乙醚萃取分离-电感耦合等离子体质谱法测定岩石样品中铊
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摘要
准确测定岩石样品中铊的含量,对于有效监控矿物开采和加工过程中的铊污染,具有重要意义。因岩石样品中铊含量很低,故一般在测定前需对铊进行分离富集以消除大量基体元素对铊测定的干扰。实验采用盐酸-硝酸-氢氟酸-高氯酸分解岩石样品,在样品溶液中加入氢溴酸使之与三价铊(Tl~(3+))发生络合反应生成溴化铊,用乙醚萃取溴化铊,实现了铊与基体元素的分离。将乙醚萃取液于60℃电热板加热挥发以除去乙醚,再用加入硝酸加热消解的方式除去残余乙醚,加硝酸和沸水浸取,以5.0ng/mL ~(185)Re为内标,~(205)Tl~+为测定对象,采用电感耦合等离子体质谱法(ICP-MS)进行测定,实现了对岩石样品中铊的测定。实验表明,铊质量浓度在5.00～40.00ng/mL范围内与铊信号强度和内标元素信号强度的比值呈线性关系,相关系数为0.999 8,方法检出限为0.004 9ng/mL。将实验方法应用于岩石实际样品,测定结果的相对标准偏差(RSD,n=6)均小于5%,加标回收率为96%～103%。采用实验方法测定岩石标准物质中铊,测定值与认定值基本一致。
The accurate determination of thallium content in rock samples was of great significance for the monitoring of thallium pollution in mineral mining and processing.Since the content of thallium in rock sample was usually very low,the separation and enrichment of thallium should be conducted before determination of thallium to eliminate the interference of many matrix elements.The rock sample was decomposed with hydrochloric acid-nitric acid-hydrofluoric acid-perchloric acid.The hydrobromic acid was added into sample solution to react with Tl~(3+) to form thallium bromide complex.The thallium bromide complex was then extracted with ether,realizing the separation of thallium from matrix elements.The ether extract liquor was heated on electric hot plate at 60℃ to remove ether by volatilization.The residual ether was further removed by digestion with heating and addition of nitric acid.After leaching with nitric acid and hot water,the content of thallium was determined by inductively coupled plasma mass spectrometry(ICP-MS)with 5.0 ng/mL ~(185)Re as internal standard and ~(205)Tl~+ as determination object.Thus,the determination method of thallium in rock sample was realized.The experimental results showed that the mass concentration of thallium in the range of 5.00-40.00 ng/mL was linear to the ratio of signal intensity to thallium and internal standard.The correlation coefficient was 0.9998.The detection limit of method was 0.004 9 ng/mL.The proposed method was applied for the analysis of rock actual samples.The relative standard deviations(RSD,n=6)of determination results were all less than 5%.The spiked recoveries were between 96% and 103%.The content of thallium in certified reference material of rock was determined,and the found results were basically consistent with the certified values.
The accurate determination of thallium content in rock samples was of great significance for the monitoring of thallium pollution in mineral mining and processing.Since the content of thallium in rock sample was usually very low,the separation and enrichment of thallium should be conducted before determination of thallium to eliminate the interference of many matrix elements.The rock sample was decomposed with hydrochloric acid-nitric acid-hydrofluoric acid-perchloric acid.The hydrobromic acid was added into sample solution to react with Tl~(3+) to form thallium bromide complex.The thallium bromide complex was then extracted with ether,realizing the separation of thallium from matrix elements.The ether extract liquor was heated on electric hot plate at 60℃ to remove ether by volatilization.The residual ether was further removed by digestion with heating and addition of nitric acid.After leaching with nitric acid and hot water,the content of thallium was determined by inductively coupled plasma mass spectrometry(ICP-MS)with 5.0 ng/mL ~(185)Re as internal standard and ~(205)Tl~+ as determination object.Thus,the determination method of thallium in rock sample was realized.The experimental results showed that the mass concentration of thallium in the range of 5.00-40.00 ng/mL was linear to the ratio of signal intensity to thallium and internal standard.The correlation coefficient was 0.9998.The detection limit of method was 0.004 9 ng/mL.The proposed method was applied for the analysis of rock actual samples.The relative standard deviations(RSD,n=6)of determination results were all less than 5%.The spiked recoveries were between 96% and 103%.The content of thallium in certified reference material of rock was determined,and the found results were basically consistent with the certified values.
引文
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[7]刘畅.微波消解-石墨炉原子吸收法测定底泥中铊的含量[J].现代农业科技,2012,20(19):211-213.LIU Chang.Determination of thallium in sediments by microwave digestion-graphite furnace atomic absorption spectrometry[J].Modern Agricultural Science and Technology,2012,20(19):211-213.
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[9]罗荣根,杨志丰,罗文,等.电感耦合等离子体原子发射光谱法测定金精矿中铊[J].冶金分析,2017,37(7):77-82.LUO Rong-gen,YANG Zhi-feng,LUO Wen,et al.Determination of thallium in gold concentrate by inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2017,37(7):77-82.
[10]谢晓雁,吴文启,李奋,等.离子交换分离-电感耦合等离子体原子发射光谱法测定锰矿中铊[J].冶金分析,2015,35(8):61-65.XIE Xiao-yan,WU Wen-qi,LI Fen,et al.Determination of thallium in manganese ore by inductively coupled plasma atomic emission spectrometry after ion exchange separation[J].Metallurgical Analysis,2015,35(8):61-65.
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[12]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):21-26.ZHANG Qin,LIU Ya-xuan,WU Jian-ling.Simultaneous determination of gallium,indium and thallium in geochemical samples by inductively coupled plasma mass spectrometry[J].Rock and Mineral Analysis,2003,22(1):21-26.
[13]卢水平,林海兰,朱瑞瑞,等.电感耦合等离子体质谱法测定地表水中铊的研究[J].环境科学与管理,2014,39(12):130-132.LU Shui-ping,LIN Hai-lan,ZHU Rui-rui,et al.Determination of thallium in surface water by using inductively coupled plasma mass spectrometry[J].Environmental Science and Management,2014,39(12):130-132.
[14]徐进力,邢夏,郝志红,等.聚氨酯泡塑吸附-电感耦合等离子体质谱法测定地球化学样品中的微量铊[J].岩矿测试,2012,31(3):430-433.XU Jin-li,XING Xia,HAO Zhi-hong,et al.Determination of thallium in geochemical samples by inductively coupled plasma-mass spectrometry with polyurethane foam adsorption[J].Rock and Mineral Analysis,2012,31(3):430-433.
[15]岩石矿物分析编写小组.岩石矿物分析[M].北京:地质出版社,1974:567-572.
[16]俞善辉,许宝海,吴斌才.4-硝基-4′-氟苯基重氮氨基偶氮苯为显色剂双波长分光光度法测定痕量三价铊[J].理化检验:化学分册,2009,31(1):1-3.YU Shan-hui,XU Bao-hai,WU Bin-cai.DW-spectrophotometric determination of trace amounts of thallium(III)with 4-nitro-4′-fluorophenyl-diazo-amlno-azobenzene as chromogenic reagent[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2009,31(1):1-3.
[2]齐剑英,李祥平,刘娟,等.环境水体中铊的测定方法研究进展[J].矿物岩石地球化学通报,2008,27(1):81-88.QI Jian-ying,LI Xiang-ping,LIU Juan,et al.Advance on the method determining thallium in environmental waters[J].Bulletin of Mineralogy,Petrology and Geochemistry,2008,27(1):81-88.
[3]林春燕,刘敬勇,陈多宏,等.环境介质中铊的分析测定方法研究[J].安徽农业科学,2009,37(9):4155-4157.LIN Chun-yan,LIU Jing-yong,CHEN Duo-hong,et al.Study on the determination methods of thallium in environmental media[J].Journal of Anhui Agricultural Sciences,2009,37(9):4155-4157.
[4]时岚.火焰原子吸收光谱法测定烟囱烟灰中的铊[J].环境监测管理与技术,2004,16(1):32-34.SHI Lan.To detect thallium in soot in stack with flame atomic absorption spectrometry[J].The Administration and Technique of Environmental Monitoring,2004,16(1):32-34.
[5]肖凡,徐崇颖,邢刚,等.碘化钾-甲基异丁基甲酮萃取-火焰原子吸收分光光度法连续测定地球化学样品中痕量银镉铊[J].岩矿测试,2007,26(1):67-70.XIAO Fan,XU Chong-ying,XING Gang,et al.Continuous determination of trace silver,cadmium and thallium in geochemical samples by flame atomic absorption spectrophotometry with KI-MIBK extraction[J].Rock and Mineral Analysis,2007,26(1):67-70.
[6]范丽汇,毛禹平.火焰原子吸收光谱法快速测定铊[J].云南冶金,2004,33(4):43-44.FAN Hui-li,MAO Yu-ping.Rapid determination of thallium with flame atomic absorption spectrometry[J].Yunnan Metallurgy,2004,33(4):43-44.
[7]刘畅.微波消解-石墨炉原子吸收法测定底泥中铊的含量[J].现代农业科技,2012,20(19):211-213.LIU Chang.Determination of thallium in sediments by microwave digestion-graphite furnace atomic absorption spectrometry[J].Modern Agricultural Science and Technology,2012,20(19):211-213.
[8]李奋,吴文启,谢晓雁,等.离子交换分离-石墨炉原子吸收光谱法测定饮用水中痕量铊[J].理化检验:化学分册,2015,51(12):1675-1678.LI Fen,WU Wen-qi,XIE Xiao-yan,et al.Determination of trace amount of thallium in potable water by GFAASwith ion-exchange separation[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2015,51(12):1675-1678.
[9]罗荣根,杨志丰,罗文,等.电感耦合等离子体原子发射光谱法测定金精矿中铊[J].冶金分析,2017,37(7):77-82.LUO Rong-gen,YANG Zhi-feng,LUO Wen,et al.Determination of thallium in gold concentrate by inductively coupled plasma atomic emission spectrometry[J].Metallurgical Analysis,2017,37(7):77-82.
[10]谢晓雁,吴文启,李奋,等.离子交换分离-电感耦合等离子体原子发射光谱法测定锰矿中铊[J].冶金分析,2015,35(8):61-65.XIE Xiao-yan,WU Wen-qi,LI Fen,et al.Determination of thallium in manganese ore by inductively coupled plasma atomic emission spectrometry after ion exchange separation[J].Metallurgical Analysis,2015,35(8):61-65.
[11]吴晓毛,吕茜茜,吴勇.电感耦合等离子体质谱法快速测定银精矿中的铊[J].黄金,2018,39(2):76-78.WU Xiao-mao,LQian-qian,WU Yong.Determination of thallium in silver concentrates by inductively coupled plasma mass spectrometry[J].Gold,2018,39(2):76-78.
[12]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):21-26.ZHANG Qin,LIU Ya-xuan,WU Jian-ling.Simultaneous determination of gallium,indium and thallium in geochemical samples by inductively coupled plasma mass spectrometry[J].Rock and Mineral Analysis,2003,22(1):21-26.
[13]卢水平,林海兰,朱瑞瑞,等.电感耦合等离子体质谱法测定地表水中铊的研究[J].环境科学与管理,2014,39(12):130-132.LU Shui-ping,LIN Hai-lan,ZHU Rui-rui,et al.Determination of thallium in surface water by using inductively coupled plasma mass spectrometry[J].Environmental Science and Management,2014,39(12):130-132.
[14]徐进力,邢夏,郝志红,等.聚氨酯泡塑吸附-电感耦合等离子体质谱法测定地球化学样品中的微量铊[J].岩矿测试,2012,31(3):430-433.XU Jin-li,XING Xia,HAO Zhi-hong,et al.Determination of thallium in geochemical samples by inductively coupled plasma-mass spectrometry with polyurethane foam adsorption[J].Rock and Mineral Analysis,2012,31(3):430-433.
[15]岩石矿物分析编写小组.岩石矿物分析[M].北京:地质出版社,1974:567-572.
[16]俞善辉,许宝海,吴斌才.4-硝基-4′-氟苯基重氮氨基偶氮苯为显色剂双波长分光光度法测定痕量三价铊[J].理化检验:化学分册,2009,31(1):1-3.YU Shan-hui,XU Bao-hai,WU Bin-cai.DW-spectrophotometric determination of trace amounts of thallium(III)with 4-nitro-4′-fluorophenyl-diazo-amlno-azobenzene as chromogenic reagent[J].Physical Testing and Chemical Analysis Part B:Chemical Analysis,2009,31(1):1-3.