Nr.: TM B Nr.: Recovery TM B Nr.: % TM B Nr.: TM B Nr.: Spiked level TM B Nr.: [mg/kg] Mean [mg/kg] Prochloraz Test Material 1st extraction 2nd extraction Mean [mg/kg] [mg/kg] [mg/kg] Standard deviation TM B Nr.: [mg/kg] TM B Nr.: TM B Nr.: Variation TM B Nr.: % TM B Nr.: TM B Nr.: Recovery TM B Nr.: % TM B Nr.: TM B Nr.: Spiked level TM B Nr.: [mg/kg] Mean [mg/kg] Table 5b: Homogeneity Data for Basil Homogenate Samples (provided by LAVES Oldenburg) Page 16 of 16