婴幼儿配方奶粉中氯丙醇脂肪酸酯的检测方法优化与污染暴露
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摘要
目的:采用气相色谱-质谱(gas chromatography-mass spectrometry,GC-MS)联用技术,建立同时测定婴幼儿配方奶粉中3-氯-1,2-丙二醇脂肪酸酯(3-monochloropropane-1,2-diol ester,3-MCPDE)、2-氯-l,3-丙二醇脂肪酸酯(2-monochloropropane-1,3-diol ester,2-MCPDE)、1,3-二氯-2-丙醇脂肪酸酯(1,3-dichloropropane-2-ol ester,1,3-DCPE)和2,3-二氯-1-丙醇脂肪酸酯(2,3-dichloropropane-1-olester,2,3-DCPE)含量的分析方法,并对市售50份婴幼儿配方奶粉中4种氯丙醇脂肪酸酯的污染水平进行调查分析和风险暴露评估。方法:婴幼儿配方奶粉经脂肪提取后,依次通过碱水解、硅藻土固相萃取小柱净化、七氟丁酰基咪唑衍生上机,同位素内标法定量。结果:该方法在20～600 ng/mL范围内线性良好(r~2≥0.998 9),检出限为0.005 mg/kg,定量限为0.015 mg/kg,检出限和定量限均以相应的氯丙醇计。0.03、0.075 mg/kg和0.15 mg/kg水平下的加标回收率在82.2%～113.9%之间,相对标准偏差均不大于8.3%。50份奶粉样品中,3-MCPDE检出率为100.0%,含量为0.037～0.208 mg/kg,2-MCPDE检出率为42.0%,含量为ND～0.060 mg/kg,1,3-DCPE和2,3-DCPE均未检出。统计不同月龄婴幼儿氯丙醇脂肪酸酯的平均暴露量,0～6月龄为3.86μg/kg、6～12月龄为2.00μg/kg、12～36月龄为1.07μg/kg。结论:该方法操作简便、准确可靠,适合婴幼儿配方奶粉中4种氯丙醇脂肪酸酯的同时测定。婴幼儿摄入氯丙醇脂肪酸酯的健康风险需引起关注。
Objective: A method for the simultaneous determination of the contents of 3-monochloropropane-1,2-diol ester(3-MCPDE), 2-monochloropropane-1,3-diol ester(2-MCPDE), 1,3-dichloropropane-2-ol ester(1,3-DCPE) and2,3-dichloropropane-1-ol ester(2,3-DCPE) in infant formula was established by gas chromatography-mass spectrometry(GC-MS). A total of 50 infant formula samples sold in Shanghai were researched for the pollution levels of four chloropropanol fatty acid esters(CPFAEs). Also we assessed the dietary exposure of infants to CPFAEs in infant formula.Methods: Fat was extracted from samples, followed by alkali hydrolysis, solid-phase extraction purification through a diatomite column and derivatization with hepta?uoro butyrylimidazole before being injected into the GC-MS system. The analytes were quanti?ed by the internal standard method. Results: The method showed a good linear relationship in the concentration range of 20–600 ng/mL(r2 ≥ 0.998 9). The limit of detection(LOD) and limit of quanti?cation(LOQ) were0.005 and 0.015 mg/kg, respectively(calculated as chlorpropanol). The recoveries of the four chloropropanols esters spiked at 0.03, 0.075 and 0.15 mg/kg were between 82.2%–113.9%, with relative standard deviations(RSDs) of less than 8.3%.3-MCPDE and 2-MCPDE were detected in 100.0% and 42.0% of the 50 infant formula samples with contamination levels in the range of 0.037–0.208 mg/kg and ND–0.060 mg/kg, respectively. However, 1,3-DCPE and 2,3-DCPE were not detected in any sample. The average exposure to CPFAEs in infant formula were 3.86, 2.00 and 1.07 μg/kg for infants aged 0–6,6–12 and 12–36 months, respectively. Conclusion: The method was easy to operate with good accuracy and reliability, and suitable for the determination of CPFAEs in infant formula. The health risk of CPFAEs through the intake of infant formula for infants should be a major concern.
Objective: A method for the simultaneous determination of the contents of 3-monochloropropane-1,2-diol ester(3-MCPDE), 2-monochloropropane-1,3-diol ester(2-MCPDE), 1,3-dichloropropane-2-ol ester(1,3-DCPE) and2,3-dichloropropane-1-ol ester(2,3-DCPE) in infant formula was established by gas chromatography-mass spectrometry(GC-MS). A total of 50 infant formula samples sold in Shanghai were researched for the pollution levels of four chloropropanol fatty acid esters(CPFAEs). Also we assessed the dietary exposure of infants to CPFAEs in infant formula.Methods: Fat was extracted from samples, followed by alkali hydrolysis, solid-phase extraction purification through a diatomite column and derivatization with hepta?uoro butyrylimidazole before being injected into the GC-MS system. The analytes were quanti?ed by the internal standard method. Results: The method showed a good linear relationship in the concentration range of 20–600 ng/mL(r2 ≥ 0.998 9). The limit of detection(LOD) and limit of quanti?cation(LOQ) were0.005 and 0.015 mg/kg, respectively(calculated as chlorpropanol). The recoveries of the four chloropropanols esters spiked at 0.03, 0.075 and 0.15 mg/kg were between 82.2%–113.9%, with relative standard deviations(RSDs) of less than 8.3%.3-MCPDE and 2-MCPDE were detected in 100.0% and 42.0% of the 50 infant formula samples with contamination levels in the range of 0.037–0.208 mg/kg and ND–0.060 mg/kg, respectively. However, 1,3-DCPE and 2,3-DCPE were not detected in any sample. The average exposure to CPFAEs in infant formula were 3.86, 2.00 and 1.07 μg/kg for infants aged 0–6,6–12 and 12–36 months, respectively. Conclusion: The method was easy to operate with good accuracy and reliability, and suitable for the determination of CPFAEs in infant formula. The health risk of CPFAEs through the intake of infant formula for infants should be a major concern.
引文
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[5]OZCAGLI E,ALPERTUNGA B,FENGA C,et al.Effects of3-monochloropropane-1,2-diol(3-MCPD)and its metabolites on DNAdamage and repair under in vitro conditions[J].Food&Chemical Toxicology,2016,89:1-7.DOI:10.1016/j.fct.2015.12.027.
[6]SVEJKOVSKA B,NOVOTNY O,DIVINOVA V,et al.Esters of3-chloropropane-1,2-diol in foodstuffs[J].Czech Journal of Food Sciences,2004,22(5):190-196.
[7]李珊.食品中氯丙醇酯的污染水平调查分析[D].武汉:武汉轻工大学,2015:24-44.
[8]ZELINKOVáZ,DOLE?AL M,VELí?EK J.Occurrence of3-chloropropane-l,2-diol fatty acid esters in infant and baby foods[J].European Food Research&Technology,2009,228(4):571-578.DOI:10.1007/s00217-008-0965-0.
[9]许欣欣,陈慧玲,刘红河,等.婴幼儿配方奶粉中3-氯丙醇酯的GC-MS法测定及暴露危险分析[J].中国食物与营养,2016,22(4):15-19.DOI:10.3969/j.issn.1006-9577.2016.04.003.
[10]刘园,卢剑.同位素内标-气相色谱-质谱法测定婴幼儿配方乳粉中氯丙醇酯类化合物[J].乳业科学与技术,2017,40(3):11-15.DOI:10.15922/j.cnki.jdst.2017.03.003.
[11]HAINES T D,ADLAF K J,PIERCEALL R M,et al.Direct determination of MCPD fatty acid esters and glycidyl fatty acid esters in vegetable oils by LC-TOFMS[J].Journal of the American Oil Chemists Society,2011,88(1):1-14.DOI:10.1007/s11746-010-1732-5.
[12]HORI K,KORIYAMA N,OMORI H,et al.Simultaneous determination of 3-MCPD fatty acid esters and glycidol fatty acid esters in edible oils using liquid chromatography time-of-flight mass spectrometry[J].LWT-Food Science and Technology,2012,48(2):204-208.DOI:10.1016/j.lwt.2012.03.014.
[13]ZHOU H R,JIN Q Z,WANG X G,et al.Direct measurement of3-chloropropane-1,2-diol fatty acid esters in oils and fats by HPLCmethod[J].Food Control,2014,36(1):111-118.DOI:10.1016/j.foodcont.2013.07.041.
[14]KüSTERS M,BIMBER U,REESER S,et al.Simultaneous determination and differentiation of glycidylesters an d3-monochloropropane-1,2-diol(MCPD)esters in different foodstuffs by GC-MS[J].Journal of Agricultural and Food Chemistry,2011,59(11):6263-6270.DOI:10.1021/jf200493b.
[15]RAZAK R A A,KUNTOM A,SIEW W L,et al.Detection and monitoring of 3-monochloropropane-1,2-diol(3-MCPD)esters in cooking oils[J].Food Control,2012,25(1):355-360.DOI:10.1016/j.foodcont.2011.10.058.
[16]ERMACORA A,HRNCIRIK K.A novel method for simultaneous monitoring of 2-MCPD,3-MCPD and glycidyl esters in oils and fats[J].Journal of the American Oil Chemists Society,2013,90(1):1-8.DOI:10.1007/s11746-012-2132-9.
[17]李珊,苗虹,崔霞,等.乳粉中氯丙醇脂肪酸酯的气相色谱-质谱检测方法的建立及其污染水平分析[J].中华预防医学杂志,2015,49(6):554-559.DOI:10.3760/cma.j.issn.0253-9624.2015.06.018.
[18]宁柠,王卫飞,李道明,等.食用油脂中缩水甘油酯的风险评估研究[J].中国油脂,2016,41(1):1-6.
[19]ZELINKOVA Z,GIRI A,WENZL T.Assessment of critical steps of a GC/MS based indirect analytical method for the determination of fatty acid esters of monochloropropanediols(MCPDEs)and of glycidol(GEs)[J].Food Control,2017(7):65-75.DOI:10.1016/j.foodcont.2017.01.024.
[20]傅武胜,严小波,吕华东,等.气相色谱/质谱法测定植物油中脂肪酸氯丙醇酯[J].分析化学,2012,40(9):1329-1335.DOI:10.3724/SP.J.1096.2012.11305.
[21]LIU Q,HAN F,XIE K,et al.Simultaneous determination of total fatty acid esters of chloropropanols in edible oils by gas chromatographymass spectrometry with solid-supported liquid-liquid extraction[J].Journal of Chromatography A,2013,1314(11):208-215.DOI:10.1016/j.chroma.2013.08.074.
[22]ERMACORA A,HRNCIRIK K.Evaluation of an improved indirect method for the analysis of 3-MCPD esters based on acid transesterification[J].Journal of the American Oil Chemists Society,2012,89(2):211-217.DOI:10.1007/s11746-011-1911-z.
[23]MIYAZAKI K,KOYAMA K,SASAKO H,et al.Indirect method for simultaneous determinations of 3-chloro-1,2-propanediol fatty acid esters and glycidyl fatty acid esters[J].Journal of the American Oil Chemists Society,2012,89(8):1403-1407.DOI:10.1007/s11746-012-2047-5.
[24]陈慧玲,许欣欣,刘红河,等.食用植物油中3-氯丙醇酯的GC-MS法测定及暴露危险分析[J].预防医学情报杂志,2016,32(9):912-915.
[25]黄翠莉,王天明,杨宁,等.GC-MS面积比法测定食用植物油中3-氯丙醇酯的研究[J].中国油脂,2015,40(11):74-78.DOI:10.3969/j.issn.1003-7969.2015.11.015.
[26]韩枫.食品中氯丙醇脂肪酸酯的检测技术、污染状况及膳食暴露研究[D].武汉:武汉轻工大学,2013:30-33.
[27]黄琦,季晓娟,王丹丹.气相色谱法测定鸡精中2种氯丙醇的方法研究[J].浙江科技学院学报,2013,25(1):33-37.
[28]Federal Institute for Risk Assessment.Infant formula and follow-up formula may contain harmful 3-MCPD fatty acid esters[R].Germany:BfR,2007.
[29]European Food Safety Authority(EFSA).Risks for human health related to the presence of 3-and 2-monochloropropanediol(MCPD),and their fatty acid esters,and glycidyl fatty acid esters in food[J].EFSA Journal,2016,14(5):4426.
[2]BUHRKE T,WEISSHAAR R,LAMPEN A.Absorption and metabolism of the food contaminant 3-chloro-1,2-propanediol(3-MCPD)and its fatty acid esters by human intestinal Caco-2 cells[J].Archives of Toxicology,2011,85(10):1201-1208.DOI:10.1007/s00204-011-0657-6.
[3]KWACK S J,KIM S S,CHOI Y W,et al.Mechanism of antifertility in male rats treated with 3-monochloro-1,2-propanediol(3-MCPD)[J].Journal of Toxicology&Environmental Health,2004,67(23/24):2001-2004.DOI:10.1080/15287390490514651.
[4]MYUNGSIL H,EUNKYUNG Y,JAYOUNG K,et al.Toxicity value for 3-monochloropropane-1,2-diol using a benchmark dose methodology[J].Regul Toxicol Pharmacol,2009,53(2):102-106.DOI:10.1016/j.yrtph.2008.12.005.
[5]OZCAGLI E,ALPERTUNGA B,FENGA C,et al.Effects of3-monochloropropane-1,2-diol(3-MCPD)and its metabolites on DNAdamage and repair under in vitro conditions[J].Food&Chemical Toxicology,2016,89:1-7.DOI:10.1016/j.fct.2015.12.027.
[6]SVEJKOVSKA B,NOVOTNY O,DIVINOVA V,et al.Esters of3-chloropropane-1,2-diol in foodstuffs[J].Czech Journal of Food Sciences,2004,22(5):190-196.
[7]李珊.食品中氯丙醇酯的污染水平调查分析[D].武汉:武汉轻工大学,2015:24-44.
[8]ZELINKOVáZ,DOLE?AL M,VELí?EK J.Occurrence of3-chloropropane-l,2-diol fatty acid esters in infant and baby foods[J].European Food Research&Technology,2009,228(4):571-578.DOI:10.1007/s00217-008-0965-0.
[9]许欣欣,陈慧玲,刘红河,等.婴幼儿配方奶粉中3-氯丙醇酯的GC-MS法测定及暴露危险分析[J].中国食物与营养,2016,22(4):15-19.DOI:10.3969/j.issn.1006-9577.2016.04.003.
[10]刘园,卢剑.同位素内标-气相色谱-质谱法测定婴幼儿配方乳粉中氯丙醇酯类化合物[J].乳业科学与技术,2017,40(3):11-15.DOI:10.15922/j.cnki.jdst.2017.03.003.
[11]HAINES T D,ADLAF K J,PIERCEALL R M,et al.Direct determination of MCPD fatty acid esters and glycidyl fatty acid esters in vegetable oils by LC-TOFMS[J].Journal of the American Oil Chemists Society,2011,88(1):1-14.DOI:10.1007/s11746-010-1732-5.
[12]HORI K,KORIYAMA N,OMORI H,et al.Simultaneous determination of 3-MCPD fatty acid esters and glycidol fatty acid esters in edible oils using liquid chromatography time-of-flight mass spectrometry[J].LWT-Food Science and Technology,2012,48(2):204-208.DOI:10.1016/j.lwt.2012.03.014.
[13]ZHOU H R,JIN Q Z,WANG X G,et al.Direct measurement of3-chloropropane-1,2-diol fatty acid esters in oils and fats by HPLCmethod[J].Food Control,2014,36(1):111-118.DOI:10.1016/j.foodcont.2013.07.041.
[14]KüSTERS M,BIMBER U,REESER S,et al.Simultaneous determination and differentiation of glycidylesters an d3-monochloropropane-1,2-diol(MCPD)esters in different foodstuffs by GC-MS[J].Journal of Agricultural and Food Chemistry,2011,59(11):6263-6270.DOI:10.1021/jf200493b.
[15]RAZAK R A A,KUNTOM A,SIEW W L,et al.Detection and monitoring of 3-monochloropropane-1,2-diol(3-MCPD)esters in cooking oils[J].Food Control,2012,25(1):355-360.DOI:10.1016/j.foodcont.2011.10.058.
[16]ERMACORA A,HRNCIRIK K.A novel method for simultaneous monitoring of 2-MCPD,3-MCPD and glycidyl esters in oils and fats[J].Journal of the American Oil Chemists Society,2013,90(1):1-8.DOI:10.1007/s11746-012-2132-9.
[17]李珊,苗虹,崔霞,等.乳粉中氯丙醇脂肪酸酯的气相色谱-质谱检测方法的建立及其污染水平分析[J].中华预防医学杂志,2015,49(6):554-559.DOI:10.3760/cma.j.issn.0253-9624.2015.06.018.
[18]宁柠,王卫飞,李道明,等.食用油脂中缩水甘油酯的风险评估研究[J].中国油脂,2016,41(1):1-6.
[19]ZELINKOVA Z,GIRI A,WENZL T.Assessment of critical steps of a GC/MS based indirect analytical method for the determination of fatty acid esters of monochloropropanediols(MCPDEs)and of glycidol(GEs)[J].Food Control,2017(7):65-75.DOI:10.1016/j.foodcont.2017.01.024.
[20]傅武胜,严小波,吕华东,等.气相色谱/质谱法测定植物油中脂肪酸氯丙醇酯[J].分析化学,2012,40(9):1329-1335.DOI:10.3724/SP.J.1096.2012.11305.
[21]LIU Q,HAN F,XIE K,et al.Simultaneous determination of total fatty acid esters of chloropropanols in edible oils by gas chromatographymass spectrometry with solid-supported liquid-liquid extraction[J].Journal of Chromatography A,2013,1314(11):208-215.DOI:10.1016/j.chroma.2013.08.074.
[22]ERMACORA A,HRNCIRIK K.Evaluation of an improved indirect method for the analysis of 3-MCPD esters based on acid transesterification[J].Journal of the American Oil Chemists Society,2012,89(2):211-217.DOI:10.1007/s11746-011-1911-z.
[23]MIYAZAKI K,KOYAMA K,SASAKO H,et al.Indirect method for simultaneous determinations of 3-chloro-1,2-propanediol fatty acid esters and glycidyl fatty acid esters[J].Journal of the American Oil Chemists Society,2012,89(8):1403-1407.DOI:10.1007/s11746-012-2047-5.
[24]陈慧玲,许欣欣,刘红河,等.食用植物油中3-氯丙醇酯的GC-MS法测定及暴露危险分析[J].预防医学情报杂志,2016,32(9):912-915.
[25]黄翠莉,王天明,杨宁,等.GC-MS面积比法测定食用植物油中3-氯丙醇酯的研究[J].中国油脂,2015,40(11):74-78.DOI:10.3969/j.issn.1003-7969.2015.11.015.
[26]韩枫.食品中氯丙醇脂肪酸酯的检测技术、污染状况及膳食暴露研究[D].武汉:武汉轻工大学,2013:30-33.
[27]黄琦,季晓娟,王丹丹.气相色谱法测定鸡精中2种氯丙醇的方法研究[J].浙江科技学院学报,2013,25(1):33-37.
[28]Federal Institute for Risk Assessment.Infant formula and follow-up formula may contain harmful 3-MCPD fatty acid esters[R].Germany:BfR,2007.
[29]European Food Safety Authority(EFSA).Risks for human health related to the presence of 3-and 2-monochloropropanediol(MCPD),and their fatty acid esters,and glycidyl fatty acid esters in food[J].EFSA Journal,2016,14(5):4426.