固相萃取-超高效液相色谱-串联质谱法测定美国进口水果中15种高风险农药及助剂残留
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摘要
建立了固相萃取-超高效液相色谱-串联质谱(SPE-UPLC-MS/MS)测定美国进口水果中15种高风险农药及助剂(乙酰甲胺磷、灭多威、噻虫嗪、噻菌、啶虫脒、西玛津、嘧霉胺、咯菌腈、啶酰菌胺、甲氧虫酰肼、腈菌唑、环酰菌胺、四氟醚唑、增效醚、毒死蜱)残留量的分析方法。样品经破壁机匀浆,乙腈涡旋提取,氨基固相萃取柱净化,岛津Shim-pack XRODS色谱柱分离(75 mm×2.0 mm,1.6μm)。采用电喷雾离子源多反应监测模式进行质谱检测,外标法定量。在0.001～0.5 mg/L范围内,15种农药及助剂的质量浓度与对应的峰面积间线性关系良好,R2≥0.999 5。以梨、葡萄和苹果3种基质为例验证了方法的准确度和精密度。结果表明:在0.005～0.5 mg/kg添加水平下,15种农药及助剂的平均回收率在80%～115%之间,相对标准偏差在5.5%～16%之间,定量限为0.005～0.01 mg/kg。该方法简便、快速、可靠,适用于同时测定水果中上述15种农药及助剂残留。
A method was developed for the quantative determination of 15 high-risk pesticide and adjuvant(acephate, methomyl, thiamethoxam, thiabendazole, acetamiprid,simazine, pyrimethanil,fludioxonil, boscalid, methoxyfenozide, myclobutanil, fenhexamid, tetraconazole, piperonyl butoxide,chlorpyrifos) residues by SPE-ultra performance liquid chromatography-tandem mass spectrometry(SPE-UPLC-MS/MS). The samples were homogenized, extracted with acetonitrile, and cleaned-up by amino solid phase extraction column. The separation was performed on a Shimadu Shim-pack XR-ODS column(75 mm × 2.0 mm, 1.6 μm). The compounds were identified by MS/MS and multiple reaction monitoring(MRM) mode, and quantified by external standard method. The linearities of 15 pesticides and adjuvants were in the concentration range of 0.001-0.5 mg/L, with the correlation coeffecients higher than 0.999 5. At the fortified levels from 0.005 mg/kg to 0.5 mg/kg in pear, grape and apple, the average recoveries of all 15 pesticides and adjuvants ranged from 80% to 115% with the relative standard deviations varied from 5.5% to 16%. The limits of quantification(LOQs) of the analytes were ranged from 0.005 to 0.01 mg/kg. This method is simple, rapid, accutate and therefore, suitable for the confirmation and quantification of the 15 pesticides and adjuvants in fruits.
A method was developed for the quantative determination of 15 high-risk pesticide and adjuvant(acephate, methomyl, thiamethoxam, thiabendazole, acetamiprid,simazine, pyrimethanil,fludioxonil, boscalid, methoxyfenozide, myclobutanil, fenhexamid, tetraconazole, piperonyl butoxide,chlorpyrifos) residues by SPE-ultra performance liquid chromatography-tandem mass spectrometry(SPE-UPLC-MS/MS). The samples were homogenized, extracted with acetonitrile, and cleaned-up by amino solid phase extraction column. The separation was performed on a Shimadu Shim-pack XR-ODS column(75 mm × 2.0 mm, 1.6 μm). The compounds were identified by MS/MS and multiple reaction monitoring(MRM) mode, and quantified by external standard method. The linearities of 15 pesticides and adjuvants were in the concentration range of 0.001-0.5 mg/L, with the correlation coeffecients higher than 0.999 5. At the fortified levels from 0.005 mg/kg to 0.5 mg/kg in pear, grape and apple, the average recoveries of all 15 pesticides and adjuvants ranged from 80% to 115% with the relative standard deviations varied from 5.5% to 16%. The limits of quantification(LOQs) of the analytes were ranged from 0.005 to 0.01 mg/kg. This method is simple, rapid, accutate and therefore, suitable for the confirmation and quantification of the 15 pesticides and adjuvants in fruits.
引文
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[10]食品安全国家标准蔬菜和水果中有机磷、有机磷、拟除虫菊酯和氨基甲酸酯类农药多残留的测定:NY/T 761—2008[S].北京:中国农业出版社,2008.National food safety standard-Pesticide multiresidue screen methods for determination of organophosphorus pesticides,organochlorine pesticides,pyrethroid pesticides and carbamate pesticides in vegetables and fruits:NY/T 761—2008[S].Beijing:China Agricultural Press,2008.
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[12]王纯强,钱永忠,章程辉,等.QuEChERS-超高效液相色谱-QDa质谱法快速测定白菜与油菜中15种氨基甲酸酯类农药及代谢物残留[J].农药学学报,2018,20(4):459-467.WANG C Q,QIAN Y Z,ZHANG C H,et al.Residue determination of 15 carbamates and their metabolites in Chinese cabages and pakchoi by QuEChERS-ultra high performance liquid chromatography-QDa mass spectrometry[J].Chin J Pestic Sci,2018,20(4):459-467.
[13]CHAMBERS E,WAGROWSKI-DIEHL D M,LU Z L,et al.Systematic and comprehensive strategy for reducing matrix effects in LC/MS/MS analyses[J].J Chromatogr B,2007,852(1-2):22-34.
[14]BOURDAT-DESCHAMPS M,LEANG S,BERNET N,et al.Multiresidue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry:Optimisation and matrix effects reduction by quick,easy,cheap,effective,rugged and safe extraction[J].J Chromatogr A,2014,1349:11-23.
[15]李福琴,石丽红,王飞,等.QuEChERS-液相色谱-串联质谱法同时检测土壤和柑橘中吡唑醚菌酯、甲基硫菌灵及其代谢物多菌灵的残留[J].色谱,2017,35(6):620-626.LI F Q,SHI L H,WANG F,et al.Simultaneous determination of pyraclostrobin and thiophanate-methyl and its metabolite carbendazim residues in soil and Citrus by QuEChERS-liquid chromatography-tandem mass spectrometry[J].Chin J Chromatogr,2017,35(6):620-626.
[16]卢平,李静,陈玉玲,等.芹菜中的乐果及氧乐果的LC-M S/MS测定方法及风险分析[J].贵州大学学报(自然科学版),2017,34(3):21-24.LU P,LI J,CHEN Y L,et al. Determination and risk assessment of dimethoate and its metabolite in celery using liquid chromatographytandem mass spectrometry[J].J Guizhou Univ(Nat Sci Ed),2017,34(3):21-24.
[17]农作物中农药残留试验准则:NY/T 788-2018[S].北京:中国农业出版社,2018.Guideline for the testing of pesticide residues in crops:NY/T788—2018[S].Beijing:China Agriculture Press,2018.
[18]食品安全国家标准食品中农药最大残留限量:GB 2763-2016[S].北京:中国标准出版社,2016.National food safety standard-Maximum residue limits for pesticides in food:GB 2763—2016[S].Beijing:Standards Press of China,2016.
[19]Code of Federal Regulations.Tolerances and exemptions from tolerances for pesticide chemicals in food[EB/OL].[2019-05-06].https://www.ecfr.gov/cgi-bin/retrieveECFR?gp=&SIDe305b8bc9ace c5 8cdbad03793e6fc2c0&mctrue&nsp40.26.1 80.c&rSUBPART&tyH TML
[2]孙佳佳.中国苹果进口贸易研究[D].杨凌:西北农林科技大学,2014.SUN J J.China apple import[D].Yangling:Northwest A&F University,2014.
[3]中国轻工业信息网.中国进口水果存在七大问题[EB/OL].(2006-03-09)[2018-04-27].http://news.21 food.cn/9/68378.html China Light Industry Information Network.There are seven majorproblems with imported fruits[EB/OL].(2006-03-09)[2018-04-27].http://news.21 food.cn/9/68378.html
[4]山东检验检疫局.警惕进境冷冻水果农药残留超标[EB/OL].(2011-08-30)[2018-04-27].http://www.foodmate.net/foodsafe/briefing/165480.html Shandong Inspection and Quarantine Bureau.Be wary of excessive pesticide residues in imported frozen fruits[EB/OL].(2011-08-30)[201 8-04-27].http://www.foodmate.net/foodsafe/brie fing/165480.html
[5]深圳特区报.泰国龙眼菲律宾香蕉检出农残超标[EB/OL].(2017-02-05)[2018-04-27].http://news.ifeng.com/a/20170205/5 0650460_O.shtml Shenzhen Daily.Pesticide residues in longgan from Thailand and bananas from Philippines exceed the standard[EB/OL].(2017-02-05)[20 18-04-27].http://news.ifeng.com/a/20170205/50650460_O.shtml
[6]陈丽,胡进.从中美水果贸易看中国水果产业存在的问题及对策[J]长江大学学报(自然科学版):农学卷,2009,6(1):88-90.CHEN L,HU J.Problems and countermeasures in the study of Chinese fruit industry from Sino-US fruit trade[J].J Yangtze Univ(Nat Sci Ed):Agric Sci Vol,2009,6(1):88-90.
[7]United States Department of Agriculture.Pesticide date program databases[DB/OL].[2018-12-20].https://www.ams.usda.gov/datasets/pdp/pdpdata
[8]食品安全国家标准水果和蔬菜中500种农药及相关化学品残留量的测定气相色谱-质谱法:GB 23200.8—2016[S].北京:中国标准出版社,2016.National food safety standard-Determination of 500 pesticides and related chemicals residues in fruits and vegetables gas chromatography-mass spectrometry:GB 23200.8—2016[S].Beijing:Standards Press of China,2016.
[9]食品安全国家标准水果和蔬菜中450种农药及相关化学品残留量的测定液相色谱-串联质谱法:GB/T 20769—2008[S].北京:中国标准出版社,2009.National food safety standard-Determination of 450 pesticides and related chemicals residues in fruits and vegetables-LC-MS-MS method:GB/T 20769—2008[S].Beijing:Standards Press of China,2009
[10]食品安全国家标准蔬菜和水果中有机磷、有机磷、拟除虫菊酯和氨基甲酸酯类农药多残留的测定:NY/T 761—2008[S].北京:中国农业出版社,2008.National food safety standard-Pesticide multiresidue screen methods for determination of organophosphorus pesticides,organochlorine pesticides,pyrethroid pesticides and carbamate pesticides in vegetables and fruits:NY/T 761—2008[S].Beijing:China Agricultural Press,2008.
[11]TAYLOR P J.Matrix effects:the Achilles heel of quantitative highperformance liquid chromatography-electrospray-tandem massspectrometry[J].Clin Biochem,2005,38(4):328-334.
[12]王纯强,钱永忠,章程辉,等.QuEChERS-超高效液相色谱-QDa质谱法快速测定白菜与油菜中15种氨基甲酸酯类农药及代谢物残留[J].农药学学报,2018,20(4):459-467.WANG C Q,QIAN Y Z,ZHANG C H,et al.Residue determination of 15 carbamates and their metabolites in Chinese cabages and pakchoi by QuEChERS-ultra high performance liquid chromatography-QDa mass spectrometry[J].Chin J Pestic Sci,2018,20(4):459-467.
[13]CHAMBERS E,WAGROWSKI-DIEHL D M,LU Z L,et al.Systematic and comprehensive strategy for reducing matrix effects in LC/MS/MS analyses[J].J Chromatogr B,2007,852(1-2):22-34.
[14]BOURDAT-DESCHAMPS M,LEANG S,BERNET N,et al.Multiresidue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry:Optimisation and matrix effects reduction by quick,easy,cheap,effective,rugged and safe extraction[J].J Chromatogr A,2014,1349:11-23.
[15]李福琴,石丽红,王飞,等.QuEChERS-液相色谱-串联质谱法同时检测土壤和柑橘中吡唑醚菌酯、甲基硫菌灵及其代谢物多菌灵的残留[J].色谱,2017,35(6):620-626.LI F Q,SHI L H,WANG F,et al.Simultaneous determination of pyraclostrobin and thiophanate-methyl and its metabolite carbendazim residues in soil and Citrus by QuEChERS-liquid chromatography-tandem mass spectrometry[J].Chin J Chromatogr,2017,35(6):620-626.
[16]卢平,李静,陈玉玲,等.芹菜中的乐果及氧乐果的LC-M S/MS测定方法及风险分析[J].贵州大学学报(自然科学版),2017,34(3):21-24.LU P,LI J,CHEN Y L,et al. Determination and risk assessment of dimethoate and its metabolite in celery using liquid chromatographytandem mass spectrometry[J].J Guizhou Univ(Nat Sci Ed),2017,34(3):21-24.
[17]农作物中农药残留试验准则:NY/T 788-2018[S].北京:中国农业出版社,2018.Guideline for the testing of pesticide residues in crops:NY/T788—2018[S].Beijing:China Agriculture Press,2018.
[18]食品安全国家标准食品中农药最大残留限量:GB 2763-2016[S].北京:中国标准出版社,2016.National food safety standard-Maximum residue limits for pesticides in food:GB 2763—2016[S].Beijing:Standards Press of China,2016.
[19]Code of Federal Regulations.Tolerances and exemptions from tolerances for pesticide chemicals in food[EB/OL].[2019-05-06].https://www.ecfr.gov/cgi-bin/retrieveECFR?gp=&SIDe305b8bc9ace c5 8cdbad03793e6fc2c0&mctrue&nsp40.26.1 80.c&rSUBPART&tyH TML