煤炭中铅同位素分析方法研究
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摘要
同位素比值是污染源解析的基础,为了探索燃煤污染源解析的可行性,本研究建立煤炭中铅同位素的分析方法。采用灰化-微波消解相结合的方式,将煤样转换为溶液状态,用PB树脂(冠醚类)萃取色层法,将铅和大量基体元素有效分离,用多接收电感耦合等离子体质谱法测定铅同位素比值。利用NIST 981标定天然铅溶液的铅同位素比值,应用建立的分析方法,测定~(208)Pb/~(207)Pb、~(206)Pb/~(207)Pb的同位素比值,相对误差小于0.03%。钠、镁、铝、铁、钛、锰等元素的去污系数均大于400。结果表明,该方法有效、可靠,测定标准煤样(NIST 1635a、NIST 1632d)、山西大同煤样和攀枝花煤样的~(208)Pb/~(207)Pb、~(206)Pb/~(207)Pb同位素比值,精密度均大于0.2%,两地煤样同位素比值变异为6%~10%,初步验证了建立全国煤炭中铅同位素比值背景数据库的可行性。
As the basis method for the pollution source apportionment,the isotope ratios were applied for analysis Pb isotopes in coal to explore the feasibility of coal pollution source apportionment.A method was established to analysis Pb isotopes in coal.First,the coal samples were dissolved by the combination of ashing and microwave digestion.Then by using PB resin extraction chromatography,Pb and a large number of matrix elements were effectively separated.After separation,the Pb isotope ratios were determined by multi-collector inductively coupled plasma mass spectrometry.The Pb isotopic ratios of natural Pb solution were calibrated with NIST 981.Using established analytical method,the measured relative error of ~(208)Pb/~(207)Pb,~(206)Pb/~(207)Pb in natural Pb solution were less than 0.03%,the decontamination coefficients of sodium,magnesium,aluminium,iron,titanium and manganese were more than 400.The results showed that the method was effective and reliable.By measuring the standard coal samples(NIST1635 a,NIST 1632 d),Shanxi Datong and Panzhihua coal samples,it was found that therelative standard deviation of ~(208)Pb/~(207)Pb,~(206)Pb/~(207)Pb were less than 0.2%.The ratio difference of ~(208)Pb/~(207)b and ~(206)Pb/~(207)Pb between Datong coal and Panzhihua coal was about 6% ~10%.Such a big difference proved that it was feasible to establish a Pb isotope background database about the coal in China.
As the basis method for the pollution source apportionment,the isotope ratios were applied for analysis Pb isotopes in coal to explore the feasibility of coal pollution source apportionment.A method was established to analysis Pb isotopes in coal.First,the coal samples were dissolved by the combination of ashing and microwave digestion.Then by using PB resin extraction chromatography,Pb and a large number of matrix elements were effectively separated.After separation,the Pb isotope ratios were determined by multi-collector inductively coupled plasma mass spectrometry.The Pb isotopic ratios of natural Pb solution were calibrated with NIST 981.Using established analytical method,the measured relative error of ~(208)Pb/~(207)Pb,~(206)Pb/~(207)Pb in natural Pb solution were less than 0.03%,the decontamination coefficients of sodium,magnesium,aluminium,iron,titanium and manganese were more than 400.The results showed that the method was effective and reliable.By measuring the standard coal samples(NIST1635 a,NIST 1632 d),Shanxi Datong and Panzhihua coal samples,it was found that therelative standard deviation of ~(208)Pb/~(207)Pb,~(206)Pb/~(207)Pb were less than 0.2%.The ratio difference of ~(208)Pb/~(207)b and ~(206)Pb/~(207)Pb between Datong coal and Panzhihua coal was about 6% ~10%.Such a big difference proved that it was feasible to establish a Pb isotope background database about the coal in China.
引文
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[19]刘瑞贤.碘化钾络合MIBK萃取富集石墨炉原子吸收法测定水中的铅[J].福建分析测试,2010,19(1):90-92.Liu Ruixian.Determination of plumbum in water by GFAAS after KI-MIBK extraction and enrichment[J].Fujian Analysis Testing,2010,19(1):90-92(in Chinese).
[20]高博,涂湘林,刘颖,等.AG-MP-1M阴离子交换树脂分离-表面热电质谱法测定沉积物中的铅同位素组成[J].岩矿测试,2008,27(1):9-11.Gao Bo,Tu Xianglin,Liu Ying,et al.Separation of lead in river sediments using AG-MP-1M anion exchange resin and measurement of lead isotope composition by thermal ionization mass spectrometry[J].Rack and Mineral Analysis,2008,27(1):9-11(in Chinese).
[21]Chiarizia R,Horwitz E P,Dietz M L.Acid dependency of the extraction of selected metal-ions bya strontium-selective extraction chromatographicResin:calculated vs experimental curves[J].Solvent Extraction and Ion Exchange,1992,10(2):337-361.
[22]刘书田.生物与环境样品放化分析中样品的前处理方法[J].同位素,1993,6(1):57-64.
[23]张丽华,肖国平,宋游,等.微波技术在生物样品预处理中的应用[J].现代科学仪器,2004,5:37-40.Zhang Lihua,Xiao Guoping,Song You,et al.Determination of multi-elements in biological sample by technology of the microwave digestion[J].Modern Scientific Instruments,2004,5:37-40(in Chinese).
[24]Mark L,Dietz,Renato C,et al.Effect of crown ethers on the ion-exchange behavior of alkaline earth metals.Toward improved ion-exchange methods for the separation and preconcentration of radium[J].Analytical Chemistry,1997,69:3 028-3 037.
[25]曹霄芸.应用多接收器电感耦合等离子体质谱法测定海南岛东部珊瑚中稳定铅同位素组成[D].上海:华东师范大学,2013.
[26]戴洁.高分辨电感耦合等离子质谱法测定珊瑚中铅的同位素组成研究[D].上海:华东师范大学,2010.
[2]陈曦,王晓燕,刘洋,等.ICP-MS用于北京市PM2.5中铅及其同位素形态分析[J].光谱学与光谱分析,2009,29(2):515-518.Chen Xi,Wang Xiaoyan,Liu Yang,et al.Speciation analysis of lead and its isotopes in fine particulate matters in Beijing by ICP-MS[J].Spectroscopy and Spectral Analysis,2009,29(2):515-518(in Chinese).
[3]杨忠平,卢文喜,辛欣,等.长春市城市土壤铅同位素组成特征及其来源解析[J].吉林大学学报(地球科学版),2008,38(4):663-669.Yang Zhongping,Lu Wenxi,Xin Xin,et al.Lead isotope signatures and source identification in urban soil of Changchun city[J].Journal of Jilin University(Earth Science Edition),2008,38(4):663-669(in Chinese).
[4]Bollhofer A,Rosman K J R.Isotope source signature for atmospheric lead:The northern hemisphere[J].Geochimica et Cosmochimica Acta,2001,65(11):1 727-1 740.
[5]Bollhofer A,Rosman K J R.Isotopic source signatures for atomospheric lead:The southern Hemisphere[J].Geochimica et Cosmochimica Acta,2000,64(19):3 251-3 262.
[6]Somoano M D,Kylander M,Weiss D J,et al.Lead isotope variability in different world wide coal deposits[J].Journal of Chemical Physics,2007,70(70):4 433-4 434
[7]Geagea M L,Stille P,Gauthier-Lafaye F,et al.Tracing of industrial aerosol source in urban environment using Pb,Sr and Nd isotopes[J].Environmental Science and Technology,2008,42(3):692-698.
[8]Gueguen F,Stille P,Geagea M L,et al.Atmospheric pollution in an urban environment by tree bark biomonitoring-PartⅡ:Pb,Sr and Nd isotopic tracing[J].Chemosphere,2012,86:641-647.
[9]Chow T J.Lead isotopes in North American coals[J].Science,1972,176:510-511.
[10]陈好寿,裴辉东,张霄宇,等.杭州大气铅主要污染源的铅同位素示踪[J].矿物岩石地球化学通报,1998,17(3):146-149.Chen Haoshou,Pei Huidong,Zhang Xiaoyu,et al.Isotope tracing of major sources of lead pollution in the atmosphere of Hangzhou city[J].Bulletin of Mineralogy,Petrology and Geochemistry,1998,17(3):146-149(in Chinese).
[11]李显芳,刘咸德,李冰,等.北京大气PM2.5中铅的同位素测定和来源研究[J].环境科学,2006,27(3):401-407.Li Xianfang,Liu Xiande,Li Bing,et al.Isotopic determinations and source study of lead in ambient PM2.5in Beijing[J].Environmental Science,2006,27(3):401-407.
[12]Chen J M,Tanb M G,Li Y L,et al.Characteristics of trace elements and lead isotope ration PM2.5from sites in Shanghai[J].Journal of Hazardous Materials,2008,156(1-3):36-43.
[13]王洁,石元值,张群峰,等.基于稳定同位素比率差异的西湖龙井茶产地的溯源分析[J].同位素,2016,29(3):129-139.Wang Jie,Shi Yuanzhi,Zhang Qunfeng,et al.Geographical tracing of the West Lake Longjing tea based on the stable isotope ratios[J].Journal of Isotopes,2016,29(3):129-139(in Chinese).
[14]白志鹏,张利文,朱坦,等.稳定同位素在环境中的应用进展[J].同位素,2007,20(1):57-64.Bai Zhipeng,Zhang Liwen,Zhu Tan,et al.The status of applying stable isotope in the studies of environmental science[J].Journal of Isotopes,2007,20(1):57-64(in Chinese).
[15]李晓彪.热电离质谱(TIMS)的Sr-Nd-Pb同位素标样测定[J].矿物学报,2009,29(1):609-610.
[16]Weiss D J,Kober B,Dolgopolova A,et al.Accurate and precise Pb isotope ratio measurements in environmental samples by MC-ICP-MS[J].International Journal of Mass Spectrometry,2004,232:205-215.
[17]Christian P,Abdelmouhcine G,Alain D.Rapid simultaneous separation of Sr,Pb and Nd by extraction chromatography prior to isotope ratios determination by TIMS and MC-ICP-MS[J].J Anal At Spectrom,2014,29:1 858-1 870.
[18]Kagaya S,Araki Y,Hasegawa K.Flame atomic absorption spectrometric determination of lead in waste water and effluent after preconcentration using a rapid coprecipitation technique with gallium phosphate[J].Fresenius J.Anal Chem,2000,366(8):842-845.
[19]刘瑞贤.碘化钾络合MIBK萃取富集石墨炉原子吸收法测定水中的铅[J].福建分析测试,2010,19(1):90-92.Liu Ruixian.Determination of plumbum in water by GFAAS after KI-MIBK extraction and enrichment[J].Fujian Analysis Testing,2010,19(1):90-92(in Chinese).
[20]高博,涂湘林,刘颖,等.AG-MP-1M阴离子交换树脂分离-表面热电质谱法测定沉积物中的铅同位素组成[J].岩矿测试,2008,27(1):9-11.Gao Bo,Tu Xianglin,Liu Ying,et al.Separation of lead in river sediments using AG-MP-1M anion exchange resin and measurement of lead isotope composition by thermal ionization mass spectrometry[J].Rack and Mineral Analysis,2008,27(1):9-11(in Chinese).
[21]Chiarizia R,Horwitz E P,Dietz M L.Acid dependency of the extraction of selected metal-ions bya strontium-selective extraction chromatographicResin:calculated vs experimental curves[J].Solvent Extraction and Ion Exchange,1992,10(2):337-361.
[22]刘书田.生物与环境样品放化分析中样品的前处理方法[J].同位素,1993,6(1):57-64.
[23]张丽华,肖国平,宋游,等.微波技术在生物样品预处理中的应用[J].现代科学仪器,2004,5:37-40.Zhang Lihua,Xiao Guoping,Song You,et al.Determination of multi-elements in biological sample by technology of the microwave digestion[J].Modern Scientific Instruments,2004,5:37-40(in Chinese).
[24]Mark L,Dietz,Renato C,et al.Effect of crown ethers on the ion-exchange behavior of alkaline earth metals.Toward improved ion-exchange methods for the separation and preconcentration of radium[J].Analytical Chemistry,1997,69:3 028-3 037.
[25]曹霄芸.应用多接收器电感耦合等离子体质谱法测定海南岛东部珊瑚中稳定铅同位素组成[D].上海:华东师范大学,2013.
[26]戴洁.高分辨电感耦合等离子质谱法测定珊瑚中铅的同位素组成研究[D].上海:华东师范大学,2010.