自动化树脂分离富集装置与ICP-MS联用在海水痕量金属元素分析中的应用
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摘要
基于自动化树脂分离富集装置对海水中痕量金属元素(Cu、Pb、Zn和Cd)的预分离富集技术和电感耦合等离子体质谱仪,建立了一种适用于河口区及近岸海域海水中痕量金属元素的分析方法,利用该方法对长江口及其邻近海域的实际海水样品进行分析。结果表明:当海水样品pH<2时,与pH为6.0±0.1的醋酸铵缓冲溶液按一定体积比例(13∶2～13∶5)混合后加载到树脂柱,4种目标元素(Cu、Pb、Zn和Cd)可以在树脂柱上实现稳定吸附;以不低于800μL的醋酸铵缓冲溶液冲洗吸附后的柱体,可以有效去除碱金属、碱土金属和阴离子等干扰物质;以不低于600μL的洗脱液(10%的硝酸溶液)以200μL/min的速率反冲吸附后的柱体,4种目标元素可同时达到较高的回收率。在最优实验条件下,新方法对Cu、Pb、Zn和Cd的检出限分别为0.014、0.002、0.049和0.001μg/L,同时表现出了自动化程度高、消耗样品和试剂体积小的优点。新方法对长江口及其邻近海域的海水中Cu、Pb、Zn和Cd的分析结果与海洋监测规范中的标准方法分析结果之间没有显著性差异(P>0.05),表明该方法的稳定性强且不受盐度的影响,适用于河口区及其邻近海域的痕量金属元素的分析工作。
In this study, we present an analytical approach which uses an automated pre-concentration device(seaFAST) with accurate volume loading and in-line pH buffering of the sample prior to loading onto the chelating resin(NOBIAS chelate-PA1) and subsequent simultaneous analysis of copper(Cu), lead(Pb), zinc(Zn) and cadmium(Cd) by Inductively Coupled Plasma Mass Spectrometry(ICP-MS). The available system extracts the trace metals from the seawater onto a chelation resin column, when the seawater sample pH<2, mixed with the buffer solution of ammonium acetate with pH(6.0±0.1) in a certain volume ratio(13∶2～13∶5). And the resin can be washed with the buffer solution of ammonium acetate no less than 800μL, which can effectively remove alkali metals, alkaline-earth metals, anions, etc. The four target elements can achieve high recovery at the same time when the resin eluted by 10% nitric acid which is no less than 600 μL at the rate of 200 μL/min. The detection limits of this method were 0.014 μg/L(Cu), 0.002 μg/L(Pb), 0.049 μg/L(Zn), 0.001 μg/L(Cd).The analytical technique has advantages of high automation and small volume of reagents and samples. There is no significant difference of the analytical results, which is the trace metals in seawater of Changjiang Estuary and its adjacent areas, between this method and the one of the specification for marine monitoring. It shows that this method is stable and not affected by salinity. It is suitable for the analysis of trace metals in the estuary and its adjacent areas.
In this study, we present an analytical approach which uses an automated pre-concentration device(seaFAST) with accurate volume loading and in-line pH buffering of the sample prior to loading onto the chelating resin(NOBIAS chelate-PA1) and subsequent simultaneous analysis of copper(Cu), lead(Pb), zinc(Zn) and cadmium(Cd) by Inductively Coupled Plasma Mass Spectrometry(ICP-MS). The available system extracts the trace metals from the seawater onto a chelation resin column, when the seawater sample pH<2, mixed with the buffer solution of ammonium acetate with pH(6.0±0.1) in a certain volume ratio(13∶2～13∶5). And the resin can be washed with the buffer solution of ammonium acetate no less than 800μL, which can effectively remove alkali metals, alkaline-earth metals, anions, etc. The four target elements can achieve high recovery at the same time when the resin eluted by 10% nitric acid which is no less than 600 μL at the rate of 200 μL/min. The detection limits of this method were 0.014 μg/L(Cu), 0.002 μg/L(Pb), 0.049 μg/L(Zn), 0.001 μg/L(Cd).The analytical technique has advantages of high automation and small volume of reagents and samples. There is no significant difference of the analytical results, which is the trace metals in seawater of Changjiang Estuary and its adjacent areas, between this method and the one of the specification for marine monitoring. It shows that this method is stable and not affected by salinity. It is suitable for the analysis of trace metals in the estuary and its adjacent areas.
引文
[1] 冯士筰,李凤岐,李少菁.海洋科学导论[M].北京:高等教育出版社,1999:115-116.FENG S Z,LI F Q,LI S J.An introduction to marine science[M].Beijing:Higher Education Press,1999:115-116.
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[4] BILLER D V,BRULAND K W.Analysis of Mn,Fe,Co,Ni,Cu,Zn,Cd,and Pb in seawater using the Nobias-chelate PA1 resin and magnetic sector inductively coupled plasma mass spectrometry (ICP-MS)[J].Marine Chemistry,2012,130-131:12-20.
[5] 梁杰,何会军,麻洪良,等.NOBIAS PA1螯合树脂富集-ICP-MS定量测定近海水体中的稀土元素[J].海洋科学,2017,41(10):58-66.LIANG J,HE H J,MA H L,et al.Determination of REEs in the seawater adjacent to China using ICP-MS with a Nobias-chelate PA1 resin[J].Marine Sciences,2017,41(10):58-66.
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[7] TAKANO S,TANIMIZU M,HIRATA T,et al.Determination of isotopic composition of dissolved copper in seawater by multi-collector inductively coupled plasma mass spectrometry after pre-concentration using an ethylenediaminetriacetic acid chelating resin[J].Analytica Chimica Acta,2013,784:33-41.
[8] 中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB 17378.4—2007 海洋监测规范第4部分:海水分析[S].北京:中国标准出版社,2008.General Administration of Quality Supervision,Inspection and Quarantine of the People’s Republic of China,Standardization Administration of the People’s Republic of China.GB 17378.4-2007 The specification for marine monitoring-part 4:seawater analysis[S].Beijing:Standards Press of China,2008.
[9] 殷学博,王晓媛,李三忠,等.电感耦合等离子体质谱测定海水中的锂、铷、硼、锶[J].海洋科学,2013,37(10):86-89.YIN X B,WANG X Y,LI S Z,et al.Determination of Li,Rb,B and Sr in seawater by ICP-MS[J].Marine Sciences,2013,37(10):86-89.
[10] 刘瑶,宋金明,林强,等.离线固相萃取螯合富集分离-ICP-MS测定海水中的稀土元素[J].海洋科学,2017,41(9):34-40.LIU Y,SONG J M,LIN Q,et al.Determination of trace rare earth elements in seawater by ICP-MS with solid-phase extraction treatment off-line[J].Marine Sciences,2017,41(9):34-40.
[11] 王丹红,林建杰,蔡春平,等.在线分离富集-ICP-MS法直接测定海水中痕量稀土元素[J].分析试验室,2016,35(7):773-776.WANG D H,LIN J J,CAI C P,et al.Determination of trace rare earth element in seawater by inductively coupled plasma mass spectrometry with online separation and enrichment technique[J].Chinese Journal of Analysis Laboratory,2016,35(7):773-776.
[12] LAGERSTR?M M E,FIELD M P,SèGURET M,et al.Auto-mated on-line flow-injection ICP-MS determination of trace metals (Mn,Fe,Co,Ni,Cu and Zn) in open ocean seawater:Application to the GEOTRACES program[J].Marine Chemistry,2013,155:71-80.
[13] 母清林,方杰,佘运勇,等.在线稀释/预浓缩-电感耦合等离子体质谱法分析海水中11种痕量元素[J].分析化学,2015,43(9):1360-1365.MU Q L,FANG J,SHE Y Y,et al.Determination of trace metals (Cr,Mo,Cu,Pb,Zn,Cd,Fe,Mn,Ni,V,Co) in seawater by inductively coupled plasma mass spectrometry with on-line injection technique[J].Chinese Journal of Analytical Chemistry,2015,43(9):1360-1365.
[14] TAKANO S,TANIMIZU M,HIRATA T,et al.A simple and rapid method for isotopic analysis of nickel,copper,and zinc in seawater using chelating extraction and anion exchange[J].Analytica Chimica Acta,2017,967:1-11.
[15] 吕海燕,王正方,傅和芳,等.浙江西沪港重金属铜的配位容量和形态分析[J].海洋学报,2003,25(3):47-52.Lü H Y,WANG Z F,FU H F,et al.Investigation of heavy metal copper complexing capacity and forms in the Xihu Harbour of Zhejiang,China[J].Acta Oceanologica Sinica,2003,25(3):47-52.
[16] 中华人民共和国国家质量监督检验检疫总局.JJF 1159-2006 四极杆电感耦合等离子体质谱仪校准规范[S].北京:中国计量出版社,2007.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China.JJF 1159-2006 Calibration specification for quadrupole inductively coupled plasma mass spectrometers[S].Beijing:China Metrology Publishing House,2007.
[17] 谭赛章,孙亚伟,可愚,等.长江口及其邻近海区主要化学要素基线值变化特征[J].上海海洋大学学报,2017,26(1):94-102.TAN S Z,SUN Y W,KE Y,et al.Variation characteristics of parameters baseline values for the Changjiang Estuary and its adjacent areas[J].Journal of Shanghai Ocean University,2017,26(1):94-102.
[18] 赖国毅,陈超.SPSS 17.0中文版常用功能与应用实例精讲[M].北京:电子工业出版社,2010:168-172.LAI G Y,CHEN C.The common function and application examples of SPSS 17.0[M].Beijing:Publishing House of Electronics Industry,2010:168-172.
[2] 王美玲,朱常桂,ITO M.高盐试样中金属离子的固相萃取分离和测定[J].核动力工程,2007,28(s2):95-98.WANG M L,ZHU C G,ITO M.Determination of trace elements in high saline samples after solid phase extraction[J].Nuclear Power Engineering,2007,28(s2):95-98.
[3] 黄志勇,陈发荣,沈金灿,等.用同位素稀释电感耦合等离子体质谱法测定海水中的痕量铅[J].质谱学报,2003,24(2):337-342.HUANG Z Y,CHEN F R,SHEN J C,et al.Determination of trace lead in seawater using isotope dilution by inductively coupled plasma mass spectrometry (ICP-MS)[M].Journal of Chinese Mass Spectrometry Society,2003,24(2):337-342.
[4] BILLER D V,BRULAND K W.Analysis of Mn,Fe,Co,Ni,Cu,Zn,Cd,and Pb in seawater using the Nobias-chelate PA1 resin and magnetic sector inductively coupled plasma mass spectrometry (ICP-MS)[J].Marine Chemistry,2012,130-131:12-20.
[5] 梁杰,何会军,麻洪良,等.NOBIAS PA1螯合树脂富集-ICP-MS定量测定近海水体中的稀土元素[J].海洋科学,2017,41(10):58-66.LIANG J,HE H J,MA H L,et al.Determination of REEs in the seawater adjacent to China using ICP-MS with a Nobias-chelate PA1 resin[J].Marine Sciences,2017,41(10):58-66.
[6] RAPP I,SCHLOSSER C,RUSIECKA D,et al.Automated preconcentration of Fe,Zn,Cu,Ni,Cd,Pb,Co,and Mn in seawater with analysis using high-resolution sector field inductively-coupled plasma mass spectrometry[J].Analytica Chimica Acta,2017,976:1-13.
[7] TAKANO S,TANIMIZU M,HIRATA T,et al.Determination of isotopic composition of dissolved copper in seawater by multi-collector inductively coupled plasma mass spectrometry after pre-concentration using an ethylenediaminetriacetic acid chelating resin[J].Analytica Chimica Acta,2013,784:33-41.
[8] 中华人民共和国国家质量监督检验检疫总局,中国国家标准化管理委员会.GB 17378.4—2007 海洋监测规范第4部分:海水分析[S].北京:中国标准出版社,2008.General Administration of Quality Supervision,Inspection and Quarantine of the People’s Republic of China,Standardization Administration of the People’s Republic of China.GB 17378.4-2007 The specification for marine monitoring-part 4:seawater analysis[S].Beijing:Standards Press of China,2008.
[9] 殷学博,王晓媛,李三忠,等.电感耦合等离子体质谱测定海水中的锂、铷、硼、锶[J].海洋科学,2013,37(10):86-89.YIN X B,WANG X Y,LI S Z,et al.Determination of Li,Rb,B and Sr in seawater by ICP-MS[J].Marine Sciences,2013,37(10):86-89.
[10] 刘瑶,宋金明,林强,等.离线固相萃取螯合富集分离-ICP-MS测定海水中的稀土元素[J].海洋科学,2017,41(9):34-40.LIU Y,SONG J M,LIN Q,et al.Determination of trace rare earth elements in seawater by ICP-MS with solid-phase extraction treatment off-line[J].Marine Sciences,2017,41(9):34-40.
[11] 王丹红,林建杰,蔡春平,等.在线分离富集-ICP-MS法直接测定海水中痕量稀土元素[J].分析试验室,2016,35(7):773-776.WANG D H,LIN J J,CAI C P,et al.Determination of trace rare earth element in seawater by inductively coupled plasma mass spectrometry with online separation and enrichment technique[J].Chinese Journal of Analysis Laboratory,2016,35(7):773-776.
[12] LAGERSTR?M M E,FIELD M P,SèGURET M,et al.Auto-mated on-line flow-injection ICP-MS determination of trace metals (Mn,Fe,Co,Ni,Cu and Zn) in open ocean seawater:Application to the GEOTRACES program[J].Marine Chemistry,2013,155:71-80.
[13] 母清林,方杰,佘运勇,等.在线稀释/预浓缩-电感耦合等离子体质谱法分析海水中11种痕量元素[J].分析化学,2015,43(9):1360-1365.MU Q L,FANG J,SHE Y Y,et al.Determination of trace metals (Cr,Mo,Cu,Pb,Zn,Cd,Fe,Mn,Ni,V,Co) in seawater by inductively coupled plasma mass spectrometry with on-line injection technique[J].Chinese Journal of Analytical Chemistry,2015,43(9):1360-1365.
[14] TAKANO S,TANIMIZU M,HIRATA T,et al.A simple and rapid method for isotopic analysis of nickel,copper,and zinc in seawater using chelating extraction and anion exchange[J].Analytica Chimica Acta,2017,967:1-11.
[15] 吕海燕,王正方,傅和芳,等.浙江西沪港重金属铜的配位容量和形态分析[J].海洋学报,2003,25(3):47-52.Lü H Y,WANG Z F,FU H F,et al.Investigation of heavy metal copper complexing capacity and forms in the Xihu Harbour of Zhejiang,China[J].Acta Oceanologica Sinica,2003,25(3):47-52.
[16] 中华人民共和国国家质量监督检验检疫总局.JJF 1159-2006 四极杆电感耦合等离子体质谱仪校准规范[S].北京:中国计量出版社,2007.General Administration of Quality Supervision,Inspection and Quarantine of the People's Republic of China.JJF 1159-2006 Calibration specification for quadrupole inductively coupled plasma mass spectrometers[S].Beijing:China Metrology Publishing House,2007.
[17] 谭赛章,孙亚伟,可愚,等.长江口及其邻近海区主要化学要素基线值变化特征[J].上海海洋大学学报,2017,26(1):94-102.TAN S Z,SUN Y W,KE Y,et al.Variation characteristics of parameters baseline values for the Changjiang Estuary and its adjacent areas[J].Journal of Shanghai Ocean University,2017,26(1):94-102.
[18] 赖国毅,陈超.SPSS 17.0中文版常用功能与应用实例精讲[M].北京:电子工业出版社,2010:168-172.LAI G Y,CHEN C.The common function and application examples of SPSS 17.0[M].Beijing:Publishing House of Electronics Industry,2010:168-172.
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