钼同位素比值的双稀释剂测定方法研究

本文报道了运用多接收器等离子体质谱测定Mo同位素组成的方法,测定过程中使用双稀释剂法校正仪器的质量分馏.Fisher-Mo标准溶液和双稀释剂的100Mo/97Mo使用Fisher-Pd标准溶液中的104pd/102pd标定,其他Mo同位素比值通过100Mo/97Mo标定;本文对运用双稀释剂技术进行Mo同位素测定的长期重...     

多接收等离子质谱（MC-ICP-MS )测定Mg同位素初步研究

常量元素Mg的同位素比值，应用在地球化学上有重要意义。笔者采用“样品-标准”交叉技术，以国际标准SRM980,AIdrich, Romil和实验室标准GSB作为实验材料，探讨浓度和基质效应影响，尝试建立高精度多接收等离子质谱(MC-ICP-MS)测定Mg同位素方法。相对于国际标准物质SRM980，本研究测得的国际标准物质Aldrich的δ26Mg和δ25Mg值分别为（2.64±0.15)‰(2σ）和（1.34±0.09)‰(2σ); Romil的δ26Mg和δ25Mg值分别为（2.46±0.15)‰(2σ）和（1.27±0.08)%(2σ)；国土资源部同位素地质重点实验室的实验室标准GSB的δ26Mg和δ25Mg值分别为（4.05±0.03)‰(2σ)和(2.05±0.03)‰(2σ)。     

多接收器等离子体质谱（MC-ICP-MS）测定Mg同位素方法研究

采用"样品-标准"交叉技术,以纯Mg试剂、水样和矿物岩石样品作为实验材料,尝试建立高精度多接收器等离子体质谱(MC-ICP-Ms)测定Mg同位素方法.应用质谱仪上窄的进样狭缝,将来自Ar载气、空气和酸中的C 2、C2H 、C2H2、CN 、NaH 等分子对Mg同位素的影响减至最小.当标准Mg浓度为3×10-6时,保持样品与标准的浓度比在0.5～2之间,对Mg同位素比值测量没有影响.大量实验表明,不同基质的行为各异:Na、Fe和Al的基质效应使δ25.Mg和δ26Mg偏负;Ca的基质效应使δ25.Mg和δ26Mg偏正;Cr的基质效应使δ25Mg和δ26Mg波动.控制[元素]/[Mg]的浓度比在0.05范围内,可以忽略同质异位素的干扰和基质效应.通过对本实验室的两个工作标准CAGS1-Mg和CAGS2-Mg的长期测量,估计出Mg同位素测量的外精度(2SD)对于δ26Mg可达0.18‰,对于δ25Mg可达0.090‰.在25Mg/24Mg对26Mg/24Mg的同位素比值图上,所有样品的Mg同位素值都落在斜率约0.5的质量分馏线上,意味着建立的MC-ICP-MS测定Mg同位素方法既精确又无干扰.相对于DSM3国际标准,样品的Mg同位素组成大致变化范围是δ26Mg值为2.790‰,δ25Mg值为1.282‰.其中,CAGS1.Mg的δ26Mg值最大,为0.399,来自新疆喀呐斯湖水的26MG值最小,为-2.091.     

MC-ICP-MS高精度测定Pb同位素比值

多接收器等离子体质谱是近年发展起来的高精度同位素分析手段之一，通过用等离子体质谱测量Pb国际标准物质NBS981和NBS982,显示出多接收器等离子体质谱分析Pb同位素的优势。利用205Tl/203Tl进行作为内标，可以实现Pb同位素的质量分馏校正，极大地提高了Pb同位素分析的重现性。相比较热电离质谱，该方法精度更高，样品的用量更少，测试时间更短，多接收器等离子体质谱测定Pb同位素技术有良好的应用前景。     

多接收器等离子体质谱仪Zn同位素测定方法研究

该研究建立了Zn同位素比值的MC-ICPMS高精度测定方法.研究内容包括:对干扰信号、介质影响、基质效应和仪器稳定性的评估等方面.重复性测定中,66Zn/64Zn、67Zn/64Zn、68Zn/64Zn外精度分别为0.1‰(2SD)、0.23‰(2sD)、0.22‰(2SD),达到国际先进水准.     

多接收器等离子体质谱(MC-ICP-MS) Pb同位素高精度研究

多接收器等离子体质谱是近年发展起来的高精度同位素分析手段之一,通过用等离子体质谱测量Pb国际标准物质NBS981和NBS982,显示出多接收器等离子体质谱分析Pb同位素的优势.利用205Tl/203Tl进行作为内标,可以实现Pb同位素的质量分馏校正,极大地提高了Pb同位素分析的重现性.相比较热电离质谱,该方法精度更高,样品的用量更少,测试时间更短,多接收器等离子体质谱测定Pb同位素技术有良好的应用前景.     

岩石样品Hf化学分离及MC-ICP-MS同位素分析：离子交换色谱法的应用

介绍的离子交换色谱分离岩石样品Lu-Hf的方法,是对现有方法的改进。整个流程以使用HCl为主,配合少量HF,即可达到有效地分离Hf和Lu的目的,Lu和Hf的回收率在90％以上。经MC—ICP。MS分析,每个国际岩石标样的两个平行样获得了在误差范围内一致^176 Hf／^177 Hf比值,其中BHVO-1、BHVO-2和BCR-2的^176 Hf／^177 Hf比值与国内外文献报道的结果在误差范围内一致。     

铁同位素的MC-ICP-MS测定方法与地质标准物质的铁同位素组成

详细报道了在低分辨和高分辨模式下运用MC-ICP-MS进行Fe同位素比值高精度测试的方法,对Fe同位素测定过程中谱峰干扰、基质效应、浓度效应、仪器测试的长期重现性等问题进行了评估,并对两种运行模式的测试结果进行了对比.在95%的可信度范围内,所建方法的外部精度优于0.5ε/ainu,达到国际同类实验室的先进水平,并且低分辨和高分辨两种模式下获得的Fe同位素测试结果是一致的.在此基础上对国家地质标准物质GBW07105(玄武岩)和GBW 07111(花岗闪长岩)进行了Fe同位素测定.相对于Fe同位素国际标样IRMM-014,GBW07105的Fe同位素成分为:ε57Fe=1.9±0.3(20),ε56Fe=1.3±0.2(2σ),ε57/56Fe=0.6±0.1(2σ);GBW 07111的Fe同位素成分为:ε57Fe=1.8±0.4(2σ),ε56Fe=1.2±0.2(2σ),ε57/56Fe=0.6±0.1(2σ).     

双稀释剂法在非传统稳定同位素测定中的应用——以钼同位素为例

仪器的质量分馏校正是提高同位素分析数据精度的关键。"同位素双稀释剂"的测定方法可实现严格的仪器质量分馏校正。文章以Mo同位素为例,详细介绍了同位素双稀释剂法的原理、计算方法以及应用多接收器等离子体质谱仪(MC-ICP-MS)进行Mo同位素组成高精度分析的方法。双稀释剂和标准样品的100Mo/97Mo使用Pd溶液的104Pd/102Pd标定,其他Mo同位素比值通过100Mo/97Mo标定。对100Mo/95Mo、98Mo/95Mo和97Mo/95Mo三组Mo同位素比值建立3个非线性方程,组成一个非线性方程组,在认为仪器质量分馏和自然分馏都符合指数法则的前提下,通过Taylor公式将非线性方程组转换成线性方程组,使用牛顿迭代法计算出样品的Mo同位素组成。在使用MC-ICP-MS分析过程中,每组数据采集20个数据点,最终的δ100Mo/95Mo、δ98Mo/95Mo和δ97Mo/95Mo是这20组数据得到的20组δ100Mo/95Mo、δ98Mo/95Mo和δ97Mo/95Mo的平均值。     

岩石样品快速Hf分离与MC-ICPMS同位素分析: 一个改进的单柱提取色谱方法

建立了一个改进的单柱Ln-Spec提取色谱分离Hf方法.用该方法可以有效地分离出岩石样品的基体元素、REE和干扰元素等,并使Hf的回收率＞90%、本底＜5×10-11g.用该方法对一些国际和国家岩石标样进行了Hf分离,采用单聚焦和双聚焦两种型号的MC-ICPMS测定了Hf同位素组成,国际标样的结果与文献值在误差范围内完全一致,国家标样的Hf同位素结果具有很好的外部重现性.     

Fe同位素的MC-ICP-MS测试方法

过渡族元素同位素研究是新兴的研究领域和国际研究前沿,是同位素地球化学研究的热点.本研究利用Neptune型多接收等离子质谱(MC-ICP-MS),采用标准-样品-标准交叉校正和以Cu为内标的方法对仪器的质量歧视进行校正,对浓度效应、基质效应、干扰元素扣除和测试的长期重现性进行了检验,建立了高精度的Fe同位素测试技术.这两种校正方法对实验室标准HSP I Fe在一段时间内δ56Fe和δ57Fe的测试结果分别为0.08‰(2SD)和0.14‰(2SD)分析精度达到国际同类实验室水平,测试结果在误差范围内与文献值完全一致.     

Accurate and High-Precision Measurement of Lithium Isotopes in Two Reference Materials by MC-ICP-MS

We report here a newly developed method for measurement of Li isotopes by use of multi-collector ICP-MS (Neptune) allowing rapid and high precision determination of Li isotope ratios at low levels of lithium (15–20 ng). The lithium reference sample solution IRMM-016 was analysed over a period of ten months with an external reproducibility of 0.24% (2s, n = 52). Chemical separation of Li from matrix was performed on the seawater sample IRMM BCR-403, for which a mean δ⁷Li value of + 31.0 ± 0.1 % (2s/√n, n = 31) was obtained. This mean value is in good agreement with those previously published for other seawater samples. BCR-403 seawater being readily available, we propose that this seawater sample be used as a reference sample for Li isotope measurements.     

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.     

Development of Cu and Zn Isotope MC-ICP-MS Measurements: Application to Suspended Particulate Matter and Sediments from the Scheldt Estuary

The present study evaluates several critical issues related to precision and accuracy of Cu and Zn isotopic measurements with application to estuarine particulate materials. Calibration of reference materials (such as the IRMM 3702 Zn) against the JMC Zn and NIST Cu reference materials were performed in wet and/or dry plasma modes (Aridus I and DSN‐100) on a Nu Plasma MC‐ICP‐MS. Different mass bias correction methods were compared. More than 100 analyses of certified reference materials suggested that the sample‐calibrator bracketing correction and the empirical external normalisation methods provide the most reliable corrections, with long term external precisions of 0.06 and 0.07‰ (2SD), respectively. Investigation of the effect of variable analyte to spike concentration ratios on Zn and Cu isotopic determinations indicated that the accuracy of Cu measurements in dry plasma is very sensitive to the relative Cu and Zn concentrations, with deviations of δ⁶⁵Cu from ?0.4‰ (Cu/Zn = 4) to +0.4‰ (Cu/Zn = 0.2). A quantitative assessment (with instrumental mass bias corrections) of spectral and non‐spectral interferences (Ti, Cr, Co, Fe, Ca, Mg, Na) was performed. Titanium and Cr were the most severe interfering constituents, contributing to inaccuracies of ?5.1‰ and +0.60‰ on δ^68/64Zn, respectively (for 500 μg l^?1 Cu and Zn standard solutions spiked with 1000 μg l^?1 of Ti or Cr). Preliminary isotopic results were obtained on contrasting sediment matrices from the Scheldt estuary. Significant isotopic fractionation of zinc (from 0.21‰ to 1.13‰ for δ⁶⁶Zn) and copper (from ?0.38‰ to 0.23‰ for δ⁶⁵Cu), suggest a control by physical mixing of continental and marine water masses, characterized by distinct Cu and Zn isotopic signatures. These results provide a stepping‐stone to further evaluate the use of Cu and Zn isotopes as biogeochemical tracers in estuarine environments.     

多接收器等离子体质谱法Zn同位素比值的高精度测定

详细报道了Zn同位素比值的多接收器等离子体质谱(MC-ICP-MS)高精度测定方法,包括:MC-ICP-MS Zn同位素测量过程中的质量歧视校正、同质异位素干扰评估、基质效应调查和同位素测量的长期重现性检验.研究表明,在测定条件下,运用标样一样品交叉法能有效地进行仪器质量歧视校正.同质异位素干扰的评估通过3种方式进行,即:在高分辨状态下同质异位数干扰信号的直接测定,低分辨状态下Zn同位素原始数据间相关关系的检验和低分辨下浓度梯度效应研究.结果表明,在低分辨模式下,尽管66Zn、67Zn、68Zn的同质异位素干扰信号很小,但的确存在,要获得准确同位素比值,必须使标样和样品的浓度在合适的范围内匹配.在基质效应方面,主要考察Fe对Zn同位素比值测定的影响.结果表明,当溶液中Fe/Zn(质量比)不大于0.2时,Fe对Zn同位素比值测定无影响.重复性测定中,δ66ZnGSB-Romil=6.96‰±0.11‰(2sd),δ67ZnGSB-Romil=10.4‰±0.20‰(2sd),δ68ZnGSB-Romil=13.8‰±0.22‰(2sd),达到国际同类实验室先进水准.运用所建立的方法,对地质岩石成分分析国家标准物质GBW 07270(闪锌矿)进行了Zn同位素平均成分测定为:δ66Zn=6.71‰±0.03‰(20),δ67Zn=10.08‰±0.05‰(20),δ68Zn=13.37‰±0.07‰(2σ).