电感耦合等离子体质谱法精确测定地质样品中的微量元素镓
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摘要
应用电感耦合等离子体质谱法(ICP-MS)对地质样品中微量元素镓进行测试分析时,存在两方面问题:一是不同消解方法各有不足,密闭式消解不能批量处理样品,而敞开式消解过程繁杂;二是质谱测试时需要选择69Ga还是71Ga,确定扣除哪些干扰和相应的扣除系数,这些因素使地质样品中镓元素的测试精度不高。本文基于一般地质样品中有机质含量低的特点,针对ICP-MS分析方法提出:①使用氢氟酸、盐酸、硝酸、高氯酸四种酸混合消解样品,采用半密闭式酸分解法,通过调整加热温度、用酸量、用酸比等加快反应进程,少量的有机质在强酸加热消解时能够反应完全,而不必要进行灰化处理;②采用丰度为39.9%的71Ga进行测试,使用经验系数0.005,利用55Mn18O对71Ga位置扣除55Mn16O的干扰。方法精密度在3%以内,方法检出限为0.06μg/g。本方法简化了样品消解过程,并可批量处理样品,降低了分析成本,在准确测定镓元素的同时还能准确地测定其他微量元素和稀土元素。
There are two problems in the quantitative analysis of trace gallium in geological samples by using Inductively Coupled Plasma-Mass Spectrometry(ICP-MS).Firstly,the usual advantages of having two kinds of digestion methods are irrelevant here because sealed digestion is not appropriate for batch processing samples and an open-system digestion process is a complex procedure.Secondly,the selection of 69 Ga or 71 Ga and the related interference correction are the main factors leading to low precision.The method based on the characteristic of low content organic matter in normal geology samples and requirements for ICP-MS measurement is improved on and discussed.The four-acid digestion system of HF-HCl-HNO 3-HClO 4 was conducted to dissolve the samples in a semi-hermetic environment.Adjustment of the heating temperature,acid amounts and ratios can speed up the reaction.The samples with low content organic matter are digested completely in the strong acids solution without ashing. 71 Ga with an abundance of 39.9% and an empirical coefficient of 0.005 was selected.The interference of 55 Mn 16 O interference on the 71 Ga peak was corrected by 55 Mn 18 O.The accuracy and precision of gallium is within 3%,and the detection limit is 0.06 μg / g.The improved method simplifies the chemical procedure and reduces the cost which is advantageous for batch processing.Moreover,this method is also suitable for other trace elements and rare earth elements.
There are two problems in the quantitative analysis of trace gallium in geological samples by using Inductively Coupled Plasma-Mass Spectrometry(ICP-MS).Firstly,the usual advantages of having two kinds of digestion methods are irrelevant here because sealed digestion is not appropriate for batch processing samples and an open-system digestion process is a complex procedure.Secondly,the selection of 69 Ga or 71 Ga and the related interference correction are the main factors leading to low precision.The method based on the characteristic of low content organic matter in normal geology samples and requirements for ICP-MS measurement is improved on and discussed.The four-acid digestion system of HF-HCl-HNO 3-HClO 4 was conducted to dissolve the samples in a semi-hermetic environment.Adjustment of the heating temperature,acid amounts and ratios can speed up the reaction.The samples with low content organic matter are digested completely in the strong acids solution without ashing. 71 Ga with an abundance of 39.9% and an empirical coefficient of 0.005 was selected.The interference of 55 Mn 16 O interference on the 71 Ga peak was corrected by 55 Mn 18 O.The accuracy and precision of gallium is within 3%,and the detection limit is 0.06 μg / g.The improved method simplifies the chemical procedure and reduces the cost which is advantageous for batch processing.Moreover,this method is also suitable for other trace elements and rare earth elements.
引文
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[19]王文峰,秦勇,刘新花,赵建岭,王钧漪,吴国代,刘炯天.内蒙古准格尔煤田煤中镓的分布赋存与富集成因[J].中国科学:地球科学,2011,41(2):181-196.
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[26]Diegor W,Longerich H,Abrajano T,Horn I.Applica-bility of a high pressure digestion technique to theanalysis of sediment and soil samples by inductivelycoupled plasma-mass spectrometry[J].AnalyticaChimica Acta,2001,431(2):195-207.
[27]林松.微波消解-电感耦合等离子体质谱法同时测定土壤样品中八种重金属元素[J].福建分析测试,2008,17(3):21-23.
[28]高晶晶,刘季花,张辉,白亚之,崔菁菁,何连花.高压密闭消解-电感耦合等离子体质谱法测定海洋沉积物中稀土元素[J].岩矿测试,2012,31(3):425-429.
[29]de Madinabeitia S G,Lorda M E S,Gil Ibarguchi J I G.Simultaneous determination of major to ultratraceelements in geological samples by fusion-dissolution andinductively coupled plasma mass spectrometry techniques[J].Analytica Chimica Acta,2008,625(2):117-130.
[30]周国兴,刘玺祥,崔德松.碱熔ICP-MS法测定岩石样品中稀土等28种金属元素[J].质谱学报,2010,31(2):120-124.
[31]Thermo Elemental Corporation.X Series Getting StartedGuide(PlasmaLab V2.3.0)[M].USA:ThermoFisher Scientific Incorporation,2004:105-149.
[2]叶家瑜,江家林主编.区域地球化学勘查样品分析方法[M].北京:地质出版社,2004:3-57.
[3]贾维斯K E(英),格雷A L(英),霍克R S(美)著.尹明,李冰译.电感耦合等离子体质谱手册[M].北京:原子能出版社,1997:85-103.
[4]Poledniok J.Speciation of scandium and gallium in soil[J].Chemosphere,2008,73:572-579.
[5]赵朝辉,李可及,邹利平,肖靖.ICP-MS同时测定土壤样品中的镓铟锗[J].矿产综合利用,2012,32(3):52-54.
[6]张勤,刘亚轩,吴健玲.电感耦合等离子体质谱法直接同时测定地球化学样品中镓铟铊[J].岩矿测试,2003,22(1):21-23.
[7]章新泉,易永,姜玉梅,苏亚勤,童迎东,刘永林,李翔.电感耦合等离子体质谱测定地质样品中多种元素[J].分析试验室,2005,24(8):58-61.
[8]江冶,陈素兰.电感耦合等离子体质谱法分析土壤及沉积物中的32个微量元素[J].地质学刊,2010,34(4):415-418.
[9]孙德忠,何红蓼.封闭酸溶-等离子体质谱法分析超细粒度地质样品中42个元素[J].岩矿测试,2007,26(1):21-25.
[10]Balaram V,Rao T G.Rapid determination of REEs andother trace elements in geological samples by microwaveacid digestion and ICP-MS[J].Atomic Spectroscopy,2004,24(6):206-212.
[11]王小如主编.电感耦合等离子体质谱应用实例[M].北京:化学工业出版社,2005:196-218.
[12]Rajendran J,Thampi P K,Balasubramanian G.Deter-mination of rare earth elements in garnet minerals,geological materials by inductively coupled plasma-atomic emission spectral and mass spectral analysis[J].Analytical Letters,2006,39(11):2297-2306.
[13]王君玉,吴葆存,李志伟,韩敏,钟莅湘.敞口酸溶-电感耦合等离子体质谱法同时测定地质样品中45个元素[J].岩矿测试,2011,30(4):440-445.
[14]刘烁.电感耦合等离子发射光谱-质谱法测定土壤中镓的方法研究[J].甘肃科技,2011,27(10):56-59.
[15]胡圣虹,陈爱芳,林守麟,袁洪林,高山.地质样品中40个微量、痕量、超痕量元素的ICP-MS分析研究[J].地球科学,2000,25(2):186-190.
[16]李国榕,王亚平,孙元方,董天姿,王海鹰.电感耦合等离子体质谱法测定地质样品中稀散元素铬镓铟碲铊[J].岩矿测试,2010,29(3):255-258.
[17]侯振辉,王晨香.电感耦合等离子体质谱法测定地质样品中35种微量元素[J].中国科技大学学报,2007,37(8):940-944.
[18]刘亚轩,张勤,黄珍玉,吴健玲.ICP-MS法测定地球化学样品中As、Cr、Ge、V等18种微量痕量元素的研究[J].化学世界,2006,47(1):16-20.
[19]王文峰,秦勇,刘新花,赵建岭,王钧漪,吴国代,刘炯天.内蒙古准格尔煤田煤中镓的分布赋存与富集成因[J].中国科学:地球科学,2011,41(2):181-196.
[20]戴特A R(英),格雷A L(英)著.李金英,姚继军译.电感耦合等离子体质谱分析的应用[M].北京:原子能出版社,1998:17-40.
[21]刘虎生,邵宏翔.电感耦合等离子体质谱技术与应用[M].北京:化学工业出版社,2005:113-189.
[22]孙德忠,安子怡,许春雪,王苏明,王亚平.四种前处理方法对电感耦合等离子体质谱测定植物样品中27种微量元素的影响[J].岩矿测试,2012,31(6):961-966.
[23]张晓静,朱风鹏,胡清源,杨杰,秦存永.ICP-MS同时测定土壤中Cr、Ni、Cu、As、T1和Pb[J].中国烟草学报,2009,15(6):18-22.
[24]全玉.电感耦合等离子体质谱法检测氧化镓中杂质元素[J].分析试验室,2009,28(12):107-109.
[25]周连文,吕元琦.土壤中微量元素的电感耦合等离子体质谱分析[J].化学工程师,2007,21(10):24-25.
[26]Diegor W,Longerich H,Abrajano T,Horn I.Applica-bility of a high pressure digestion technique to theanalysis of sediment and soil samples by inductivelycoupled plasma-mass spectrometry[J].AnalyticaChimica Acta,2001,431(2):195-207.
[27]林松.微波消解-电感耦合等离子体质谱法同时测定土壤样品中八种重金属元素[J].福建分析测试,2008,17(3):21-23.
[28]高晶晶,刘季花,张辉,白亚之,崔菁菁,何连花.高压密闭消解-电感耦合等离子体质谱法测定海洋沉积物中稀土元素[J].岩矿测试,2012,31(3):425-429.
[29]de Madinabeitia S G,Lorda M E S,Gil Ibarguchi J I G.Simultaneous determination of major to ultratraceelements in geological samples by fusion-dissolution andinductively coupled plasma mass spectrometry techniques[J].Analytica Chimica Acta,2008,625(2):117-130.
[30]周国兴,刘玺祥,崔德松.碱熔ICP-MS法测定岩石样品中稀土等28种金属元素[J].质谱学报,2010,31(2):120-124.
[31]Thermo Elemental Corporation.X Series Getting StartedGuide(PlasmaLab V2.3.0)[M].USA:ThermoFisher Scientific Incorporation,2004:105-149.