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.     

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.     

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.     

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.     

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.     

MC-ICP-MS高精度测定Li同位素分析方法

以不同浓度Li元素标准样品和K、Ca、Na、Mg、Fe单元素标准样品的混合溶液为研究对象,采用3根阳离子交换树脂（AG 50W X8,200~400目）填充的聚丙烯交换柱和石英交换柱对Li进行分离富集,淋洗液分别为28 mol/L HCl、015 mol/L HCl以及05 mol/L HCl 30%乙醇,淋洗液体积小,仅为38 mL。分离回收率高,均大于976%。国际标样AGV 2（相对于IRMM 016）、BHVO 2（相对于IRMM 016）和IRMM 016（相对于L SVEC）的δ7Li值分别为(513±094)‰(2σ,n=10)、(408±060)‰(2σ,n=4)和(0038±073)‰(2σ,n=10),与前人分析结果吻合,分析精度与国际同类实验室水平相当。并对比了马里兰大学同位素实验室和笔者实验室对同种岩石矿物样品的分析结果,在误差范围内具有很好的一致性。此外,对美国地质调查局提供的准标样NKT 1霞石岩（相对于IRMM 016）给出了定值,δ7Li值为(871±046)‰(2σ,n=4)。因此,本方法可用于测定天然样品的Li同位素组成。     

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.     

锂同位素地球化学在地热流体水岩反应中的应用——以川西现代富锂热泉研究为例

高温流体的化学组成及同位素特征是深部环境信息的重要载体.本文基于锂同位素地球化学方法系统分析了川西现代热泉地热流体的水化学特征、水岩反应过程、补给来源、水岩反应温度及循环深度.研究结果显示,茶洛热泉水化学相类型为HCO3-Na型,与地表水和冷地下水的HCO3-Ca型存在明显区别.利用锂同位素温标估算茶洛热泉的水岩反应体...     

Sodic Pyroxene and Sodic Amphibole as Potential Reference Materials for In Situ Lithium Isotope Determinations by SIMS

Two large pegmatitic crystals of sodic pyroxene (aegirine) and sodic amphibole (arfvedsonite) from the agpaitic igneous Ilímaussaq Complex, south Greenland were found to be suitable as reference materials for in situ Li isotope determinations. Lithium concentrations determined by SIMS and micro‐drilled material analysed by MC‐ICP‐MS generally agreed within analytical uncertainty. The arfvedsonite crystal was homogeneous with [Li] = 639 ± 51 μg g^?1 (2s, n = 69, MC‐ICP‐MS and SIMS results). The aegirine crystal shows strongly developed sector zoning, which is a common feature of aegirines. Using qualitative element mapping techniques (EPMA), the homogeneous core of the crystal was easily distinguished from the outermost sectors of the crystals. The core had a mean [Li] of 47.6 ± 3.6 μg g^?1 (2s, n = 33) as determined by SIMS. The seven micro‐drilled regions measured by solution MC‐ICP‐MS returned slightly lower concentrations (41–46 μg g^?1), but still overlap with the SIMS data within uncertainty. Based on MC‐ICP‐MS and SIMS analyses, the variation in δ⁷Li was about 1‰ in each of the two crystals, which is smaller than that in widely used glass reference materials, making these two samples suitable to serve as reference materials. There was, however, a significant offset between the results of MC‐ICP‐MS and SIMS. The latter deviated from the MC‐ICP‐MS results by ?6.0 ± 1.9‰ (2s) for the amphibole and by ?3.9 ± 1.9‰ (2s) for the aegirine. This indicates the presence of a significant matrix effect in SIMS determinations of Li isotopes for amphibole and pyroxene relative to the basalt glasses used for calibration. Based on the MC‐ICP‐MS results, mean δ⁷Li values of +0.7 ± 1.2‰ (2s, n = 10) for the arfvedsonite crystal and of ?3.7 ± 1.2‰ (2s, n = 7) for the core of the aegirine crystal were calculated. Adopting these values, SIMS users can correct for the specific IMF (instrumental mass fractionation) of the ion probe used. We propose that these two crystals serve as reference materials for in situ Li isotope determinations by SIMS and pieces of these two crystals are available from the first author upon request.     

四川甲基卡锂矿床花岗岩体Li同位素组成及其对稀有金属成矿的制约

四川康定甲基卡超大型锂矿是我国最大的硬岩型锂矿床之一,矿区中南部呈岩株状出露的二云母花岗岩常被认为是成矿伟晶岩的"矿源岩",对其开展Li同位素地球化学研究,对探讨矿区稀有金属的来源与演化具有重要意义.研究工作基于详细的野外地质调查,采用MC-ICP-MS方法对岩体锂同位素组成开展了研究.研究结果显示,岩体Li含量介于192×10-6~470×10-6,均值为309×10-6,δ7Li值介于-1.56‰~+0.90‰,均值为-0.24‰,与平均上地壳值基本一致,具有高Li低δ7Li的特征.δ7Li与Li、Rb、Ga、SiO₂及ε_Nd（t）不存在明显的相关性,岩体锂同位素组成反映了其形成时的源区特征,未受岩浆结晶分异作用和蚀变作用的影响.岩体岩石地球化学、同位素地球化学资料表明,岩浆来源以三叠系西康群砂泥岩的部分熔融为主,可能有部分深源物质的加入.此外,岩体Li同位素的变化规律表明伟晶岩的成矿流体来源于二云母花岗岩.岩体Li含量与Li同位素组合不仅可用来划分锂矿床类型,而且对稀有金属找矿具有一定的指导意义.      

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.     

An Inter-Laboratory Assessment of the Thorium Isotopic Composition of Synthetic and Rock Reference Materials

We present a concerted international effort to cross-calibrate five synthetic Th isotope reference materials (UCSC Th "A", OU Th "U", WUN, IRMM-35 and IRMM-36), and six rock reference materials (UCSC TML, Icelandic ATHO, USGS BCR-2, USGS W-2, USGS BHVO-2, LV18) using multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). We then compare our new values with a compilation of literature mass spectrometric data for these reference materials and derive recommended "consensus"²³⁰Th/²³²Th values for each. We also present isotope dilution U and Th concentration data for four rock reference materials (UCSC TML, Icelandic ATHO, USGS BCR-2, USGS W-2).     

Development of Synthetic Clinopyroxene Reference Materials for In Situ Lithium Isotope Measurement by LA-MC-ICP-MS

The isotopic composition of lithium (Li) in clinopyroxene (Cpx), determined via in situ micro-analysis, has been employed as a potential geochemical tool for studying various geological processes such as crust-mantle recycling, silicate weathering and fluid-rock interaction. To obtain precise and accurate Li isotopic compositions in Cpx by LA-MC-ICP-MS, synthetic Cpx matrix-matched reference materials (RMs) were prepared in this study. Six Cpx-matrix RMs were prepared by mixing metallic oxides with GSP-2 (granodiorite) or pure L-SVEC solution and melting them into glasses (GSP-2 + oxide; L-SVEC + oxide). Two representative synthetic glasses, CPXA01 and CPXB01, were subjected to a series of analyses to investigate the possible qualification of the RMs for in situ Li isotope measurement by LA-MC-ICP-MS, including elemental homogeneity analysis (elemental mapping analysis and spot analysis), Li isotopic homogeneity analysis and accurate Li isotopic determination. The applicability of the synthetic Cpx-matrix RMs was highlighted by comparing the δ⁷Li values of three natural Cpx calibrated against the synthetic Cpx-matrix RMs and other commonly used RMs with different matrices (NIST SRM 612, BCR-2G, GOR128-G, StHs6/80-G, KL2-G and T1-G), respectively. Additionally, CPXB01-05 RMs with the same matrix but different Li contents were prepared to explore the Li content mismatch effect, which is significant for accurate determination of in situ Li isotopic composition by LA-MC-ICP-MS. The results of the cross-calibration of Li isotopes in CPXA01 and CPXB01 suggested no obvious Li isotopic fractionation between the two types of glasses (GSP-2 + oxide; L-SVEC + oxide). Thus, the two methods of producing Cpx-matrix RMs are suitable for preparing the matrix-matched RMs for in situ microanalysis for Li isotopes.     

Li同位素组成对太古宙海水相关的表生环境过程的初步限定

研究试图利用Li同位素地球化学对太古代海水相关的表生环境过程进行初步的限定.通过对来自南非Kaapvaal克拉通的海相碳酸盐岩样品进行Li同位素分析,发现在3.0~2.9 Ga期间形成的碳酸盐岩δ7Li值为~+1‰,而在2.6~2.5 Ga期间,碳酸盐岩δ7Li值达到7‰~10‰.经过反演计算得到对应时代的海水Li同位素组成分别为~+12‰和~+20‰,均明显低于现代海水值（~+31‰）,但是2.6~2.5 Ga期间的海水δ7Li值要比3.0~2.9 Ga时高出8‰.作为大陆硅酸岩风化的有效示踪剂,太古代海水较低的Li同位素组成表明当时的地表风化以源岩溶解为主,次生矿物形成极少,在3.0~2.5 Ga期间,海水整体温度下降以及次生矿物形成增加可能共同导致了海水δ7Li值的升高.通过对太古代碳酸盐岩的Li同位素研究能够有效反演古海水的Li同位素组成,并为了解太古代表生风化过程对海水的影响提供了新的信息.      

高精度测量岩石样品Ce同位素组成的TIMS方法

介绍了对岩石样品的Ce同位素组成进行高精度测量的TIMS方法.采用α-羟基异丁酸(α-HIBA) 离子交换法分离和纯化岩石样品中的La、Ce元素, Ce同位素组成和La、Ce含量测定在Triton热电离质谱仪上完成.质谱标样JMC304的138Ce/142Ce比值统计值为0.0225762±0.0000015, 与大部分文献值一致.应用该方法对USGS玄武岩标样BCR-2和峨眉山玄武岩EQB的138Ce/142Ce比值和La、Ce含量进行了分析, 其结果分别为: 0.0225572±0.0000010、25.2±0.3μg/g、55.8±0.9μg/g和0.0225755±0.0000003、54.2±0.4μg/g、117.4±1.3μg/g.BCR-2的La、Ce含量测定结果与其证书值在误差范围内一致, 其分析精度为0.001%~0.005%.所有样品的140Ce/142Ce比值测定结果统计值为7.9439±0.0002, 介于文献最低值7.941与最高值7.947之间, 可能代表了该比值的最佳估计值.      

Suppression of Matrix Effects in ICP-MS by High Power Operation of ICP: Application to Precise Determination of Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U at ng g-1 Levels in Milligram Silicate Samples

We found that the suppression of signals for ⁸⁸Sr, ¹⁴⁰Ce and ²³⁸U in rock solution caused by rock matrix in ICP-MS (matrix effects) was reduced at high power operation (1.7 kW) of the ICP. To make the signal suppression by the matrix negligible, minimum dilution factors (DF) of the rock solution for Sr, Ce and U were 600, 400 and 113 at 1.1, 1.4 and 1.7 kW, respectively. Based on these findings, a rapid and precise determination method for Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U using FI (flow injection)-ICP-MS was developed. The amount of the sample solution required for FI-ICP-MS was 0.2 ml, so that 1.8 mg sample was sufficient for analysis with a detection limit of several ng g^-1. Using this method, we determined the trace element concentrations in the USGS rock reference materials, DTS-1, PCC-1, BCR-1 and AGV-1, and the GSJ rock reference materials, JP-1, JB-1, -2, -3, JA-1, -2 and -3. The reproducibilities (RSD %) in replicate analyses (n=5) of BCR-1, AGV-1, JB-1, -2, -3, JA-1, -2, and -3 were < 6 %, and typically 2.5%. The difference between the average concentrations of this study for BCR-1 and those of the reference values were < 2%. Therefore, it was concluded that the method can give reliable data for trace elements in silicate rocks.     

High-Precision Trace Element Data for the USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, DTS-1, DTS-2, GSP-1 and GSP-2 by ID-TIMS and MIC-SSMS

Different batches of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2, DTS-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1, DTS-1 and GSP-1 have been analysed by isotope dilution using thermal ionisation mass spectrometry (ID-TIMS) and by multi-ion counting spark source mass spectrometry (MIC-SSMS). The concentrations of K, Rb, Sr, Ba and the rare earth elements were determined with overall analytical uncertainties of better than 1% (ID-TIMS) and 3% (MIC-SSMS). The analyses of different aliquots and batches of BCR-2, BHVO-2, AGV-2 and GSP-2, respectively, agree within 1%, i.e. approximately the analytical uncertainties of the data. This indicates an homogeneous distribution of the trace elements in these RMs. Differences in element concentrations of up to 17% in different aliquots of the depleted RM DTS-2 are outside the analytical uncertainty of our data. They may be attributed to a slightly heterogeneous distribution of trace elements in this dunite sample. Our trace element data for BCR-2, BHVO-2, AGV-2 and GSP-2 agree within about 3% with preliminary reference values published by the USGS. They also agree within 1-6% with those of the original RMs BCR-1, BHVO-1, AGV-1 and GSP-1. Large compositional differences are found between DTS-2 and DTS-1, where the concentrations of K, Rb, Sr and the light REE differ by factors of 2 to 24.     

Multi-Element Isotope Dilution Sector Field ICP-MS: A Precise Technique for the Analysis of Geological Materials and its Application to Geological Reference Materials

We present a multi-element technique for the simultaneous determination of twelve trace elements in geological materials by combined isotope dilution (ID) sector field inductively coupled plasma-mass spectrometry (SF-ICP-MS) following simple sample digestion. In addition, the concentrations of fourteen other trace elements have been obtained using the ID determined elements as internal standards. This method combines the advantages of ID (high precision and accuracy) with those of SF-ICP-MS (multi-element capability, fast sample processing without element separation) and overcomes the most prevailing drawbacks of ICP-MS (matrix effects and drift in sensitivity). Trace element concentration data for BHVO-1 (n = 5) reproduced to within 1–3% RSD with an accuracy of 1–2% relative to respective literature values for ID values and 2–3% for all other values. We have applied this technique to the analysis of seventeen geological reference materials from the USGS, GSJ and IAG. The sample set also included the new USGS reference glasses BCR-2G, BHVO-2G and BIR-1G, as well as the MPI-DING reference glasses KL2-G and ML3B-G, and NIST SRM 612. Most data agreed within 3–4% with respective literature data. The concentration data for the USGS reference glasses agreed in most cases with respective data of the original rock powder within the combined standard uncertainty of the method (2–3%), except the U concentration of BIR-1G, which showed a three times higher concentration compared to BIR-1.     

The behavior of lithium and its isotopes in oilfield brines: evidence from the Heletz-Kokhav field, Israel

Twenty-four brine samples from the Heletz-Kokhav oilfield, Israel, have been analyzed for chemical composition and Li isotope ratios. The chemical composition of the brines, together with geological evidence, suggests derivation from (Messinian) seawater by evaporation that proceeded well into the gypsum stability field but failed to reach the stage of halite crystallization. The present salinity of the samples (18-47 g Cl/L) was achieved by dilution of the original evaporitic brine by local fresh waters. Like brines from other sedimentary basins, the Li/Cl ratios in the Heletz-Kokhav samples show a prominent Li enrichment (five-fold to eight-fold) relative to modern seawater. The isotopic ratios of Li, expressed in the δ ⁶Li notation, vary from −26.3 to −17.9‰, all values being significantly higher than that of modern seawater (−32‰) irrespective of their corresponding Li concentration (1.0-2.3 mg/L). The isotopic composition of Li and the Li/Cl ratio in the oilfield brines were acquired in two stages: (a) The original evaporated seawater gained isotopically light Li during the diagenetic interaction between the interstitial Messinian brine and the basin sediments. A parent brine with an elevated Li/Cl ratio was formed. The brine was later diluted in the oilfields. (b) The δ ⁶Li values of the final brines were determined during epigenetic interaction with the Heletz-Kokhav aquifer rocks. At the same time, the Li/Cl ratio inherited from stage (a) remained largely unchanged. This work represents the first use of lithium isotopic composition to elucidate the origin and evolution of formation waters in sedimentary basins.     

Calcium Isotopic Composition of Various Reference Materials and Seawater

A compilation of δ^44/40Ca (δ^44/40Ca) data sets of different calcium reference materials is presented, based on measurements in three different laboratories (Institute of Geological Sciences, Bern; Centre de Géochimie de la Surface, Strasbourg; GEOMAR, Kiel) to support the establishment of a calcium isotope reference standard. Samples include a series of international and internal Ca reference materials, including NIST SRM 915a, seawater, two calcium carbonates and a CaF₂ reference sample. The deviations in δ^44/40Ca for selected pairs of reference samples have been defined and are consistent within statistical uncertainties in all three laboratories. Emphasis has been placed on characterising both NIST SRM 915a as an internationally available high purity Ca reference sample and seawater as representative of an important and widely available geological reservoir. The difference between δ^44/40Ca of NIST SRM 915a and seawater is defined as -1.88 O.O4%o (δ^44/42Ca_{NISTSRM915a/Sw}= -0.94 0.07%o). The conversion of values referenced to NIST SRM 915a to seawater can be described by the simplified equation δ^44/40Ca_Sa/Sw=δ^44/40Ca_{Sa/NIST SRM 915a} - 1.88 (δ^44/42Ca_Sa/Sw=δ^44/42Ca_{Sa/NIST SRM 915a} - 0.94). We propose the use of NIST SRM 915a as general Ca isotope reference standard, with seawater being defined as the major reservoir with respect to oceanographic studies.