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.
引文
[1]郭武棣.液体制剂[M].3版.北京:化学工业出版社,2004:96-99.
[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].