Separation and Precise Measurement of Lithium Isotopes in Three Reference Materials Using Multi Collector‐Inductively Coupled Plasma Mass Spectrometry

Lithium separation technique for three reference materials has been established together with precise determination of lithium isotope using a Neptune multi collector-inductively coupled plasma mass spectrometry (MC-ICP-MS). The solutions of lithium element standard reference materials, potassium, calcium, sodium, magnesium and iron single element, were used to evaluate analytical methods applied. Three separate stages of ion-exchange chromatography were carried out using organic cation-exchange resin (AG 50W-X8). Lithium was enriched for the three stages using different eluants, which are 2.8 M HCl, 0.15 M HCl and 0.5 M HCl in 30% ethanol, respectively. The columns for the first and second stages are made of polypropylene, and those for the third stage are made of quartz. Total reagent volume for the entire chemical process was 35 mL for three reference materials. The recovery yielded for the three stages is 98.9–101.2% with an average of 100.0%, 97.6–101.9% with an average of 99.9%, and 99.8–103.3% with an average of 100.6%, respectively. The precision of this technique is conservatively estimated to be ±0.72–1.04‰ (2σ population), which is similar to the precision obtained by different authors in different laboratories with MC-ICP-MS. The δ7Li values (7Li/6Li relative to the IRMM-016 standard) determined for andesite (AGV-2) and basalt (BHVO-2) are 5.68‰ (n=18), 4.33‰ (n=18), respectively. The δ7Li value (7Li/6Li relative to the L-SVEC standard) determined for IRMM-016 is –0.01‰ (n=15). All these analytical results are in good agreement with those previously reported. In addition, the results for the same kinds of samples analyzed at the MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, are consistent with those obtained at the Plasma Laboratory, University of Maryland, within analytical uncertainty. According to these experiment results, it is concluded that this proposed procedure is a suitable method for determining the lithium isotopic composition of natural samples.     

Precise/ Small Sample Size Determinations of Lithium Isotopic Compositions of Geological Reference Materials and Modern Seawater by MC-ICP-MS

The Li isotope ratios of four international rock reference materials, USGS BHVO-2, GSJ JB-2, JG-2, JA-1 and modern seawater (Mediterranean, Pacific and North Atlantic) were determined using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). These reference materials of natural samples were chosen to span a considerable range in Li isotope ratios and cover several different matrices in order to provide a useful benchmark for future studies. Our new analytical technique achieves significantly higher precision and reproducibility (< ± O.3%o 2s) than previous methods, with the additional advantage of requiring very low sample masses of ca . 2 ng of Li.     

钼同位素的MC-ICP-MS测定方法研究

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.     

A Simplified, Accurate and Fast Method for Lithium Isotope Analysis of Rocks and Fluids, and δ7Li Values of Seawater and Rock Reference Materials

We report a new approach to conduct fast and accurate lithium isotope ratio measurements by MC-ICP mass spectrometry after wet chemical sample preparation. In contrast to most previously published methods our MC-ICP-MS set-up did not use a desolvating system to achieve appropriate ion beam intensities and, therefore, was less affected by matrix-induced shifts of the instrumental mass bias. As the total lithium background and build-up in the sample introduction system was low, previous sample residues could be washed out by an extended uptake of the new sample. Elimination of a nitric acid rinse step increased the sample throughput by a factor of two and allowed the instrumental mass bias drift to be tracked more precisely. δ⁷Li values of powdered silicate rock reference materials and seawater obtained in this study revealed good accuracy and an overall analytical uncertainty of typically 0.5‰ (2s). On the basis of a comparison between our lithium isotope data and compiled literature data, we recommend preliminary average δ⁷Li values for seawater (+30.8‰) and several silicate rock reference materials (BHVO-1: +5.0‰; JA-1: +5.6‰; JB-2: +4.8‰). The compilation of published δ⁷Li values for seawater suggests that the observed large lithium isotope differences are due to inter-method and/or interlaboratory bias. Most recently published δ⁷Li values for seawater show little variation and confirm a constant lithium isotope composition (at the sub ‰ level) of seawater in well mixed ocean basins.     

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.     

Stable W Isotope Measurements of Geological Reference Materials and Tungsten Ore Minerals by Double Spike MC-ICP-MS

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 δ^186/184W 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 δ^186/184W values ranging from 0.017‰ to 0.144‰. The δ^186/184W 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.     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

常用锂同位素地质标准物质的多接收器电感耦合等离子体质谱分析研究

锂同位素研究是非传统稳定同位素地球化学研究的前沿,已广泛应用于从地表到地幔的岩石圈及流体等固体地球科学的研究领域。准确测定锂同位素比值是应用该同位素体系的前提。本文报道了国际上7种常用地质标准物质(BHVO-2、JB-2、BCR-2、AGV-2、NKT-1、L-SVEC、IRMM-016)的锂同位素组成数据。分析中采用硝酸-氢氟酸混合酸消解岩石标准样品,通过3根阳离子交换树脂(AG50W-X8,200~400目)填充的聚丙烯交换柱和石英交换柱对锂进行分离富集,利用Neptune型多接收器电感耦合等离子体质谱(MC-ICPMS)测定锂同位素比值,使用标准-样品交叉法(SSB)校正仪器的质量分馏。实验得到这7种常用地质标准物质的锂同位素组成与测试精度(2SD)分别为:δ7LiBHVO-2—L-SVEC=4.7‰±1.0‰(n=53),δ7LiJB-2—L-SVEC=4.9‰±1.0‰(n=20),δ7LiBCR-2—L-SVEC=4.4‰±0.8‰(n=8),δ7LiAGV-2—L-SVEC=6.1‰±0.4‰(n=14),δ7LiNKT-1—L-SVEC=9.8‰±0.2‰(n=3),δ7LiL-SVEC—L-SVEC=-0.3‰±0.3‰(n=10),δ7LiIRMM-016—L-SVEC=0.0‰±0.5‰(n=10),这些数据在误差范围内与国际上已发表的数据一致。Li同位素分析精度可以达到大约0.5‰,长期的分析精度即外部重现性≤±1.0‰,达到了国际同类实验室水平。7种常用地质标准物质的锂同位素组成数据的发表为锂同位素研究提供了统一的标准,使地质样品的锂同位素数据的质量监控成为可能。在基质效应的研究中,使用不同量的IRMM-016配制的标准溶液过柱,深入探讨了样品量对锂同位素测定值的影响,结果表明,在现有测试精度下,只要分析样品的锂含量达到100μg/L,且不超过树脂的承载量,样品的锂同位素组成在误差范围内与真值吻合,样品量的大小不影响锂同位素测定结果的准确性。     

多接收器电感耦合等离子体质谱法测定土壤标准物质铜同位素组成

近年来,铜同位素在表生环境和生物地球化学中的应用越来越广泛,尤其是土壤的铜同位素组成可以示踪环境污染物来源及生物地球化学过程。目前,对土壤铜同位素进行研究时,主要以硅酸岩标准物质为标样来衡量土壤样品铜同位素测定的准确性和精确性。但土壤与硅酸岩中铜、基质离子及有机质的含量等存在很大差异（如：硅酸岩中的铜含量>80μg/g,一些土壤中的铜含量很低, < 20μg/g）,将硅酸岩标准物质作为标样来监测土壤样品的数据质量缺乏代表性。为了弥补这一缺陷,本文精确测定4个国家土壤标准物质（GBW07443、GBW07425、GBW07427、GBW07389）的铜同位素组成,并将其作为检验土壤样品铜同位素测定过程中的标准。实验中采用高温高压反应釜消解样品,利用AG MP-1M树脂进行纯化,全流程空白 < 2ng,回收率≥ 98%,通过多接收器电感耦合等离子体质谱仪（MC-ICP-MS）采用标样-样品-标样间插法进行仪器分馏校正,δ65Cu的长期测试外精度优于0.05‰（n=306,2SD）。GBW07443、GBW07425、GBW07427和GBW07389的铜同位素组成分别为-0.04‰±0.04‰（n=9,2SD）、-0.07‰±0.05‰（n=12,2SD）、-0.06‰±0.04‰（n=12,2SD）、-0.02‰±0.06‰（n=12,2SD）。这些土壤标准物质的铜同位素组成均位于0附近,大致为自然界土壤铜同位素比值变化范围（-0.5‰~+0.5‰）的中间值,且样品容易获得,其化学和铜同位素组成均一,适合作为监控土壤铜同位素化学及质谱分析数据可靠性的标准物质。     

Accurate Measurement of Lithium Isotopes in Eleven Carbonate Reference Materials by MC‐ICP‐MS with Soft Extraction Mode and 1012 Ω Resistor High‐Gain Faraday Amplifiers

Lithium isotopes in carbonate rocks and minerals can serve as important tools for assessing palaeoclimates and palaeoenvironments. However, carbonate bulk rock samples are commonly mixtures of carbonate and silicate minerals, which require the complete digestion of the carbonate without digesting the silicate. Additionally, the low Li content (ng g^?1 level) in carbonates provides an additional challenge. Hence, despite their wide applications, few carbonates have had their δ⁷Li values characterised, particularly carbonate reference materials, which hinders comparisons of Li isotope measurement results obtained in different laboratories and the further application of Li isotopes in geological studies. This study aimed to provide precise and accurate δ⁷Li values for carbonate reference materials based on an evaluation of sample leaching and the Li purification method for carbonates, as well as the adoption of soft extraction and 10¹² Ω amplifiers to increase the intensity/blank ratio and matrix effect on Li isotope measurement. The precision and accuracy of the proposed procedure were verified by analysing synthetic carbonate samples and mono‐elemental Li solutions. With the developed method we provide δ⁷Li values for eleven carbonate reference materials with a precision of ~ 0.4‰. The accuracy of the δ⁷Li values was validated using the standard addition method.     

锆石Hf同位素：MC-ICP-MS和LA-MC-ICP-MS分析结果的比较

采用单柱离子色谱法高效提取锆石中的Hf元素,用MC—ICP—MS测定锆石Hf同位素组成。三个锆石样品及其平行样的分析结果显示,同一样品的Hf同位素组成在误差范围内高度一致,表明用单柱离子交换色谱法能够有效分离锆石的Hf元素,可以保证Hf同位素分析结果的再现。对比MC—ICP—MS和LA—MC—ICP—MS分析结果发现,同一样品锆石的Hf同位素在误差范围内一致,具有很好的可对比性。但对颗粒较小的锆石,缩小激光束斑使之不超出锆石颗粒的范围,能够获得更好的结果。     

Three Secondary Reference Materials for Lithium Isotope Measurements: Li7-N, Li6-N and LiCl-N Solutions

The CRPG (Nancy, France) has prepared secondary reference materials for Li isotope measurements by mixing ⁷Li or ⁶Li 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 δ⁷Li 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 δ⁷Li 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.     

Tourmaline Reference Materials for the In Situ Analysis of Oxygen and Lithium Isotope Ratio Compositions

Three tourmaline reference materials sourced from the Harvard Mineralogical and Geological Museum (schorl 112566, dravite 108796 and elbaite 98144), which are already widely used for the calibration of in situ boron isotope measurements, are characterised here for their oxygen and lithium isotope compositions. Homogeneity tests by secondary ion mass spectrometry (SIMS) showed that at sub‐nanogram test portion masses, their ¹⁸O/¹⁶O and ⁷Li/⁶Li isotope ratios are constant within ± 0.27‰ and ± 2.2‰ (1s), respectively. The lithium mass fractions of the three materials vary over three orders of magnitude. SIMS homogeneity tests showed variations in ⁷Li/²⁸Si between 8% and 14% (1s), which provides a measure of the heterogeneity of the Li contents in these three materials. Here, we provide recommended values for δ¹⁸O, Δ’¹⁷O and δ⁷Li for the three Harvard tourmaline reference materials based on results from bulk mineral analyses from multiple, independent laboratories using laser‐ and stepwise fluorination gas mass spectrometry (for O), and solution multi‐collector inductively coupled plasma‐mass spectroscopy (for Li). These bulk data also allow us to assess the degree of inter‐laboratory bias that might be present in such data sets. This work also re‐evaluates the major element chemical composition of the materials by electron probe microanalysis and investigates these presence of a chemical matrix effect on SIMS instrumental mass fractionation with regard to δ¹⁸O determinations, which was found to be < 1.6‰ between these three materials. The final table presented here provides a summary of the isotope ratio values that we have determined for these three materials. Depending on their starting mass, either 128 or 512 splits have been produced of each material, assuring their availability for many years into the future.     

Lithium Isotope Composition of Marine Biogenic Carbonates and Related Reference Materials

In this study, the accuracy and the precision corresponding to Li isotopic measurements of low level samples such as marine and coastal carbonates are estimated. To this end, a total of fifty‐four analyses of a Li‐pure reference material (Li7‐N) at concentrations ranging from 1 to 6 ng ml^?1 were first performed. The average δ⁷Li values obtained for solutions with and without chemical purification were 30.3 ± 0.4‰ (2s, n = 19) and 30.2 ± 0.4‰ (2s, n = 36), respectively. These results show that the chosen Li chemical extraction and purification procedure did not induce any significant isotope bias. Two available carbonate reference materials (JCt‐1 and JCp‐1) were analysed, yielding mean δ⁷Li values of 18.0 ± 0.27‰ (2s, n = 6) and 18.8 ± 1.8‰ (2s, n = 9), respectively. Small powder aliquots (< 15 mg) of JCp‐1 displayed significant isotope heterogeneity and we therefore advise favouring JCt‐1 for interlaboratory comparisons. The second part of this study concerns the determination of δ⁷Li value for biogenic carbonate samples. We performed a total of twenty‐nine analyses of seven different tropical coral species grown under controlled and similar conditions (24.0 ± 0.1 °C). Our sample treatment prior to Li extraction involved removal of organic matter before complete dissolution in diluted HCl. Our results show (a) a constant δ⁷Li within each skeleton and between the different species (δ⁷Li = 17.3 ± 0.7‰), and (b) a Li isotope fractionation of ?2‰ compared with inorganic aragonite grown under similar conditions. Comparison with literature data suggests a significant difference between samples living in aquaria and those grown in natural conditions. Finally, we investigate ancient (fossil) carbonate material and foraminifera extracted from marine sedimentary records. Different leaching procedures were tested using various HCl molarities. Results indicate that carbonate preferential dissolution must be carried out at an acid molarity < 0.18 mol l^?1. Possible contamination from silicate minerals can be verified using the Al/Ca ratio, but the threshold value strongly depends on the carbonate δ⁷Li value. When the silicate/carbonate ratio is high in the sediment sample (typically > 2), contamination from silicates cannot be avoided, even at low HCl molarity (? 0.1 mol l^?1). Finally, bulk carbonate and foraminifera extracted from the same core sample exhibited significant discrepancies: δ⁷Li values of foraminifera were more reproducible but were significantly lower. They were also associated with lower Sr/Ca and higher Mn/Ca ratios, suggesting a higher sensitivity to diagenesis, although specific vital effects cannot be fully ruled out.     

Problems and Suggestions Concerning the Notation of Cadmium Stable Isotope Compositions and the Use of Reference Materials

Notations for Cd stable isotope compositions and the use of reference materials are discussed. It is proposed that Cd stable isotope data should be reported as variations of the ¹¹⁴Cd/¹¹⁰Cd ratio/ using either the δ^114/110Cd or ε^114/110Cd notations. Future publications should report results for BAM-1012 Cd, the only currently available international Cd isotope reference material. It is also recommended that "Münster Cd" and a range of specified geological reference materials are used as additional reference materials. The final choice of a primary "zero-delta" reference standard remains the most important outstanding question.     

Optimisation of Lithium Chromatography for Isotopic Analysis in Geological Reference Materials by MC‐ICP‐MS

The lithium isotope system can be an important tracer for various geological processes, especially tracing continental weathering. The key to this application is the accurate and precise determination of lithium isotopic composition. However, some of the previously established column separation methods are not well behaved when applied to chemically diverse materials, due to the significant variations in matrix/lithium ratios in some materials. Here, we report a new dual‐column system for lithium purification to achieve accurate and precise analysis of lithium isotopic compositions using a multi‐collector inductively coupled plasma‐mass spectrometer (MC‐ICP‐MS). Compared with single‐column systems, our dual‐column system yielded a consistent elution range of the lithium‐bearing fraction (7–16 ml) for samples with a large range of lithium loads and matrix compositions, so that column re‐calibration is not required. In addition, this method achieved complete lithium recovery and low matrix interference (e.g., Na/Li ≤ 1) with a short elution time (~ 6 h, excluding evaporation), with the entire procedure completed in 1.5 days. We report high precision Li isotopic compositions in twelve chemically diverse materials including seawater, silicates, carbonates, manganese nodules and clays. New recommended Li isotopic values and associated uncertainties are presented as reference values for quality control and inter‐laboratory calibration for future research and were consistent with previously published data. However, significant lithium isotopic variances (~ 1‰) in BHVO‐2 from different batches suggest Li isotopic heterogeneity in this reference material and that Li isotopic studies using this reference material should be treated with caution.     

锂同位素及其地质应用研究进展

锂同位素示踪是近几年发展起来的一门新兴的稳定同位素地球化学方法,锂有两个稳定同位素：^6Li和^7Li。自在界锂同位素的组成变化很大,其δ^6Li值变化幅度超过60‰,现代大洋水的δ^6Li值为－31．0‰,洋中脊玄武岩（BORB）的δ^6Li值为－4．7‰--3.7‰,由于锂同位素存在大的分馏和不同地质体中在截然不同的δ^6Li值,因此锂同位素地质应用前景十分广泛。目前,锂同位素在研究星云形成过程和宇宙事件,洋壳蚀变和海底热液活动,壳－幔物质循环和板块俯冲作用过程,判断卤水起源和演化等方面的研究中成效显著。     

水中系列氢氧同位素标准物质的研制

我国氢氧同位素国家一级标准物质经过二十余年的使用,现已不能满足需求,急需研制代表当今分析技术水平的新的氢氧同位素国家标准物质。本文研制了系列(4个)水中氢氧同位素标准物质,其中三个采自天然水样,一个为人工配制的贫氘水,三种天然水样基本涵盖了我国境内天然水的氢氧同位素组成范围。每种标准物质随机抽取30瓶的均匀性子样,每份子样做双份分析,进行均匀性检验,四种标准物质的均匀性检验得到的F值都小于相应的自由度的临界值,显示四种标准物质的均匀性良好。标准物质的δ¹⁸O和δD值经过2年的稳定性检验,特征量值变化在不确定度范围,由此判定δD、δ¹⁸O值稳定性良好。采用国际间实验室采用不同原理的方法协同定值,11家国内外实验室分别采用Cr还原法、激光法、H₂-H₂O平衡法、高温热转换元素分析法进行水中氢同位素定值,采用CO₂-H₂O平衡法进行氧同位素定值;定值不确定度显著降低,δ¹⁸O的扩展不确定度小于0.08‰,δD的扩展不确定度小于0.9‰。该标准物质已被国家质检总局批准确为国家一级标准物质,批准号为GBW 04458~GBW 04461。     

High‐Precision Measurement of Stable Cr Isotopes in Geological Reference Materials by a Double‐Spike TIMS Method

Chromium (Cr) isotopes have been widely used in various fields of Earth and planetary sciences. However, high‐precision measurements of Cr stable isotope ratios are still challenged by difficulties in purifying Cr and organic matter interference from resin using double‐spike thermal ionisation mass spectrometry. In this study, an improved and easily operated two‐column chemical separation procedure using AG50W‐X12 (200–400 mesh) resin is introduced. This resin has a higher cross‐linking density than AG50W‐X8, and this higher density generates better separation efficiency and higher saturation. Organic matter from the resin is a common cause of inhibition of the emission of Cr during analysis by TIMS. Here, perchloric and nitric acids were utilised to eliminate organic matter interference. The Cr isotope ratios of samples with lower Cr contents could be measured precisely by TIMS. The long‐term intermediate measurement precision of δ^53/52Cr_{NIST SRM 979} for BHVO‐2 is better than ± 0.031‰ (2s) over one year. Replicated digestions and measurements of geological reference materials (OKUM, MUH‐1, JP‐1, BHVO‐1, BHVO‐2, AGV‐2 and GSP‐2) yield δ^53/52Cr_{NIST SRM 979} results ranging from ?0.129‰ to ?0.032‰. The Cr isotope ratios of geological reference materials are consistent with the δ^53/52Cr_{NIST SRM 979} values reported by previous studies, and the measurement uncertainty (± 0.031‰, 2s) is significantly improved.     

Apatite Reference Materials for SIMS Microanalysis of Isotopes and Trace Elements

Twelve apatite samples have been tested as secondary ion mass spectrometry (SIMS) reference materials. Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis shows that the SLAP, NUAN and GR40 apatite gems are internally homogeneous, with most trace element mass fractions having 2 standard deviations (2s) ≤ 2.0%. BR2, BR5, OL2, AFG2 and AFB1, which have U > 63 μg g^-1, ²⁰⁶Pb/²⁰⁴Pb > 283, and homogeneous SIMS U-Pb data, have respective isotope dilution thermal ionisation mass spectrometry (ID-TIMS) ages of 2053.83 ± 0.21 Ma, 2040.34 ± 0.09 Ma, 868.87 ± 0.25 Ma, 478.71 ± 0.22 Ma and 473.25 ± 0.09 Ma. Minor U-Pb heterogeneity exists and accurate SIMS results require correction with the 3D Concordia-constrained common Pb composition. Among the studied samples, AFG2 and BR5 are the most homogeneous U-Pb reference materials. The SIMS sulfur isotopic compositions of eight of the apatites shows they are homogeneous, with 2s for both 10³δ³⁴S and 10³δ³³S < 0.55‰. One apatite, BR96, has Δ³³S = -0.36 ± 0.2‰. The apatite samples have ID-TIMS ⁸⁷Sr/⁸⁶Sr between 0.704214 ± 0.000030 and 0.723134 ± 0.000035.