Hajeb, Parvaneh

Herrmann, Susan Strange

Poulsen, Mette Erecius

Online Research Database In Technology

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Downloaded from orbit.dtu.dk on: Nov 09, 2017Expansion of cereal multi residue method with pesticides planned for review underregulation No 396/2005 Article 12Herrmann, Susan Strange; Hajeb, Parvaneh; Poulsen, Mette EreciusPublication date:2016Document VersionPublisher's PDF, also known as Version of recordLink back to DTU OrbitCitation (APA):Herrmann, S. S., Hajeb, P., & Poulsen, M. E. (2016). Expansion of cereal multi residue method with pesticidesplanned for review under regulation No 396/2005 Article 12. Poster session presented at 11th EuropeanPesticide Residue Workshop, Limassol, Cyprus.Expansion of cereal multi residue method with pesticides planned for review under regulation No 396/2005 Article 12 Herrmann, S.S., Hajeb, P. and Poulsen, M.E. National Food Institute, Technical University of Denmark, Mørkhøj Bygade 19, DK-2860 Søborg, Denmark. e-mail : sher@food.dtu.dk        Introduction MS Chromatogram of flour stored at -20°C (red) and room temperature (green)  Add 10 ml acetonitrile and shake vigorously by hand for 1 min. (1. extraction) Add 4 g MgSO4, 1 g NaCl, 1 g Na3 citrate dihydrate and 0.5 g Na2H citrate sesquihydrate. Shake vigorously for 1 min. (2. Extraction with phase separation).  Centrifuge for 10 min at 4500 rpm. Store 8 ml of the supernatant in the freezer  (-80˚C for 1 hour or over night).  Centrifuge for 5 min. while extract is cold at 4500 rpm.  Take aliquot of supernatant for LC-MS/MS analysis with out clean-up. Clean-up by transferring 6 ml of the supernatant to a tube containing  150 mg PSA and 900 mg MgSO4.  Close the tube and shake vigorously for 30 seconds.  Centrifuge for 5 min. at 4500 rpm.  Shake 5 g (±0.05 g) of flour, 10 g of cold water and a  ceramic homogenizer briefly by hand Extraction method  Withdraw 4 ml of the supernatant and pH adjust  with 40 µl 5% formic acid in acetonitrile Dilute the extract 1:1 with acetonitrile in the auto sampler vial  Conclusion Validation results   Spike level mg/kg 0.01 LC-MS/MS with PSA clean-up no clean-up LOQ  Recovery %  RSDr      %  RSDR     %  Recovery %  RSDr      %  RSDR     %  w. cleanup/ no cleanup 6-benzylaminopurine / 6-benzyladenine 85 6 6 85 6 6 0.01 Amisulbrom (+GC) 97 40 44 93 18 19 n.a./0.01 Carbetamide  (+GC) 112 6 6 104 6 6 0.01 Cyflufenamide (+GC) 109 6 6 103 7 9 0.01 Difenacoum 112 9 29 96 11 10 0.02/0.01 Ethirimol 85 5 9 91 6 6 0.01 Fenpyrazamine  (+GC) 106 7 11 98 8 10 0.01 Novaluron (+GC) 102 10 13 106 12 11 0.01 Penoxsulam 98 9 8 109 7 8 0.01 Profoxydim 88 26 26 82 19 20 0.02/0.01 Propaquizafop (+GC) 101 5 6 94 10 10 0.01 Pyridalyl (+GC) 78 12 19 20 73 147 0.01/n.a. Quizalofop  (free acid) 43 19 52 107 8 9 n.a./0.01 Spinetoram 111 7 8 98 8 11 0.01 Spirotetramat cis-enol 66 11 62 119 7 7 n.a./0.01 Spirotetramat cis-keto-hydroxy  (+GC) 104 8 10 105 7 7 0.01 Spirotetramat enol-glucoside 75 11 14 90 10 12 0.01 Spirotetramat mono-hydroxy 104 7 9 105 6 6 0.01 Tembotrione 91 15 16 111 12 11 0.01 Thiencarbazone-methyl (+GC) 107 12 11 107 8 7 0.01 Triazoxide 100 18 19 90 18 17 0.01 Triflusulfuron-methyl (+GC) 99 6 10 111 7 6 0.01               Mean (accepted only) 98 9 11 100 9 10 Maksimum  (accepted only) 112 18 19 119 19 20 Minimum  (accepted only) 75 5 6 82 6 6   Spike level mg/kg 0.01 Spike level mg/kg 0.02 GC-MS/MS with PSA clean-up with PSA clean-up  Recovery %  RSDr      %  RSDR     %  Recovery %  RSDr      %  RSDR     % LOQ (mg/kg) Amisulbrom  (+LC wo. clean-up) 94 16 16 96 13 12 0.01 Cyflufenamide (+LC) 112 8 8 105 5 5 0.01 Fenpyrazamine (+LC) 107 10 16 108 7 12 0.01 Novaluron (+LC) 87 14 24 85 12 18 0.01 Propaquizafop (+LC) 93 8 20 99 9 20 0.01 Pyridalyl (+LC w. clean-up) 80 7 32 82 11 24 0.02 Spirotetramat cis-keto-hydroxy (+LC) 106 31 29 110 11 15 0.02 Thiencarbazone-methyl (+LC) 83 22 22 81 15 14 0.01 Triflusulfuron-methyl (+LC) 87 16 28 91 8 11 0.02 Article 12 in Regulation No. 396/2005 states that assessment of existing MRLs should be performed by the Authority within a period of 12 months from the date of the inclusion or non-inclusion of an active substance in Annex I to Directive 91/414/EEC. All compounds included in the present validation are included in the so called MRL progress list, which lists the active compounds coming up for review under article 12 in Regulation No. 396/2005. In connection with the review, information on the availability of methods for enforcement, availability of standards and achievable LOQs are needed. In order to obtain this information the present validation work was performed.  Validation, of the 22 pesticides or metabolites of pesticides, was performed on oat, rye and wheat samples spiked with 0.01, 0.02 and 0.1 mg/kg using QuEChERS extraction according to CEN method 15662 for dry matrices. Though extracts were withdrawn prior to dSPE in order to determine if specific analytes were adsorbed by the PSA.  Analyse by LC-MS/MS and/or GC-MS/MS  All 22 analytes were LC-MS/MS amenable, and 9 also GC-MS/MS amenable. Using the QuEChERS CEN method 15662 for cereals, including the dSPE with PSA, 17 analytes were validated at 0.01 mg/kg using LC-MS/MS.   If the results for oat were excluded the RSDr and RSDR would for several analytes be reduced, e.g. for difenacoum (LC) and spirotetramat-keto-hydroxy (GC).  21 analytes were amenable to QuEChERS without dSPE clean-up and detection by LC-MS/MS. Only for pyridalyl were the inclusion of the dSPE step required. Excluding the dSPE step reduced the RSDR for several analytes considerately.  Extract of oat  EURL-CF: EU Reference Laboratory for pesticide Residues in Cereals and Feeding stuff, DTU National Food Institute, Moerkhoej Bygade 19, DK-2860 Soeborg, Denmark   e-mail :  eurl-cf@foood.dtu.dk,  www.eurl-pesticides.eu   

Expansion of cereal multi residue method with pesticides planned for review under regulation No 396/2005 Article 12

http://orbit.dtu.dk/ws/files/124123760/2016_Poster_Widening_of_multi_method_scope_final_corrected.pdf

Expansion of cereal multi residue method with pesticides planned for review under regulation No 396/2005 Article 12

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