QuEChERS在线凝胶色谱气相色谱质谱法测定植物油中34种农药残留

阮华等
1引言
植物油是人类生活的必需消费品,其质量安全直接关系到消费者的身体健康。我国规定了棉籽油、花生油、大豆油及菜籽油中拟除虫菊酯类和有机磷类农药的残留限量(005~05 mg/kg)\[1\]。目前,对于植物油的农药多残留检测前处理方法主要是采用液液萃取(LLE)\[2\],结合固相萃取(SPE)\[3,4\],凝胶色谱(GPC)\[5\]或基质固相分散(MSPD)\[6\]进行。随着前处理技术的发展,新的前处理技术被应用到植物油中农药残留的检测中,如在线GPC系统\[7,8\]及QuEChERS法\[9~12\]。这类方法的出现,使得样品前处理变得简单,有时甚至不需进行前处理。但也存在如基质干扰较严重\[7,8\]、检出限偏高\[7\]、处理时间长\[9~12\]等问题。
本研究将QuEChERS方法结合在线GPCGCMS系统用于检测植物油中的多农药残留,将毒鼠强以及多种中高毒农药纳入到研究范围,与已报道的方法\[9~13\]相比,采用QuEChERS法处理样品时不需调节pH值,无需进行冷冻除脂,且所需样品量少,进一步减小溶剂消耗; 在线GPCGCMS系统中的GPC部分可以很好地弥补QuEChERS法去除干扰物质不彻底的问题,利用大体积进样(LVI)技术,可将GCMS的灵敏度进一步提高,而且能够抑制部分基质效应。本方法具有较高的灵敏度及精密度,较低的分析成本,可用于葵花油、大豆油和玉米油中34种农药残留快速筛查与检测。
23实验方法
对浓度为100 mg/L的13种农药标准品(甲拌磷、地虫硫磷、治螟磷、苯线磷、甲基对硫磷、对硫磷、特丁硫磷、乙基嘧啶磷、蝇毒磷、狄氏剂、异狄氏剂、克百威、氟虫腈等)各2支,毒鼠强取用1支,全部转移至50 mL容量瓶。对20种农药固体标准品(久效磷、杀螟硫磷、甲胺磷、氯唑磷、丁基嘧啶磷、亚胺硫磷、乙硫磷、杀扑磷、甲基立枯磷、伏杀磷、丙溴磷、乙拌磷、丙线磷、三氯杀螨醇、林丹、氰戊菊酯、p,p滴滴滴、p,p滴滴伊、o,p滴滴涕、p,p滴滴涕)每种称取10 mg,加入到10 mL容量瓶中,先用少量丙酮溶解,然后用正己烷定容, 配制成质量浓度均为1000 mg/L的储备液,吸取200 μL储备液转移到同一50 mL容量瓶中本研究采用氟胺氰菊酯和灭螨猛校准混合物(10 mg/L)进行时间定位(大多数农药分子量介于氟胺氰菊酯和灭螨猛之间),在22节GPC条件下,氟胺氰菊酯和灭螨猛保留时间相差小于2 min(图1)。本研究收集340~540 min馏分到200 μL定量环中,使得34种农药完全进入GCMS系统中进行分析检测。其它馏分由GPC排到系统外,由此可使样品中的杂质进一步去除,进而减小基质效应、降低分析背景、改善色谱峰形,且GPC系统克服了常规 GPC消耗溶剂量大、自动化差、操作繁琐等问题。
GPC系统与GCMS系统采用程序升温大体积进样口连接(PTVLVI),利用大体积进样技术,可将GCMS的灵敏度进一步提高, PTVLVI技术可以快速的加热或者冷却,减少热不稳定农药的分解,且较高的载气流速可以减少目标分析物在衬管中的停留时间,在一定程度上抑制基质效应。
32萃取剂及萃取方式的选择
按24节处理步骤,在3支10 mL玻璃试管中各加入040 g葵花油样品,并按01 μg/g加入标准溶液。比较了乙腈丙酮(1∶1, V/V)、正己烷饱和的乙腈及乙腈3种萃取剂的萃取效率。样品经不同萃取剂萃取后的净化效果见图2。结果表明,采用乙腈丙酮(1∶1, V/V)萃取时基质干扰严重,不适合作为此方法的萃取剂;
34基质效应
基质效应是农药分析需要考虑的问题\[18\]。本研究在采用纯溶剂配制的标准曲线进行定量时,除甲胺磷、治螟磷、林丹、氯唑磷、丁基嘧啶磷、甲基立枯磷、乙基嘧啶磷,其余24种农药(除p,p′DDE, p,p′DDD, p,p′DDT)均有不同程度的基质增强效应。采用欧盟DG SANCO\[15\]中的规定,利用不含农药的空白基质匹配制标准溶液,使之达到与样品中农药同等的响应。
4结论
本实验采用QuEChERS方法对葵花油样品前处理方法进行了优化,结合GPCGCMS建立了一套可同时测定葵花油、大豆油和玉米油中31种 (不包括p,p′DDE, p,p′DDD, p,p′DDT) 中高毒农药的快速筛查方法,检出限、定量限、回收率和相对标准偏差均能满足农药多残留检测方法的要求, p,p′DDE, p,p′DDD, p,p′DDT满足定性要求。采用QuEChERS法结合GPCGCMS在线联用,一方面GPC系统弥补了QuEChERS前处理方法去干扰物质不彻底的问题,提高了方法的灵敏度、分析结果的准确性,且在线GPC系统从进样到完成色谱柱冲洗仅需要使用10 mL有机溶剂,符合绿色化学的理念; 另一方面,采用QuEChERS法进行样品前处理,食品安全国家标准食品中农药最大残留限量 中华人民共和国国家标准 GB/T 27632012
2Anagnostopoulos C, Miliadis G E Talanta, 2013, 112: 1-10
3Muhamad H, Zainudin B H, Abu Bakar N K Food Chem, 2012, 134(4): 2489-2496
4Chee B Y, Chiew L C Eur J Lipid Sci, 2012, 114(12): 1358-1361
5Hoh E, Lehotay S J, Mastovska K, Ngo H L, Vetter W, Pangallo K C, Reddy C M Environ Sci Technol, 2009, 43(9): 3240-3247
6García Reyes J F, Ferrer C, Thurman E M, FernndezAlba A R, Ferrer I J Agric Food Chem, 2006, 54(18): 6493-6500
7Díaz Plaza E M, Cortés J M, Vzquez A, Villén J J Chromatogr A, 2007, 1174(1): 145-150
8Jongenotter B, Janssen H LCGC, 2002, 15(6): 338-357
9Jiang Y, Li Y, Jiang Y, Li J, Pan C J Agric Food Chem, 2012, 60(20): 5089-5098
10Sobhanzadeh E, Bakar N K A, Abas M R B, Nemati K Environ Monit Assess, 2012, 184(9): 5821-5828
11Park J Y, Yang A, Park J H, ElAty A MA, Oh J H, Do J A, Kwon K, Shim K H, Choi O J, Shim J H J Korean Chem Soc, 2012, 55(4): 541-549
12DONG Jing, PAN YuXiang, ZHU LiPing, SUN Jun, PAN ShouQi Journal of Instrumental Analysis, 2008, 27(1): 66-69
董 静, 潘玉香, 朱莉萍, 孙 军, 潘守奇 分析测试学报, 2008, 27(1): 66-69
13YU YanBin, LIU ZongXing, TAN PiGong, L ChunYing, HOU YanZhuo Chinese J AnalChem, 2013, 41(8): 1259-1263
于彦彬, 谭丕功, 刘宗兴, 吕春莹, 侯彦卓 分析化学, 2013, 41(8): 1259-1263
14Hercegov A, Dmtrov M, Krulicov D, Matisov E J Sep Sci, 2006, 29(8): 1102-1109
15European Commission Document No SANCO/12495/2011 Method Validation and Quality Control Procedures for Pesticide Residues Analysis in Food and Feed http: //eceuropaeu/food/plant/plant_protection_products/guidance_documents/docs/qualcontrol_enpdf
16WANG LianZhu, ZHOU Yu, CHEN Yong, WANG RuiLong, LIN ZiXu, LIN DeJuan, ZHEN ShaoHui Chinese Journal of Chromatography, 2012, 30(2): 146-153
王连珠, 周 昱, 陈 泳, 王瑞龙, 林子旭, 林德娟, 郑少惠 色谱, 2012, 30(2): 146-153
17Polgr L, Kmellr B, GarcíaReyes J F, Fodor P Anal Methods, 2012, 4(4): 1142-1148
18Fenik J, Tankiewicz M, Biziuk M TrAC, Trends Anal Chem, 2011, 30(6): 814-826
19Lehotay S J, Kok A D, Hiemstra M, Bodegraven P V J AOAC Int , 2005, 88(2): 595-614
20Li L, Xu Y, Pan C, Zhou Z, Jiang S, Liu F J AOAC Int, 2007, 90(5): 1387-1394
21García Reyes J F, Ferrer C, Gómez Ramos M J, Fernndez Alba A R, MolinaDíaz A TrAC, Trends Anal Chem, 2007, 26(3): 239-251
AbstractA method for the simultaneous determination of 34 pesticides in sunflower oil, soybean oil and corn oil was developed The samples were extracted and purified by a modified QuEChERS method, and then the supernatant was analyzed by online gel permeation chromatographygas chromatographymass spectrometry (GPCGCMS) The linear range was from 001 to 02 mg/L with a good correlation coefficients (r≥09913) The average recoveries of 31 pesticides (except p,p′DDE, p,p′DDD, p,p′DDT For detail, please reference to section 36) ranged from 703% to 1154%, 695% to 1126% and 702% to 1161% spiked at 005 μg/g and 01 μg/g with the relative standard deviations (RSDs, n=6) less than 133%, 135% and 121% in sunflower oil, soybean oil and corn oil samples, respectively The LODs of this method ranged from 00692 to 228, 00559 to 201 and 00584 to 214 μg/kg (S/N=3) in sunflower oil, soybean oil and corn oil samples respectively The convenient operation and versatility of this method are suitable for the fast screening and detection of 34 pesticide residues in sunflower oil, soybean oil and corn oil
KeywordsQuEChERS; Gel permeation chromatographygas chromatographymass spectrometry; Vegetable oil; Pesticide residues; Fast screening
6García Reyes J F, Ferrer C, Thurman E M, FernndezAlba A R, Ferrer I J Agric Food Chem, 2006, 54(18): 6493-6500
7Díaz Plaza E M, Cortés J M, Vzquez A, Villén J J Chromatogr A, 2007, 1174(1): 145-150
8Jongenotter B, Janssen H LCGC, 2002, 15(6): 338-357
9Jiang Y, Li Y, Jiang Y, Li J, Pan C J Agric Food Chem, 2012, 60(20): 5089-5098
10Sobhanzadeh E, Bakar N K A, Abas M R B, Nemati K Environ Monit Assess, 2012, 184(9): 5821-5828
11Park J Y, Yang A, Park J H, ElAty A MA, Oh J H, Do J A, Kwon K, Shim K H, Choi O J, Shim J H J Korean Chem Soc, 2012, 55(4): 541-549
12DONG Jing, PAN YuXiang, ZHU LiPing, SUN Jun, PAN ShouQi Journal of Instrumental Analysis, 2008, 27(1): 66-69
董 静, 潘玉香, 朱莉萍, 孙 军, 潘守奇 分析测试学报, 2008, 27(1): 66-69
13YU YanBin, LIU ZongXing, TAN PiGong, L ChunYing, HOU YanZhuo Chinese J AnalChem, 2013, 41(8): 1259-1263
于彦彬, 谭丕功, 刘宗兴, 吕春莹, 侯彦卓 分析化学, 2013, 41(8): 1259-1263
14Hercegov A, Dmtrov M, Krulicov D, Matisov E J Sep Sci, 2006, 29(8): 1102-1109
15European Commission Document No SANCO/12495/2011 Method Validation and Quality Control Procedures for Pesticide Residues Analysis in Food and Feed http: //eceuropaeu/food/plant/plant_protection_products/guidance_documents/docs/qualcontrol_enpdf
16WANG LianZhu, ZHOU Yu, CHEN Yong, WANG RuiLong, LIN ZiXu, LIN DeJuan, ZHEN ShaoHui Chinese Journal of Chromatography, 2012, 30(2): 146-153
王连珠, 周 昱, 陈 泳, 王瑞龙, 林子旭, 林德娟, 郑少惠 色谱, 2012, 30(2): 146-153
17Polgr L, Kmellr B, GarcíaReyes J F, Fodor P Anal Methods, 2012, 4(4): 1142-1148
18Fenik J, Tankiewicz M, Biziuk M TrAC, Trends Anal Chem, 2011, 30(6): 814-826
19Lehotay S J, Kok A D, Hiemstra M, Bodegraven P V J AOAC Int , 2005, 88(2): 595-614
20Li L, Xu Y, Pan C, Zhou Z, Jiang S, Liu F J AOAC Int, 2007, 90(5): 1387-1394
21García Reyes J F, Ferrer C, Gómez Ramos M J, Fernndez Alba A R, MolinaDíaz A TrAC, Trends Anal Chem, 2007, 26(3): 239-251
AbstractA method for the simultaneous determination of 34 pesticides in sunflower oil, soybean oil and corn oil was developed The samples were extracted and purified by a modified QuEChERS method, and then the supernatant was analyzed by online gel permeation chromatographygas chromatographymass spectrometry (GPCGCMS) The linear range was from 001 to 02 mg/L with a good correlation coefficients (r≥09913) The average recoveries of 31 pesticides (except p,p′DDE, p,p′DDD, p,p′DDT For detail, please reference to section 36) ranged from 703% to 1154%, 695% to 1126% and 702% to 1161% spiked at 005 μg/g and 01 μg/g with the relative standard deviations (RSDs, n=6) less than 133%, 135% and 121% in sunflower oil, soybean oil and corn oil samples, respectively The LODs of this method ranged from 00692 to 228, 00559 to 201 and 00584 to 214 μg/kg (S/N=3) in sunflower oil, soybean oil and corn oil samples respectively The convenient operation and versatility of this method are suitable for the fast screening and detection of 34 pesticide residues in sunflower oil, soybean oil and corn oil
KeywordsQuEChERS; Gel permeation chromatographygas chromatographymass spectrometry; Vegetable oil; Pesticide residues; Fast screening
6García Reyes J F, Ferrer C, Thurman E M, FernndezAlba A R, Ferrer I J Agric Food Chem, 2006, 54(18): 6493-6500
7Díaz Plaza E M, Cortés J M, Vzquez A, Villén J J Chromatogr A, 2007, 1174(1): 145-150
8Jongenotter B, Janssen H LCGC, 2002, 15(6): 338-357
9Jiang Y, Li Y, Jiang Y, Li J, Pan C J Agric Food Chem, 2012, 60(20): 5089-5098
10Sobhanzadeh E, Bakar N K A, Abas M R B, Nemati K Environ Monit Assess, 2012, 184(9): 5821-5828
11Park J Y, Yang A, Park J H, ElAty A MA, Oh J H, Do J A, Kwon K, Shim K H, Choi O J, Shim J H J Korean Chem Soc, 2012, 55(4): 541-549
12DONG Jing, PAN YuXiang, ZHU LiPing, SUN Jun, PAN ShouQi Journal of Instrumental Analysis, 2008, 27(1): 66-69
董 静, 潘玉香, 朱莉萍, 孙 军, 潘守奇 分析测试学报, 2008, 27(1): 66-69
13YU YanBin, LIU ZongXing, TAN PiGong, L ChunYing, HOU YanZhuo Chinese J AnalChem, 2013, 41(8): 1259-1263
于彦彬, 谭丕功, 刘宗兴, 吕春莹, 侯彦卓 分析化学, 2013, 41(8): 1259-1263
14Hercegov A, Dmtrov M, Krulicov D, Matisov E J Sep Sci, 2006, 29(8): 1102-1109
15European Commission Document No SANCO/12495/2011 Method Validation and Quality Control Procedures for Pesticide Residues Analysis in Food and Feed http: //eceuropaeu/food/plant/plant_protection_products/guidance_documents/docs/qualcontrol_enpdf
16WANG LianZhu, ZHOU Yu, CHEN Yong, WANG RuiLong, LIN ZiXu, LIN DeJuan, ZHEN ShaoHui Chinese Journal of Chromatography, 2012, 30(2): 146-153
王连珠, 周 昱, 陈 泳, 王瑞龙, 林子旭, 林德娟, 郑少惠 色谱, 2012, 30(2): 146-153
17Polgr L, Kmellr B, GarcíaReyes J F, Fodor P Anal Methods, 2012, 4(4): 1142-1148
18Fenik J, Tankiewicz M, Biziuk M TrAC, Trends Anal Chem, 2011, 30(6): 814-826
19Lehotay S J, Kok A D, Hiemstra M, Bodegraven P V J AOAC Int , 2005, 88(2): 595-614
20Li L, Xu Y, Pan C, Zhou Z, Jiang S, Liu F J AOAC Int, 2007, 90(5): 1387-1394
21García Reyes J F, Ferrer C, Gómez Ramos M J, Fernndez Alba A R, MolinaDíaz A TrAC, Trends Anal Chem, 2007, 26(3): 239-251
AbstractA method for the simultaneous determination of 34 pesticides in sunflower oil, soybean oil and corn oil was developed The samples were extracted and purified by a modified QuEChERS method, and then the supernatant was analyzed by online gel permeation chromatographygas chromatographymass spectrometry (GPCGCMS) The linear range was from 001 to 02 mg/L with a good correlation coefficients (r≥09913) The average recoveries of 31 pesticides (except p,p′DDE, p,p′DDD, p,p′DDT For detail, please reference to section 36) ranged from 703% to 1154%, 695% to 1126% and 702% to 1161% spiked at 005 μg/g and 01 μg/g with the relative standard deviations (RSDs, n=6) less than 133%, 135% and 121% in sunflower oil, soybean oil and corn oil samples, respectively The LODs of this method ranged from 00692 to 228, 00559 to 201 and 00584 to 214 μg/kg (S/N=3) in sunflower oil, soybean oil and corn oil samples respectively The convenient operation and versatility of this method are suitable for the fast screening and detection of 34 pesticide residues in sunflower oil, soybean oil and corn oil
KeywordsQuEChERS; Gel permeation chromatographygas chromatographymass spectrometry; Vegetable oil; Pesticide residues; Fast screening
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