Determination of Lithium Contents in Silicates by Isotope Dilution ICP-MS and its Evaluation by Isotope Dilution Thermal Ionisation Mass Spectrometry

A precise and simple method for the determination of lithium concentrations in small amounts of silicate sample was developed by applying isotope dilution-inductively coupled plasma-mass spectrometry (ID-ICP-MS). Samples plus a Li spike were digested with HF-HClO₄, dried and diluted with HNO₃, and measured by ICP-MS. No matrix effects were observed for ⁷Li/⁶Li in rock solutions with a dilution factor (DF) of 97 at an ICP power of 1.7 kW. By this method, the determination of 0.5 μg g^-1 Li in a silicate sample of 1 mg can be made with a blank correction of < 1%. Lithium contents of ultrabasic to acidic silicate reference materials (JP-1, JB-2, JB-3, JA-1, JA-2, JA-3, JR-1 and JR-2 from the Geological Survey of Japan, and PCC-1 from the US Geological Survey) and chondrites (three different Allende and one Murchison sample) of 8 to 81 mg were determined. The relative standard deviation (RSD) was typically < 1.7%. Lithium contents of these samples were further determined by isotope dilution-thermal ionisation mass spectrometry (ID-TIMS). The relative differences between ID-ICP-MS and ID-TIMS were typically < 2%, indicating the high accuracy of ID-ICP-MS developed in this study.     

Nickel Isotope Variations in Terrestrial Silicate Rocks and Geological Reference Materials Measured by MC‐ICP‐MS

Although initial studies have demonstrated the applicability of Ni isotopes for cosmochemistry and as a potential biosignature, the Ni isotope composition of terrestrial igneous and sedimentary rocks, and ore deposits remains poorly known. Our contribution is fourfold: (a) to detail an analytical procedure for Ni isotope determination, (b) to determine the Ni isotope composition of various geological reference materials, (c) to assess the isotope composition of the Bulk Silicate Earth relative to the Ni isotope reference material NIST SRM 986 and (d) to report the range of mass‐dependent Ni isotope fractionations in magmatic rocks and ore deposits. After purification through a two‐stage chromatography procedure, Ni isotope ratios were measured by MC‐ICP‐MS and were corrected for instrumental mass bias using a double‐spike correction method. Measurement precision (two standard error of the mean) was between 0.02 and 0.04‰, and intermediate measurement precision for NIST SRM 986 was 0.05‰ (2s). Igneous‐ and mantle‐derived rocks displayed a restricted range of δ^60/58Ni values between ?0.13 and +0.16‰, suggesting an average BSE composition of +0.05‰. Manganese nodules (Nod A1; P1), shale (SDO‐1), coal (CLB‐1) and a metal‐contaminated soil (NIST SRM 2711) showed positive values ranging between +0.14 and +1.06‰, whereas komatiite‐hosted Ni‐rich sulfides varied from ?0.10 to ?1.03‰.     

Abundances of Sulfur,Selenium, Tellurium,Rhenium and Platinum‐Group Elements in Eighteen Reference Materials by Isotope Dilution Sector‐Field ICP‐MS and Negative TIMS

Geological reference materials (RMs) with variable compositions and NIST SRM 612 were analysed by isotope dilution mass spectrometry for bulk rock concentrations of chalcogen elements (sulfur, selenium and tellurium), rhenium and platinum‐group elements (PGEs: Ru, Pd, Os, Ir and Pt), including the isotope amount ratios of ¹⁸⁷Os/¹⁸⁸Os. All concentrations were obtained from the same aliquot after HCl‐HNO₃ digestion in a high pressure asher at 320 °C. Concentrations were determined after chemical separation by negative TIMS, ICP‐MS and hydride generation ICP‐MS (Se, Te). As in previous studies, concentrations of the PGEs in most RMs were found to be highly variable, which may be ascribed to sample heterogeneity at the < 1 g level. In contrast, S, Se and Te displayed good precision (RSD < 5%) in most RMs, suggesting that part of the PGE budget is controlled by different phases, compared with the chalcogen budget. The method may minimise losses of volatile chalcogens during the closed‐system digestion and indicates the different extent of heterogeneity of chalcogens, Re and PGEs in the same sample aliquot. OKUM, SCo‐1, MRG‐1, DR‐N and MAG‐1 are useful RMs for the chalcogens. NIST SRM 612 displays homogenous distribution of S, Se, Te, Pt and Pd in 30 mg aliquots, in contrast with micro‐scale heterogeneity of Se, Pd and Pt.     

Rare Earth and Other Trace Element Content of NRCC HISS-1 Sandy Marine Sediment Reference Material

The National Research Council (NRC), Ottawa, Canada sandy marine sediment reference material HISS-1 was characterised for thirty-seven trace elements by neutron activation optimised irradiation, cooling and counting protocols using the low power Miniature Neutron Source Reactor (MNSR) as a neutron source. This INAA methodology quantified twenty additional elements including ten rare earth (Ce, Dy, Eu, Ho, La, Lu, Nd, Sm, Tb and Yb) and ten other elements (Ba, Br, Cs, Ga, Hf, Rb, Sc, Ta, Th and Zr) missing in the final NRCC certification. A large number of values produced by different irradiation schemes together with the use of certified reference materials in the quantification step that showed good precision, provided confidence in the results. The reliability of the REE data was checked by plotting chondrite-normalised graphs.     

Noble metals in black shales of the Sukhoi Log gold deposit (East Siberia): evidence from scintillation arc atomic-emission spectrometry

Scintillation arc atomic-emission spectrometry (SAES) is used to study noble metals (NM), including Au, Ag, Pt, Pd, Ir, Os, Rh, and Ru, in black shales of the Sukhoi Log gold deposit (Irkutsk Region, Russia), with a focus on NM total contents in samples and on the compositions and sizes of NM-bearing particles. The estimated sizes of gold particles and their distribution are confirmed by results of scanning electron microscopy combined with energy dispersive X-ray microanalysis (SEM-EDX). The SAES results are in satisfactory agreement with earlier SEM-EDX data on NM species but reveal a much greater number and diversity of element associations.     

Chemical Separation and Isotopic Variations of Cu and Zn From Five Geological Reference Materials

This paper presents an adapted anion exchange column chemistry protocol which allowed separation of high-purity fractions of Cu and Zn from geological materials. Isobaric and non-spectral interferences were virtually eliminated for consequent multiple-collector ICP-MS analysis of the isotopic composition of these metals. The procedure achieved ∼ 100% recoveries, thus ensuring the absence of column-induced isotopic fractionation. By employing these techniques, we report isotopic analyses for Cu and Zn from five geological reference materials: BCR-027 blende ore (BCR), δ⁶⁵Cu = 0.52 ± 0.15‰ (n = 10) and δ⁶⁶Zn = 0.33 ± 0.07‰ (n = 8); BCR-030 calcined calamine ore (BCR), δ⁶⁶Zn = -0.06 ± 0.09‰ (n = 8); BCR-1 basalt (USGS), δ⁶⁶Zn = 0.29 ± 0.12‰ (n = 8); NOD-P-1 manganese nodule (USGS), δ⁶⁵Cu = 0.46 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.78 ± 0.09‰ (n = 9); SU-1 Cu-Co ore (CCRMP), δ⁶⁵Cu = -0.018 ± 0.08‰ (n = 10) and δ⁶⁶Zn = 0.13 ± 0.17‰ (n = 6). All uncertainties are ± 2s; copper isotope ratios are reported relative to NIST SRM-976, and zinc isotope ratios relative to the Lyon-group Johnson Matthey metal (batch 3-0749 L) solution, JMC Zn. These values agree well with the limited data previously published, and with results reported for similar natural sample types. Samples were measured using a GVi IsoProbe MC-ICP-MS, based at the Natural History Museum, London. Long-term measurement reproducibility has been assessed by repeat analyses of both single element and complex matrix samples, and was commonly better than ± 0.07‰ for both δ⁶⁶Zn and δ⁶⁵Cu.     

La-Ce法岩石标准物质和Ce同位素标准溶液研制

报道了La-Ce法岩石标准物质的研制结果。标准物质选自峨眉山玄武岩中的新鲜微晶玄武岩（编号EQB）,具有间隐结构,矿物组成相对均一。岩石经粉碎和均一化加工,成为粉末后分装成1000小瓶。经均匀性和稳定性检验合格后,对该岩石标准物质的Ce同位素比值和La、Ce元素含量进行了测定和定值统计,其结果分别表示为：138Ce／142Ce=0．0225755±0．0000003,Ce=（117．4±1．3）μg／g,La=（55．8±0．9）μg／g。对二氧化铈化学试剂进行了溶液制备,以用于Ce同位素分析仪器标准物质。标准溶液编号为CBRICeO2,其138Ce／142Ce比值的测定统计值为0．0225748±0．0000006。为检验所制标准物质分析数据的准确度,对国际标样进行了比对测量,其中JMC304标准溶液的138Ce／142Ce比值测定结果为0．0225762±0．0000015,USGS玄武岩标样BCR-2的La和Ce元素含量测定结果分别为（25．2±0．6）μg／g（2σ）和（54．2±0．8）μg／g（2σ）,所获数值与文献报道值或证书值在误差范围内相符。     

黄金标准样品的X—射线荧光光谱定量分析

应用化学计量学-X-射线光谱分析软件包CMXRS V2.1,在基本参数法进行基体效应校正的基础上,选择合适的样条函数,并采用微孔面罩及石蜡衬底等实验技术,测定了29个黄金标准样品中的Au、Ag、Cu和Zn。结果证明,方法可行。Au含量在99％以上的样品,Au的分析误差不超过0.14％,Au含量小于99％的样品,Au的分析误差不超过0.25％。     

Geostandards and Geoanalytical Research Bibliographic Review 2019

This bibliographic review gives an outline of publications in 2019 focusing on reference materials (RMs) used in geochemistry and related fields, such as palaeoclimate and environmental research.