采用QuEChERS前处理方法联合气相色谱串联三重四级杆质谱法(gas chromatography-triple quadrupole mass spectrometry, GC-MS/MS),建立了同时测定石榴中19种有机磷农药残留的分析方法。使用优化后的QuEChERS方法对石榴进行前处理,选用乙酸乙酯为提取剂、N－丙基乙二胺(primary secondary amine sorbent, PSA)为净化剂,经Rtx-5MS色谱柱分离后在多反应监测模式(multiple reaction monitoring mode, MRM)下进行测定。结果表明:该方法在0.01～1.0 mg/L的线性范围内线性关系良好,相关系数(r)均大于0.99,最低检出限(S/N=3)为0.9～3.7 μg/kg,定量限(S/N=10)为3～12.2 μg/kg,加标回收率为73.5%～120.9%,相对标准偏差(RSD)为1.1%～15.7%。利用该方法对市售石榴进行有机磷农药进行检测,其中检出微量的久效磷和乐果2种农药。该方法快速、准确、灵敏度高,适用于石榴中有机磷农药的多残留检测。
QuEChERS and gas chromatography-triple quadrupole mass spectrometry were adopted as an efficient method to detect and analyze nineteen organophosphorus pesticide residues in pomegranates. The sample was prepared by optimized QuEChERS, extracted with ethyl acetate and purified by primary secondary amine sorbent (PSA) adsorbent. The nineteen organophosphorus pesticide residues were separated by an Rtx-5MS column, and determined using MS/MS in multiple reactions monitoring mode. All correlation coefficients of calibration curves were over 0.99 in the linear concentration range 0.01-1.0 mg/L. The detection limit (S/N=3) was 0.9-3.7 μg/kg, and the quantitation limit (S/N=10) was 3-12.2 μg/kg. The recovery rate was 73.5%-120.9% with relative standard deviations (RSDs) between 1.1% and 15.7%. Two kinds of pesticides, monocrotophos and dimethoate, were detected from pomegranates available from the market by this method. This method proved to be rapid, accurate, and with high sensitivity. It can be applied for simultaneous determination of organophosphorus pesticide residues in pomegranates
[1] 叶天. 陕西石榴籽的抗氧化特性及活性成分分析[D]; 上海:上海交通大学, 2012:1-2.
[2] 李巨秀,张小宁,李伟伟.不同品种石榴花色苷、总多酚含量及抗氧化活性比较研究[J].食品科学,2011,32(23):143-146.
[3] 汤东生,王斌,毛忠顺,等.石榴园常用除草剂和杀菌剂对石榴枯萎病菌和枯草芽孢杆菌生长的影响[J].江苏农业科学,2011,39(5):154-156.
[4] 姚昕,涂勇.不同生物农药对石榴褐斑病菌的室内毒力测定试验[J].现代农业科技,2015,21:125-126.
[5] 吴继国.蔬菜有机磷农药残留的臭氧降解及其产物的细胞毒性研究[D],广州:中山大学,2007:5-7.
[6] 刘开,孔祥虹,何强,等.GC-MS/MS法测定植物提取物中39种有机磷农药的残留量[J].分析实验室,2015,34(12):1 432-1 437.
[7] 刘开.GC-MS/MS检测石榴皮等植物提取物中多种农药残留的技术条件研究[D].西安:陕西师范大学,2014:3-10.
[8] KAUSHIK BANERJEE,DASHARATH P QULKAR,SHUBHANGI B PATIL, et al. Single-laboratory validation and uncertainty analysis of 82 pesticides determined in pomegranate, apple, and orange by ethyl acetate extraction and liquid chromatorgraphy/tandem mass spectrometry[J]. Journal of AOAC International, 2008,91(6):1 435-1 445.
[9] MERLE M PLASSMANN, MAGDALENA SCHMIDT, WERNER BRACK, et al. Detecting a wide range of environmental contaminants in human blood samples-combining QuEChERS with LC-MS and GC-MS methods[J]. Anal Bioanal Chem,2015,407:7 047-7 054.
[10] 陈晓水,边照阳,杨飞,等.对比3种不同的QuEChERS前处理方式在气相色谱-串联质谱检测分析烟草中上百种农药残留中的应用[J].色谱,2013,31(11):1 116-1 128.
[11] 潘孝博,伊雄海,时逸吟,等.液相色谱-高分辨飞行时间质谱法快速筛查食品中香港规例农药残留[J].分析化学,2016,44(7):1 125-1 132.
[12] 李蓉,卢俊文,杨汝辉,等.气相色谱-串联质谱法测定水果中多种农药残留[J].中国卫生检验杂志,2012,22(11):2 562-2 565.
[13] RIZZETTI T M, KEMMERICH M L, MARTINS M L, et al. Optimization of a QuEChERS based method by means of central composite design for pesticide multiresidue determination in orange juice by UHPLC-MS/MS[J]. Food Chemistry, 2016, 196:25-33.
[14] HUIJUN LIU, BAOYUAN GUO, HUILI WANG, et al. Determination of bromothalonil residues and degradation in apple and soil by QuEChERS and GC-MS/MS[J]. Bull Environ Contam Toxicol,2014(92):451-454.
[15] KECHEN ZHU, PUYU LI, MENGYUAN FENG, et al. Dissipation and residues of picoxystrobin in peanut and field soil by QuEChERS and HPLC-MS/MS[J]. Environ Monit Assess, 2015,187:539-549.
[16] 黄何何,张缙,徐敦明,等. QuEChERS-高效液相色谱-串联质谱法同时测定水果中21种植物生长调节剂的残留量[J].色谱,2014,32(7):707-716.
[17] PENG YIN, XIN LIU, HONGPING CHEN, et al. Determination of 16 phthalate esters in tea samples using a modified QuEChERS sample preparation method combined with GC-MS/MS[J]. Food Additives＆Contaminants, 2014,31(8):1 406-1 413.
[18] GRACIA MARTINEZ, ASCENSION MORALES, ALBA MAESTRO, et al. Determination of nine fungicides in grape and wine using QuEChERS extraction and LC/MS/MS analysis[J]. Residues and trace elements, 2015,98(6):1 745-1 751.
[19] 沈丹玉,汤富彬,钟冬莲,等. QuEChERS-气相色谱检测鸡腿菇中的有机磷类农药残留[J].湖南农业科学,2011(21):67-70.
[20] 吴春梅,程雪梅,李亮,等. QuEChERS-GPC-GC-MS快速测定蔬菜中24种农药残留[J].热带农业科学,2012,32(2):52-56.
[21] 刘永,唐英斐,宋金凤,等.固相萃取-液相色谱-串联质谱法测定蔬菜中4种有机磷农药及其代谢产物[J].色谱,2014,32(2):139-144.
[22] 孙欣,齐莉,秦廷亭,等. QuEChERS-气相色谱-三重四级杆质谱法检测黄瓜中的19种邻苯二甲酸酯[J].色谱,2014,32(11):1 260-1 265.
[23] 程志,张蓉,刘韦华,等.气相色谱-串联质谱法快速筛查测定中药材中144种农药残留[J].色谱,2014,32(1):57-68.
[24] 彭晓俊,曾丽珠,伍长春,等. 基于QuEChERS法提取液相色谱-串联质谱法测定新会陈皮中的9种真菌毒素和农药残留[J]. 分析测试学报,2017,36(6):738-742.
[25] 徐炎炎,李森,张芹,等.气质联用和液质联用中基质效应的分析和总结[J].农药,2017,56(3):162-167.
[26] 褚能明,孟霞,康月琼,等.分散固相萃取-气相色谱-串联质谱法测定茉莉花茶中86种农药残留[J].食品科学,2016,37(24):239-246.
