中药材中六六六和滴滴涕残留量检测方法的优化实验
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摘要
目的利用气相色谱检测技术,采用浓硫酸磺化法作为净化方式,建立能应用于中药材中有机氯农药六六六和滴滴涕残留的检测方法。方法以丙酮-石油醚(1+1)为溶剂,高速分散匀浆法提取,浓硫酸磺化法净化,气相色谱法测定中药材中六六六和滴滴涕残留量。结果供试品制备方法以丙酮+石油醚(1+1)作为提取剂,在高速分散均质机中匀浆提取2 min,用0.5 ml浓硫酸净化一次即可。优选的色谱条件为DB-1701毛细管柱(30 m×0.32 mm,0.25μm),进样口温度180℃,载气流速1.0 ml/min,采用程序升温方式。4种六六六与4种滴滴涕的异构体完全分离,在0.002 5～0.040 0μg/ml之间线性关系良好,相关系数(r)均≥0.999 1,方法的检出限(RSN=3)范围为0.000 5～0.002 8 mg/kg。在0.025、0.050、0.100 mg/kg的添加水平下,六六六、滴滴涕的加标回收率在75.8%～104.2%之间,相对标准偏差(RSD)为0.53%～9.83%。结论优化后的方法快速、灵敏、准确,适用于中药材中六六六、滴滴涕的快速筛查和定量分析。
[Objective] To develop an efficient gas chromatography(GC)method for the determination of residues of hexachlorocyclohexanes(HCHs) and dichlorodiphenyltrichloroethanes(DDTs)in Chinese medicinal herbs based on sulfonation reaction.[Methods]Using acetone-petroleum ether(1+1) as solvent,with high-speed dispersion homogenization extraction and concentrated solution sulfonation purification,the residues of HCHs and DDTs in Chinese medicinal herbs were determined by GC.[Results]The pesticide residues in the samples were extracted with acetone/petroleum ether(1∶1,V/V)by high speed dispersive homogenizer for 2 min,then cleaned up by 0.5 ml concentrated sulfuric acid. Chromatographic separation was achieved on a DB-1701 capillary column(30 m×0.32 mm,0.25 μm) by programing temperature with a flow rate of 1.0 ml/min,and the temperature of injection port was 180 ℃. On above conditions,four kinds of HCHs and four kinds of DDTs could be well separated as well as showed good linearities with concentrations between 0.002 5-0.040 0 μg/m(all r>0.999 1),and the limits of detection(LODs)(RSN=3)of the GC method were in the range of 0.000 5-0.002 8 mg/kg. The recoveries of these analytes from blank sample ranged from 75.8% to 104.2%,with relative standard deviation(RSD) ranging from 0.53% to 9.83% at three spiked levels of 0.025,0.050 and 0.100 mg/kg.[Conclusion]The optimal method allows for a simple,rapid and reliable screening and quantitative analysis of HCHs and DDTs residues in Chinese medicinal herbs.
[Objective] To develop an efficient gas chromatography(GC)method for the determination of residues of hexachlorocyclohexanes(HCHs) and dichlorodiphenyltrichloroethanes(DDTs)in Chinese medicinal herbs based on sulfonation reaction.[Methods]Using acetone-petroleum ether(1+1) as solvent,with high-speed dispersion homogenization extraction and concentrated solution sulfonation purification,the residues of HCHs and DDTs in Chinese medicinal herbs were determined by GC.[Results]The pesticide residues in the samples were extracted with acetone/petroleum ether(1∶1,V/V)by high speed dispersive homogenizer for 2 min,then cleaned up by 0.5 ml concentrated sulfuric acid. Chromatographic separation was achieved on a DB-1701 capillary column(30 m×0.32 mm,0.25 μm) by programing temperature with a flow rate of 1.0 ml/min,and the temperature of injection port was 180 ℃. On above conditions,four kinds of HCHs and four kinds of DDTs could be well separated as well as showed good linearities with concentrations between 0.002 5-0.040 0 μg/m(all r>0.999 1),and the limits of detection(LODs)(RSN=3)of the GC method were in the range of 0.000 5-0.002 8 mg/kg. The recoveries of these analytes from blank sample ranged from 75.8% to 104.2%,with relative standard deviation(RSD) ranging from 0.53% to 9.83% at three spiked levels of 0.025,0.050 and 0.100 mg/kg.[Conclusion]The optimal method allows for a simple,rapid and reliable screening and quantitative analysis of HCHs and DDTs residues in Chinese medicinal herbs.
引文
[1]ERIC SJH,SHUGENG C,BRUCE AL,et al. Heavy metal and pesticide content in commonly prescribed individual raw Chinese Herbal Medicines[J].Sci Total Environ,2011,409(20):4297-4305.
[2]孔令军,张娅婷,谷令彪,等.中药材农药残留的研究进展[J].中国实验方剂学杂志,2015,21(21):231-234.
[3]JINGLAN F,PENGTUAN H,FEI Z,et al. HCHs and DDTs in Yellow River of Henan section-a typical agricultural area in China:levels,distributions and risks[J].Environ Geochem Health,2016,38(6):1241-1253.
[4]康传志,郭兰萍,周涛,等.中药材农残研究现状的探讨[J].中国中药杂志,2016,41(2):155-159.
[5]刘红梅,黎小鹏,李文英,等.全自动索氏提取-气相色谱法检测土壤中六六六和滴滴涕农药残留量[J].广东农业科学,2012,39(11):188-190.
[6]许仁杰,蔡春平,丁立平,等.双重净化-气相色谱法同时测定蛋及蛋制品中六六六、滴滴涕和指示性多氯联苯[J].食品科学,2016,37(24):222-227.
[7]曹方方,于建钊,费金岩,等.气相色谱-双柱双电子捕获检测器测定鱼肉中的有机氯农药[J].理化检验-化学分册,2017,53(3):258-262.
[8]赵丹莹,郭蒙京,李堃.干蘑菇类中有机氯农药的超声提取气相色谱测定法[J].职业与健康,2013,29(7):832-835.
[9]王伟,赵利,端允.加速溶剂一步提取与净化-气相色谱法测定土壤中六六六和滴滴涕残留量的实验[J].山西科技,2017,32(5):41-45.
[10]陈兴连,耿彗春,杨东顺,等. Florisil固相萃取-气相色谱法测定蜂蜜中的六六六、滴滴涕残留量[J].食品安全质量检测学报,2017,8(1):227-232.
[11]贾玮,凌云,郝静,等.在线凝胶渗透色谱串联气相色谱-质谱快速测定粮谷及油料作物中29种农药残留[J].分析测试学报,2012,31(10):1217-1222.
[12]赵鹏,施家威,李继革,等.基质固相分散-气相色谱串联质谱法测定孕妇血清中22种持久性有机污染物[J].分析化学,2015,43(5):651-657.
[13]何曼莉,谢建军,陈捷,等.凝胶渗透色谱-固相萃取-气相色谱法同时测定药食两用中药材中17种有机氯类农药残留量[J].食品安全质量检测学报,2015,6(3):893-901.
[14] RONG X,JIANWEI W,YONGANG L,et al. Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe(QuEChERS)pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection[J].Chemosphere,2011,84(7):908-912.
[15]QING G,XIA L,LI T,et al. Simultaneous Determination of 26 Pesticide Residues in 5 Chinese Medicinal Materials Using Solid-phase Extraction and GC-ECD Method[J]. Chin J Nat Med,2009,7(3):210-216.
[2]孔令军,张娅婷,谷令彪,等.中药材农药残留的研究进展[J].中国实验方剂学杂志,2015,21(21):231-234.
[3]JINGLAN F,PENGTUAN H,FEI Z,et al. HCHs and DDTs in Yellow River of Henan section-a typical agricultural area in China:levels,distributions and risks[J].Environ Geochem Health,2016,38(6):1241-1253.
[4]康传志,郭兰萍,周涛,等.中药材农残研究现状的探讨[J].中国中药杂志,2016,41(2):155-159.
[5]刘红梅,黎小鹏,李文英,等.全自动索氏提取-气相色谱法检测土壤中六六六和滴滴涕农药残留量[J].广东农业科学,2012,39(11):188-190.
[6]许仁杰,蔡春平,丁立平,等.双重净化-气相色谱法同时测定蛋及蛋制品中六六六、滴滴涕和指示性多氯联苯[J].食品科学,2016,37(24):222-227.
[7]曹方方,于建钊,费金岩,等.气相色谱-双柱双电子捕获检测器测定鱼肉中的有机氯农药[J].理化检验-化学分册,2017,53(3):258-262.
[8]赵丹莹,郭蒙京,李堃.干蘑菇类中有机氯农药的超声提取气相色谱测定法[J].职业与健康,2013,29(7):832-835.
[9]王伟,赵利,端允.加速溶剂一步提取与净化-气相色谱法测定土壤中六六六和滴滴涕残留量的实验[J].山西科技,2017,32(5):41-45.
[10]陈兴连,耿彗春,杨东顺,等. Florisil固相萃取-气相色谱法测定蜂蜜中的六六六、滴滴涕残留量[J].食品安全质量检测学报,2017,8(1):227-232.
[11]贾玮,凌云,郝静,等.在线凝胶渗透色谱串联气相色谱-质谱快速测定粮谷及油料作物中29种农药残留[J].分析测试学报,2012,31(10):1217-1222.
[12]赵鹏,施家威,李继革,等.基质固相分散-气相色谱串联质谱法测定孕妇血清中22种持久性有机污染物[J].分析化学,2015,43(5):651-657.
[13]何曼莉,谢建军,陈捷,等.凝胶渗透色谱-固相萃取-气相色谱法同时测定药食两用中药材中17种有机氯类农药残留量[J].食品安全质量检测学报,2015,6(3):893-901.
[14] RONG X,JIANWEI W,YONGANG L,et al. Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe(QuEChERS)pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection[J].Chemosphere,2011,84(7):908-912.
[15]QING G,XIA L,LI T,et al. Simultaneous Determination of 26 Pesticide Residues in 5 Chinese Medicinal Materials Using Solid-phase Extraction and GC-ECD Method[J]. Chin J Nat Med,2009,7(3):210-216.