气相色谱-同位素稀释质谱法测定肉中多环芳烃含量
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摘要
采用分子印迹固相萃取技术,建立肉中多环芳烃残留的气相色谱-同位素稀释质谱检测方法。以萘-D8为内标、正己烷-二氯甲烷(7∶3,V/V)混合溶液为提取试剂,经过匀浆、超声提取、离心、分子印迹固相萃取等步骤,在优化仪器条件下进行定性、定量分析。在5～100 ng/mL范围内,16种多环芳烃峰面积与内标物峰面积的比值均与质量浓度的比值呈良好的线性关系,线性相关系数不小于0.999 9,肉及肉制品中检出限为0.125～0.625μg/kg。3个加标水平下的样品回收率在85.7%～109%之间,相对标准偏差(n=6)在0.75%～4.90%之间。该方法前处理效率高,定量法灵敏、准确,适合于监控肉类中多环芳烃的含量。
Using molecularly imprinted solid phase extraction, a gas chromatography-isotope dilution mass spectrometry(GC-IDMS) method was developed for the determination of polycyclic aromatic hydrocarbons(PAHs) in meat samples. Naphthalene-D8 was used as an internal standard, and a mixed solvent of n-hexane-dichloromethane(7:3, V/V) was used as an extraction solvent. The sample preparation consisted of homogenization, ultrasonic extraction, centrifugation, and purification by molecularly imprinted solid phase extraction cartridge. The qualitative and quantitative analysis were conducted under optimized instrumental conditions. The calibration curves showed a good linearity within the concentration range of 5–100 ng/mL with correlation coefficient no less than 0.999 9 and the limit of detection(LOD) was 0.125–0.625 μg/kg for meat and meat products. The recoveries at three spiked levels ranged from 85.7% to 109% with relative standard deviations(RSDs) of 0.75%–4.90%. The results indicated that this method was efficient, sensitive and accurate and could be successfully applied in the quantification of PAHs in meat.
Using molecularly imprinted solid phase extraction, a gas chromatography-isotope dilution mass spectrometry(GC-IDMS) method was developed for the determination of polycyclic aromatic hydrocarbons(PAHs) in meat samples. Naphthalene-D8 was used as an internal standard, and a mixed solvent of n-hexane-dichloromethane(7:3, V/V) was used as an extraction solvent. The sample preparation consisted of homogenization, ultrasonic extraction, centrifugation, and purification by molecularly imprinted solid phase extraction cartridge. The qualitative and quantitative analysis were conducted under optimized instrumental conditions. The calibration curves showed a good linearity within the concentration range of 5–100 ng/mL with correlation coefficient no less than 0.999 9 and the limit of detection(LOD) was 0.125–0.625 μg/kg for meat and meat products. The recoveries at three spiked levels ranged from 85.7% to 109% with relative standard deviations(RSDs) of 0.75%–4.90%. The results indicated that this method was efficient, sensitive and accurate and could be successfully applied in the quantification of PAHs in meat.
引文
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[9]石龙凯,刘玉兰.液相色谱-串联质谱法检测食用油脂中多环芳烃[J].中国粮油学报,2015, 30(12):114-119. DOI:10.3969/j.issn.1003-0174.2015.12.021.
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[15]周天啸,高俊伟,彭姚珊,等.气相色谱-串联质谱法测定纸质及塑料食品包装材料中12种多环芳烃的含量[J].理化检验:化学分册,2016,52(12):1388-1393.DOI:10.11973/lhj y-hx201612006.
[16]赵波,黎玉清,张素坤,等.气相色谱-三重四极杆串联质谱法检测环境空气中的多环芳烃[J].色谱,2014, 32(9):9960-9966.DOI:10.3724/SP.J.1123.2014.05027.
[17]曾浩,汤桦,陈大舟,等.同位素稀释三重串联四级杆质谱法测定鱼组织中24种多环芳烃[J].分析试验室,2011,30(9):11-15.DOI:10.3969/j.issn.1000-0720.2011.09.003.
[18]许婷,汤桦,陈大舟,等.同位素稀释-气相色谱-三重四极杆串联质谱法分析食用油中18种多环芳烃[J].质谱学报,2015, 36(2):120-127.DOI:10.7538/zpxb.youxian.2014.0053.
[19] LUDIVINE F, NATHALIE D, DOUGLAS N R,et al. Optimizing separation conditions of 19 polycyclic aromatic hydrocarbons bycyclodextrin-modified capillary electrophoresis and application to edible oils[J]. Talanta, 2014, 119:572-581. DOI:10.1016/j.talanta.2013.11.062.
[20] RYCHLIK M,AS AM S. Stable isotope dilution assays in my cotoxin analysis[J]. Analytical and Bioanalytical Chemistry, 2008, 390:617-628.DOI:10.1007/s00216-007-1717-x.
[21]李杰,于瑞祥,许卓妮,等.同位素稀释-气相色谱-质谱法测定发酵乳中氨基甲酸乙酯[J].质谱学报,2015, 36(3):268-273.DOI:10.7538/zpxb.youxian.2015.0006.
[22]李杰,许卓妮,于瑞祥,等.超高效液相色谱-串联质谱法测定减肥类保健品中的西布曲明[J].理化检验:化学分册,2015,51(7):995-998.DOI:10.11973/lhj y-hx201507026.
[23]章汝平,郭萍,李锦辉.气相色谱-质谱法测定肉松、鱼干中的多环芳烃[J].食品科技,2008, 33(6):213-217. DOI:10.3969/j.issn.1005-9989.2008.06.067.
[24]国家卫生和计划生育委员会,国家食品药品监督管理局.食品中多环芳烃的测定:GB 5009.265-2016[S].北京:中国标准出版社,2016:1-10.
[25]马润恬,师彦平.样品分析中分子印迹固相萃取的新技术进展[J].色谱,2016,34(3):223-225.DOI:10.3724/SP.J.1123.2016.02019.
[26]俞晔.HPLC-FLD和GC-MS-MS检测油脂、油料中多环芳烃方法的建立及应用[D].无锡:江南大学,2015:26-45.
[27]李成,张雪娜,师耀龙,等.分子印迹固相萃取-气相色谱/质谱联用法测定污泥中多环芳烃[J].环境化学,2017, 36(1):190-197.DOI:10.7524/j.issn.0254-6108.2017.01.2016032203.
[28]国家卫生和计划生育委员会,国家食品药品监督管理局.食品中污染物限量:GB2762-2017[S].北京:中国标准出版社,2017:10.
[29] European Commission. Amending Regulation(EC)No 1881/2006as regards maximum levels for polycyclic aromatic hydrocarbons in cocoa fibre, banana chips, food supplements, dried herbs and dried spices:Commission Regulation(EU)2015/1933[S]. European Union Website,2015:3.
[30]国家质量监督检验检疫总局,国家标准化管理委员会.实验室质量控制规范食品理化检测:GB/T27404-2008[S].北京:中国标准出版社,2008:31-32.
[2]王国庆,王宗义,程明捷,等.冷冻除脂-气相色谱-串联质谱法检测食用植物油中30种多环芳烃[J].食品科学,2017, 38(3):218-220.DOI:10.7506/spkx1002-6630-201808044.
[3]曹梦思,王君,张立实,等.我国食用油脂中欧盟优控15+1种多环芳烃的污染状况分析[J].中国食品学报,2016, 16(12):198-205.DOI:10.16429/j.1009-7848.2016.12.026.
[4]王建华,杨君,刘靖靖,等.同位素稀释-气相色谱-串联质谱法测定植物油中的15种欧盟优控多环芳烃[J].分析试验室,2014, 33(1):48-53.DOI:10.13595/j.cnki.issn1000-0720.2014.0011.
[5]王峰,张志杰,林慧,等.高效液相色谱-二极管阵列检测器-荧光检测器法测定植物油中的18种多环芳烃[J].食品科学,2014, 35(6):142-145.DOI:10.7506/spkx1002-6630-201406030.
[6] KENAN D, CEVAT I. Determination of polycyclic aromatic hydrocarbons in edible oil and barbecued food by HPLC/UV-vis detection[J]. Food Chemistry,2012, 133(1):193-199.DOI:10.1016/j.foodchem.2012.01.001.
[7] PETTER O,IOANNIS S, JAN H, et al. Class separation of lipids and polycyclic aromatic hydrocarbons in normal phase high performance liquid chromatography:a prospect for analysis of aromativs in edible vegetable oils and biodiesel exhaust particulates[J].Journal of Chromatography A, 2014, 1360:39-46. DOI:10.1016/j.chroma.2014.07.064.
[8]刘玉兰,张小涛,赵欢欢.液相色谱-串联质谱法检测食用油脂中苯并芘[J].农业机械,2012, 30(1):45-48. DOI:10.16167/j.cnki.1000-9868.2012.30.001.
[9]石龙凯,刘玉兰.液相色谱-串联质谱法检测食用油脂中多环芳烃[J].中国粮油学报,2015, 30(12):114-119. DOI:10.3969/j.issn.1003-0174.2015.12.021.
[10] SHI L K, LIU Y L,LIU H M,et al. One-step solvent extraction followed by liquid chromatography-atmospheric pressure photoionization tandem mass spectrometry for the determination of polycyclic aromatic hydrocarbons in edible oils[J].Analytical and Bioanalytical Chemistry,2015,407(13):3605-3616. DOI:10.1007/s00216-015-8571-z.
[11] SHI L K,ZHANG D D,LIU Y L.Incidence and survey of polycyclic aromatic hydrocarbons in edible vegetable oils in China[J]. Food Control,2016,62:165-170.DOI:10.1016/j.foodcont.2015.10.037.
[12] MIYAWAKI T,TOBIBSHI K,TAKENAKA S,et al.A rapid method,combining microwave-assisted extraction and gas chromatographymass spectrometry with a database.,for determining organochlorine pesticides and polycyclic aromatic hydrocarbons in soils and sediments[J]. Soil and Sediment Contamination:an International Journal,2018,27(1):31-45.DOI:10.1080/15320383.2017.1360245.
[13] WU R T,LI N, SHU R,et al.Determination of polycyclic aromatic hydrocarbons in mosses by ultrasonic-assisted extraction and gas chromatography-tandem mass spectrometry[J]. Analytical Letters,2017,50(1):243-257.DOI:10.1080/00032719.2016.1166371.
[14] XU F Y, FENG X M, SHI N R,et al.Development and validation of a subcritical 1,1,1,2-tetrafluoroethane extraction technique:gas chromatography-mass spectrometry method for the simultaneous determination of polycyclic aromatic hydrocarbons,polychlorinated biphenyls,and polybrominated biphenyl ethers in aquatic products[J].Journal of Separation Science,2017,40(21):4213-4221.DOI:10.1002/jssc.201700043.
[15]周天啸,高俊伟,彭姚珊,等.气相色谱-串联质谱法测定纸质及塑料食品包装材料中12种多环芳烃的含量[J].理化检验:化学分册,2016,52(12):1388-1393.DOI:10.11973/lhj y-hx201612006.
[16]赵波,黎玉清,张素坤,等.气相色谱-三重四极杆串联质谱法检测环境空气中的多环芳烃[J].色谱,2014, 32(9):9960-9966.DOI:10.3724/SP.J.1123.2014.05027.
[17]曾浩,汤桦,陈大舟,等.同位素稀释三重串联四级杆质谱法测定鱼组织中24种多环芳烃[J].分析试验室,2011,30(9):11-15.DOI:10.3969/j.issn.1000-0720.2011.09.003.
[18]许婷,汤桦,陈大舟,等.同位素稀释-气相色谱-三重四极杆串联质谱法分析食用油中18种多环芳烃[J].质谱学报,2015, 36(2):120-127.DOI:10.7538/zpxb.youxian.2014.0053.
[19] LUDIVINE F, NATHALIE D, DOUGLAS N R,et al. Optimizing separation conditions of 19 polycyclic aromatic hydrocarbons bycyclodextrin-modified capillary electrophoresis and application to edible oils[J]. Talanta, 2014, 119:572-581. DOI:10.1016/j.talanta.2013.11.062.
[20] RYCHLIK M,AS AM S. Stable isotope dilution assays in my cotoxin analysis[J]. Analytical and Bioanalytical Chemistry, 2008, 390:617-628.DOI:10.1007/s00216-007-1717-x.
[21]李杰,于瑞祥,许卓妮,等.同位素稀释-气相色谱-质谱法测定发酵乳中氨基甲酸乙酯[J].质谱学报,2015, 36(3):268-273.DOI:10.7538/zpxb.youxian.2015.0006.
[22]李杰,许卓妮,于瑞祥,等.超高效液相色谱-串联质谱法测定减肥类保健品中的西布曲明[J].理化检验:化学分册,2015,51(7):995-998.DOI:10.11973/lhj y-hx201507026.
[23]章汝平,郭萍,李锦辉.气相色谱-质谱法测定肉松、鱼干中的多环芳烃[J].食品科技,2008, 33(6):213-217. DOI:10.3969/j.issn.1005-9989.2008.06.067.
[24]国家卫生和计划生育委员会,国家食品药品监督管理局.食品中多环芳烃的测定:GB 5009.265-2016[S].北京:中国标准出版社,2016:1-10.
[25]马润恬,师彦平.样品分析中分子印迹固相萃取的新技术进展[J].色谱,2016,34(3):223-225.DOI:10.3724/SP.J.1123.2016.02019.
[26]俞晔.HPLC-FLD和GC-MS-MS检测油脂、油料中多环芳烃方法的建立及应用[D].无锡:江南大学,2015:26-45.
[27]李成,张雪娜,师耀龙,等.分子印迹固相萃取-气相色谱/质谱联用法测定污泥中多环芳烃[J].环境化学,2017, 36(1):190-197.DOI:10.7524/j.issn.0254-6108.2017.01.2016032203.
[28]国家卫生和计划生育委员会,国家食品药品监督管理局.食品中污染物限量:GB2762-2017[S].北京:中国标准出版社,2017:10.
[29] European Commission. Amending Regulation(EC)No 1881/2006as regards maximum levels for polycyclic aromatic hydrocarbons in cocoa fibre, banana chips, food supplements, dried herbs and dried spices:Commission Regulation(EU)2015/1933[S]. European Union Website,2015:3.
[30]国家质量监督检验检疫总局,国家标准化管理委员会.实验室质量控制规范食品理化检测:GB/T27404-2008[S].北京:中国标准出版社,2008:31-32.