高效液相色谱法测定农药产品中非法添加的限制性农药氨基甲酸酯的含量
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摘要
农药样品0.400g于甲醇80mL中超声溶解10min。用甲醇定容其体积为100.0mL,分取部分溶液(约50mL),离心分离5min,取其上清液过0.45μm滤膜过滤,滤液供高效液相色谱法分析。选用Besil C18-B色谱柱为固定相,柱温为30℃,以不同比例的(A)水和(B)甲醇组成的混合液为流动相,以1mL·min~(-1)的流量进行梯度洗脱,使样品中添加的12种限制使用的氨基甲酸酯类农药完全分离;采用二极管阵列检测器,在波长215nm处检测。结果表明:12种氨基甲酸酯农药的浓度在5.0～100.0mg·L~(-1)内与其峰面积呈线性关系,检出限(3S/N)在0.1～0.2mg·kg~(-1)之间。以空白农药样品为基质,按标准加入法进行回收试验,回收率在97.2%～106%之间,测定值的相对标准偏差(n=6)在1.5%～3.8%之间。
Pesticide sample(0.400 g)was dissolved ultrasonically in 80 mL of methanol for 10 min,and the solution was diluted to 100.0 mL with methanol.An aliquot of the sample solution(ca.50 mL)was taken and centrifuged for 5 min.The supernatant was taken and filtered through a filtering membrane of 0.45μm.The filtrate was used for HPLC analysis.Besil C_(18)-B column was selected as stationary phase with column temperature at 30℃.Mixtures of(A)water and(B)methanol in various proportions were used as mobile phase in gradient elution with a flow rate of 1 mL·min~(-1),to effect a satisfactory separation of the 12 carbamates.UV-detection was made at the wavelength of 215 nm using diode array detector.As shown by the results,linear relationships between values of peak area and mass concentration of the 12 carbamate pesticides in the range of 5.0-100.0 mg·L~(-1),with detection limits(3 S/N)in the range of 0.1-0.2 mg·kg~(-1).Test for recovery by standard addition method was made using a blank pesticide sample as matrix,giving results in the range of 97.2%-106%,and RSDs(n=6)ranged from 1.5% to 3.8%.
Pesticide sample(0.400 g)was dissolved ultrasonically in 80 mL of methanol for 10 min,and the solution was diluted to 100.0 mL with methanol.An aliquot of the sample solution(ca.50 mL)was taken and centrifuged for 5 min.The supernatant was taken and filtered through a filtering membrane of 0.45μm.The filtrate was used for HPLC analysis.Besil C_(18)-B column was selected as stationary phase with column temperature at 30℃.Mixtures of(A)water and(B)methanol in various proportions were used as mobile phase in gradient elution with a flow rate of 1 mL·min~(-1),to effect a satisfactory separation of the 12 carbamates.UV-detection was made at the wavelength of 215 nm using diode array detector.As shown by the results,linear relationships between values of peak area and mass concentration of the 12 carbamate pesticides in the range of 5.0-100.0 mg·L~(-1),with detection limits(3 S/N)in the range of 0.1-0.2 mg·kg~(-1).Test for recovery by standard addition method was made using a blank pesticide sample as matrix,giving results in the range of 97.2%-106%,and RSDs(n=6)ranged from 1.5% to 3.8%.
引文
[1]曹立冬,杨晶,李凤敏,等.农药隐性成分现状、危害、检测技术及管理措施[J].农药科学与管理,2014,35(1):10-13.
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[5]陈建波,马琳,黄兰淇,等.超高效液相色谱-四极杆-飞行时间质谱法快速筛查农药制剂中非法添加的杀虫剂[J].色谱,2016,34(9):880-887.
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[11]RANDA O,LATIFA L E A,NJIB B H.Chemometrically assisted optimization and validation of reversed phase liquid chromatography method for the analysis of carbamates pesticides[J].Chemometrics and Intelligent Laboratory Systems,2016,154(5):38-44.
[12]徐远金,李永库.中药材中氨基甲酸酯类农药的高效液相色谱-质谱分析[J].理化检验-化学分册,2006,42(11):877-884.
[13]刘祥萍,孙文芳,黄薇,等.超高效液相色谱-串联质谱法测定芦蒿中7种氨基甲酸酯类农药及其食物残留量[J].理化检验-化学分册,2016,52(11):1262-1266.
[14]CHENG X,WANG Q J,ZHANG S,et al.Determination of four kinds of carbarnate pesticides by capillary zone electrophoresis with amperometric detection at apolyamide-modified carbon paste electrode[J].Talanta,2007,71(3):1083-1087.
[15]张国文,王福民,潘军辉.主成分回归-分光光度法同时测定西维因和异丙威[J].理化检验-化学分册,2008,44(8):715-718.
[2]孔志英,张强.农药产品中隐性成分的危害与治理对策[J].农药科学与管理,2014,35(10):11-14.
[3]WANG J,LEUNG D.Applications of ultra-performance liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry on analysis of 138pesticides in fruit and vegetable-based infant foods[J].Journal of Agricultural and Food Chemistry,2009,57(6):2162-2173.
[4]洪华,张晓强,武中平,等.SPE-GC-MS快速定性定量杀虫剂产品中11种违禁添加菊酯类隐性成分[J].农药,2013,52(11):812-814.
[5]陈建波,马琳,黄兰淇,等.超高效液相色谱-四极杆-飞行时间质谱法快速筛查农药制剂中非法添加的杀虫剂[J].色谱,2016,34(9):880-887.
[6]陈建波,吴爱娟,赵莉,等.超高效液相色谱-四极杆-飞行时间质谱法快速筛查农药制剂中非法添加的化学杀菌剂[J].分析化学,2017,45(3):441-447.
[7]苍涛,汪志威,王新全,等.九种农药制剂和一种叶面肥中有机磷和氨基甲酸酯类隐性成分的快速检测[J].农药学学报,2016,18(2):227-231.
[8]于峰.农药克百威和丁硫克百威的质谱分析[J].质谱学报,2000,21(3/4):63-64.
[9]胡德龙,张雯,龙俊,等.5种氨基甲酸酯类农药混合溶液标准物质的研制[J].理化检验-化学分册,2013,49(6):743-746.
[10]YANG E Y,SHIN H S.Trace level determinations of carbamate pesticides in surface water by gas chromatography-mass spectrometry after derivatization with 9-xanthydrol[J].Journal of Chromatography A,2013,1305:328-332.
[11]RANDA O,LATIFA L E A,NJIB B H.Chemometrically assisted optimization and validation of reversed phase liquid chromatography method for the analysis of carbamates pesticides[J].Chemometrics and Intelligent Laboratory Systems,2016,154(5):38-44.
[12]徐远金,李永库.中药材中氨基甲酸酯类农药的高效液相色谱-质谱分析[J].理化检验-化学分册,2006,42(11):877-884.
[13]刘祥萍,孙文芳,黄薇,等.超高效液相色谱-串联质谱法测定芦蒿中7种氨基甲酸酯类农药及其食物残留量[J].理化检验-化学分册,2016,52(11):1262-1266.
[14]CHENG X,WANG Q J,ZHANG S,et al.Determination of four kinds of carbarnate pesticides by capillary zone electrophoresis with amperometric detection at apolyamide-modified carbon paste electrode[J].Talanta,2007,71(3):1083-1087.
[15]张国文,王福民,潘军辉.主成分回归-分光光度法同时测定西维因和异丙威[J].理化检验-化学分册,2008,44(8):715-718.