气相色谱-串联质谱法检测水产品运输水和暂养水中丁香酚残留
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摘要
建立了流通环节中水产品运输和暂养水样中丁香酚残留的气相色谱-串联质谱检测方法。运输和暂养水样经固相分散基质萃取,再逐步经聚合氧化铝(PAC)、N-丙基乙二胺(PSA)和氯化钠(Na Cl)净化后,用二氯甲烷和正己烷萃取,然后浓缩至干并定容检测,采用电喷雾(ESI)正离子模式同时扫描,选择反应监控模式(SRM)配合基质匹配溶液内标法定量检测。结果显示:本方法的丁香酚检出限(LOD)为0. 5μg/L,其定量限(LOQ)为1. 5μg/L;在LOQ添加水平时,信噪比S/N为10. 95,并在1. 5～50. 0μg/L线性范围内,回收率为82. 3%～109. 9%,RSD <6. 9%;线性回归方程为Y=-0. 006 424+0. 000 391 7X,相关系数r为0. 993 6。本方法简单、稳定、灵敏、省时,能够满足实际检测需要,适用于环境水样等复杂基质检验检测。为验证本方法的检测可行性,已将本方法应用于2014年排查的沪浙闽地区18个运输水样和26个暂养水样的检测,阳性检出率大于20%,为水产品质量监控提供了技术支持。
A method of gas chromatography-tandem mass spectrometry( GC-MS/MS) was established for the determination of eugenol residues in transport water and temporary water during the transportation circulation of aquatic products. The samples were prepared by a simple solid phase dispersion matrix method with successively purifying using sorbents including polyaluminum chloride( PAC),primary secondary amine( PSA) and sodium chloride( NaCl),followed with organic solvent extraction with dichloromethane and n-hexane,and then the organic solvent layer was directly concentrated to dryness for detection. The eugenol residues were determined using the positive electrospray ionization( ESI) mode with select reaction monitor( SRM) mode and calculated by internal standard method with matrix matching. The results showed that the limit of detection( LOD) for eugenol was 0. 5 μg/L,and the limit of quantitation( LOQ) was 1. 5 μg/L,at the signal-to-noise ratio( S/N) of 10. 95. The recoveries were maintained at 82. 3%-109. 9% with a linear range of 1. 5-50. 0 μg/L,the relative standard deviation( RSD) was less than 6. 9%,and the linear regression equation is Y =-0. 006 424 + 0. 000 391 7X with the correlation coefficient r of 0. 993 6. This method was simple,stable,sensitive,time-saving and was considered to be capable of meeting the actual needs for residue analysis in complex matrix such as environmental water samples. In order to demonstrate the availability of this method,it was applied to the investigation of 18 transport water samples and 26 temporary water samples from Shanghai,Zhejiang and Fujian in 2014. The positive rate was more than 20%,which was worth paying attention to the eugenol residual problem.
A method of gas chromatography-tandem mass spectrometry( GC-MS/MS) was established for the determination of eugenol residues in transport water and temporary water during the transportation circulation of aquatic products. The samples were prepared by a simple solid phase dispersion matrix method with successively purifying using sorbents including polyaluminum chloride( PAC),primary secondary amine( PSA) and sodium chloride( NaCl),followed with organic solvent extraction with dichloromethane and n-hexane,and then the organic solvent layer was directly concentrated to dryness for detection. The eugenol residues were determined using the positive electrospray ionization( ESI) mode with select reaction monitor( SRM) mode and calculated by internal standard method with matrix matching. The results showed that the limit of detection( LOD) for eugenol was 0. 5 μg/L,and the limit of quantitation( LOQ) was 1. 5 μg/L,at the signal-to-noise ratio( S/N) of 10. 95. The recoveries were maintained at 82. 3%-109. 9% with a linear range of 1. 5-50. 0 μg/L,the relative standard deviation( RSD) was less than 6. 9%,and the linear regression equation is Y =-0. 006 424 + 0. 000 391 7X with the correlation coefficient r of 0. 993 6. This method was simple,stable,sensitive,time-saving and was considered to be capable of meeting the actual needs for residue analysis in complex matrix such as environmental water samples. In order to demonstrate the availability of this method,it was applied to the investigation of 18 transport water samples and 26 temporary water samples from Shanghai,Zhejiang and Fujian in 2014. The positive rate was more than 20%,which was worth paying attention to the eugenol residual problem.
引文
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[6]苏明明,孙兴权,杨春光,等.渔用麻醉剂MS-222、丁香酚在鲜活水产品运输中的应用及检测方法研究进展[J].食品安全质量检测学报,2015,6(1):25-29.
[7]梁政远,安丽娜,董在杰,等.丁香油对罗非鱼的麻醉作用及其对血液指标和激素水平的影响[J].上海海洋大学学报,2009,18(5):629-635.
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[10] Hu X,Zheng Y,Wu G,et al. Optimization of solid phase extraction clean up and validation of quantitative determination of carbazochrome sodium sulfonate in human plasma by liquid chromatography-electrospray ionization tandem mass spectrometry[J]. J Chromatogr B,2014,1(1):951-952.
[11] Meinertz J R,Schreier T M,Porcher S T,et al. Depletion of eugenol residues from the skin-on fillet tissue of rainbow trout exposed to14C-labeled eugenol[J]. Aquaculture,2014,430:74-78.
[12] Li J,Liu H,Wang C,et al. Determination of eugenol in fish and shrimp muscle tissue by stable isotope dilution assay and solid-phase extraction coupled gas chromatography-triple quadrupole mass spectrometry[J]. Anal Bioanaly Chem,2016,408(24):6537-6544.
[13]陈焕,黄和,高平,等.分散固相萃取-气相色谱法同时测定水产品中六种丁香酚类麻醉剂的残留量[J].食品工业科技,2015,36(8):88-92.
[14]陈焕,黄和,高平,等.高效液相色谱法测定水产品中丁香酚类麻醉剂的残留量[J].食品与发酵工业,2014,40(12):156-160.
[15]高平,黄和,刘文侠,等.固相萃取-高效液相色谱-荧光检测法测定水产品中4种丁香酚类化合物[J].中国食品卫生杂志,2016,28(1):56-61.
[16] Beaudry F,Guénette S A,Vachon P. Determination of eugenol in rat plasma by liquid chromatography-quadrupole ion trap mass spectrometry using a simple off-line dansyl chloride derivatization reaction to enhance signal intensity[J]. Biome Chromatogr BMC,2006,20(11):1216-1222.
[17]张子为,刘广学,谢德媚,等.顶空-固相微萃取-气相色谱-质谱联用技术对灌胃细辛后小鼠脑、肝和血液中7个挥发性主要成分的定量分析研究[J].中国中药杂志,2016,41(2):285-293.
[18]焦亚琴,吕世明,谭艾娟,等.高效液相色谱法测定鲤鱼血浆中丁香酚含量[J].基因组学与应用生物学,2016,35(8):2022-2026.
[19] Schulz K,Schlenz K,Malt S,et al. Headspace solidphase microextraction-gas chromatography-mass spectrometry for the quantitative determination of the characteristic flavouring agent eugenol in serum samples after enzymatic cleavage to validate post-offence alcohol drinking claims[J]. J Chromatogr A,2008,1211(1):113-119.
[20] Bilia A R,Flamini G,Taglioli V,et al. GC–MS analysis of essential oil of some commercial Fennel teas[J].Food Chem,2002,76(3):307-310.
[21] Meinertz J R,Hess K R. Evaluation of analytical techniques to determine AQUI-S20E(Eugenol)concentrations in water[J]. Aquaculture,2014,418-419:62-66.
[22]赵东豪,王强,王旭峰,等.超高效液相色谱-串联质谱法检测鱼肉和暂养水中丁香酚残留量[J].食品科学,2016,37(24):252-256.
[23]柯常亮,刘奇,陈洁文,等.气相色谱-串联质谱联用法测定水中丁香酚残留[J].中国渔业质量与标准,2014,4(4):49-55.
[24]刘海新,余颖,汤水粉,等.气相色谱质谱法测定养殖水体中丁香酚含量不确定度评定[J].渔业研究,2016,38(4):310-317.
[2]杨亚军,刘希望,赵晓乐,等.丁香酚解热作用机理研究进展[J].中兽医医药杂志,2016(5):24-27.
[3] Endo T,Ogishima K,Tanaka H,et al. Studies on the anesthetic effect of eugenol in some fresh water fishes[J].Nihon Suisan Gakkai shi,1972,38(7):761-767.
[4]王正全,崔云云,倪玲,等.运输暂养水体中丁香酚残留检测研究进展[J].中国渔业质量与标准,2018,8(2):57-65.
[5]李晋成,刘欢,王群,等.水产品中丁香酚的残留风险评估研究进展[J].食品安全质量检测学报,2014(11):3598-3602.
[6]苏明明,孙兴权,杨春光,等.渔用麻醉剂MS-222、丁香酚在鲜活水产品运输中的应用及检测方法研究进展[J].食品安全质量检测学报,2015,6(1):25-29.
[7]梁政远,安丽娜,董在杰,等.丁香油对罗非鱼的麻醉作用及其对血液指标和激素水平的影响[J].上海海洋大学学报,2009,18(5):629-635.
[8] Cupp A R,Hartleb C F,Fredricks K T,et al. Effectiveness of eugenol sedation to reduce the metabolic rates of cool and warm water fish at high loading densities[J].Aquac Res,2016,47(1):234-242.
[9] Meinertz J R,Schreier T M,Porcher S T,et al. Evaluation of a method for quantifying eugenol concentrations in the fillet tissue from freshwater fish species[J]. J Aoac Int,2016,99(2):558-564.
[10] Hu X,Zheng Y,Wu G,et al. Optimization of solid phase extraction clean up and validation of quantitative determination of carbazochrome sodium sulfonate in human plasma by liquid chromatography-electrospray ionization tandem mass spectrometry[J]. J Chromatogr B,2014,1(1):951-952.
[11] Meinertz J R,Schreier T M,Porcher S T,et al. Depletion of eugenol residues from the skin-on fillet tissue of rainbow trout exposed to14C-labeled eugenol[J]. Aquaculture,2014,430:74-78.
[12] Li J,Liu H,Wang C,et al. Determination of eugenol in fish and shrimp muscle tissue by stable isotope dilution assay and solid-phase extraction coupled gas chromatography-triple quadrupole mass spectrometry[J]. Anal Bioanaly Chem,2016,408(24):6537-6544.
[13]陈焕,黄和,高平,等.分散固相萃取-气相色谱法同时测定水产品中六种丁香酚类麻醉剂的残留量[J].食品工业科技,2015,36(8):88-92.
[14]陈焕,黄和,高平,等.高效液相色谱法测定水产品中丁香酚类麻醉剂的残留量[J].食品与发酵工业,2014,40(12):156-160.
[15]高平,黄和,刘文侠,等.固相萃取-高效液相色谱-荧光检测法测定水产品中4种丁香酚类化合物[J].中国食品卫生杂志,2016,28(1):56-61.
[16] Beaudry F,Guénette S A,Vachon P. Determination of eugenol in rat plasma by liquid chromatography-quadrupole ion trap mass spectrometry using a simple off-line dansyl chloride derivatization reaction to enhance signal intensity[J]. Biome Chromatogr BMC,2006,20(11):1216-1222.
[17]张子为,刘广学,谢德媚,等.顶空-固相微萃取-气相色谱-质谱联用技术对灌胃细辛后小鼠脑、肝和血液中7个挥发性主要成分的定量分析研究[J].中国中药杂志,2016,41(2):285-293.
[18]焦亚琴,吕世明,谭艾娟,等.高效液相色谱法测定鲤鱼血浆中丁香酚含量[J].基因组学与应用生物学,2016,35(8):2022-2026.
[19] Schulz K,Schlenz K,Malt S,et al. Headspace solidphase microextraction-gas chromatography-mass spectrometry for the quantitative determination of the characteristic flavouring agent eugenol in serum samples after enzymatic cleavage to validate post-offence alcohol drinking claims[J]. J Chromatogr A,2008,1211(1):113-119.
[20] Bilia A R,Flamini G,Taglioli V,et al. GC–MS analysis of essential oil of some commercial Fennel teas[J].Food Chem,2002,76(3):307-310.
[21] Meinertz J R,Hess K R. Evaluation of analytical techniques to determine AQUI-S20E(Eugenol)concentrations in water[J]. Aquaculture,2014,418-419:62-66.
[22]赵东豪,王强,王旭峰,等.超高效液相色谱-串联质谱法检测鱼肉和暂养水中丁香酚残留量[J].食品科学,2016,37(24):252-256.
[23]柯常亮,刘奇,陈洁文,等.气相色谱-串联质谱联用法测定水中丁香酚残留[J].中国渔业质量与标准,2014,4(4):49-55.
[24]刘海新,余颖,汤水粉,等.气相色谱质谱法测定养殖水体中丁香酚含量不确定度评定[J].渔业研究,2016,38(4):310-317.