碱提取-丙基化衍生法同时测定土壤中的甲基汞和乙基汞
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摘要
建立了碱提取-丙基化衍生方式同时测定土壤中甲基汞和乙基汞的方法。优化了仪器分析条件,研究了碱提取温度、提取时间、缓冲溶液加入量和衍生化试剂加入量对测定结果的影响。应用本方法对5种实际土壤样品进行测定,甲基汞和乙基汞的方法检出限分别为0.5μg/kg和0.3μg/kg,相对标准偏差分别为1.3%～17%和0.94%～16%,平均回收率分别为88.2%～110%和66.1%～110%。该法适用于批量土壤样品中甲基汞和乙基汞的分析测定。
An alkali extraction-allylicderivatization method for the determination of trace levels of methylmercury and ethylmercury in soils was established in this paper. The instrumental analysis parameters were optimized. The effects of alkali extraction temperature and time, the amounts of buffer solution and derivatization reagent on the determination results were also studied. The method was applied to analyze five soil samples. The detection limits of methylmercury and ethylmercury in soils were 0.5 μg/kg and 0.3 μg/kg, respectively. And concentrations of methylmercury were determined with spiked recoveries of 88.2%-110% and relative standard deviations of 1.3%-17%(n=8), while concentrations of ethylmercury were determined with spiked recoveries of 66.1%-110% and relative standard deviations of 0.94%-16%(n=8). The proposed method has high sensitivity and is easy to operate. It's suitable for determination of methylmercury and ethylmercury in large-quantity soil samples.
An alkali extraction-allylicderivatization method for the determination of trace levels of methylmercury and ethylmercury in soils was established in this paper. The instrumental analysis parameters were optimized. The effects of alkali extraction temperature and time, the amounts of buffer solution and derivatization reagent on the determination results were also studied. The method was applied to analyze five soil samples. The detection limits of methylmercury and ethylmercury in soils were 0.5 μg/kg and 0.3 μg/kg, respectively. And concentrations of methylmercury were determined with spiked recoveries of 88.2%-110% and relative standard deviations of 1.3%-17%(n=8), while concentrations of ethylmercury were determined with spiked recoveries of 66.1%-110% and relative standard deviations of 0.94%-16%(n=8). The proposed method has high sensitivity and is easy to operate. It's suitable for determination of methylmercury and ethylmercury in large-quantity soil samples.
引文
[1] CAPELO J L,MADURO C,MOTA A M.Advanced Oxidation Processes for Degradation of Organomercurials:Determination of Inorganic and Total Mercury in Urine by FI-CV-AAS[J].Journal of Analytical Atomic Spectrometry,2004,19:414-416.
[2] TU Q,JOHNSON W,BUCKLEY B.Mercury Speciation Analysis in Soil Samples by Ion Chromatography,Post-Column Cold Vapor Generation and Inductively Coupled Plasma Mass Spectrometry[J].J Journal of Analytical Atomic Spectrometry,2003,18:696-701.
[3] CLARKSON T W.The Three Modern Faces of Mercury[J].Environmental Health Perspectives,2002,110(Supplement 1):11-23.
[4] MERGLER D,ANDERSON H A,CHAN L H M.Methymercury Exposure and Health Effects in Humans:A Worldwide Concern[J].A Journal of the human Environment,2007,36(1):3-11.
[5] CLARKSON T W.The Toxicology of Mercury[J].Critical Reviews in Clinical Laboratory Science,1997,34(4):369-403.
[6] BAILEY E A,GRAY J E,THEODORAKOS P M.Mercury in Vegetation and Soils at Abandoned Mercury Mines in Southwestern Alaska[J].Geochemistry-Exploration Environment Analysis,2002,2:275-285.
[7] 仇广乐,冯新斌,王少锋,等.贵州汞矿矿区不同位置土壤中总汞和甲基汞污染特征的研究[J].环境科学,2006,27(3):550-555.QIU Guangle,FENG Xinbin,WANG Shaofeng,et al.Total Mercury and Methylmercury in Soils Collected from Guizhou Hg-Mined Areas[J].Environmental Science,2006,27(3):550-555.
[8] United States Environmental Protection Agency.Methyl Mercury in Water by Distillation,Aqueous Ethylation,Purge and Trap,and CVAFS:EPA-1630[S].Washington:Office of Science and Technology Engineering and Analysis Division,2001.
[9] 陈邵鹏,顾海东,秦宏兵.高效液相色谱-氢化物发生-原子荧光光谱联用技术测定水中烷基汞[J].中国环境监测,2012,28(5):79-82.CHEN Shaopeng,GU Haidong,QIN Hongbing.Determination of Mercuryalkylide in Water Using High Performance Liquid Chromatography with Hydride Generation Atomic Fluorescene Detection[J].Environmental Monitoring in China,2012,28(5):79-82.
[10] 王炜,刘景泰,王晓雯.高效液相色谱-电感耦合等离子体质谱联用测水中有机汞[J].中国环境监测,2014,30(6):149-152.WANG Wei,LIU Jingtai,WANG Xiaowen.Simultaneous Determination of Organic Mercury in Water by HPLC-ICP-MS[J].Environmental Monitoring in China,2014,30(6):149-152.
[11] 陈贺,周慧兰.液液萃取-HPLC-ICPMS联用技术测定水体中甲基汞[J].中国环境监测,2015,31(1):110-112.CHEN He,ZHOU Huilan.Determination of Methyl Mercury in Water by HPLC-ICPMS with Liquid-Liquid Extraction[J].Environmental Monitoring in China,2015,31(1):110-112.
[12] 顾昱晓,孟梅,邵俊娟,等.在线吹扫捕集-气相色谱-原子荧光光谱法测定土壤中甲基汞[J].分析化学,2013,41(11):1 754-1 757.GU Yuxiao,MENG Mei,SHAO Junjuan,et al.Determination of Methylmercury in Soil Samples with Online Purge and Trap Gas Chromatography-Atomic Fluorescence Spectrometry[J].Chinese Journal of Analysis Chemistry.2013,41(11):1 754-1 757.
[13] HEMPEL M,HINTELMANN H.WILKEN R D.Determination of Organic Mercury Species in Soils by High-Performance Liquid Chromatography with Ultraviolet Detection[J].Analyst,1992,117(3):669-672.
[14] HORVAT M,BLOOM N S,LIANG L.Comparison of Distillation with Other Current Isolation Methods for the Determination of Methylmercury Compounds in Low Level Environmental Samples:Part 1.Sediments[J].Analytica Chimica Acta,1993,281:135-152.
[15] LUIS C,SERGI D,JOSEP M B.J.Simultaneous Determination of Methyl-and Ethyl-Mercury by Solid-Phasemicroextraction Followed by Gas Chromatography Atomic Fluorescence Detection[J].Journal of Chromatography A,2009,1216:8 828-8 834.
[16] PATRICIA G,REINALDO C C,ZOLTAN M,et al.A Comparison of Alkyl Derivatization Methods for Speciation of Mercury Based on Solid Phase Microextraction Gas Chromatography with Furnace Atomization Plasma Emission Spectrometry Detection[J].Journal of Analytical Atomic Spectrometry,2003,18:902-909.
[17] CAI Y,BAYONA J M.Determination of Methylmercury in Fish and River Water Samples Using in Situ Sodium Tetraethyl Borate Derivatization Following by Solid Phase Microwave Extraction and Gas Chromatography-Mass Spectrometry[J].Journal of Chromatography A,1995,696:113-122.
[2] TU Q,JOHNSON W,BUCKLEY B.Mercury Speciation Analysis in Soil Samples by Ion Chromatography,Post-Column Cold Vapor Generation and Inductively Coupled Plasma Mass Spectrometry[J].J Journal of Analytical Atomic Spectrometry,2003,18:696-701.
[3] CLARKSON T W.The Three Modern Faces of Mercury[J].Environmental Health Perspectives,2002,110(Supplement 1):11-23.
[4] MERGLER D,ANDERSON H A,CHAN L H M.Methymercury Exposure and Health Effects in Humans:A Worldwide Concern[J].A Journal of the human Environment,2007,36(1):3-11.
[5] CLARKSON T W.The Toxicology of Mercury[J].Critical Reviews in Clinical Laboratory Science,1997,34(4):369-403.
[6] BAILEY E A,GRAY J E,THEODORAKOS P M.Mercury in Vegetation and Soils at Abandoned Mercury Mines in Southwestern Alaska[J].Geochemistry-Exploration Environment Analysis,2002,2:275-285.
[7] 仇广乐,冯新斌,王少锋,等.贵州汞矿矿区不同位置土壤中总汞和甲基汞污染特征的研究[J].环境科学,2006,27(3):550-555.QIU Guangle,FENG Xinbin,WANG Shaofeng,et al.Total Mercury and Methylmercury in Soils Collected from Guizhou Hg-Mined Areas[J].Environmental Science,2006,27(3):550-555.
[8] United States Environmental Protection Agency.Methyl Mercury in Water by Distillation,Aqueous Ethylation,Purge and Trap,and CVAFS:EPA-1630[S].Washington:Office of Science and Technology Engineering and Analysis Division,2001.
[9] 陈邵鹏,顾海东,秦宏兵.高效液相色谱-氢化物发生-原子荧光光谱联用技术测定水中烷基汞[J].中国环境监测,2012,28(5):79-82.CHEN Shaopeng,GU Haidong,QIN Hongbing.Determination of Mercuryalkylide in Water Using High Performance Liquid Chromatography with Hydride Generation Atomic Fluorescene Detection[J].Environmental Monitoring in China,2012,28(5):79-82.
[10] 王炜,刘景泰,王晓雯.高效液相色谱-电感耦合等离子体质谱联用测水中有机汞[J].中国环境监测,2014,30(6):149-152.WANG Wei,LIU Jingtai,WANG Xiaowen.Simultaneous Determination of Organic Mercury in Water by HPLC-ICP-MS[J].Environmental Monitoring in China,2014,30(6):149-152.
[11] 陈贺,周慧兰.液液萃取-HPLC-ICPMS联用技术测定水体中甲基汞[J].中国环境监测,2015,31(1):110-112.CHEN He,ZHOU Huilan.Determination of Methyl Mercury in Water by HPLC-ICPMS with Liquid-Liquid Extraction[J].Environmental Monitoring in China,2015,31(1):110-112.
[12] 顾昱晓,孟梅,邵俊娟,等.在线吹扫捕集-气相色谱-原子荧光光谱法测定土壤中甲基汞[J].分析化学,2013,41(11):1 754-1 757.GU Yuxiao,MENG Mei,SHAO Junjuan,et al.Determination of Methylmercury in Soil Samples with Online Purge and Trap Gas Chromatography-Atomic Fluorescence Spectrometry[J].Chinese Journal of Analysis Chemistry.2013,41(11):1 754-1 757.
[13] HEMPEL M,HINTELMANN H.WILKEN R D.Determination of Organic Mercury Species in Soils by High-Performance Liquid Chromatography with Ultraviolet Detection[J].Analyst,1992,117(3):669-672.
[14] HORVAT M,BLOOM N S,LIANG L.Comparison of Distillation with Other Current Isolation Methods for the Determination of Methylmercury Compounds in Low Level Environmental Samples:Part 1.Sediments[J].Analytica Chimica Acta,1993,281:135-152.
[15] LUIS C,SERGI D,JOSEP M B.J.Simultaneous Determination of Methyl-and Ethyl-Mercury by Solid-Phasemicroextraction Followed by Gas Chromatography Atomic Fluorescence Detection[J].Journal of Chromatography A,2009,1216:8 828-8 834.
[16] PATRICIA G,REINALDO C C,ZOLTAN M,et al.A Comparison of Alkyl Derivatization Methods for Speciation of Mercury Based on Solid Phase Microextraction Gas Chromatography with Furnace Atomization Plasma Emission Spectrometry Detection[J].Journal of Analytical Atomic Spectrometry,2003,18:902-909.
[17] CAI Y,BAYONA J M.Determination of Methylmercury in Fish and River Water Samples Using in Situ Sodium Tetraethyl Borate Derivatization Following by Solid Phase Microwave Extraction and Gas Chromatography-Mass Spectrometry[J].Journal of Chromatography A,1995,696:113-122.