柱前还原衍生-顶空气相色谱法测定冰冻鱼和虾中甲醛
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摘要
目的建立柱前还原衍生-顶空气相色谱法测定冰冻鱼和虾中甲醛的新方法,解决目前食品中甲醛测定方法样品前处理复杂、稳定性差的问题。方法取一定量匀浆后海鲜样品,加入0.10 mol/L硼氢化钠-1.0 mol/L氢氧化钠(1:10,V/V)还原剂,使样品中甲醛还原为甲醇,离心后取上清液于顶空瓶中,90℃下以顶空进样器加热30 min后进样,经DB-WAX色谱柱(60 m×0.32 mm,0.5μm)分离、FID检测,外标法定量。结果还原液对浓度<15.6 mg/L的甲醛标准溶液还原效率可达100%,且无基质干扰。在0.4 mg/L～15.6 mg/L浓度内,相关系数>0.998 7,加标回收率为87.3%～107.3%,方法检出限为0.4 mg/kg,相对标准偏差<8.1%。本法对鱼、虾样品的测定结果与国家标准方法SC/T 3025—2006测定结果一致。结论本法操作简便,准确、稳定,适用于冰冻鱼和虾样品中甲醛的测定。
Objective To establish a new method for determining formaldehyde in frozen fish and shrimp by headspace gas chromatography with pre-column reducing derivatization, which can solve the problem of complex pretreatment and poor stability when determining formaldehyde in food. Methods Reducing agent, 0.1 mol/L NaBH_4-1.0 mol/L NaOH(10:1, V/V), was added in a certain amount of homogenized seafood samples. Formaldehyde in the sample can be reduced to methanol, which can be determined by headspace gas chromatography with FID detector after headspace(90 ℃, 30 min) and centrifuge treatment. It was separated by DB-WAX column(60 m×0.32 mm, 0.5 μm), detected by FID, and quantified by external standard method. Results The reducing solution had a reduction efficiency of 100% for formaldehyde solution with a concentration of less than 15.6 mg/L and no matrix interference. In 0.4 mg/L-15.6 mg/L, the correlation coefficient was greater than 0.998, and the recoveries were within 87.3%-107.3%. The detection limit was 0.4 mg/kg, and the relative standard deviation was less than 8.1%. The test results of fish and shrimp samples in this method were consistent with the results of the national standard method SC/T 3025—2006. Conclusion This method can determine formaldehyde concentration simply, rapidly, accurately and steadily. It is suitable for determining formaldehyde in frozen fish and shrimp.
Objective To establish a new method for determining formaldehyde in frozen fish and shrimp by headspace gas chromatography with pre-column reducing derivatization, which can solve the problem of complex pretreatment and poor stability when determining formaldehyde in food. Methods Reducing agent, 0.1 mol/L NaBH_4-1.0 mol/L NaOH(10:1, V/V), was added in a certain amount of homogenized seafood samples. Formaldehyde in the sample can be reduced to methanol, which can be determined by headspace gas chromatography with FID detector after headspace(90 ℃, 30 min) and centrifuge treatment. It was separated by DB-WAX column(60 m×0.32 mm, 0.5 μm), detected by FID, and quantified by external standard method. Results The reducing solution had a reduction efficiency of 100% for formaldehyde solution with a concentration of less than 15.6 mg/L and no matrix interference. In 0.4 mg/L-15.6 mg/L, the correlation coefficient was greater than 0.998, and the recoveries were within 87.3%-107.3%. The detection limit was 0.4 mg/kg, and the relative standard deviation was less than 8.1%. The test results of fish and shrimp samples in this method were consistent with the results of the national standard method SC/T 3025—2006. Conclusion This method can determine formaldehyde concentration simply, rapidly, accurately and steadily. It is suitable for determining formaldehyde in frozen fish and shrimp.
引文
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[10] 中华人民共和国农业部.NY/T 1283—2007 香菇中甲醛含量的测定[S].北京:中国标准出版社,2007.
[11] 赵丹莹.食品中甲醛污染物的来源和检测方法[J].职业与健康,2016,32(17):2441-2445.
[12] 王佰华,张薇君.衍生-气相色谱法测定水产品中的游离甲醛[J].分析试验室,2007,26(3):88-90.
[13] 汤施展,黄丽,陈中祥,等.柱前衍生化-气相色谱法测定水产品中的游离甲醛[J].中国渔业质量与标准,2016,6(2):51-56.
[14] Hu HC,Tian YX,Chai XS,et al.Rapid determination of residual formaldehyde in formaldehyde related polymer latexes by headspace gas chromatography[J].J Ind Eng Chem,2013,19(3):748-751.
[15] 中华人民共和国国家卫生和计划生育委员会,国家食品药品监督管理总局.GB 5009.266—2016 食品安全国家标准食品中甲醇的测定[S].北京:中国标准出版社,2016.
[2] Duong A,Steinmaus C,McHale CM,et al.Reproductive and developmental toxicity of formaldehyde:a systematic review[J].Mutat Res,2011,728(3):118-138.
[3] Wang HX,Zhou DX,Zheng LR,et al.Effects of paternal occupation exposure to formaldehyde on reproductive outcomes[J].J Occup Environ Med,2012,54(5):518-524.
[4] IARC working group on the evaluation of carcinogenic risks to humans.Chemical agents and related occupations[J].IARC Monographs on the Evaluation of Carcinogenic Risks to Humans,2012,100(Pt F):401-436.
[5] 余超,何洁仪,刘于飞,等.2006-2015年广州市部分食品甲醛监测结果分析[J].中国食品卫生杂志,2017,29(2):213-217.
[6] 申屠基康,钟惠英,朱励华,等.鲜冻水产品及其加工品中甲醛含量状况调查[J].中国食品卫生杂志,2006,18(6):549-551.
[7] 中华人民共和国农业部.SC/T 3025—2006 水产品中甲醛的测定[S].北京:中国标准出版社,2006.
[8] 中华人民共和国国家质量监督检验检疫总局.GB/T 21126—2007 小麦粉、大米粉及其制品中甲醛次硫酸氢钠含量的测定[S].北京:中国标准出版社,2007.
[9] 中华人民共和国国家质量监督检验检疫总局.SN/T 1547—2011 进出口食品中甲醛的测定液相色谱法[S].北京:中国标准出版社,2011.
[10] 中华人民共和国农业部.NY/T 1283—2007 香菇中甲醛含量的测定[S].北京:中国标准出版社,2007.
[11] 赵丹莹.食品中甲醛污染物的来源和检测方法[J].职业与健康,2016,32(17):2441-2445.
[12] 王佰华,张薇君.衍生-气相色谱法测定水产品中的游离甲醛[J].分析试验室,2007,26(3):88-90.
[13] 汤施展,黄丽,陈中祥,等.柱前衍生化-气相色谱法测定水产品中的游离甲醛[J].中国渔业质量与标准,2016,6(2):51-56.
[14] Hu HC,Tian YX,Chai XS,et al.Rapid determination of residual formaldehyde in formaldehyde related polymer latexes by headspace gas chromatography[J].J Ind Eng Chem,2013,19(3):748-751.
[15] 中华人民共和国国家卫生和计划生育委员会,国家食品药品监督管理总局.GB 5009.266—2016 食品安全国家标准食品中甲醇的测定[S].北京:中国标准出版社,2016.