共查询到18条相似文献，搜索用时 62 毫秒
1.
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 总被引：3，自引：0，他引：3
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。 相似文献
2.
钼同位素的MC-ICP-MS测定方法研究 总被引：2，自引：1，他引：1
本文报道了运用多接收器等离子体质谱进行Mo同位素组成测定的方法,测定过程中的仪器质量歧视校正采用样品-标样交叉法.实验对Mo同位素测定过程中的谱峰干扰、基体效应、浓度效应、酸度效应和重现性等问题进行了详细研究.结果表明Zr的存在对Mo同位素测定不会产生影响;Sr不适合作为Mo同位素测定的元素内标;当m(Ag)/m(Mo)≤1时,Ag的存在不会对Mo同位素测定产生影响;当样品相对于标样的Mo浓度变化不大于50%时,Mo同位素分析不受浓度影响;以HNO3为进样介质时,HNO3的浓度(0.1mol/L~0.2 mol/L)对Mo同位素分析没有影响.CAGS-Mo相对于Alfa-Mo的δ100.95Mo、δ98/95Mo和δ97/95Mo分别为-0.34‰±0.10‰(2sd)、-0.22‰±0.05‰(2sd)和-0.13‰±0.08‰(2sd),在95%的置信区间内,该方法的外部精度不大于0.06‰/amu. 相似文献
3.
本研究建立了适用于玄武岩、纯橄岩和页岩样品的阳离子树脂铬元素化学分离方法, 并采用双稀释剂校正化学分离和质谱仪测量过程中的质量分馏。在化学分离过程中铬有3个淋洗峰, 反映了盐酸体系中铬至少具有3种络合物。页岩样品中Al、Ti含量较高, 在淋洗过程中会有过载现象。采用了SRM 979对50Cr-54Cr双稀释剂进行了标定, 双稀释剂的铬同位素组成为50Cr/52Cr=41.66, 54Cr/52Cr=22.28。铬元素标准NIST 3112a相对于SRM 979的δ53Cr= –0.063±0.05‰(2SD, N=22)。玄武岩、纯橄岩等标准物质的结果与已发表数据在误差范围内一致, 精度达到国际同类实验室平均水平。 相似文献
4.
5.
6.
7.
多接收器等离子体质谱法Zn同位素比值的高精度测定 总被引：9，自引：3，他引：9
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). 相似文献
8.
铅同位素研究新进展—“双稀释剂”测定方法和“AGSO—CSIRO”模式年龄 总被引：4，自引：1，他引：4
适当的仪器质量分馏校正是提高同位素分析数据精度的关键。重新“复活”了的铅同位素“双稀释剂”测定方法可实现严格的仪器质量分别校正,以区域锆石Ｕ－Ｐｂ年龄为控制点的“ＡＧＳＯ－ＣＳＩＲＯ”铅同位素模式年龄方法可获得精度很高的定年结果,铅同位素研究的应用必将因此而得到更大的发展。 相似文献
9.
多接收等离子质谱（MC-ICP-MS )测定Mg同位素初步研究 总被引：3，自引：3，他引：3
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)。 相似文献
10.
《地学前缘》2017,(5):402-415
近年来随着质谱和分析技术的进步,Ca同位素的分析精度获得了很大的提高,出现了很多高温条件下Ca同位素地球化学的研究成果。双稀释剂的合理使用在Ca同位素的分析中起关键作用。本文系统地阐述了前人对Ca同位素测试时所使用的双稀释剂技术,提供相应的计算程序,并且系统地归纳近年来高温条件下Ca同位素地球化学研究的新成果,包括单矿物对之间Ca同位素的分馏、陨石和地幔Ca同位素组成的不均一性和陨石的εCa异常及K-Ca定年等。斜方辉石和橄榄石相比于共生的单斜辉石更富集重Ca同位素,并且Δ44/40 CaOpx-Cpx受斜方辉石Ca含量和Ca—O键长的影响。地幔矿物之间具有不相同的Ca同位素组成说明地幔Ca同位素组成的不均一性。陨石及其内部难熔包裹体的Ca同位素组成变化范围很大,并且普遍存在εCa的异常。顽火辉石球粒陨石与地球具有相近的Ca同位素组成,表明它们可能具有相同的起源。但是高温条件下Ca同位素的分馏研究仍处于起步阶段,未来对于地球主要储库的Ca同位素组成、岩浆过程(部分熔融和分离结晶)和洋壳俯冲过程的Ca同位素分馏仍然需要更多地研究。 相似文献
11.
Tianli Zhang Jia Liu Qun Zhang Yingnan Zhang Liping Qin 《Geostandards and Geoanalytical Research》2023,47(1):169-183
This study presents high-precision W isotopic measurement results using the 180W-183W double spike technique with MC-ICP-MS. The effects of isobaric and polyatomic interferences on W isotopic measurements were evaluated. The δ186/184W values were not significantly affected when the solution had Hf/W ≤ 3 × 10-4, Ta/W ≤ 1, Os/W ≤ 0.06, Ce/W ≤ 0.0075, Nd/W ≤ 3.5 and Sm/W ≤ 5. The intermediate measurement precisions of both standard solutions (NIST SRM 3163 and Alfa Aesar W) and geological reference materials (NOD-A-1) were better than ±0.024‰ (2s). We also obtained a precision of 0.026‰ for a minimum sample loading mass of 5 ng, allowing the analysis of samples with low W contents. Replicated measurements of geological reference materials (AGV-2, BCR-2, BHVO-2, GSP-2, RGM-1, SDC-1, NOD-A-1 and NOD-P-1) yielded δ186/184W values ranging from 0.017‰ to 0.144‰. The δ186/184W values of two major tungsten ore minerals (scheelite and wolframite) were reported and compared herein. Scheelites had systematically slightly heavier W isotopic compositions than wolframites, which may reflect differences in the crystal structure. The resolvable variations of stable/mass-dependent W isotopic compositions in rocks and ore minerals make W isotopes a novel tool for studying hydrothermal mineralisation processes and the W cycle of geological reservoirs. 相似文献
12.
Mo同位素的研究在地学领域应用广泛,它可以示踪Mo的全球循环、古海洋氧化还原条件、成矿过程、天体演化过程等。应用多接收电感耦合等离子体质谱法(MC-ICP-MS)分析Mo同位素比值前需对样品进行分离纯化,以富集Mo和去除Zr、Ru、Fe、Mn等干扰元素。处理某些Fe含量特别高且Ca含量也高的特殊地质样品(如含大量黄铁矿的钙质泥岩、钙质页岩等),若根据传统的阴阳离子交换树脂双柱法,需多次使用阳离子交换树脂分离Fe,步骤较繁琐且Mo回收率也会降低,而根据传统的阴离子交换树脂单柱法,使用1mol/L氢氟酸-0.5mol/L盐酸介质会产生较多CaF_2沉淀影响分离纯化效果。针对此类特殊地质样品,本实验使用同一阴离子树脂柱(AG1-X8,100～200目)对样品进行两次淋洗,第一次使用6mol/L盐酸,第二次使用1mol/L氢氟酸-0.1mol/L盐酸和6mol/L盐酸。结果表明Mo的回收率96%,干扰元素的去除效果好,尤其是Ru的去除率接近100%,比原方法提高了约12%。对实际样品进行实验的结果也显示,Mo的回收率和干扰元素的去除都符合要求,δ~(98/95)Mo测定值与文献报道值一致。改进后的阴离子交换树脂单柱-二次淋洗法适用于Fe、Ca含量较高的特殊样品,降低了分析成本,也适用于绝大多数地质样品。 相似文献
13.
Meng‐Shu Liu Qun Zhang Yingnan Zhang Zhaofeng Zhang Fang Huang Hui‐Min Yu 《Geostandards and Geoanalytical Research》2020,44(1):169-182
This study presents a high‐precision Cd isotope measurement method for soil and rock reference materials using MC‐ICP‐MS with double spike correction. The effects of molecular interferences (e.g., 109Ag1H+, 94Zr16O+, 94Mo16O+ and 70Zn40Ar+) and isobaric interferences (e.g., Pd, In and Sn) to Cd isotope measurements were quantitatively evaluated. When the measured solution has Ag/Cd ≤ 5, Zn/Cd ≤ 0.02, Mo/Cd ≤ 0.4, Zr/Cd ≤ 0.001, Pd/Cd ≤ 5 × 10?5 and In/Cd ≤ 10?3, the measured Cd isotope data were not significantly affected. The intermediate measurement precision of pure Cd solutions (BAM I012 Cd, Münster Cd and AAS Cd) was better than ± 0.05‰ (2s) for δ114/110Cd. The δ114/110Cd values of soil reference materials (NIST SRM 2709, 2709a, 2710, 2710a, 2711, 2711a and GSS‐1) relative to NIST SRM 3108 were in the range of ?0.251 to 0.632‰, the δ114/110Cd values of rock reference materials (BCR‐2, BIR‐1, BHVO‐2, W‐2, AGV‐2, GSP‐2 and COQ‐1) varied from ?0.196‰ to 0.098‰, and that of the manganese nodule (NOD‐P‐1) was 0.163 ± 0.040‰ (2s, n = 8). The large variation in Cd isotopes in soils and igneous rocks indicates that they can be more widely used to study magmatic and supergene processes. 相似文献
14.
Jean Carignan Nathalie Vigier Romain Millot 《Geostandards and Geoanalytical Research》2007,31(1):7-12
The CRPG (Nancy, France) has prepared secondary reference materials for Li isotope measurements by mixing 7 Li or 6 Li spikes and either L-SVEC or IRMM-016 certified reference materials to produce solutions having a known Li concentration and isotopic composition. The Li7-N and Li6-N solution samples (1.5 mol l−1 HNO3 ) have nominal δ7 Li isotopic compositions of 30.1‰ and -9.7‰ respectively relative to L-SVEC and concentrations of 100 mg l−1 . Repeated measurement of these samples using the QUAD-ICP-MS at the CRPG yielded δ7 Li of 30.4 ± 1.1‰ (n = 13) and -8.9 ± 0.9‰ (n = 9) at the 2s level of confidence. An additional LiCl-N solution was measured and yielded a delta value of 9.5 ± 0.6‰ (n = 3). Identical results were obtained at the BRGM (Orléans, France) from determinations performed with a Neptune MC-ICP-MS (30.2 ± 0.3‰, n = 89 for the Li7-N, -8.0 ± 0.3‰, n = 38 for the Li6-N and 10.1 ± 0.2‰, n = 46 for LiCl-N at the 2s level of confidence). The deviation of measured composition relative to the nominal value for the Li6-N solution might be explained by either contamination during preparation or an error during sample weighing. These secondary reference materials, previously passed through ion exchange resin or directly analysed, may be used for checking the accuracy of Li isotopic measurements over a range of almost 40‰ and will be available to the scientific community upon request to J. Carignan or N. Vigier, CRPG. 相似文献
15.
Magnesium Isotope Compositions of Natural Reference Materials 总被引：1，自引：0，他引：1
Emile B. Bolou-Bi Nathalie Vigier Agnès Brenot Anne Poszwa 《Geostandards and Geoanalytical Research》2009,33(1):95-109
This study presents a chemical protocol for the separation of Mg that is particularly adapted to alkali‐rich samples (granite, soil, plants). This protocol was based on a combination of two pre‐existing methods: transition metals were first removed from the sample using an AG‐MP1 anion‐exchange resin, followed by the separation of alkalis (Na, K) and bivalent cations (Ca2+, Mn2+ and Sr2+) using a AG50W‐X12 cation‐exchange resin. This procedure allowed Mg recovery of ～ 10 0 ± 8%. The [Σcations]/[Mg] molar ratios in all of the final Mg fractions were lower than 0.05. The Mg isotope ratios of eleven reference materials were analysed using two different MC‐ICP‐MS instruments (Isoprobe and Nu Plasma). The long‐term reproducibility, assessed by repeated measurements of Mg standard solutions and natural reference materials, was 0.14‰. The basalt (BE‐N), limestone (Cal‐S) and seawater (BCR‐403) reference materials analysed in this study yielded δ26Mg mean values of ?0.28 ± 0.08‰, ?4.37 ± 0.11‰ and ?0.89 ± 0.10‰ respectively, in agreement with published data. The two continental rocks analysed, diorite (DR‐N) and granite (GA), yielded δ26Mg mean values of ?0.50 ± 0.08‰ and ?0.75 ± 0.14‰, respectively. The weathering products, soil (TILL‐1) and river water (NIST SRM 1640), gave δ26Mg values of ?0.40 ± 0.07‰ and ?1.27 ± 0.14‰, respectively. We also present, for the first time, the Mg isotope composition of bulk plant and organic matter. Rye flour (BCR‐381), sea lettuce (Ulva lactuva) (BCR‐279), natural hairgrass (Deschampsia flexuosa) and lichen (BCR‐482) reference materials gave δ26Mg values of ?1.10 ± 0.14‰, ?0.90 ± 0.19‰, ?0.50 ± 0.22‰ and ?1.15 ± 0.27‰ respectively. Plant δ26Mg values fell within the range defined by published data for chlorophylls. 相似文献
16.
随着实验技术的进步以及多接收电感耦合等离子体质谱仪（MC-ICP-MS）和热电离质谱仪（TIMS）的发展,近年来Ba 同位素的分析方法取得了显著进展。分析精度（δ138/134Ba,2SD）从之前的1 ‰ 提高到好于0.05 ‰。文章综述了近年来高精度Ba 同位素分析方法（溶液法）的发展历程,总结了国内外实验室关于不同类型样品的消解、Ba 元素化学纯化流程以及Ba 同位素质谱测定等方法,并对国内外多个实验室已发表的各类标准物质的Ba 同位素组成进行统计。研究结果可为Ba 同位素激光原位分析提供参考,为后续分馏机理解析和应用研究提供技术支撑。 相似文献
17.
Accurate Isotopic and Concentration Analyses of Small Amounts of Pb Using Isotope Dilution Coupled with the Double Spike Technique 总被引：1，自引：0，他引：1
Takeshi Kuritani Tomohiro Usui Tetsuya Yokoyama Eizo Nakamura 《Geostandards and Geoanalytical Research》2006,30(3):209-220
A new method has been developed for the simultaneous determination of Pb abundance and Pb isotopic composition with high precision and accuracy for small test portion masses by thermal ionisation mass spectrometry. In this method, a 205 pb-204 pb double spike is added to samples prior to the chemical separation of Pb, and the isotopic composition of the spike-sample mixture is determined rigorously by the double spike technique using a 207 Pb-204 Pb spike. The isotopic composition and concentration of Pb in the sample are then obtained by utilising the principle of isotope dilution. Using this technique, replicate determinations of Pb from NIST SRM 981 and GSJ JP-1 (peridotite; 0.07 μg g−1 Pb) were performed. The measured concentration and isotopic data were identical, within uncertainty, to published data or to data that were determined independently in this study. The application of this method to U-Pb dating and the determination of the "initial" Pb isotopic composition was also tested. Lead isotopic compositions and the concentrations of Pb, Th and U were determined for a single batch of samples, through the addition of 205 pb-204 pb, 230 Th and 235 U spikes to samples prior to chemical separation. Also in these experiments, we confirmed that this routine gives accurate data for Pb, Th and U concentrations and Pb isotopic compositions. 相似文献
18.
Development of Cu and Zn Isotope MC-ICP-MS Measurements: Application to Suspended Particulate Matter and Sediments from the Scheldt Estuary 总被引：1，自引：0，他引：1
Jérôme C.J. Petit Jeroen de Jong Lei Chou Nadine Mattielli 《Geostandards and Geoanalytical Research》2008,32(2):149-166
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 δ68/64Zn, 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. 相似文献
