超声辅助提取-高效液相色谱-电感耦合等离子体质谱快速测定海鲜样品中的汞形态
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摘要
目的建立超声辅助提取的样品快速制备方法,并采用高效液相色谱-电感耦合等离子体质谱(HPLC-ICPMS)联用分析海鲜样品中汞形态的简单方法。方法采用含有巯基乙醇、L-半胱氨酸的HCl溶液从海鲜样品中提取甲基汞和无机汞,超声辅助提取15 min。用含有0. 05%V/V巯基乙醇和0. 4%m/V L-半胱氨酸的乙酸铵溶液在C18反相柱上5 min内实现甲基汞和无机汞的分离。结果无机汞和甲基汞在1μg/L～20μg/L浓度内呈良好线性,相关系数≥0. 996,海鲜样品基质的加标回收率为93. 2%～100. 2%,相对标准偏差为2. 7%～7. 5%。无机汞和甲基汞方法检出限分别为0. 25μg/kg和0. 1μg/kg。采用本方法检测标准参考物质,获得了一致结果,进一步验证方法准确性。结论本研究方法样品制备时间短,可靠性好,方法适用于本地市场的海鲜样品中汞形态分析。
Objective To establish a rapid and simple method for mercury speciation in seafood samples by high performance liquid chromatography-inductively coupled plasma mass spectrometry(LC-ICP-MS) with a fast sample preparation procedure. Methods Mercury species were extracted from food samples with a solution containing mercaptoethanol,L-cysteine and HCl and sonication for 15 min. Separation of mercury species was accomplished in less than 5 min on a C18 reverse phase column with a mobile phase containing 0. 05% V/V mercaptoethanol,0. 4% m/V L-cysteine and ammonium acetate. Results The method showed a good linearity(r≥0. 999) in the ranges of 0. 1 μg/L-20 μg/L for inorganic mercury and methyl mercury,with the average recovery rates of 93. 2%-100. 2% and the relative standard deviation(RSD) of 2. 7%-7. 5%. The detection limits were 0. 25 μg/kg and 0. 1 μg/kg for inorganic mercury and methylmercury,respectively. The detection of standard material by this method received the consistent results,and the accuracy of the method was verified.Conclusion The method has short preparation time and good reliability,and the method is suitable for mercury speciation analysis in seafood samples in the local market.
Objective To establish a rapid and simple method for mercury speciation in seafood samples by high performance liquid chromatography-inductively coupled plasma mass spectrometry(LC-ICP-MS) with a fast sample preparation procedure. Methods Mercury species were extracted from food samples with a solution containing mercaptoethanol,L-cysteine and HCl and sonication for 15 min. Separation of mercury species was accomplished in less than 5 min on a C18 reverse phase column with a mobile phase containing 0. 05% V/V mercaptoethanol,0. 4% m/V L-cysteine and ammonium acetate. Results The method showed a good linearity(r≥0. 999) in the ranges of 0. 1 μg/L-20 μg/L for inorganic mercury and methyl mercury,with the average recovery rates of 93. 2%-100. 2% and the relative standard deviation(RSD) of 2. 7%-7. 5%. The detection limits were 0. 25 μg/kg and 0. 1 μg/kg for inorganic mercury and methylmercury,respectively. The detection of standard material by this method received the consistent results,and the accuracy of the method was verified.Conclusion The method has short preparation time and good reliability,and the method is suitable for mercury speciation analysis in seafood samples in the local market.
引文
[1]中华人民共和国卫生部. GB 2762—2012食品安全国家标准食品污染物限量[S].北京:中国标准出版社,2012.
[2] D9ker S,Bo爧gelmez II. Rapid extraction and reverse phase-liquid chromatographic separation of mercury(II)and methylmercury in fish samples with inductively coupled plasma mass spectrometric detection applying oxygen addition into plasma[J]. Food Chem,2015,184:147-153.
[3]欧阳珮珮,黄诚,丘福保.高效液相色谱-电感耦合等离子体质谱法同时测定水产品中的无机汞、甲基汞和乙基汞[J].中国卫生检验杂志,2016,26(1):50-53.
[4] Chen X,Han C,Cheng H,et al. Rapid extraction and reverse phase-liquid chromatographic separation of mercury(II)and methylmercury in fish samples with inductively coupled plasma mass spectrometric detection applying oxygen addition into plasma[J]. J Chromatog A,2013,1314(11):86-93.
[5] Santoyo MM,Figueroa JA,Wrobel K,et al. Analytical speciation of mercury in fish tissues by reversed phase liquid chromatography-inductively coupled plasma mass spectrometry with Bi3+as internal standard[J]. Talanta,2009,79(3):706-711.
[6]张珂,高舸,张钦龙.超声辅助酸提取-液相色谱-电感耦合等离子体质谱法测定鱼肉中3种汞形态[J].中国食品卫生杂志,2017,29(5):581-584.
[7] Zmozinski AV,Carneado S,Ibá1ez-Palomino C,et al. Method development for the simultaneous determination of methylmercury and inorganic mercury in seafood[J]. Food Control,2014,46:351-359.
[8] Rahman GMM,Fahrenholz T,Kingston HM. Application of speciated isotope dilution mass spectrometry to evaluate methods for efficiencies,recoveries,and quantification of mercury species transformations in human hair[J]. J anal Atom Spectrom,2008,24(1):83-92.
[9] Gibicˇar D,Logar M,Horvat N,et al. Simultaneous determination of trace levels of ethylmercury and methylmercury in biological samples and vaccines using sodium tetra(n-propyl)borate as derivatizing agent[J]. Anal BioanaL Chem,2007,388(2):329-340.
[10] Liang L,Lazoff S. Evaluation of the procedure for alkaline digestion solvent estimation for methyl mercury artifact formation[J]. Talanta,1999,48(1):231-233.
[11] Qvarnstr9m J,Frech W. Mercury species transformations during sample pre-treatment of biological tissues studied by HPLCICP-MS[J]. J Anal Atom Spectrom,2002,17(11):1486-1491.
[12]中华人民共和国国家质量监督检验检疫总局. GB 5009. 17—2014食品安全国家标准食品中总汞及有机汞的测定[S].北京:中国质检出版社,2016.
[13]中华人民共和国国家质量监督检验检疫总局. GB 5009. 268—2016食品中多元素的测定[S].北京:中国质检出版社,2017.
[14] Chiou CS,Jiang SJ,Danadurai KSK. Determination of mercury compounds in fish by microwave-assisted extraction and liquid chromatography-vapor generation-inductively coupled plasma mass spectrometry[J]. Spectrochimica Acta part B,2001,56(7):1133-1142.
[2] D9ker S,Bo爧gelmez II. Rapid extraction and reverse phase-liquid chromatographic separation of mercury(II)and methylmercury in fish samples with inductively coupled plasma mass spectrometric detection applying oxygen addition into plasma[J]. Food Chem,2015,184:147-153.
[3]欧阳珮珮,黄诚,丘福保.高效液相色谱-电感耦合等离子体质谱法同时测定水产品中的无机汞、甲基汞和乙基汞[J].中国卫生检验杂志,2016,26(1):50-53.
[4] Chen X,Han C,Cheng H,et al. Rapid extraction and reverse phase-liquid chromatographic separation of mercury(II)and methylmercury in fish samples with inductively coupled plasma mass spectrometric detection applying oxygen addition into plasma[J]. J Chromatog A,2013,1314(11):86-93.
[5] Santoyo MM,Figueroa JA,Wrobel K,et al. Analytical speciation of mercury in fish tissues by reversed phase liquid chromatography-inductively coupled plasma mass spectrometry with Bi3+as internal standard[J]. Talanta,2009,79(3):706-711.
[6]张珂,高舸,张钦龙.超声辅助酸提取-液相色谱-电感耦合等离子体质谱法测定鱼肉中3种汞形态[J].中国食品卫生杂志,2017,29(5):581-584.
[7] Zmozinski AV,Carneado S,Ibá1ez-Palomino C,et al. Method development for the simultaneous determination of methylmercury and inorganic mercury in seafood[J]. Food Control,2014,46:351-359.
[8] Rahman GMM,Fahrenholz T,Kingston HM. Application of speciated isotope dilution mass spectrometry to evaluate methods for efficiencies,recoveries,and quantification of mercury species transformations in human hair[J]. J anal Atom Spectrom,2008,24(1):83-92.
[9] Gibicˇar D,Logar M,Horvat N,et al. Simultaneous determination of trace levels of ethylmercury and methylmercury in biological samples and vaccines using sodium tetra(n-propyl)borate as derivatizing agent[J]. Anal BioanaL Chem,2007,388(2):329-340.
[10] Liang L,Lazoff S. Evaluation of the procedure for alkaline digestion solvent estimation for methyl mercury artifact formation[J]. Talanta,1999,48(1):231-233.
[11] Qvarnstr9m J,Frech W. Mercury species transformations during sample pre-treatment of biological tissues studied by HPLCICP-MS[J]. J Anal Atom Spectrom,2002,17(11):1486-1491.
[12]中华人民共和国国家质量监督检验检疫总局. GB 5009. 17—2014食品安全国家标准食品中总汞及有机汞的测定[S].北京:中国质检出版社,2016.
[13]中华人民共和国国家质量监督检验检疫总局. GB 5009. 268—2016食品中多元素的测定[S].北京:中国质检出版社,2017.
[14] Chiou CS,Jiang SJ,Danadurai KSK. Determination of mercury compounds in fish by microwave-assisted extraction and liquid chromatography-vapor generation-inductively coupled plasma mass spectrometry[J]. Spectrochimica Acta part B,2001,56(7):1133-1142.