农药乳油中有害溶剂检测与方法优化
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摘要
为了提高生产质控效率,建立并优化了两种农药乳油中甲醇、苯、甲苯、N,N-二甲基甲酰胺、乙苯、二甲苯和萘7种有害溶剂含量的气相色谱分析方法。以正癸烷为内标,采用Agilent DB-5毛细管柱和SE-54毛细管柱分离,氢火焰离子化检测器(FID)测定。结果表明:以Agilent DB-5毛细管柱和SE-54毛细管柱的检测方法分别在4.7~14.1mg/L和3.07~47.26mg/L范围内线性良好,相关系数均>0.998,检测周期分别为19.25min和14.5min,相对标准偏差(RSD)均<1.19%,这7种有害溶剂的回收率在90.19%~97.37%之间。这两种方法简单快速准确,可为农药乳油生产中7种有害溶剂的检测提供参考。
In order to improve the efficiency of production quality control, two gas chromatography methodsfor the determination of seven harmful solvents, includingmethanol, benzene,toluene, N,N-dimethyl formamide, ethybenzene, xyleneand naphthalene in pesticides emulsifiable concentrate(EC) formulation were established and optimized. Decane was used as internal standard(IS). Capillary column Agilent DB-5 and SE-54 were used as separation columns and flame ionization detector( FID) as detector. The results showed that two methods, which used capillary columns Agilent DB-5 and SE-54 as separation columns respectively, had good linear relationships at the concentration ranges 4.7~14.1mg/L and 3.07~47.26 mg/L, respectively. The correlation coefficients were all above 0.998 and the detection periods were 19.25 min and 14.5min, respectively. The relative standard deviations( RSD) were all less than 1.19%.The recovery rates of seven harmful solvents ranged from 90.19% to 97.37%. These two methods were simple, quick and accurate, which provided reference for the determination of seven harmful solvents in pesticides emulsifiable concentrate formulation.
In order to improve the efficiency of production quality control, two gas chromatography methodsfor the determination of seven harmful solvents, includingmethanol, benzene,toluene, N,N-dimethyl formamide, ethybenzene, xyleneand naphthalene in pesticides emulsifiable concentrate(EC) formulation were established and optimized. Decane was used as internal standard(IS). Capillary column Agilent DB-5 and SE-54 were used as separation columns and flame ionization detector( FID) as detector. The results showed that two methods, which used capillary columns Agilent DB-5 and SE-54 as separation columns respectively, had good linear relationships at the concentration ranges 4.7~14.1mg/L and 3.07~47.26 mg/L, respectively. The correlation coefficients were all above 0.998 and the detection periods were 19.25 min and 14.5min, respectively. The relative standard deviations( RSD) were all less than 1.19%.The recovery rates of seven harmful solvents ranged from 90.19% to 97.37%. These two methods were simple, quick and accurate, which provided reference for the determination of seven harmful solvents in pesticides emulsifiable concentrate formulation.
引文
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[2]王小芬,张树来,李厚勇,等.二甲苯对雌性动物生殖系统毒性作用的实验研究[J].职业医学,1996(5):51-52.
[3]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.
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[5]Sales J A,Cardeal Z D L.Headspace solid-phase microextraction gas chromatography method for the determination of methanol in aspartame sweeteners[J].Food Addit Contam,2003,20(6):519-523.
[6]Cao L,Jiang H,Yang J,et al.Simultaneous Determination of Benzene and Toluene in Pesticide Emulsifiable Concentrate by Headspace GC-MS[J].J Anal Methods Chem,2013,2013:1-5.
[7]冷阳.理顺思路把握导向,推进乳油中溶剂的更新换代[J].今日农药,2014(6):26-29.
[8]Inert Ingredients in Pesticide Products Policy Statement,“U.S.52 Federal Register(FR)Notice 13305,”1987,http://www.epa.gov/opprd001/inerts/fr52.htm.
[9]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.
[10]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,2007,28(3):48-49.
[11]汪建沃.农药乳油中有害溶剂限量标准的实施及对策[J].农药市场信息,2014,12:18.
[12]Ezquerro O,Ortiz G,Pons B,et al.Determination of benzene,toluene,ethylbenzene and xylenes in soils by multiple headspace solid-phase microextraction[J].J Chromatogr A,2004,1035(1):17-22.
[13]Esteve-Turrillas F A,Armenta S,Garrigues S,et al.Headspace-mass spectrometry determination of benzene,toluene and the mixture of ethylbenzene and xylene isomers in soil samples using chemometrics[J].Anal Chim Acta,2007,587(1):89-96.
[14]Eisert R,Levsen K.Solid-phase microextraction coupled to gas chromatography:a new method for the analysis of organics in water[J].J Chromatogr A,1996,733(1-2):143-157.
[15]Ju H K,Park J H,Kwon S W.Evaluation of headspacegas chromatography/mass spectrometry for the analysis of benzene in vitamin C drinks;pitfalls of headspace in benzene detection[J].Biomed Chromatogr,22(8):900-905.
[16]Liu H,Tang Q,Markovich R J,et al.A general static-headspace gas chromatographic method for determination of residual benzene in oral liquid pharmaceutical products[J].J Pharmaceut Biomed,54(2):417-421.
[17]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.
[18]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.
[19]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.
[20]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.[21][H]GPH 5-1,化学药物质量控制分析方法验证技术指导原则[S].
[22]HG/T 4576-2013,农药乳油有害溶剂限量[S].
[2]王小芬,张树来,李厚勇,等.二甲苯对雌性动物生殖系统毒性作用的实验研究[J].职业医学,1996(5):51-52.
[3]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.
[4]Upham J,Acott P D,O’Regan P,et al.The pesticide adjuvant,Toximul,alters hepatic metabolism through effects on downstream targets of PPARα[J].Biochimica et Biophysica Acta(BBA)-Molecular Basis of Disease,2007,1772(9):1057-1064.
[5]Sales J A,Cardeal Z D L.Headspace solid-phase microextraction gas chromatography method for the determination of methanol in aspartame sweeteners[J].Food Addit Contam,2003,20(6):519-523.
[6]Cao L,Jiang H,Yang J,et al.Simultaneous Determination of Benzene and Toluene in Pesticide Emulsifiable Concentrate by Headspace GC-MS[J].J Anal Methods Chem,2013,2013:1-5.
[7]冷阳.理顺思路把握导向,推进乳油中溶剂的更新换代[J].今日农药,2014(6):26-29.
[8]Inert Ingredients in Pesticide Products Policy Statement,“U.S.52 Federal Register(FR)Notice 13305,”1987,http://www.epa.gov/opprd001/inerts/fr52.htm.
[9]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.
[10]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,2007,28(3):48-49.
[11]汪建沃.农药乳油中有害溶剂限量标准的实施及对策[J].农药市场信息,2014,12:18.
[12]Ezquerro O,Ortiz G,Pons B,et al.Determination of benzene,toluene,ethylbenzene and xylenes in soils by multiple headspace solid-phase microextraction[J].J Chromatogr A,2004,1035(1):17-22.
[13]Esteve-Turrillas F A,Armenta S,Garrigues S,et al.Headspace-mass spectrometry determination of benzene,toluene and the mixture of ethylbenzene and xylene isomers in soil samples using chemometrics[J].Anal Chim Acta,2007,587(1):89-96.
[14]Eisert R,Levsen K.Solid-phase microextraction coupled to gas chromatography:a new method for the analysis of organics in water[J].J Chromatogr A,1996,733(1-2):143-157.
[15]Ju H K,Park J H,Kwon S W.Evaluation of headspacegas chromatography/mass spectrometry for the analysis of benzene in vitamin C drinks;pitfalls of headspace in benzene detection[J].Biomed Chromatogr,22(8):900-905.
[16]Liu H,Tang Q,Markovich R J,et al.A general static-headspace gas chromatographic method for determination of residual benzene in oral liquid pharmaceutical products[J].J Pharmaceut Biomed,54(2):417-421.
[17]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.
[18]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.
[19]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.
[20]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.[21][H]GPH 5-1,化学药物质量控制分析方法验证技术指导原则[S].
[22]HG/T 4576-2013,农药乳油有害溶剂限量[S].