CCS-SP-156 茶叶中290种农药残留组分--Accucore aQ

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泊街冉
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1 FENXI CESHI XUEBAO Journal of Instrumental Analysis Vol. 32 No. 1 9 ~ * * QuEChERS N- PSA Thermo Accucore aq 100 mm 2. 1 mm 2. 6 μm MRM ~ 200 μg L MRL 2MRL 4MRL % ~ 119% LOQ S /N μg kg QuEChERS O TQ doi /j. issn A Determination of 290 Pesticide Residues in Tea by High Performance Liquid Chromatography - Tandem Mass Spectrometry JIA Wei 1 2 HUANG Jun-rong 1* LING Yun 2 FENG Feng 2 ZHENG Yue-ming 2 CHU Xiao-gang 2* 1. College of Life Science and Engineering Shaanxi University of Science and Technology Xi'an China 2. Chinese Academy of Inspection and Quarantine Beijing China Abstract A simple and rapid method was developed for the simultaneous determination of 290 pesticide residues in tea. The sample was prepared by the modified QuEChERS quick easy cheap effective rugged and safe method extracted with acetonitrile followed by liquid - liquid partitioning formed by adding sodium chloride and anhydrous magnesium sulfate. The extract was separated on a Thermo Accucore aq 100 mm 2. 1 mm 2. 6 μm column detected by high performance liquid chromatography - tandem mass spectrometry under multiple reaction monitoring mode and quantified by the external standard method. The calibration curves of 290 pesticide residues were linear in the range of μg L - 1 with correlation coefficients more than The recoveries for all compounds in tea at the fortified levels of 1MRL 2MRL and 4MRL were 67% - 119%. The limits of quantitation LOQs S /N 10 for 290 pesticides were less than μg kg - 1. The established method was successfully used for the screening and determination of real samples such as green tea black tea oolong tea and pu er tea bought at supermarket. The method was simple rapid and reliable and could meet the requirement for simultaneous determination of 290 pesticide residues in tea. Key words high performance liquid chromatography - tandem mass spectrometry QuEChERS pesticide residues tea CAC BAK10B * Tel E - mail xgangchu@ 163. com Tel E - mail huangjunrong2000@ 163. com

2 10 32 MRL ~ ~ ~ mg /kg mg /kg 1 ELISA 2 GC GC - MS 5-7 HPLC 8 - LC - MS LC - MS /MS ELISA GC HPLC GC - MS LC - MS - LC - MS /MS LC - MS /MS QuEChERS Oringinal AOAC CEN QuECh- ERS QuEChERS TSQ Quantum Ultra - Thermo Fisher Scientific Avnti J - 26 PI Beckman Coulter Vortex. Genie2T Scientific Industries Yamata SA μm Pall Caliper HPLC Thermo Fisher Scientific C 18 N- PSA 40 ~ 60 μm 100 GCB 40 ~ 120 μm Supelco h Sigma Sigma Milli-Q 290 Dr. Ehrenstorfer mg /L ml 15 ml μg /L μl 5 ml 5 8 mmol /L μg /L Accucore aq 100 mm 2. 1 mm 2. 6 μm Accucore C mm 2. 1 mm 2. 6 μm Thermo Fisher Scientific 35 A 0. 1% - 4 mmol /L B 0. 1% - 4 mmol /L 0 ~ 1 min 100% A 1 ~ 35 min 100% ~ 0% A 35 ~ 40 min 0% A 40 ~ min 0% ~ 100% A ~ 45 min

3 % A 300 μl /min % 0. 2 Pa 10 μl kpa 3 L / min V V Tube lens 152 V Skimmer 20 V s EZ MRM mm 10 g g 50 ml 20 ml 30 min 20 ml 1% g 30 s 6. 0 g 1. 5 g 30 s 5 min r / min 5 min 10 ml 75 mg GCB 400 mg PSA 1. 2 g 30 s 0. 7 ml 30 s r /min 5 min μm 200 μl 300 μl 500 μl 8 mmol /L DMSA 90 70% 130% ESI + ESI MRM Thermo Scientific Accucore 2. 6 μm Accucore RP - MS C 18 aq 3 HPLC 100 mm 2. 1 mm 2. 6 μm 290 Accucore aq Parathion Fenitrothion Dimethoate Schradan Dioxacarb Mefenacet Fig. 1 Chromatographic response of 6 pesticides in different mobile phases

4 % - 4 mmol /L 0. 1% - 4 mmol /L μg /L Fig. 2 Total ion current chromatograms of 290 pesticides standard at 20 μg / L prepared in oolong tea A. standard solution prepared with the solvent B. matrix-matched standard solution min g 6. 0 g 10 μg /L Mefenacet Ethoprophos Fenamidone Cumyluron Dipropetryn Azoxystrobin 6 3

5 PSA 18 ph 2003 Oringinal AOAC CEN g 3 2 QuEChERS 10 μg /L 1% AOAC n = g 1. 0 g Fig. 3 Comparison of recoveries of two versions of QuEChERS sample preparation method for oolong tea CEN Oringinal 10 μg /L samples spiked with 10 μg /L pesticides n = 7 Para- thion Fenitrothion Dimethoate Schradan Dioxacarb Carbendazim 6 4 ph 5. 0 ~ QuEChERS 10 μg /L ph n = ~ Fig. 4 Comparison of recoveries of three versions of QuEChERS sample preparation method for oolong tea samples spiked with 10 μg /L pesticides n = Oringinal AOAC CEN C 18 GCB C 18 C mg C 18 C μg /L Mefenacet Ethoprophos Fenamidone Cumyluron Dipropetryn Azoxystrobin QuEChERS 10 μg /L 5 n = 7 Fig. 5 Comparison of recoveries of two versions of C 18 QuEChERS sample preparation method for oolong tea samples spiked with 10 μg /L pesticides n = 7 CEN

6 14 32 GCB GCB PSA GCB 10 ml mg GCB 30 s r /min 5 min 75 mg GCB GCB 6 6 GCB Fig. 6 Influence of toluene volume used in purification on recoveries of 8 pesticides Ethoprophos Azaconazole Fenbuconazole Tebufenpyrad Carbofuran Pyrimethanil GCB 75 mg GCB 10 μg /L ml GCB Dichlorvos Fenuron 10 ml 75 mg GCB 400 mg PSA 1. 2 g 30 s 0. 7 ml 2003 Oringinal AOAC CEN PSA QuEChERS = 1 - / 100% % 2. 5% 79. 3% 20 μg /L s 1 ~ 9 María μg /L y x μg /L r ~ 200 μg /L S /N mg /kg CAC MRL mg /kg % ~ 119% 7

7 % MRL mg /kg r 2 n = 7 Table 1 Retention times mass spectrometric parameters correlation coefficients r 2 recoveries and precisions of 290 pesticides n = 7 No. Pesticide Linear range Spiked t R Transition Recovery RSD CE /ev ρ / μg r 2 w / mg /min m /z R 珔 /% s L - 1 kg - 1 r /% 1 Aldicarb sulfoxide / * / ~ Methamidophos /94. 0 * / ~ Omethoate / * / ~ Pymetrozine / * / ~ Acephate / * / ~ Cyromazine /85. 2 * / ~ Fonophos / * / ~ Dinotefuran / * / ~ Aminocarb / * / ~ Propamocarb / * / ~ Methomyl / * / ~ Carbendazim / * / ~ Nitenpyram / * / ~ Thiabendazole / * / ~ Thiamethoxam / * / ~ Mexacarbate / * / ~ Dicrotophos / * / ~ Dichlorvos / * / / ~ Fuberidazole / * / / ~ Fenuron /72. 1 * / ~ Clothianidin / * / ~ Diamidafos / * /95. 2 * ~ Vamidothion / * / ~ Ethidimuron / * / ~ Mevinphos / * / ~ Carbofuran-3-hydroxy / * / ~ Phorate /75. 1 * / ~ Imidacloprid / * / ~ Bendiocarb / * / ~ Dioxacarb / * / ~ Dimethoate / * / ~ Schradan / * / ~ / Dimetilan /72. 2 * / ~ Butoxycarboxin /86. 2 * / ~ Pirimicarb / * / ~ Monocrotophos / * / ~ Acetamiprid / * / ~ Acibenzolar-S-methyl / * ~ S / Ethirimol / * / ~ Tricyclazole / * / ~ Thiacloprid / * / ~ Matoxuron /72. 2 * / ~ Allidochlor /98. 2 * / / ~ Pyroquilon / * / ~ / Tebuthiuron / * / ~

8 No. Pesticide Linear range Spiked t R Transition Recovery RSD CE /ev ρ / μg r 2 w / mg /min m /z R 珔 /% s L - 1 kg - 1 r /% 46 Carbetamide / * / ~ Oxamyl /72. 1 * / ~ Fenpiclonil / * / ~ Hexazinone / * / ~ / Simazine / * / ~ Chlorpropham / * / ~ Desmetryn / * / ~ / Simetryne / * / ~ Octhilinone / * / ~ / Flucarbazone / * / ~ Thidiazuron / * / ~ Metribuzin / * / ~ Mephospholan / * / ~ / Oxadixyl / * / ~ Ancymidol / * / ~ / Cyanazine / * / ~ Imazaquin / * / / ~ Azamethiphos / * / / ~ Prometon / * / ~ Secbumeton / * / ~ Bentazone / * / ~ Thiophanate methyl / * / ~ Propoxur / * / ~ Diphenylamine / * / ~ / Terbumeton / * / ~ Bufencarb /77. 2 * / ~ Carbofuran / * / ~ Methabenzhiazuron / * / ~ Pyracarbolid / * / ~ Florasulam / * / ~ Imazapyr / * / ~ Zoxamide / * / ~ Flumetsulam / * / ~ Fenthion sulfone / * / ~ Mefluidide / * / ~ / Pyrosulam / * / ~ Fenthion sulfoxide / * / ~ Chlortoluron / * / ~ Ametryn / * / ~ Methoprotryne / * / ~ Fluometuron /72. 1 * / ~ Cycluron /89. 1 * / ~ Ethiofencarb / * / ~ Forchlorfenuron / * / ~ Pyrimethanil / * / ~ Ethaboxam / * / ~ Flutriafol /70. 1 * / ~

9 No. Pesticide Linear range Spiked t R Transition Recovery RSD CE /ev ρ / μg r w / mg /min m /z R /% s L - 1 kg - 1 r /% 94 Isoproturon /72. 0 * / ~ Metalaxyl / * / ~ Diuron /72. 0 * / ~ Azaconazole / * / / ~ Diazinon oxon / * / ~ Metosulam / * / ~ Isoprocarb / * / ~ Norflurazon / * / ~ Imazamox / * / ~ Atrazine / * / ~ Azafenidrin / * / / ~ Terbufos sulfone / * / ~ / Propachlor / * / ~ / Metazachlor / * / ~ Demeton-O /89. 1 * / ~ Demeton-S /89. 3 * / ~ Pyrifenox /93. 1 * / / ~ Flonicamid / * / ~ Prothoate /97. 0 * / ~ Carbary / * / ~ Ethoxyquin / * / ~ Diphenamid / * / / ~ Nuarimol / * / ~ Amicarbazone /85. 2 * / ~ Prometryn / * / ~ Penoxsulam / * / ~ Propanil / * / ~ Imazalil / * / ~ Chlorantraniliprole / * / ~ Terbutryn / * / ~ Coumaphos oxon / * / / ~ Siduron / * / ~ Paclobutrazole /70. 0 * / ~ Triadimenol /70. 0 * / ~ Fensulfothion / * / ~ Clofentezine / * / ~ Furalaxyl /95. 0 * / ~ Cyproconazole / * / ~ Fenitrothion / * / ~ Triticonazole /70. 0 * / ~ Desmedipham / * / ~ Phenmedipham / * / ~ Benthiavalicarb / * / ~ Butocarboxin /91. 4 * / ~ Promecarb / / * ~ Isofenfos O-analog / * / ~ Spirotetramat / * / ~ Carpropamid / * / / ~

10 No. Pesticide t R /min Transition m /z 142 Fludioxonil / * / / Halofenozide / * / / Dimethametryn / * Linear range Spiked Recovery RSD CE /ev ρ / μg r w / mg R /% s L - 1 kg - 1 r /% ~ ~ / ~ Iprovalicarb / * / ~ Diclobutrazol / * / ~ Etaconazole / * / ~ Fenamiphos / * / ~ Uniconazole /70. 2 * / ~ Parathion / * / ~ Mefenacet / * / ~ Ethoprophos /97. 1 * / ~ Fenamidone / * / ~ Cumyluron / * / ~ / Dipropetryn / * / ~ / Azoxystrobin / * / ~ Profenophos / * / / ~ Salflufenacil / * / ~ Tepraloxydim / * / ~ Epoxiconazole / * / ~ Triadimefon / * / ~ Daimuron / * / ~ / Di-allate / * / ~ / Propazine / * / ~ Bromuconazole / * / ~ / Mepanipyrim / * / ~ Pyridaphenthion / * / ~ Napropamide / * / ~ Fenamiphos sulfone / * / ~ Tebuconazole /70. 2 * / ~ Asulam / * / ~ Mandipropamid / * / ~ Bupirimate / * / ~ Tebupirimfos / * / ~ Tetraconazole / * / ~ Ethalfluralin / * / ~ Isoxaben / * / ~ Dodemorph / * / / ~ Demeton S methyl /61. 3 * / ~ Isoprothiolane / * / ~ Mepronil / * / ~ Metolachlor / * / ~ / Phorate sulfone /94. 1 * / ~ Metobromuron / * / ~ Bifenazate / * / ~ Penconazole / * / ~ Flusiazole / * / ~ Prothioconazole / * / ~ Nitrothal isopropyl / * / ~

11 No. Pesticide Linear range Spiked t R Transition Recovery RSD CE /ev ρ / μg r w / mg /min m /z R /% s L - 1 kg - 1 r /% 190 Fenbuconazole / * / ~ Metconazole /70. 1 * / ~ Isoxathion / * / ~ / Isozophos /97. 0 * / ~ Triazophos / * / ~ Prochloraz / * / ~ Propiconazole / * / ~ Flutolanil / * / ~ Benodanil / * / ~ / EPTC / * / ~ Rotenone / * / ~ Dimoxystrobin / * / ~ Pinoxaden / * / ~ Phosmet / * / ~ Neburon /57. 2 * / ~ Ethion monoxon / * / ~ Ditalimfos / * / ~ Fluoxastrobin / * / ~ Fenpropimorph / * / ~ Spiroxamine / * / ~ Benalaxyl / * / ~ Diniconazole / * / ~ Propetamphos / * / ~ Fluquinconazole / * / ~ Quinalphos / * / ~ / Tebufenozide / * / ~ Ipconazole /70. 2 * / ~ Difenoconazole / * / ~ Etrimfos / * / ~ Chlorbromuron / * / ~ / Cadusafos / * / ~ Flubendiamide / * / / ~ Pyraclofos / * / / ~ Naphthol / * / ~ Anilofos / * / ~ / Orbencarb / * / / ~ Methacrifos /79. 2 * / / ~ Triflumizole / * / ~ Diazinon / * / ~ Isocarbophos / * / ~ Vernolate / * / / ~ Pirimiphos methyl / * / ~ Thiazopyr / * / ~ Crotoxyphos / * / ~ Tetramethrin / * / / ~ Dimethylvinphos /99. 1 * / ~

12 No. Pesticide Linear range Spiked t R Transition Recovery RSD CE /ev ρ / μg r w / mg /min m /z R /% s L - 1 kg - 1 r /% 236 Pencycuron / * / ~ Dimepiperate / * / ~ / Isofenfos / * / ~ Teflubenzuron / * / ~ Pretilachlor / * / ~ Flumioxazin / * / ~ / Piperophos / * / ~ / Hexaflumuron / * / ~ Buprofezin / * / ~ Haloxyfop methyl / * / ~ / Imibenconazole / * / ~ Tebufenpyrad / * / ~ Ethofumesate / * / ~ Bromadiolone / * / ~ / Spinosyn A / * / ~ Quinoxyfen / * / ~ Clethodim / * / ~ Isocarbamid / * / ~ Tolfenpyrad / * / ~ Trifloxystrobin / * / ~ Novaluron / * / ~ Piperonyl butoxide / * / ~ Sethoxydim / * / ~ Esprocarb /91. 0 * / ~ Alachlor / * / ~ Furathiocarb / * / ~ Tralkoxydim / * / ~ Pyriproxyfen /96. 0 * / ~ Spinosyn D / * / ~ Linuron / * / ~ Lufenuron / * / ~ Emamectin B1b / * / ~ B1b 268 Phorate oxon sulfone /97. 0 * / ~ / Tridemorph / * / ~ Pirimiphos ethyl / * / ~ Metaflumizone / * / ~ / Fluazinam / * / ~ Noviflumuron / * / ~ Fenazaquin /57. 2 * / ~ Warfarin / * / ~ Fenpyroximate / * / ~ Etoxazole / * / ~ Emamectin / * / ~ Eprinomectin B1a / * / ~ B1a 280 Sulfuramid / * / ~ /269. 1

13 No. Pesticide t R /min Transition m /z 281 Spinetoram / * / / Pyridaben / * 283 DEF / * 284 Dichlorfenthion / * Linear range Spiked Recovery RSD CE /ev ρ / μg r 2 w / mg R 珔 /% s L - 1 kg - 1 r /% ~ / ~ / ~ / ~ Hexaconazole / * / ~ Brodifacoum / * / ~ Phenothrin / * / / ~ Ivermectin B1a B1a / * / ~ Pyridate / * / ~ Allethrin /91. 2 * / ~ / * quantitation ion **represents the analytes were detected under the negative electrospray ionization ESI - mode rest of analytes were detected under the positive electrospray ionization ESI + mode Acetamiprid Methamidophos 28 μg /kg 37 μg /kg 1 Imidacloprid Thiamethoxam 12 μg /kg 19 μg /kg 1 Acephate Dimethoate Omethoate Triazophos Phosmet Triadimefon Buprofezin Isocarbophos Quinalphos Pyridaben Imidacloprid μg / kg HPLC - MS /MS QuEChERS 290 Thermo Fisher Scientific James Chang Jia Wang 1 General Administration of Quality Supervision Inspection and Quarantine of the People s Republic of China. Pesticide Residue Limits http / /www. tbtsps. com / FOODSAFE /XLBZ /Pages /pesticide. aspx. 2 Nuria S Bego a V Berta B Marco M. Talanta Flaviane A S Anna I G C Maria E L R Q Reinaldo F T Ant nio A N Gevany P P. Food Chem Liu D Min S G. J. Chromatogr. A Chen L ShangGuan L M Wu Y Y Xu L J Fu F F. Food Control Li B Zeng F G Dong Q C Cao Y Fan H T Deng C F. Phys. Procedia Milagros M Angeles M Amadeo R. J. Chromatogr Virginia P Elena D Bezhan C Antonio L Maria G Maria L M. J. Chromatogr. A Claudia O Wolfgang S. J. Chromatogr. A Emilia F Anna S. J. Chromatogr. B Oscar N Héctor G Imma F Encarnación M Maria T G. J. Chromatogr. A László P Juan F G R Péter F Attila G Mihály D László A Bienvenida G Antonio M. J. Chromatogr. A

14 Zhu W X Yang J Z Liu Y F Wei W. J. Instrum. Anal Xu J Chen J Ye H Y Wang L Sun L H Lai Z F. J. Instrum. Anal Anastassiades M Lehotay S J Stajnbaher D Schenck F J. J. AOAC Int Lehotay S J Kateřina M Alan R L. J. AOAC Int Anastassiades M. pren Determination of Pesticide Residues Using GC - MS and /or LC - MS /MS Following Acetonitrile Extraction / Ppartitioning and Ccleanup by Dispersive SPE - QuEChERS Method. European Commitee for Standardization. 18 Lehotay S J. J. AOAC Int Anastasios E Helen B Spyros A Despina T. J. Chromatogr. A María L G P Patricia P B Roberto R G José L M V Antonia G F. J. Chromatogr. A 櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏櫏 CN /TH CODEN FCEXES BM 6013 ISSN % 70% CA 94% 2006 CA 38 AA CAJCED CJFD / http / /www. fxcsxb. com E - mail china. com

衛生福利部國家中醫藥研究所編制表職稱官等職等員額備考所長簡任第十二職等一本職稱之官等職等及必要時得比照專科以上學校校長之資格聘任, 均為組織法律所定副所長

衛生福利部國家中醫藥研究所編制表職稱官等職等員額備考所長簡任第十二職等一本職稱之官等職等及必要時得比照專科以上學校校長之資格聘任, 均為組織法律所定副所長衛生勞動篇法規衛生福利部令中華民國 103 年 9 月 12 日衛部人字第 1032261172 號修正衛生福利部國家中醫藥研究所編制表, 並自中華民國一百零二年七月二十三日生效附修正衛生福利部國家中醫藥研究所編制表部長邱文達 33927