Carius管溶样-负离子热表面电离质谱准确测定辉钼矿铼-锇同位素地质年龄

将样品、混合稀释剂和逆王水加入到Carius管中,于230℃溶样10h.利用蒸馏法分离Os,萃取和阴离子交换法分离Re.采用负离子热表面电离质谱精确测定了所研制的年龄标准参考物辉钼矿(HLP)的Re-Os年龄.对取自12个小瓶中17个样品所测平均年龄为221.3±0.3Ma,置信度95%.中值年龄和平均绝对偏差为221.34±0.12Ma.美国克罗拉多州立大学AIRIE小组19次单独取样所测HLP的平均年龄为221.3±1.0Ma,置信度95%.中值年龄和平均绝对偏差为221.34±0.24Ma.     

铼—锇定年法中碱熔分解样品方法的改进

为改进铼锇测年的准确度 ,试验了 4种熔样和稀释剂加入方式 ,最后选择了锆埚熔样和加入混合稀释剂溶液的方法。先用NaOH溶液中和混合稀释剂溶液 ,在碱性稀释剂溶液烤干后 ,再分层加入NaOH、样品、NaOH、Na2 O2 进行高温熔融。采用同位素稀释 -等离子体质谱 (ID-ICP -MS)对所研制的Re -Os年龄参考样辉钼矿JDC的年龄进行了 4次测定 ,测定值为1 39.1 0± 0 .2 6Ma ,相对标准偏差为 0 .2 %。采用 φ =5 %的NH3·H2 O和浓H2 O2 交替清洗测量系统 ,可更有效地消除ICP -MS测量中Os的记忆效应。浓HNO3浸煮和加热烘烤可较有效地除去Teflon器皿中残留的Os。     

A Study of the Rhenium-Osmium Geochronometry of Molybdenites1

Abstract This study deals with the first application of the isotope dilution-inductively coupled plasma mass spectrometry in the rhenium-osmium geochronometry in China. The chemical separation procedure included decomposition of samples by means of alkali fusion, extraction of rhenium by acetone and extraction of osmium by distillation. The recovery of both elements in the entire process was more than 90% . The blanks of analyses were 0.07 ng for rhenium and 0.01 ng for ¹⁸⁷Os. The mineralization ages of molybdenites from four molybdenum deposits in China were determined by using this method, with a precision (2σ) of about ±3% . These results agree satisfactorily with their geological backgrounds. The Re-Os method can directly determine ages of metal deposits and reflect the true ages more reliably than other dating methods that only determine the ages of country rocks from which mineralization ages are inferred. As many hydrothermal sulphide deposits usually contain molybdenites, this method has bright prospects of wide application.     

How chalcophile is rhenium? An experimental study of the solubility of Re in sulphide mattes

Although the Re/Os isotopic system has proved to be a valuable aid in understanding the evolution of the Earth's mantle, interpretation of the data is currently hindered by limited knowledge of the high-temperature geochemical behaviour of Re. In particular, the extent to which Re in the mantle is hosted by sulphide or silicate phases is poorly known. We report the results of an experimental study of the solubility of Re in sulphide melts (called here “mattes”) coexisting with a Re-rich Re–Fe alloy in the system Fe–Re–S–O over a range of fO₂, fS₂ and temperatures, which allow extrapolation to conditions pertinent to the Earth's mantle. The solubility of Re in mattes increases with increasing fS₂, with Re dissolving as Re⁴⁺ at high fS₂ and Re⁰ at low fS₂. The effect of fO₂ is negligible except at high fO₂ where O in the matte becomes important. At constant fS₂, an increase in temperature leads to an increase in the solubility of Re⁰ in the matte, but a decrease in the solubility of Re⁴⁺. These results, coupled with data for the Re solubility in silicate melts taken from the literature, allow the calculation of Re matte/silicate–melt partition coefficients (D_Re^matte/sil) for a range of conditions. The calculated D_Re^matte/sil show a large dependence on fO₂, and a lesser dependency on fS₂, with Re behaving as a chalcophile element for relatively reduced MORB-type mantle and as a lithophile element for the oxidised sources of island-arc basalts. The sensitivity of Re to fS₂ and fO₂ reconciles the apparent discrepancies between previous estimates of this parameter, which can vary by more than five orders of magnitude within the range of fS₂ and fO₂ covered by terrestrial basaltic magmas.     

丹巴杨柳坪地区铜镍硫化物矿床发现铼矿物

铼是地壳中质量分数最少的元素之一,独立的铼矿物十分罕见,我国过去未有发现铼矿物的报道。近年来,我们在对丹巴杨柳坪铜镍矿床进行深入的矿物学研究中,偶然发现了四边形铼矿物Re1其化学简式(Re,Cu,Os,Fe,Ni,Pb)1S2(国际矿物协会未命名委员会指定编号:UM2014-01-S:Re)和三角形铼矿物Re2化学简式(Re,Cu,Fe)1S2(国际矿物协会未命名委员会指定编号:UM2014-02-S:Re)。通过能谱和拉曼光谱分析发现,2种铼矿物的成分和结构明显不同于已报道的铼矿物,具备了成为新矿物的有利前提。尽管目前缺乏电子探针和单晶衍射数据进行验证,但已有成分和结构数据表明,这2种铼矿物有可能为新的矿物种,虽未正式申请并通过国际矿物协会新矿物命名委员获批,但国际矿物协会未命名委员会已指定上述2种铼矿物的未命名编号,我们也因此获得了申请该2种铼矿物可能申请获批成为新矿物的优先权。     

Effective Correction of Mass Bias for Rhenium Measurements by MC-ICP-MS

The geochemistry of Re-Os and the recent use of Re as a non-traditional stable isotope both need accurate and precise quantification of ¹⁸⁷Re/¹⁸⁵Re ratios. This paper reports rhenium isotopic data obtained from the analysis of a standard solution and geological samples by MC-ICP-MS. We show that measured isotopic ratios are modified by matrix effects that cannot be accounted for by the standard solution bracketing technique. The bias resulting from measurements on a spiked (¹⁸⁵Re-enriched) sample is shown to alter the apparent Re concentration by several percent. When spiking samples and calibrators with tungsten, simultaneous measurement of tungsten and rhenium isotopes compensates for the matrix-induced modification of mass bias. Rhenium and tungsten are shown to have different fractionation factors. This may be due to the fact that the two elements fractionate in a different but systematic way, or that the reference isotopic ratios used for elemental Re and W are incoherent with one another. The consistency of fractionation through time can be used to obtain an empirical relationship between W and Re measured ratios from a standard solution to obtain a sample's fractionation-corrected ¹⁸⁷Re/¹⁸⁵Re spiked ratio on samples containing pg g⁻¹ levels of Re, even if some matrix capable of affecting mass bias remains in the final solution.     

Quantitative Separation of Molybdenum and Rhenium from Geological Materials for Isotopic Determination by MC-ICP-MS

We have developed a new chemical procedure for the quantitative separation of molybdenum (Mo) and rhenium (Re) from a wide variety of geological samples. A single pass anion exchange separation provided complete recovery of pure Mo and Re in a form that was ideal for subsequent isotope and abundance determination by multi-collector inductively coupled plasma-mass spectroscopy (MC-ICP-MS). An enriched ¹⁰⁰Mo-⁹⁷Mo solution, mixed with the sample before digestion, enabled natural mass-dependant isotopic fractionation of Mo to be determined with an external reproducibility of < 0.12‰ (δ⁹⁸Mo/⁹⁵Mo, 2 s ). Determination of the concentration of Mo and Re in the same sample was achieved by isotope dilution, with instrumental mass-fractionation of Re being corrected by the simultaneous measurement of the ¹⁹¹Ir/¹⁹³Ir ratio. We have applied the new procedure to a variety of samples, including seawater, basalt and organic-rich mudrock. The procedure is ideally suited to palaeoredox studies requiring the precise determination of the Mo isotope composition and the Re/Mo ratio from the same sample.     

铼-锇同位素定年法中丙酮萃取铼的系统研究

文章较为系统地研究了铼-锇定年法中丙酮萃取铼的实验条件,对萃取介质的碱度和萃取剂的用量进行了优化,并对振荡萃取时间以及碱洗进行了选择。优化后的实验条件对铼有较高的回收率,对其他杂质元素也有较高的分离系数,不仅简化了实验流程,而且节约了化学试剂。     

电感耦合等离子体发射光谱法测定钼矿石和铜矿石中的铼

采用氧化镁-硝酸钠-过氧化氢处理试样,不需分离富集,电感耦合等离子体发射光谱法直接测定钼矿石及铜矿石中的铼,筛选了不同溶矿方法和仪器参数条件。方法检出限为0.014μg/g,相对标准偏差(RSD,n=11)小于5.00%,经国家一级钼矿石及铜矿石标准物质分析验证,结果与标准值吻合。     

多接收器等离子体质谱精确测定铼含量及其同位素丰度

利用多接收器等离子体质谱建立了快速精确测定铼含量及其同位素丰度的方法。溶液中加入铱元素进行铼同位素的质量分馏校正,在常规的溶液雾化进样条件下,采用同位素稀释法可准确测定纳克级的铼含量。铼标样A的自然同位素丰度的测量结果为185Re(37.437±0.008)%、187Re(62.563±0.008)%(2σ,n=5);铼稀释剂的同位素丰度测量结果为185Re(5.576±0.018)%、187Re(94.424±0.018)%(2σ,n=7);与未进行分馏校正的同位素组成的测量结果相比,精度和准确度均有提高。利用同位素稀释法测得铼标样A的浓度为(516.48±0.35)ng/g(2σ,n=5);测量精度和准确度均优于0.10%;利用反同位素稀释法对铼稀释剂B进行了详细的测量,平均测量结果为(62.74±0.26)ng/g(2σ,n=15),在分析误差范围内与其标定值完全一致;与未进行分馏校正的浓度测量结果相比,铼同位素丰度及铼含量的测量准确度均明显提高。