蒸馏法富集纯化Os实验条件研究及其在负离子热电离质谱测量中的应用
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摘要
微蒸馏是富集纯化Os的一项重要化学前处理技术,提高Os回收率对提高Os的负离子热电离质谱(NTIMS)测量精度尤为重要。在微蒸馏过程中,蒸馏温度、吸收液体积、蒸馏时间等对Os回收率具有重要影响,但目前微蒸馏的实验条件不够明确,导致Os回收率不稳定,影响NTIMS测量精度,易增加所得Re-Os年龄误差。本文以自制的含Os溶液为对象,以ICP-MS为测量手段,对微蒸馏过程中多种实验条件对Os回收率的影响进行深入研究,以期获得最佳微蒸馏实验条件,满足后续NTIMS对Os信号强度的测量要求。结果表明:在溶液蒸干温度为120℃并保持15 min,微蒸馏温度为80℃,氢溴酸吸收液体积为15μL,微蒸馏时间为2 h的条件下,获得Os回收率为80%~90%,能够满足多种地质样品尤其是中酸性岩浆岩、热液硫化物等pg级地质样品的NTIMS测量要求,在保证Os信号强度的情况下提高了分析效率。
BACKGROUND: Micro-distillation is an important chemical pretreatment technology for the enrichment and purification of Os. It is particularly important to improve Os recovery by optimizing the micro-distillation experimental conditions to ensure the accurate measurement of Os by NTIMS. The micro-distillation temperature,absorbing solution volume,and reaction time have significant influence on the recovery of Os. However,the optimum experimental conditions for micro-distillation are not clear,thus resulting in unstable Os recovery,affecting NTIMS measurement accuracy,and easily resulting in increased Re-Os dating error.OBJECTIVES: To evaluate the influence of different experimental conditions on the yield of Os during the microdistillation for improving the recovery of Os,ensuring the intensity and stability of the Os measurement signal by NTIMS.METHODS: A self-made Os-containing solution was chosen as the research object and ICP-MS was used as the measurement method. The element Ir was used as the internal standard to monitor the Os signal,and the Os recovery was calculated by the sample signal count.RESULTS: The results show that the maximum recovery of Os was obtained when the HBr solution was evaporated at 120℃ for 15 min,the micro-distillation temperature was 80℃,the HBr absorption solution was 15 μL,and the micro-distillation reaction time was 2 h. The Os recoveries were 80%-90% under the optimum experimental condition.CONCLUSIONS: Os recovery under the optimum micro-distillation experimental conditions satisfies the measurement requirements of NTIMS,especially for pg level geological samples. It also increases the Os signal intensity and improves the efficiency of experiments.
BACKGROUND: Micro-distillation is an important chemical pretreatment technology for the enrichment and purification of Os. It is particularly important to improve Os recovery by optimizing the micro-distillation experimental conditions to ensure the accurate measurement of Os by NTIMS. The micro-distillation temperature,absorbing solution volume,and reaction time have significant influence on the recovery of Os. However,the optimum experimental conditions for micro-distillation are not clear,thus resulting in unstable Os recovery,affecting NTIMS measurement accuracy,and easily resulting in increased Re-Os dating error.OBJECTIVES: To evaluate the influence of different experimental conditions on the yield of Os during the microdistillation for improving the recovery of Os,ensuring the intensity and stability of the Os measurement signal by NTIMS.METHODS: A self-made Os-containing solution was chosen as the research object and ICP-MS was used as the measurement method. The element Ir was used as the internal standard to monitor the Os signal,and the Os recovery was calculated by the sample signal count.RESULTS: The results show that the maximum recovery of Os was obtained when the HBr solution was evaporated at 120℃ for 15 min,the micro-distillation temperature was 80℃,the HBr absorption solution was 15 μL,and the micro-distillation reaction time was 2 h. The Os recoveries were 80%-90% under the optimum experimental condition.CONCLUSIONS: Os recovery under the optimum micro-distillation experimental conditions satisfies the measurement requirements of NTIMS,especially for pg level geological samples. It also increases the Os signal intensity and improves the efficiency of experiments.
引文
[1]Selby D,Creaser R A.Re-Os geochronology and systematics in molybdenite from the Endako porphyry molybdenum deposit,British Columbia,Canada[J].Economic Geology,2001,96(1):197-204.
[2]Du A D,Pirajno F,Qu W J,et al.Re-Os molybdenite and Ar-Ar phlogopite dating of Cu-Fe-Au-Mo(W)deposits in Southeastern Hubei,China[J].Mineralogy&Petrology,2007,90(3-4):249-270.
[3]屈文俊,陈江峰,杜安道,等.Re-Os同位素定年对岩浆型Cu-Ni硫化物矿床成矿时代的制约[J].矿床地质,2012,31(1):151-160.Qu W J,Chen J F,Du A D,et al.Re-Os dating:Constraints on mineralization age of magmatic Cu-Ni sulfide ore deposit[J].Mineral Deposits,2012,31(1):151-160.
[4]Selby D,Creaser R A.Re-Os geochronology of organic rich sediments:An evaluation of organic matter analysis methods[J].Chemical Geology,2003,200(3-4):225-240.
[5]Kendall B S,Creaser R A,Ross G M,et al.Constraints on the timing of marinoan‘Snowball Earth’glaciation by187Re-187Os dating of a neoproterozoic,post-glacial black shale in Western Canada[J].Earth&Planetary Science Letters,2004,222(3-4):729-740.
[6]李超,屈文俊,王登红,等.Re-Os同位素体系在沥青及灰岩中的应用研究:以青海玉树地区东莫扎抓铅锌矿为例[J].矿物学报,2011(增刊):602-603.Li C,Qu W J,Wang D H,et al.Application of Re-Os isotopic system in bitumen and limestone:The example of Dongmozhazhua Pb-Zn deposits,Yushu area,Qinghai Province[J].Acta Mineralogica Sinica,2011(Supplement):602-603.
[7]裴浩翔,付勇,李超,等.贵州道坨锰矿成矿时代及环境的Re-Os同位素证据[J].科学通报,2017,62(28-29):3346-3355.Pei H X,Fu Y,Li C,et al.Mineralization age and metallogenic environment of Daotuo manganese deposits in Guizhou:Evidence from Re-Os isotopes[J].Chinese Science Bulletin,2017,62(28-29):3346-3355.
[8]Mahdaoui F,Reisberg L,Michels R,et al.Effect of the progressive precipitation of petroleum asphaltenes on the Re-Os radioisotope system[J].Chemical Geology,2013,358(4):90-100.
[9]王杰,腾格尔,刘文汇,等.川西矿山梁下寒武统沥青脉油气生成时间的厘定——来自于固体沥青Re-Os同位素等时线年龄的证据[J].天然气地球科学,2016,27(7):1290-1298.Wang J,Tenger,Liu W H,et al.Definition of petroleum generating time for Lower Cambrian bitumen of the Kuangshanliang in the West Sichuan Basin,China:Evidence from Re-Os isotopic isochron age[J].Natural Gas Geoscience,2016,27(7):1290-1298.
[10]Creaser R A,Selby D.Re-Os elemental and isotopic systematics in petroleum:A potentially powerful tracer[J].Geochimica et Cosmochimica Acta,2006,70(18):116.
[11]Lu X Z,Kendall B,Stein H J,et al.Temporal record of osmium concentrations and187Os/188Os in organic-rich mudrocks:Implications for the osmium geochemical cycle and the use of osmium as a paleoceanographic tracer[J].Geochimica et Cosmochimica Acta,2017,216(1):221-241.
[12]段瑞春,王浩,凌文黎,等.缺氧沉积物及其衍生物的Re-Os同位素定年与示踪[J].华南地质与矿产,2010(3):57-67.Duan R C,Wang H,Ling W L,et al.Progress in Re-Os isotope geochronology and tracing studies of anoxic sediments and their derivatives[J].Geology and Mineral Resources of South China,2010(3):57-67.
[13]李杰,梁细荣,董彦辉,等.利用多接收器电感耦合等离子体质谱仪(MC-ICPMS)测定镁铁-超镁铁质岩石中的铼-锇同位素组成[J].地球化学,2007,36(2):153-160.Li J,Liang X R,Dong Y H,et al.Measurements of Re-Os isotopic composition in mafic-ultramafic rocks by multicollector inductively coupled plasma mass spectrometer(MC-ICPMS)[J].Geochimica,2007,36(2):153-160.
[14]杜安道,屈文俊,李超,等.铼-锇同位素定年方法及分析测试技术的进展[J].岩矿测试,2009,28(3):288-304.Du A D,Qu W J,Li C,et al.A review on the development of Re-Os isotopic dating methods and techniques[J].Rock and Mineral Analysis,2009,28(3):288-304.
[15]Morgan J W,Walker R J.Isotopic determinations of rhenium and osmium in meteorites by using fusion,distillation and ion-exchange separations[J].Analytica Chimica Acta,1989,222(1):291-300.
[16]杜安道,赵敦敏,高洪涛.负离子热表面电离质谱测定中的铼、锇同位素试样化学分离方法研究[J].质谱学报,1998,19(3):11-18.Du A D,Zhao D M,Gao H T,et al.A study on Re-Os chemical separation method for NTIMS[J].Journal of Chinese Mass Spectrometry Society,1998,19(3):11-18.
[17]Brauns C M.A rapid,low-blank technique for the extraction of osmium from geological samples[J].Chemical Geology,2001,176(1-4):379-384.
[18]李超,屈文俊,周利敏,等.Carius管直接蒸馏快速分离锇方法研究[J].岩矿测试,2010,29(1):14-16.Li C,Qu W J,Zhou L M,et al.Rapid separation of osmium by direct distillation with Carius tube[J].Rock and Mineral Analysis,2010,29(1):14-16.
[19]周利敏,高炳宇,王礼兵,等.Carius管直接蒸馏快速分离锇方法的改进[J].岩矿测试,2012,31(3):413-418.Zhou L M,Gao B Y,Wang L B,et al.Improvements on the separation method of osmium by direct distillation in Carius tube[J].Rock and Mineral Analysis,2012,31(3):413-418.
[20]何红蓼,杜安道,邹晓秋,等.铼-锇测年法中锇的化学行为研究[J].分析化学,1994,22(2):109-114.He H L,Du A D,Zou X Q,et al.Chemical behavior of osmium in the rhenium-osmium geochronometry[J].Chinese Journal of Analytical Chemistry,1994,22(2):109-114.
[21]Roybarman M.Mesure du Rapport187Os/186Os dans les Basaltes et les Peridotites:Contribution a la Systematique187Re-187Os dans le Manteau[M].Thesis:Universitéde ParisⅦ.1993.
[22]孙卫东,彭子成,王兆荣,等.负热电离质谱技术在饿同位素测定中的应用[J].质谱学报,1997,18(2):7-15.Sun W D,Peng Z C,Wang Z R,et al.Application of negative thermal ionization mass spectrometry in Os isotope determination[J].Journal of Chinese Mass Spectrometry Society,1997,18(2):7-15.
[23]V9lkening J,Walczyk T,Heumann K G.Osmium isotope ratio determinations by negative thermal ionization mass spectrometry[J].International Journal of Mass Spectrometry and Ion Processes,1991,105(2):147-159.
[24]Walczyk T,Hebeda E H,Heumann K G.Osmium isotope ratio measurements by negative thermal ionization mass spectrometry(NTI-MS)[J].Fresenius Journal of Analytical Chemistry,1991,341(9):537-541.
[25]Birck J L,Barman M R,Capmas F.Re-Os isotopic measurements at the femtomole level in natural samples[J].Geostandards Newsletter,1997,21(1):19-27.
[26]刘绪良,戴冬梅,高洪涛.微蒸馏方法分离富集Os同位素测定辉钼矿Os-Os年龄[J].聊城师院学报(自然科学版),2001,14(3):36-39.Liu X L,Dai D M,Gao H T.Osmium isotope separated and enriched to date Os-Os age of molybdenite with method of mircodistillation[J].Journal of Liaocheng Teachers University(Natural Science),2001,14(3):36-39.
[27]Cohen A S,Waters F G.Separation of osmium from geological materials by solvent extraction for analysis by thermal ionisation mass spectrometry[J].Analytica Chimica Acta,1996,332(2-3):269-275.
[28]Sharma M,Chen C,Blazina T.Osmium contamination of seawater samples stored in polyethylene bottles[J].Limnology&Oceanography:Methods,2012,10(9):618-630.
[29]vorc L,Tomcík P,Durdiak J,et al.Analytical methods for the detection of osmium tetroxide:A review[J].Polish Journal of Environmental Studies,2012,21(1):7-13.
[30]Reisberg L,Meisel T.The Re-Os isotopic system:A review of analytical techniques[J].Geostandards and Geoanalytical Research,2002,26(3):249-267.
[2]Du A D,Pirajno F,Qu W J,et al.Re-Os molybdenite and Ar-Ar phlogopite dating of Cu-Fe-Au-Mo(W)deposits in Southeastern Hubei,China[J].Mineralogy&Petrology,2007,90(3-4):249-270.
[3]屈文俊,陈江峰,杜安道,等.Re-Os同位素定年对岩浆型Cu-Ni硫化物矿床成矿时代的制约[J].矿床地质,2012,31(1):151-160.Qu W J,Chen J F,Du A D,et al.Re-Os dating:Constraints on mineralization age of magmatic Cu-Ni sulfide ore deposit[J].Mineral Deposits,2012,31(1):151-160.
[4]Selby D,Creaser R A.Re-Os geochronology of organic rich sediments:An evaluation of organic matter analysis methods[J].Chemical Geology,2003,200(3-4):225-240.
[5]Kendall B S,Creaser R A,Ross G M,et al.Constraints on the timing of marinoan‘Snowball Earth’glaciation by187Re-187Os dating of a neoproterozoic,post-glacial black shale in Western Canada[J].Earth&Planetary Science Letters,2004,222(3-4):729-740.
[6]李超,屈文俊,王登红,等.Re-Os同位素体系在沥青及灰岩中的应用研究:以青海玉树地区东莫扎抓铅锌矿为例[J].矿物学报,2011(增刊):602-603.Li C,Qu W J,Wang D H,et al.Application of Re-Os isotopic system in bitumen and limestone:The example of Dongmozhazhua Pb-Zn deposits,Yushu area,Qinghai Province[J].Acta Mineralogica Sinica,2011(Supplement):602-603.
[7]裴浩翔,付勇,李超,等.贵州道坨锰矿成矿时代及环境的Re-Os同位素证据[J].科学通报,2017,62(28-29):3346-3355.Pei H X,Fu Y,Li C,et al.Mineralization age and metallogenic environment of Daotuo manganese deposits in Guizhou:Evidence from Re-Os isotopes[J].Chinese Science Bulletin,2017,62(28-29):3346-3355.
[8]Mahdaoui F,Reisberg L,Michels R,et al.Effect of the progressive precipitation of petroleum asphaltenes on the Re-Os radioisotope system[J].Chemical Geology,2013,358(4):90-100.
[9]王杰,腾格尔,刘文汇,等.川西矿山梁下寒武统沥青脉油气生成时间的厘定——来自于固体沥青Re-Os同位素等时线年龄的证据[J].天然气地球科学,2016,27(7):1290-1298.Wang J,Tenger,Liu W H,et al.Definition of petroleum generating time for Lower Cambrian bitumen of the Kuangshanliang in the West Sichuan Basin,China:Evidence from Re-Os isotopic isochron age[J].Natural Gas Geoscience,2016,27(7):1290-1298.
[10]Creaser R A,Selby D.Re-Os elemental and isotopic systematics in petroleum:A potentially powerful tracer[J].Geochimica et Cosmochimica Acta,2006,70(18):116.
[11]Lu X Z,Kendall B,Stein H J,et al.Temporal record of osmium concentrations and187Os/188Os in organic-rich mudrocks:Implications for the osmium geochemical cycle and the use of osmium as a paleoceanographic tracer[J].Geochimica et Cosmochimica Acta,2017,216(1):221-241.
[12]段瑞春,王浩,凌文黎,等.缺氧沉积物及其衍生物的Re-Os同位素定年与示踪[J].华南地质与矿产,2010(3):57-67.Duan R C,Wang H,Ling W L,et al.Progress in Re-Os isotope geochronology and tracing studies of anoxic sediments and their derivatives[J].Geology and Mineral Resources of South China,2010(3):57-67.
[13]李杰,梁细荣,董彦辉,等.利用多接收器电感耦合等离子体质谱仪(MC-ICPMS)测定镁铁-超镁铁质岩石中的铼-锇同位素组成[J].地球化学,2007,36(2):153-160.Li J,Liang X R,Dong Y H,et al.Measurements of Re-Os isotopic composition in mafic-ultramafic rocks by multicollector inductively coupled plasma mass spectrometer(MC-ICPMS)[J].Geochimica,2007,36(2):153-160.
[14]杜安道,屈文俊,李超,等.铼-锇同位素定年方法及分析测试技术的进展[J].岩矿测试,2009,28(3):288-304.Du A D,Qu W J,Li C,et al.A review on the development of Re-Os isotopic dating methods and techniques[J].Rock and Mineral Analysis,2009,28(3):288-304.
[15]Morgan J W,Walker R J.Isotopic determinations of rhenium and osmium in meteorites by using fusion,distillation and ion-exchange separations[J].Analytica Chimica Acta,1989,222(1):291-300.
[16]杜安道,赵敦敏,高洪涛.负离子热表面电离质谱测定中的铼、锇同位素试样化学分离方法研究[J].质谱学报,1998,19(3):11-18.Du A D,Zhao D M,Gao H T,et al.A study on Re-Os chemical separation method for NTIMS[J].Journal of Chinese Mass Spectrometry Society,1998,19(3):11-18.
[17]Brauns C M.A rapid,low-blank technique for the extraction of osmium from geological samples[J].Chemical Geology,2001,176(1-4):379-384.
[18]李超,屈文俊,周利敏,等.Carius管直接蒸馏快速分离锇方法研究[J].岩矿测试,2010,29(1):14-16.Li C,Qu W J,Zhou L M,et al.Rapid separation of osmium by direct distillation with Carius tube[J].Rock and Mineral Analysis,2010,29(1):14-16.
[19]周利敏,高炳宇,王礼兵,等.Carius管直接蒸馏快速分离锇方法的改进[J].岩矿测试,2012,31(3):413-418.Zhou L M,Gao B Y,Wang L B,et al.Improvements on the separation method of osmium by direct distillation in Carius tube[J].Rock and Mineral Analysis,2012,31(3):413-418.
[20]何红蓼,杜安道,邹晓秋,等.铼-锇测年法中锇的化学行为研究[J].分析化学,1994,22(2):109-114.He H L,Du A D,Zou X Q,et al.Chemical behavior of osmium in the rhenium-osmium geochronometry[J].Chinese Journal of Analytical Chemistry,1994,22(2):109-114.
[21]Roybarman M.Mesure du Rapport187Os/186Os dans les Basaltes et les Peridotites:Contribution a la Systematique187Re-187Os dans le Manteau[M].Thesis:Universitéde ParisⅦ.1993.
[22]孙卫东,彭子成,王兆荣,等.负热电离质谱技术在饿同位素测定中的应用[J].质谱学报,1997,18(2):7-15.Sun W D,Peng Z C,Wang Z R,et al.Application of negative thermal ionization mass spectrometry in Os isotope determination[J].Journal of Chinese Mass Spectrometry Society,1997,18(2):7-15.
[23]V9lkening J,Walczyk T,Heumann K G.Osmium isotope ratio determinations by negative thermal ionization mass spectrometry[J].International Journal of Mass Spectrometry and Ion Processes,1991,105(2):147-159.
[24]Walczyk T,Hebeda E H,Heumann K G.Osmium isotope ratio measurements by negative thermal ionization mass spectrometry(NTI-MS)[J].Fresenius Journal of Analytical Chemistry,1991,341(9):537-541.
[25]Birck J L,Barman M R,Capmas F.Re-Os isotopic measurements at the femtomole level in natural samples[J].Geostandards Newsletter,1997,21(1):19-27.
[26]刘绪良,戴冬梅,高洪涛.微蒸馏方法分离富集Os同位素测定辉钼矿Os-Os年龄[J].聊城师院学报(自然科学版),2001,14(3):36-39.Liu X L,Dai D M,Gao H T.Osmium isotope separated and enriched to date Os-Os age of molybdenite with method of mircodistillation[J].Journal of Liaocheng Teachers University(Natural Science),2001,14(3):36-39.
[27]Cohen A S,Waters F G.Separation of osmium from geological materials by solvent extraction for analysis by thermal ionisation mass spectrometry[J].Analytica Chimica Acta,1996,332(2-3):269-275.
[28]Sharma M,Chen C,Blazina T.Osmium contamination of seawater samples stored in polyethylene bottles[J].Limnology&Oceanography:Methods,2012,10(9):618-630.
[29]vorc L,Tomcík P,Durdiak J,et al.Analytical methods for the detection of osmium tetroxide:A review[J].Polish Journal of Environmental Studies,2012,21(1):7-13.
[30]Reisberg L,Meisel T.The Re-Os isotopic system:A review of analytical techniques[J].Geostandards and Geoanalytical Research,2002,26(3):249-267.