表面活性剂结合QuEChERS-气相色谱-串联质谱法同时测定大豆油中有机氯农药、多氯联苯及多环芳烃
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摘要
建立了气相色谱-串联质谱(GC-MS/MS)同时测定大豆油中34种有机氯农药(OCPs)、12种多氯联苯(PCBs)及6种多环芳烃(PAHs)残留量的检测方法。首先使用表面活性剂作为乳化剂制备相对稳定的油/水乳状液,采用乙腈-二甲苯(9∶1,V/V)为提取剂,以QuEChERS前处理方法对其提取2次后净化,随后进行GC-MS/MS检测。对8种表面活性剂及添加浓度进行优化,结果表明,表面活性剂的添加可显著提高大豆油中OCPs、PCBs及PAHs的提取率,最佳添加方案为大豆油∶水∶Tween60=1∶3∶0.01(m/m/m)。该方法在1/2.5/5/10～400μg/L浓度范围内的线性关系良好,相关系数R2为0.993 8～0.999 7。在5～100μg/kg添加浓度水平内,相对标准偏差为1.59%～20.50%,34种OCPs在大豆油中的添加回收率为64.35%～120.63%,12种PCBs的添加回收率为49.65%～97.76%,6种PAHs的添加回收率为74.05%～101.52%。该方法操作简单、油脂去除效果良好,灵敏度、精密度及回收率均可满足国内外相关标准中大豆油中残留限量的要求。
A method of gas chromatography-tandem mass spectrometry(GC-MS/MS)was developed for determination of 34 kinds of organochlorine pesticides(OCPs),12 kinds of polychlorinated biphenyls(PCBs)and 6 kinds of polycyclic aromatic hydrocarbons(PAHs)in soybean oil.Firstly,1 g soybean oil and 3 g purified water were emulsified with surfactant,then extracted with 5 mL acetonitrile-xylene mixture(9∶1,V/V)by QuEChERS method,and detected by GC-MS/MS.The optimal experiments of adding surfactants about species and concentrations showed that the adding of surfactants can significantly increase the extraction efficiency of OCPs,PCBs,PAHs in soybean oil,and the appropriate surfactant is Tween 60.The calibration curves show a good linearity for all the congeners,and the relative coefficient is 0.993 8-0.999 7.The relative standard deviations(RSDs)are in the range of 1.59%-20.50%,and the spiked recoveries of OCPs range from 64.35% to 120.63%,that of PCBs are in the range of49.65%-97.76%,and PAHs range from 74.05%to 101.52%.The developed analytical method is quick and easy maneuverability with satisfactory effect on the removing of oil,which is suitable for the determination of OCPs,PCBs,PAHs in soybean oil.
A method of gas chromatography-tandem mass spectrometry(GC-MS/MS)was developed for determination of 34 kinds of organochlorine pesticides(OCPs),12 kinds of polychlorinated biphenyls(PCBs)and 6 kinds of polycyclic aromatic hydrocarbons(PAHs)in soybean oil.Firstly,1 g soybean oil and 3 g purified water were emulsified with surfactant,then extracted with 5 mL acetonitrile-xylene mixture(9∶1,V/V)by QuEChERS method,and detected by GC-MS/MS.The optimal experiments of adding surfactants about species and concentrations showed that the adding of surfactants can significantly increase the extraction efficiency of OCPs,PCBs,PAHs in soybean oil,and the appropriate surfactant is Tween 60.The calibration curves show a good linearity for all the congeners,and the relative coefficient is 0.993 8-0.999 7.The relative standard deviations(RSDs)are in the range of 1.59%-20.50%,and the spiked recoveries of OCPs range from 64.35% to 120.63%,that of PCBs are in the range of49.65%-97.76%,and PAHs range from 74.05%to 101.52%.The developed analytical method is quick and easy maneuverability with satisfactory effect on the removing of oil,which is suitable for the determination of OCPs,PCBs,PAHs in soybean oil.
引文
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[16]TUZIMSKI T,REJCZAK T.Application of HPLC-DAD after SPE/QuEChERS with ZrO2-based sorbent in d-SPE clean-up step for pesticide analysis in edible oils[J].Food Chemistry,2016,190(1):71-79.
[17]花锦,张小燕,杜利君.QuEChERS-超高效液相色谱-串联质谱法同时测定油料和植物油中77种农药残留量[J].食品安全质量检测学,2015,6(5):1 691-1 697.HUA Jin,ZHANG Xiaoyan,DU Lijun.Simultaneous determination of 77 pesticides in oil plants and plant oil by high performance liquid chromatography-tandem mass spectrometry with QuEChERS[J].Journal of Food Safety and Quality,2015,6(5):1 691-1 697(in Chinese).
[18]周雅文,贾美娟,刘金凤,张华清,马建业,徐宝财.表面活性剂的性能与应用(ⅩⅩⅢ)---表面活性剂在农药中的应用[J].日用化学工业,2015,45(1):606-610.ZHOU Yawen,JIA Meijuan,LIU Jinfeng,ZHANG Huaqing,MA Jianye,XU Baocai.Performance and applications of surfactants(ⅩⅩⅢ)-application of surfactants in pesticides[J].China Surfactant Detergent&Cosmetics,2015,45(1):606-610(in Chinese).
[19]姜娈.非离子型表面活性剂的研究[J].化学工程师,2011,(3):26-27,47.JIANG Luan.Study of non-ionic surfactants[J].Chemical Engineer,2011,(3):26-27,47(in Chinese).
[20]ZHAO Q Z,ZHAO M,WANG C,WANG J S.Relationship between HLB value of emulsifier and whipping properties of the whipping cream[J].Journal of Shaanxi University of Science&Technology,2006,24(1):1-6.
[21]MYERS D.Surfactant science and technology[M].2nd ed.New York:VCH Publishers,Inc,1992:97-104.
[22]EU SANTE/11945/2015.Guidance document on analytical quality control and method validation procedures for pesticides residues analysis in food and feed[S].Directorate-Genaral for Health and Food Safety,European Union,2015.
[2]ARREBOLA J,BELHASSEN H,ARTACHO-CORDON F,GHALI R,GHORBEL H,BOUS-SEN H,PEREZ-CARRACOSA F,EXPOSITOJ,HEDHILI A,OLEA N.Risk of female breast cancer and serum concentrations of organochlorine pesticides and polychlorinated biphenyls:a case-control study in Tunisia[J].Science of the Total Environ,2015,520:106-113.
[3]KOUTROS S,LANGSETH H,GRIMSRUDT,BARR D,VERMEULEN R,PORTENGENL,WACHOLDER S,FREEMAN L,BLAIRA,HAYES R,ROTHMAN N,ENGEL L.Prediagnostic serum organochlorine concentrations and metastatic prostate cancer:a nested case-control study in the Norwegian Janus Serum Bank Cohort[J].Environmental Health Perspectives,2015,123(9):867-872.
[4]PARADA H,WOLFF M,ENGEL L,WHITEA,ENG S,CLEVELAND R,KHANKARI N,TEITELBAUM S,NEUGUT A,GAMMONM.Gammon organochlorine insecticides DDTand chlordane in relation to survival following breast cancer[J].International Journal of Cancer,2016,138(3):565-575.
[5]LOUIS L,LERRO C,FRIESEN M,ANDRE-OTTI G,KOUTROS S,SANDLER D,BLAIRA,ROBSON M,FREEMAN L.A prospective study of cancer risk among agricultural health study farm spouses associated with personal use of organochlorine insecticides[J].Environmental Health,2017,16(1):95.
[6]ATTAULLAHA M,YOUSUFB M,SHAUKATC S,ANJUM S,ANSARI M,BU-NERI I,TAHIR M,AMIN M,AHMAD N,KHAN S.Serum organochlorine pesticides residues and risk of cancer:a case-control study[J].Saudi Journal of Biological Sciences,2018,27(7):1 284-1 290.
[7]HERCEG S,GORDANA R,DARIJAKLINCˇIC'AV,KLINCˇIC'A D,SARIC'C M,UPAND I,AN-TANASIJEVIC'D,POPOVIC'A.Organochlorine pesticides(OCPs)and polychlorinated biphenyls(PCBs)in Cyprinidae fish:towards hints of their arrangements using advanced classification methods[J].Environmental Research,2018,165:349-357.
[8]GB 2763-2016.食品中农药最大残留限量[S].北京:中国标准出版社,2016.
[9]GB 2762-2017.食品中污染物限量[S].北京:中国标准出版社,2017.
[10]Commission Regulation(EU)No 589/2014.Laying down methods of sampling and analysis for the control of levels of dioxins,dioxin-like PCBs and non-dioxin-like PCBs in certain foodstuffs and repealing Regulation[S].Offical Journal of the European Union,2014.
[11]SN/T 4428-2016.出口油料中多种农药残留量的测定液相色谱-质谱/质谱法[S].北京:中国标准出版社,2008.
[12]LIU Y H,MO R H,ZHONG D L,SHEN D Y,NI Z L,TANG F B.The fate of organophosphorus pesticides during camellia oil production[J].Journal of Food Science,2015,80(8):1 926-1 932.
[13]LIKUDIS Z,COSTARELLI V,VITORATOSA,APOSTOLOPOULOS C.Determination of pesticide residues in olive oils with protected geographical indication or designation of origin[J].International Journal of Food Science and Technology,2014,49(2):484-492.
[14]FRENICH A,MORENO J,VIDAL J,LIEBANASF.Application of gas chromatography coupled to triple quadrupole mass spectrometry for the multiresidue analysis of pesticides in olive oil[J].Journal of Agricultural and Food Chemistry.2007,55(21):8 346-8 352.
[15]JIANG Y P,LI Y J,JIANG Y T,LI J G,PANC P.Determination of multiresidues in rapeseed,rapeseed oil,and rapeseed meal by acetonitrile extraction,low-temperature cleanup,and detection by liquid chromatography with tandem mass spectrometry[J].Journal of Agricultural and Food Chemistry,2012,60(20):5 089-5 098.
[16]TUZIMSKI T,REJCZAK T.Application of HPLC-DAD after SPE/QuEChERS with ZrO2-based sorbent in d-SPE clean-up step for pesticide analysis in edible oils[J].Food Chemistry,2016,190(1):71-79.
[17]花锦,张小燕,杜利君.QuEChERS-超高效液相色谱-串联质谱法同时测定油料和植物油中77种农药残留量[J].食品安全质量检测学,2015,6(5):1 691-1 697.HUA Jin,ZHANG Xiaoyan,DU Lijun.Simultaneous determination of 77 pesticides in oil plants and plant oil by high performance liquid chromatography-tandem mass spectrometry with QuEChERS[J].Journal of Food Safety and Quality,2015,6(5):1 691-1 697(in Chinese).
[18]周雅文,贾美娟,刘金凤,张华清,马建业,徐宝财.表面活性剂的性能与应用(ⅩⅩⅢ)---表面活性剂在农药中的应用[J].日用化学工业,2015,45(1):606-610.ZHOU Yawen,JIA Meijuan,LIU Jinfeng,ZHANG Huaqing,MA Jianye,XU Baocai.Performance and applications of surfactants(ⅩⅩⅢ)-application of surfactants in pesticides[J].China Surfactant Detergent&Cosmetics,2015,45(1):606-610(in Chinese).
[19]姜娈.非离子型表面活性剂的研究[J].化学工程师,2011,(3):26-27,47.JIANG Luan.Study of non-ionic surfactants[J].Chemical Engineer,2011,(3):26-27,47(in Chinese).
[20]ZHAO Q Z,ZHAO M,WANG C,WANG J S.Relationship between HLB value of emulsifier and whipping properties of the whipping cream[J].Journal of Shaanxi University of Science&Technology,2006,24(1):1-6.
[21]MYERS D.Surfactant science and technology[M].2nd ed.New York:VCH Publishers,Inc,1992:97-104.
[22]EU SANTE/11945/2015.Guidance document on analytical quality control and method validation procedures for pesticides residues analysis in food and feed[S].Directorate-Genaral for Health and Food Safety,European Union,2015.