气相色谱-质谱联用检测农药制剂中8种有机溶剂类助剂的含量及市场样品筛查
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摘要
建立了农药制剂中甲醇、甲苯、乙苯、邻二甲苯、对二甲苯、间二甲苯、N,N-二甲基甲酰胺(DMF)和二甲基亚砜(DMSO) 8种有机溶剂类助剂的气相色谱-质谱联用(GC-MS)测定方法,并运用该方法对市售的206种液体农药制剂进行了检测,获得市售农药制剂中目标助剂的含量。农药制剂经乙腈稀释10 000倍后,在选择离子监测(SIM)模式下测定,8种助剂的质量浓度与对应的峰面积间线性相关性良好,r为0.999 2～0.999 8;8种助剂在100～1 000 mg/kg添加水平下,回收率为76%～116%,相对标准偏差(RSD)均小于17%;8种助剂的定量限(LOQ)在100～500 mg/kg之间。对206种市售液体农药制剂的筛查结果表明:8种助剂的检出率在0.5%～31.1%之间,超标率在7.2%～14.5%之间,液体农药制剂中苯类溶剂使用量较高。该方法可为农药加工、管理和助剂限量标准制定提供依据,农药制剂中有毒溶剂的使用应引起生产企业和农药管理部门的重视。
An analytical method was developed to simultaneously determine inert ingredients, such asmethanol, toluene, ethylbenzene, O-xylene, para-xylene, meta-xylene, N, N-dimethylformamide(DMF) and dimethyl sulfoxide(DMSO) in pesticide formulations using gas chromatography-mass spectrometry. The method was applied to the detection of inert ingredients in 206 commercial liquid pesticide formulations. The pesticide formulations were diluted 10 000 times by acetonitrile, and the target inert ingredients were detected in selective ion monitor(SIM) mode. The linearity of 8 inert ingredients ranged from 0.999 2 to 0.999 8. The recoveries were between 76% to 116%, with the relative standard deviations(RSD) were lower than 17% at the spiked level of 100-1 000 mg/kg. The limits of quantitations(LOQ) were 100-500 mg/kg. The level of inert ingredients ranged from 0.5%-31.1% in 206 commercial liquid pesticide products. The content of inert ingredients in 7.2%-14.5% of the pesticide products were higher than the proposed maximum residue limits. High application rates of benzene organic solvents were detected in liquid pesticide formulations. This new method could supply reference for pesticide production, pesticide administration and fixation of maximum residue limits. Our results indicated that the usage of the harmful organic solvent in pesticides production was a noteworthy problem.
An analytical method was developed to simultaneously determine inert ingredients, such asmethanol, toluene, ethylbenzene, O-xylene, para-xylene, meta-xylene, N, N-dimethylformamide(DMF) and dimethyl sulfoxide(DMSO) in pesticide formulations using gas chromatography-mass spectrometry. The method was applied to the detection of inert ingredients in 206 commercial liquid pesticide formulations. The pesticide formulations were diluted 10 000 times by acetonitrile, and the target inert ingredients were detected in selective ion monitor(SIM) mode. The linearity of 8 inert ingredients ranged from 0.999 2 to 0.999 8. The recoveries were between 76% to 116%, with the relative standard deviations(RSD) were lower than 17% at the spiked level of 100-1 000 mg/kg. The limits of quantitations(LOQ) were 100-500 mg/kg. The level of inert ingredients ranged from 0.5%-31.1% in 206 commercial liquid pesticide products. The content of inert ingredients in 7.2%-14.5% of the pesticide products were higher than the proposed maximum residue limits. High application rates of benzene organic solvents were detected in liquid pesticide formulations. This new method could supply reference for pesticide production, pesticide administration and fixation of maximum residue limits. Our results indicated that the usage of the harmful organic solvent in pesticides production was a noteworthy problem.
引文
[1]刘占山,柏连阳,王义成,等.农药制剂中助剂安全性探讨及管理建议[J].农药科学与管理,2009,30(8):21-25.LIU Z S,BAI L Y,WANG Y C,et al.Discussion on safety of adjuvants in pesticide preparations and management suggestions[J].Pestic Sci Adm,2009,30(8):21-25.
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[10]王素利,董见南,吴厚斌,等.甲苯和二甲苯农药溶剂助剂分析[J].农药,2009,48(12):894-895.WANG S L,DONG J N,WU H B,et al.Analytical method for toluene and xylene adjuvant in pesticide formulation[J].Agrochemicals,2009,48(12):894-895.
[11]董见南,王素利,刘丰茂,等.农药乳油中7种助剂的顶空气相色谱测定方法[J].农药学学报,2012,14(2):208-213.DONG J N,WANG S L,LIU F M,et al.Analysis of seven adjuvants in emulsifiable concentrate with headspace gas chromatography[J].Chin J Pestic Sci,2012,14(2):208-213.
[12]夏丽娟,高立明,许艳秋,等.液体农药制剂中甲醇含量的检测[J].农药科学与管理,2011,32(6):40-44.XIA L J,GAO L M,XU Y Q,et al.Analysis of methanol in liquid pesticide formulation[J].Pestic Sci Adm,2011,32(6):40-44.
[13]江华,曹立冬,孔令娥,等.顶空气相色谱法检测农药乳油制剂中甲醇含量[J].农药学学报,2012,14(1):56-60.JIANG H,CAO L D,KONG L E,et al.Determination of methanol in pesticide emulsifiable concentrate by headspace gas chromatography[J].Chin J Pestic Sci,2012,14(1):56-60.
[14]唐祥凯,冯德建,史谢飞,等.农药制剂中39种有机溶剂的气相色谱-质谱测定方法研究[J].中国测试,2017,43(2):42-46.TANG X K,FENG D J,SHI X F,et al.Study on the determination of39 kinds of organic solvents in pesticide products by GC-MS[J].China Meas Test,2017,43(2):42-46.
[15]农药产品质量分析方法确认指南:NY/T2887-2016[EB/OL](2016-05-23)[2016-10-01].http://www.moa.gov.cn/gk/tzgg_1/gg/201605/t20160524_5148229.htm.Guidelines on vilidation of analytical Analysis methods for agrochemicals:NY/T2887-2016[EB/OL](2016-05-23)[2016-10-01].http://www.moa.gov.cn/gk/tzgg_1/gg/201605/t20160524_5148229.htm.
[16]佚名.农业部农药检定所《关于征求〈农药助剂禁限用名单〉(征求意见稿)意见的通知》[J].中国食品,2015(15):135.Anonymous.Notice of Institute for the Control of Agrochemicals on the opinions on soliciting the list of prohibited restrictions on pesticide adjuvants(the draft for consultation)[J].Chin Food,2015(15):135.
[2]任晓东,吴厚斌,王以燕.台湾地区农药产品中有机溶剂的管理[J].农药科学与管理,2007,25(3):48-49.REN X D,WU H B,WANG Y Y.Management of organic solvents in pesticide products in Taiwan[J].Pestic Sci Adm,2007,25(3):48-49.
[3]卜元卿,王昝畅,智勇,等.农药制剂中助剂使用状况调研及风险分析[J].农药,2014,53(12):932-936.BU Y Q,WANG Z C,ZHI Y,et al.Investigation and risk analysis of pesticide inert ingredients in pesticide products[J].Agrochemicals,2014,53(12):932-936.
[4]卜元卿,王昝畅,智勇,等.368种农药制剂中助剂使用状况调查研究[C]//2014中国环境科学学会学术年会论文集.成都:中国环境科学学会,2014:1-8.BU Y Q,WANG Z C,ZHI Y,et al.Investigation on the use of auxiliaries in 368 pesticide formulations[C]//Proceedings of China Society of Environmental Sciences Academic Annual Meeting.Chengdu:Chinese Society for Environmental Sciences,2014:1-8.
[5]马立利,吴厚斌,刘丰茂.农药助剂及其危害与管理[J].农药,2008,47(9):637-640.MA L L,WU H B,LIU F M.The development,hazards and management of pesticide adjuvants[J].Agrochemicals,2008,47(9):637-640.
[6]吴志凤,刘绍仁.加拿大对农药助剂的管理[J].农药科学与管理,2006,27(2):50-53.WU Z F,LIU S R.Management of pesticide adjuvants in Canada[J].Pestic Sci Adm,2006,27(2):50-53.
[7]中华人民共和国工业和信息化部公告工原[2009]第29号[J].中国农药,2009(2):45.Announcement of the ministry of industry and information technology of the People's Republic of China,Gongyuan[2009]No.29[J].J China Agrochem,2009(2):45.
[8]农药乳油中有害溶剂限量:HG/T 4576-2013[S].北京:化学工业出版社,2014.Limit of harmful solvents of emulsifiable concentrate pesticide:HG/T4576-2013[S].Beijing:Chemical Industry Press,2014.
[9]刘亚静,赵鹏,曹立冬,等.农药乳油中有害溶剂检测与方法优化[J].农药科学与管理,2015,36(7):29-34.LIU Y J,ZHAO P,CAO L D,et al.Determination of harmful solvents and method optimization in pesticides emulsifiable concentrate formulation[J].Pestic Sci Adm,2015,36(7):29-34.
[10]王素利,董见南,吴厚斌,等.甲苯和二甲苯农药溶剂助剂分析[J].农药,2009,48(12):894-895.WANG S L,DONG J N,WU H B,et al.Analytical method for toluene and xylene adjuvant in pesticide formulation[J].Agrochemicals,2009,48(12):894-895.
[11]董见南,王素利,刘丰茂,等.农药乳油中7种助剂的顶空气相色谱测定方法[J].农药学学报,2012,14(2):208-213.DONG J N,WANG S L,LIU F M,et al.Analysis of seven adjuvants in emulsifiable concentrate with headspace gas chromatography[J].Chin J Pestic Sci,2012,14(2):208-213.
[12]夏丽娟,高立明,许艳秋,等.液体农药制剂中甲醇含量的检测[J].农药科学与管理,2011,32(6):40-44.XIA L J,GAO L M,XU Y Q,et al.Analysis of methanol in liquid pesticide formulation[J].Pestic Sci Adm,2011,32(6):40-44.
[13]江华,曹立冬,孔令娥,等.顶空气相色谱法检测农药乳油制剂中甲醇含量[J].农药学学报,2012,14(1):56-60.JIANG H,CAO L D,KONG L E,et al.Determination of methanol in pesticide emulsifiable concentrate by headspace gas chromatography[J].Chin J Pestic Sci,2012,14(1):56-60.
[14]唐祥凯,冯德建,史谢飞,等.农药制剂中39种有机溶剂的气相色谱-质谱测定方法研究[J].中国测试,2017,43(2):42-46.TANG X K,FENG D J,SHI X F,et al.Study on the determination of39 kinds of organic solvents in pesticide products by GC-MS[J].China Meas Test,2017,43(2):42-46.
[15]农药产品质量分析方法确认指南:NY/T2887-2016[EB/OL](2016-05-23)[2016-10-01].http://www.moa.gov.cn/gk/tzgg_1/gg/201605/t20160524_5148229.htm.Guidelines on vilidation of analytical Analysis methods for agrochemicals:NY/T2887-2016[EB/OL](2016-05-23)[2016-10-01].http://www.moa.gov.cn/gk/tzgg_1/gg/201605/t20160524_5148229.htm.
[16]佚名.农业部农药检定所《关于征求〈农药助剂禁限用名单〉(征求意见稿)意见的通知》[J].中国食品,2015(15):135.Anonymous.Notice of Institute for the Control of Agrochemicals on the opinions on soliciting the list of prohibited restrictions on pesticide adjuvants(the draft for consultation)[J].Chin Food,2015(15):135.
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