气相色谱-质谱法测定水体中乙酰甲胺磷和甲胺磷残留量
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摘要
目的建立气相色谱-质谱法(gas chromatography-mass spectrometry,GC-MS)同时检测乙酰甲胺磷和甲胺磷的残留量。方法通过正交试验优化并确定升温程序参数,利用液液萃取方法从水中提取乙酰甲胺磷及甲胺磷后,采用基质匹配标准溶液对两种农药的回收率进行校准。结果升温程序应采用一阶程序升温,初始温度为95℃,升温速度为10℃/min,末温为280℃;进样口采用惰性衬管;添加水平为0.1~1 mg/L时,回收率在80.3%~110.5%之间,相对标准偏差在5.5%~6.5%之间。乙酰甲胺磷和甲胺磷在用纯溶剂(丙酮)和空白基质配制0.01~0.5 mg/L浓度范围内线性关系良好(r~2>0.999),乙酰甲胺磷和甲胺磷的检出限分别为0.02mg/L、0.008 mg/L,定量检测分别为0.066 mg/L、0.027 mg/L。结论该方法的精密性、重复性和稳定性良好,可适用于乙酰甲胺磷和甲胺磷残留量的检测。
Objective To establish a method for detection of acephate and methamidophos by gas chromatography-mass spectrometry(GC-MS). Methods The temperature program of GC was optimized and determined by orthogonal experiment, and pesticides were extracted from aqueous solution by liquid-liquid extraction. In addition, the recovery rates of extraction from aqueous solution were corrected by matrix-matched standard calibration. Results The temperature program used first order temperature programming as follows: the temperature of column was from 95 ℃ to 280 ℃ at a speed of 10 ℃/min,. The inert liner was inert. Under the optimized conditions, the average recoveries of the method ranged from 80.3% to 110.5% at the spiked levels of 0.1~1 mg/L with the relative standard deviations of 5.5%~6.5%. Acephate and methamidophos had good linear relationship in the range of 0.01~0.5 mg/L(r~2>0.999), the limits of detection(LODs) were 0.02 mg/L and 0.008 mg/L, and the limits of quantitation(LOQs) were 0.066 mg/L and 0.027 mg/L for acephate and methamidophos, respectively. Conclusion The established method had good precision, repeatability and stability, which can be applied to the detection of acephate and methamidophos.
Objective To establish a method for detection of acephate and methamidophos by gas chromatography-mass spectrometry(GC-MS). Methods The temperature program of GC was optimized and determined by orthogonal experiment, and pesticides were extracted from aqueous solution by liquid-liquid extraction. In addition, the recovery rates of extraction from aqueous solution were corrected by matrix-matched standard calibration. Results The temperature program used first order temperature programming as follows: the temperature of column was from 95 ℃ to 280 ℃ at a speed of 10 ℃/min,. The inert liner was inert. Under the optimized conditions, the average recoveries of the method ranged from 80.3% to 110.5% at the spiked levels of 0.1~1 mg/L with the relative standard deviations of 5.5%~6.5%. Acephate and methamidophos had good linear relationship in the range of 0.01~0.5 mg/L(r~2>0.999), the limits of detection(LODs) were 0.02 mg/L and 0.008 mg/L, and the limits of quantitation(LOQs) were 0.066 mg/L and 0.027 mg/L for acephate and methamidophos, respectively. Conclusion The established method had good precision, repeatability and stability, which can be applied to the detection of acephate and methamidophos.
引文
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[9]王玲.乙酰甲胺磷农药的高效液相色谱法测定[J].宁夏农林科技,2011,52(12):231?232.Wang L.Determination of acephate pesticides by high performance liquid chromatography[J].Ningxia J Agric Fores Sci Tech,2011,52(12):231?232.
[10]姚陆铭,刘燕红,武天龙.乙酰甲胺磷在扁豆中残留的研究[J].农药科学与管理,2012,33(11):29?32.Yao LM.Liu YH,Wu TL.Residue analysis of acephate in lablab purpureus[J].Pest Sci Admin,2012,33(11):29?32.
[11]张水坝,易军,叶江雷,等.气相色谱法测定茶叶中的噻嗪酮、甲胺磷、乙酰甲胺磷及三唑磷残留[J].色谱,2004,22(02):154?157.Zhang SB,Yi J,Ye JL,et al.Determination of buprofezin,methamidophos,acephate,and triazophos residues in chinese tea samples by gas chromatography[J].Chin J Chromatogr,2004,22(02):154?157.
[12]贺敏,铁柏清,戴荣彩,等.青油菜中乙酰甲胺磷、甲胺磷残留量的GC/MS分析[J].农药,2008,47(02):122?124.He M,Tie BQ,Dai RC,et al.Residue analysis method of acephate and methamidophos in rape plants by GC/MS[J].Agrochemicals,2008,47(02):122?124.
[13]刘瑞江,张业旺,闻崇炜,等.正交试验设计和分析方法研究[J].实验技术与管理,2010,9(27):52?55.Liu RJ,Zhang YW,Wen CW,et al.Study on the design and analysis methods of orthogonal experiment[J].Exp Technol Manag,2010,9(27):52?55.
[14]刘虎威.气相色谱方法及应用[M].北京:化学工业出版社,2000.Liu HW.The method and application of gas chromatography[M].Beijing:Chemical Industry Press,2000.
[15]冯丽丽,胡晓芳,于晓娟,等.气相色谱法测定有机磷农药残留的常见问题探讨[J].环境监测管理与技术,2013,25(03):47?50.Feng LL,Hu XF,Wang XJ,et al.Research on some problems in determination of organophosphorus pesticideby gas chrom-atography[J].Admin Tech Environ Monit,2013,35(03):47?50.
[16]黄宝勇,欧阳喜辉,潘灿平.色谱法测定农产品中农药残留时的基质效应[J].农药学学报,2005,7(04):299?305.Huang BY,Ouyyang CH,Pan CP.Matrix effects in the analysis of pesticide residue in agro-products by chromatographic methods[J].Chin J Pest Sci,2005,7(04):299?305.
[17]HajslováJ,ZrostlíkováJ.Matrix effects in(ultra)trace analysis of pesticide residues in food and biotic matrices[J].J Chromatogr A,2003,1000(1-2):181-197.
[2]洪文英,吴燕君,王道泽,等.乙酰甲胺磷及其高毒代谢物甲胺磷在白菜中的残留动态[J].农业环境科学学报,2011,30(5):860?866.Hong WY,WU YJ,Wang DZ,et al.Residue dynamics of acephate and its metabolite methamidophos in cabbage[J].J Agro-Environ Sci,2011,30(5):860?866.
[3]Wang X,Li Z,Zhang H,et al.Environmental behavior of the chiral organophosphorus insecticide a and its chiral metabolite methamidophos:enantioselective transformation and degradation in soils[J].Environ Sci Technol,2013,47(16):9233.
[4]张慧涵,朱光艳,汪清,等.土壤中乙酰甲胺磷向番茄果实中的转运代谢与积累[J].安徽农业大学学报,2014,41(05):892?894.Zhang HH,Zhu GY,Wang Q,et al.Absorption,transport,metabolism and accumulation of acephate from soil to tomato[J].J Anhui Agric Univ,2014,41(05):892?894.
[5]陈恩祥,周艳琳,陈新来,等.乙酰甲胺磷在辣椒上的残留消解动态研究[J].安徽农业科学,2014,42(29):10177?10178.Chen AX,Zhou YL,Chen XL,et al.Residues degradation dynamics of acephate in pepper[J].J Anhui Agric Sci,2014,42(29):10177?10178.
[6]沈群超,胡仕孟,胡寅侠,等.不同剂型的乙酰甲胺磷在小白菜中的残留动态研究[J].农学学报,2014,4(09):33?36.Shen QC,Hu SM,Hu YX,et al.Residue dynamics about acephate of different formulations in cabbage[J].J Agric,2014,4(09):33?36
[7]沈群超,吴华新,胡寅侠,等.乙酰甲胺磷在豇豆上安全使用的研究[J].江西农业学报,2014,26(06):46?48.Shen QC,Wu HX,Hu YX,et al.Safety evaluation of acephate in cowpea[J].Acta Agric Jiangxi,2014,26(06):46?48.
[8]刘莉,袁名安,王艳,等.乙酰甲胺磷乳油热稳定性及甲胺磷的消解动态[J].浙江农业科学,2014,1(12):1804?1806.Li L,Yuan MA,Wang Y,et al.The thermostability of acephate emulsifiable concentrates and the dissipation dynamics of methamidophos[J].J Zhejiang Agric Sci,2014,1(12):1804?1806.
[9]王玲.乙酰甲胺磷农药的高效液相色谱法测定[J].宁夏农林科技,2011,52(12):231?232.Wang L.Determination of acephate pesticides by high performance liquid chromatography[J].Ningxia J Agric Fores Sci Tech,2011,52(12):231?232.
[10]姚陆铭,刘燕红,武天龙.乙酰甲胺磷在扁豆中残留的研究[J].农药科学与管理,2012,33(11):29?32.Yao LM.Liu YH,Wu TL.Residue analysis of acephate in lablab purpureus[J].Pest Sci Admin,2012,33(11):29?32.
[11]张水坝,易军,叶江雷,等.气相色谱法测定茶叶中的噻嗪酮、甲胺磷、乙酰甲胺磷及三唑磷残留[J].色谱,2004,22(02):154?157.Zhang SB,Yi J,Ye JL,et al.Determination of buprofezin,methamidophos,acephate,and triazophos residues in chinese tea samples by gas chromatography[J].Chin J Chromatogr,2004,22(02):154?157.
[12]贺敏,铁柏清,戴荣彩,等.青油菜中乙酰甲胺磷、甲胺磷残留量的GC/MS分析[J].农药,2008,47(02):122?124.He M,Tie BQ,Dai RC,et al.Residue analysis method of acephate and methamidophos in rape plants by GC/MS[J].Agrochemicals,2008,47(02):122?124.
[13]刘瑞江,张业旺,闻崇炜,等.正交试验设计和分析方法研究[J].实验技术与管理,2010,9(27):52?55.Liu RJ,Zhang YW,Wen CW,et al.Study on the design and analysis methods of orthogonal experiment[J].Exp Technol Manag,2010,9(27):52?55.
[14]刘虎威.气相色谱方法及应用[M].北京:化学工业出版社,2000.Liu HW.The method and application of gas chromatography[M].Beijing:Chemical Industry Press,2000.
[15]冯丽丽,胡晓芳,于晓娟,等.气相色谱法测定有机磷农药残留的常见问题探讨[J].环境监测管理与技术,2013,25(03):47?50.Feng LL,Hu XF,Wang XJ,et al.Research on some problems in determination of organophosphorus pesticideby gas chrom-atography[J].Admin Tech Environ Monit,2013,35(03):47?50.
[16]黄宝勇,欧阳喜辉,潘灿平.色谱法测定农产品中农药残留时的基质效应[J].农药学学报,2005,7(04):299?305.Huang BY,Ouyyang CH,Pan CP.Matrix effects in the analysis of pesticide residue in agro-products by chromatographic methods[J].Chin J Pest Sci,2005,7(04):299?305.
[17]HajslováJ,ZrostlíkováJ.Matrix effects in(ultra)trace analysis of pesticide residues in food and biotic matrices[J].J Chromatogr A,2003,1000(1-2):181-197.