Uranium and Thorium Concentration and Isotopic Composition in Five Glass (BHVO‐2G,BCR‐2G,NKT‐1G,T1‐G,ATHO‐G) and Two Powder (BHVO‐2, BCR‐2) Reference Materials

Here we report uranium and thorium isotopic ratios and elemental concentrations measured in solid reference materials from the USGS (BHVO‐2G, BCR‐2G, NKT‐1G), as well as those from the MPI‐DING series (T1‐G, ATHO‐G). Specifically created for microanalysis, these naturally‐sourced glasses were fused from rock powders. They cover a range of compositions, elemental concentrations and expected isotopic ratios. The U‐Th isotopic ratios of two powdered source materials (BCR‐2, BHVO‐2) were also characterised. These new measurements via multi‐collector thermal ionisation mass spectrometry and multi‐collector inductively coupled plasma‐mass spectrometry can now be used to assess the relative performance of techniques and facilitate comparison of U‐Th data amongst laboratories in the geoscience community for in situ and bulk analyses.     

Chemical Characterisation of the USGS Reference Glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G Using EPMA, ID-TIMS, ID-ICP-MS and LA-ICP-MS

The USGS reference glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G were investigated by different analytical techniques. All these materials have a geological (basaltic) matrix and are therefore useful in igneous geochemistry as matrix-matched reference materials for microanalytical techniques. The new GS glasses have trace elements in groups at concentration levels of about < 0.01, 5, 50 and 500 μg g^-1. Their major element compositions have been determined by EPMA, and trace elements have been analysed by LA-ICP-MS and two isotope dilution techniques using TIMS and ICP-MS. EPMA and LA-ICP-MS analyses indicated that the USGS reference glasses are homogeneous at the μm to mm scale with respect to major (variations < 1-2%) and most trace elements (variations 1-4%). Trace element data obtained from the different analytical techniques agreed within an uncertainty of 1-5%, indicating that between method results are comparable. Therefore, the preliminary working values for the four USGS GS glasses calculated from these data have a low level of uncertainty.     

Assessment of Nanosecond Laser Ablation Multi‐Collector Inductively Coupled Plasma‐Mass Spectrometry for Pb and Sr Isotopic Determination in Archaeological Glass: Mass Bias Correction Strategies and Results for Corning Glass Reference Materials

This work presents an evaluation of various methods for in situ high‐precision Sr and Pb isotopic determination in archaeological glass (containing 100–500 μg g^?1 target element) by nanosecond laser ablation multi‐collector‐inductively coupled plasma‐mass spectrometry (ns‐LA‐MC‐ICP‐MS). A set of four soda‐lime silicate glasses, Corning A–D, mimicking the composition of archaeological glass and produced by the Corning Museum of Glass (Corning, New York, USA), were investigated as candidates for matrix‐matched reference materials for use in the analysis of archaeological glass. Common geological reference materials with known isotopic compositions (USGS basalt glasses BHVO‐2G, GSE‐1G and NKT‐1G, soda‐lime silicate glass NIST SRM 610 and several archaeological glass samples with known Sr isotopic composition) were used to evaluate the ns‐LA‐MC‐ICP‐MS analytical procedures. When available, ns‐LA‐MC‐ICP‐MS results for the Corning glasses are reported. These were found to be in good agreement with results obtained via pneumatic nebulisation (pn) MC‐ICP‐MS after digestion of the glass matrix and target element isolation. The presence of potential spectral interference from doubly charged rare earth element (REE) ions affecting Sr isotopic determination was investigated by admixing Er and Yb aerosols by means of pneumatic nebulisation into the gas flow from the laser ablation system. It was shown that doubly charged REE ions affect the Sr isotope ratios, but that this could be circumvented by operating the instrument at higher mass resolution. Multiple strategies to correct for instrumental mass discrimination in ns‐LA‐MC‐ICP‐MS and the effects of relevant interferences were evaluated. Application of common glass reference materials with basaltic matrices for correction of ns‐LA‐MC‐ICP‐MS isotope data of archaeological glasses results in inaccurate Pb isotope ratios, rendering application of matrix‐matched reference materials indispensable. Correction for instrumental mass discrimination using the exponential law, with the application of Tl as an internal isotopic standard element introduced by pneumatic nebulisation and Corning D as bracketing isotopic calibrator, provided the most accurate results for Pb isotope ratio measurements in archaeological glass. Mass bias correction relying on the power law, combined with intra‐element internal correction, assuming a constant ⁸⁸Sr/⁸⁶Sr ratio, yielded the most accurate results for ⁸⁷Sr/⁸⁶Sr determination in archaeological glasses     

LA-MC-ICPMS分析古老熔体包裹体Pb同位素组成中的误差评价

目前应用LA-MC-ICPMS分析熔体包裹体Pb同位素,由于没有同时测试U和Th的信号,导致熔体包裹体Pb同位素的研究仅局限于中生代以来的样品。本文应用LA-MC-ICPMS分析了玻璃样品以及存在显著U-Th衰变影响的古老熔体包裹体的Pb同位素组成,评价了U/Pb和Th/Pb分析误差对初始Pb同位素比值校正的影响。实验中以国际玻璃标样NKT-1G为外部标样,采用"标样-样品-标样法"进行仪器漂移和质量歧视校正,结果表明,国际玻璃标样BHVO-2G、TB-1G的208Pb/206Pb和207Pb/206Pb分析精度优于0.30%(2RSD),与推荐值的偏差小于0.30%,然而232Th/206Pb和238U/206Pb分析结果显示了较大分散性(外精度约5.0%)。根据误差传递计算,样品的年龄对初始铅的误差有很大影响。对于古生代以来的样品(年龄小于540 Ma),即使测试的232Th/206Pb和238U/206Pb与真值偏差达到10%,经过U-Th衰变校正后的Pb同位素比值与真值的偏差依然小于0.80%。因此本方法可以将熔体包裹体等地质样品的Pb同位素研究由新生代样品(年龄小于65 Ma)扩展到古生代样品。     

一次溶样分离地质样品中Pb-Sr-Nd方法的可行性研究

现有的地质样品中Pb、Sr、Nd分离分析方法是对Pb和Sr - Nd分别采用两份样品进行分离,多消耗一份样品量,因而制约了样品量少的研究.本文提出了基于HNO3 - HF - HClO4混合酸熔融样品,采用AG1 - X8、AG50W - X8和HDEHP组合离子交换柱,对同一份地质样品一次溶样,连续分离Pb、Sr、Nd.用该方法对国际标准样品AGV -2、BHVO-2中的Pb、Sr、Nd进行分离,回收率均优于95％,全流程空白分别为Pb＜ 0.2 ng,Sr＜1.5 ng,Nd＜1.1 ng.用多接收器-电感耦合等离子体质谱(MC -ICP - MS)进行同位素比值测定,结果表明本研究提出的一份样品连续分离后的同位素测定结果与传统方法利用两份样品分别进行分离的结果在误差范围内完全一致.本文的研究可实现微量岩石样品的Pb、Sr、Nd同位素准确分析,对于珍贵样品的同位素组成研究具有重要意义.     

Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses

We have measured ⁸⁷Sr/⁸⁶Sr and ¹⁴³ Nd/¹⁴⁴ Nd isotope ratios in different batches and aliquots of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1 and GSP-1 by thermal ionisation mass spectrometry. In addition, we also analysed the eight Max-Planck-Institut-Dingwell (MPI-DING) reference glasses. Nearly all isotope ratios obtained in the different aliquots and batches agree within uncertainty limits indicating excellent homogeneity of the USGS powders and the MPI-DING glasses. With the exception of GSP-2, the new USGS RMs are also indistinguishable from the ratios found in the original USGS RMs (⁸⁷Sr/⁸⁶Sr: 0.704960, 0.704958 (BCR-1, -2), 0.703436, 0.703435 (BHVO-1, -2), 0.703931, 0.703931 (AGV-1, -2); ¹⁴³ Nd/¹⁴⁴ Nd: 0.512629, 0.512633 (BCR-1, -2), 0.512957, 0.512957 (BHVO-1, -2); 0.512758, 0.512755 (AGV-1, -2)). This means that for normalisation purposes in Sr and Nd isotope geochemistry BCR-2, BHVO-2 and AGV-2 can well replace BCR-1, BHVO-1 and AGV-1 respectively.     

Lead isotopes by LA-MC-ICPMS: Tracking the emergence of mantle signatures in an evolving silicic magma system

At Long Valley (LV) model Sr isotope phenocryst ages and absolute U-Pb zircon ages from precaldera Glass Mountain (GM) and caldera-related Bishop Tuff (BT) rhyolites show that these crystals track >1 Myr of evolution of a voluminous rhyolite magmatic system. In detail, strong disparities between the different age populations complicate ideas for a unified model for rhyolite generation, differentiation, and storage. To better elucidate the age discrepancies a new in situ Pb isotope technique has been developed to measure the compositions of 113 individual LV feldspars (mainly sanidine) and their host glasses by UV laser ablation MC-ICPMS. Given sufficient signal the accuracy and precision of this technique approaches that of double-spike thermal ionization mass spectrometry. The utility of our technique for many geologic materials is, however, limited to determining Pb isotope ratios that include ²⁰⁶Pb, ²⁰⁷Pb, and ²⁰⁸Pb, but exclude ²⁰⁴Pb. New zircon ²³⁸U-²⁰⁶Pb crystallization ages were also obtained for two older Glass Mountain domes.A >1.5‰ difference between the Pb isotope compositions of feldspars from older (1.7-2.2 Ma) precaldera Glass Mountain (GM) rhyolites and younger LV rhyolites, including the BT, is found. The Pb isotope data for feldspars and their host glasses lie along a regional trend line between young basalts and evolved crust compositions, spanning ∼15% of that isotopic difference, and show a secular change towards increasing mantle contribution. Most feldspars have Pb isotope compositions that are similar to their host glasses and, as such, there persists an apparent >100 k.y. difference between Sr model feldspar ages and zircon ages for some GM rhyolites. Collectively, the feldspars define a Sr-Pb isotope mixing curve. Evidence for mixing complicates the interpretation that the Sr isotope data solely reflect radiogenic ingrowth. Where isotopically heterogeneous feldspar populations occur, there is greater uncertainty about the veracity of the Sr model ages. Specifically, we find no Pb isotope evidence that BT feldspars grew from older GM-like magmas.The distinct Pb isotope signatures for individual rhyolites and their feldspars support evidence based on zircon dating that LV volcanism did not erupt from a single long-lived magma chamber but rather tapped a number of different magmas. Moreover, contrary to the conventional model of gradual build-up prior to cataclysmic eruption, secular changes in the U-Pb age constraints on magma residence times and the magmas’ distinct Pb isotopic compositions suggest that, at Long Valley, eruptive volumes increase with shorter magma residence time and correlate with greater mantle input. Evidently, the plumbing and therefore activity at Long Valley was influenced by the evolving interaction between source and crustal magma system.     

Pb and Sr isotopes in volcanic rocks from the Aleutian Islands and Pribilof Islands,Alaska

The Pb and Sr isotope ratios of Plio-Pleistocene volcanic rocks from the Aleutian volcanic arc are used as tracers of the lithospheric subduction process at the converging Pacific and Bering plates. Aleutian arc lavas do not have the same Pb isotopic compositions as volcanic rocks of the subducted Pacific ocean crust or the nearby Pribilof Islands, but appear to contain an ‘old continental crustal component’ with high ²⁰⁷Pb/²⁰⁴Pb ratio, as has been found in some other volcanic arcs.⁸⁷Sr/⁸⁶Sr ratios in the Aleutian volcanic arc rocks average 0.70322, slightly higher than fresh volcanic rocks from normal ridge segments, but within the range of values from ‘Icelandic’ ridge segments, oceanic islands and the Pribolof Islands. The Pb and Sr isotopic compositions of Aleutian lavas show a positive correlation and the range of values does not change for volcanoes distributed along strike in the arc, even though the crustal type in the hanging wall of the Benioff zone changes from oceanic in the west to continental in the east. Since the basement of the continental arc segment is older than the basement of the oceanic segment, and probably has a different isotopic character, the constancy of isotopic ratios along the arc argues against contamination by wall rocks of the type exposed in the arc.A sufficient explanation for the isotopic data is the mixture of several per cent of continent-derived sediment with melt derived from the underthrust oceanic crust and overlying mantle. This small amount of contaminant is difficult to document by geophysical observations. Such a model implies extensive recycling of Ba, Pb, K and Rb through volcanism at convergent plate margins like the Aleutians.     

GSD‐1G and MPI‐DING Reference Glasses for In Situ and Bulk Isotopic Determination

This paper contains the results of an extensive isotopic study of United States Geological Survey GSD‐1G and MPI‐DING reference glasses. Thirteen different laboratories were involved using high‐precision bulk (TIMS, MC‐ICP‐MS) and microanalytical (LA‐MC‐ICP‐MS, LA‐ICP‐MS) techniques. Detailed studies were performed to demonstrate the large‐scale and small‐scale homogeneity of the reference glasses. Together with previously published isotopic data from ten other laboratories, preliminary reference and information values as well as their uncertainties at the 95% confidence level were determined for H, O, Li, B, Si, Ca, Sr, Nd, Hf, Pb, Th and U isotopes using the recommendations of the International Association of Geoanalysts for certification of reference materials. Our results indicate that GSD‐1G and the MPI‐DING glasses are suitable reference materials for microanalytical and bulk analytical purposes.     

Precise and Accurate In Situ Determination of Lead Isotope Ratios in NIST,USGS, MPI‐DING and CGSG Glass Reference Materials using Femtosecond Laser Ablation MC‐ICP‐MS

Lead isotope ratio data were obtained with good precision and accuracy using a 266 nm femtosecond laser ablation (fLA) system connected to a multi‐collector ICP‐MS (MC‐ICP‐MS) and through careful control of analytical procedures. The mass fractionation coefficient induced by 266 nm femtosecond laser ablation was approximately 28% lower than that by 193 nm excimer laser ablation (eLA) with helium carrier gas. The exponential law correction method for Tl normalisation with optimum adjusted Tl ratio was utilised to obtain Pb isotopic data with good precision and accuracy. The Pb isotopic ratios of the glass reference materials NIST SRM 610, 612, 614; USGS BHVO‐2G, BCR‐2G, GSD‐1G, BIR‐1G; and MPI‐DING GOR132‐G, KL2‐G, T1‐G, StHs60/80‐G, ATHO‐G and ML3B‐G were determined using fLA‐MC‐ICP‐MS. The measured Pb isotopic ratios were in good agreement with the reference or published values within 2s measurement uncertainties. We also present the first high‐precision Pb isotopic data for GSE‐1G, GSC‐1G, GSA‐1G and CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 glass reference materials obtained using the femtosecond laser ablation MC‐ICP‐MS analysis technique.     

Baseline determination of the atmospheric Pb,Sr and Nd isotopic compositions in the Rhine valley,Vosges mountains (France) and the Central Swiss Alps

The Pb, Sr and Nd isotopic compositions of biomonitors (lichen, moss, bark) and soil litter from different regions in the Rhine valley, as well as of <0.45 μm particles separated out of ice of the Rhône and Oberaar glaciers and lichens from the Swiss Central Alps, have been determined in order to deduce the natural baseline of the atmospheric isotopic compositions of these regions, which are suggested to be close to the isotopic compositions of the corresponding basement rocks or soils at the same sites. ²⁰⁶Pb/²⁰⁷Pb and ⁸⁷Sr/⁸⁶Sr isotope ratios are positively correlated. Most polluted samples from traffic-rich urban environments have the least radiogenic Pb and Sr isotopic compositions with ²⁰⁶Pb/²⁰⁷Pb and ⁸⁷Sr/⁸⁶Sr ratios of 1.11 and 0.7094, respectively. These ratios are very different from those of the atmospheric baseline for the Vosges mountains and the Rhine valley (²⁰⁶Pb/²⁰⁷Pb: 1.158–1.167; ⁸⁷Sr/⁸⁶Sr: 0.719–0.725; ε_Nd: −7.5 to −10.1). However, this study indicates that the baseline of the atmospheric natural Pb and Sr isotopic compositions is affected by anthropogenic (traffic, industrial and urban) emissions even in remote areas. Lichen samples from below the Rhône and Oberaar glaciers reflect the baseline composition close to the Grimsel pass in the Central Swiss Alps (⁸⁷Sr/⁸⁶Sr: 0.714 − 0.716; ε_Nd: −3.6 to −8.1). The ¹⁴³Nd/¹⁴⁴Nd isotope ratios are highly variable (8ε units) and it is suggested that the variation of the ¹⁴³Nd/¹⁴⁴Nd is controlled by wet deposition and aerosols originating from the regional natural and industrial urban environments and from more distant regions like the Sahara in North Africa. The least anthropogenetically affected samples collected in remote areas have isotopic compositions closest to those of the corresponding granitoid basement rocks.     

Isotope Dilution MC-ICP-MS Rare Earth Element Analysis of Geochemical Reference Materials NIST SRM 610, NIST SRM 612, NIST SRM 614, BHVO-2G, BHVO-2, BCR-2G, JB-2, WS-E, W-2, AGV-1 and AGV-2

We present data for the concentrations of eleven rare earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu) in eleven international geochemical reference materials obtained by isotope dilution multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). We have analysed both rock powders and synthetic silicate glasses, and the latter provide precise data to support the use of these as reference materials for in situ trace element determination techniques. Our data also provide precise measurements of the abundance of mono-isotopic Pr in both glasses and powders, which allows more accurate constraints on the anomalous redox-related behaviour of Ce during geochemical processes. All materials were analysed in replicate providing data that typically reproduce to better than one percent. Sm/Nd ratios in all these materials also reproduce to better than 0.2% and are accurate to < 0.2% and can thus be used as calibrants for Sm-Nd geochronology. Our analyses agree well with existing data on these reference materials. In particular, for NIST SRM 610, USGS BHVO-2, AGV-1 and AGV-2, our measured REE abundances are typically within < 2% (and mostly 1%) of REE concentrations previously determined by isotope dilution analysis and thermal ionisation mass spectrometry, consistent with the higher degree of precision and accuracy obtained from isotope dilution techniques. Close agreement of results between basaltic glass reference materials USGS BHVO-2G and BCR-2G and the BHVO-2 and BCR-2 powders from which they were created suggests that little fractionation, concentration or dilution of REE contents occurred during glass manufacture.     

High‐Precision Sr‐Nd‐Hf‐Pb Isotopic Composition of Chinese Geological Standard Glass Reference Materials CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5 by MC‐ICP‐MS and TIMS

To assess the homogeneity of and provide the first Sr‐Nd‐Hf‐Pb isotopic reference values for the Chinese Geological Standard Glasses CGSG‐1, CGSG‐2, CGSG‐4 and CGSG‐5, we measured these isotopes in several measurement sessions over the course of nearly 3 years. The results were obtained by high‐precision MC‐ICP‐MS and TIMS. Our investigation indicates that these CGSG glass reference materials are homogenous with regard to Sr‐Nd‐Hf‐Pb isotopic distribution and are therefore suitable geochemical materials for Sr‐Nd‐Hf‐Pb isotope measurements. Clear differences in Sr‐Nd‐Hf‐Pb isotopic composition were observed between the glasses and the original powdered rock reference materials (CGSG‐2 and GSR‐7, and especially CGSG‐5 and GSR‐2) because of flux addition during preparation of the glasses. The new Sr‐Nd‐Hf‐Pb isotope data provided here might be useful to the geochemical community for in situ and bulk analysis.     

大别山麻粒岩和TTG片麻岩的Sr,Nd,Pb同位素地球化学

北大别4个麻粒岩和4个TTG片麻岩样品的Sr,Nd同位素分析结果表明，样品普遍具有较高的锶同位素比值（^87Sr/^86Sr=0.7066-0.7461)，较低的Nd同位素比值（^143Nd/^144Nd=0.5108-0.5124)，表现出明显的壳源特征，结合铅同位素的组成来看，北大别麻粒岩及TTG片麻岩的同位素成分相当于－下地壳。岩石的特源为古老的地壳，大约在2－3Ga之间，少数样品的同位素特征可能暗示源区有年轻地壳物质的加入。     

Improvements in Digestion Protocols for Trace Element and Isotope Determinations in Stream and Lake Sediment Reference Materials (JSd-1, JSd-2, JSd-3, JLk-1 and LKSD-1)

Total dissolution is a critical step in geochemical analysis. Despite the number of published protocols, this issue still draws attention for sediment samples, which are particularly difficult to dissolve due to the common occurrence and high abundance of refractory phases such as zircon. We present tests of different chemical digestion procedures carried out on reference materials (RM) of stream (JSd-1, JSd-2 and JSd-3) and lake (JLk-1 and LKSD-1) sediments from the Geological Survey of Japan (GSJ) and the Canadian Certified Reference Material Programme (CCRPM). We demonstrate that the fusion technique is not appropriate for our studies as not all elements of interest were recovered and blank levels were too high to permit further Sr and Pb isotopic composition measurements. Similarly, conventional HF+HNO₃ dissolution methods were not efficient enough for detrital samples. Our preferred method involved using high pressure Teflon® vessel bombs in association with HClO₄. This protocol ensured a complete dissolution of the powder, as well as a complete recovery of trace elements. Moreover, blank levels were sufficiently low that Sr or Pb isotope compositions could be measured from the same mother solution. We also tested the homogeneity of RM powders by performing tests on various amount of powder.     

Determination of Thallium in the USGS Glass Reference Materials BIR‐1G,BHVO‐2G and BCR‐2G and Application to Quantitative Tl Concentrations by LA‐ICP‐MS

Here, we present determinations of thallium (Tl) concentrations in the USGS reference materials BIR‐1G, BHVO‐2G and BCR‐2G measured by solution ICP‐MS. The Tl content in these three glasses spans a range of about 2–230 ng g^?1, which is similar to the values published for the respective powder materials. The determined range of Tl concentrations in these three glass reference materials makes them ideal for investigating Tl concentrations in basaltic and andesitic volcanic glasses. We also performed a series of laser ablation ICP‐MS measurements on the three samples, which show that this technique is able to determine Tl concentrations in glass samples with concentrations as low as 2 ng g^?1.     

High‐Precision Fe and Mg Isotope Ratios of Silicate Reference Glasses Determined In Situ by Femtosecond LA‐MC‐ICP‐MS and by Solution Nebulisation MC‐ICP‐MS

In this study, a technique for high precision in situ Fe and Mg isotope determinations by femtosecond‐laser ablation‐multi collector‐ICP‐MS (fs‐LA‐MC‐ICP‐MS) was developed. This technique was employed to determine reference values for a series of common reference glasses that may be used for external standardisation of in situ Fe and Mg isotope determinations in silicates. The analysed glasses are part of the MPI‐DING and United States Geological Survey (USGS) reference glass series, consisting of basaltic (BIR‐1G, BCR‐2G, BHVO‐2G, KL2‐G, ML3B‐G) and komatiitic (GOR128‐G and GOR132‐G) compositions. Their Fe and Mg isotope compositions were determined by in situ fs‐LA‐MC‐ICP‐MS and by conventional solution nebulisation multi‐collector ICP‐MS. We determined δ⁵⁶Fe values for these glasses ranging between ‐0.04‰ and 0.10‰ (relative to IRMM‐014) and δ²⁶Mg values ranging between ‐0.40‰ and ‐0.15‰ (relative to DSM‐3). Our fs‐LA‐MC‐ICP‐MS results for both Fe and Mg isotope compositions agreed with solution nebulisation analyses within analytical uncertainties. Furthermore, the results of three USGS reference glasses (BIR‐1G, BHVO‐2G and BCR‐2G) agreed with previous results for powdered and dissolved aliquots of the same reference materials. Measurement reproducibilities of the in situ determinations of δ⁵⁶Fe and δ²⁶Mg values were usually better than 0.12‰ and 0.13‰ (2s), respectively. We further demonstrate that our technique is a suitable tool to resolve isotopic zoning in chemically‐zoned olivine crystals. It may be used for a variety of different applications on isotopically‐zoned minerals, e.g., in magmatic or metamorphic rocks or meteorites, to unravel their formation or cooling rates.     

Strontium, Neodymium and Lead Isotope Analyses of NIST Glass Certified Reference Materials: SRM 610, 612, 614

The NIST glass certified reference materials, SRM 610-617, have been widely adopted by the geological community as calibration samples for a variety of in situ trace element analytical techniques. There is now an urgent requirement for similar reference materials for in situ isotopic analytical techniques. We have analysed SRM 610, 612 and 614 for their Pb, Sr and Nd isotopic compositions using thermal ionisation mass spectrometry. Large differences in isotopic composition were observed between each CRM, suggesting a significant trace element content in the initial starting material (base glass). As a result, isotopic compositions for one CRM cannot be extrapolated to another, and each must be calibrated for use independently. We present the first compilation of working values for these glasses.     

A lead isotopic study of the Stillwater Complex,Montana: constraints on crustal contamination and source regions

Analyses of the Pb isotopic compositions of plagioclase from 23 samples covering the stratigraphic thickness of the Stillwater Complex indicate a narrow range of apparent initial isotopic compositions (²⁰⁶Pb/ ²⁰⁴Pb=13.95; ²⁰⁷Pb/²⁰⁴Pb=14.95–15.01; ²⁰⁸Pb/²⁰⁴Pb=33.6). The uniformity of our data is in contrast to, but not necessarily contradictory to, other recent investigations which give indications that the complex formed by repeated injection of magmas with at least two distinct compositions that were presumably derived from different source regions. Samples from the Basal series of the complex have consistently higher ²⁰⁷Pb/²⁰⁴Pb ratios, suggesting either minor contamination from adjacent country rocks or a slight distinction between parental magmas. Apparent initial Pb isotopic compositions of the complex are very radiogenic compared to Late Archean model-mantle values, but are nearly identical to initial Pb isotopic compositions found for the the adjacent, slightly older (2.73–2.79 Ga), Late Archean crustal suite in the Beartooth Mountains. Contamination of magmas parental to the Stillwater Complex by the Late Archean crustal suite is rejected for two reasons: (1) Th and U concentrations in Stillwater rocks and plagioclase are very low (about 0.08 and 0.02 ppm respectively), yet Th/U ratios are uniform at about 4, in contrast to the highly variable (2–26) but often high Th/U ratios found for the Late Archean crustal complex; (2) it seems improbable that any contamination process would have adjusted the isotopic compositions of the diverse magmas entering the Stillwater chamber to near-identical values. The preferred hypothesis to explain the Pb isotopic data for the Stillwater Complex and the associated Late Archean crustal suite involves a major Late Archean crust-forming event that resulted in a compositionally complex crust/mantle system with relatively homogeneous and unusual Pb isotopic compositions. The parental magmas of the Stillwater Complex were generated at different levels within this crust/mantle system, before isotopic contrasts could develop by radioactive decay within compositionally discrete reservoirs. This situation limits the utility of all isotopic tracer systems in discriminating among the various mantle and crustal reservoirs that may have affected the final isotopic character of the Stillwater magmas. The late Archean crustal complex and the Stillwater Complex melts were ultimately derived from the same distinct mantle without obvious direct interaction with the Middle to Early Archean crust present in the region.     

Variable initial Pb isotopic compositions of rocks associated with the UG2 chromitite, eastern Bushveld Complex

An investigation of the Pb isotopic compositions of plagioclase and sulfide in a stratigraphic interval including the UG2 chromitite of the eastern Bushveld Complex has been conducted to determine the Pb isotopic composition(s) of the magma(s) that crystallized to form this part of the intrusion, gain a better understanding of why coexisting plagioclase and sulfide commonly exhibit widely different Pb isotopic compositions, and explore the use of Pb isotopes in deducing post-accumulation history. Analyses were obtained in situ with a NuPlasma multicollector ICP-MS coupled with 193 nm Excimer or 213 nm lasers.Most plagioclase compositions fall on the ²⁰⁷Pb/²⁰⁴Pb vs ²⁰⁶Pb/²⁰⁴Pb geochron of 2.06 Ga, which is the solidification age of the intrusion. The measured ratios have not been affected by radiogenic ingrowth, and plagioclase generally remained closed to Pb exchange after initial cooling. The array of plagioclase compositions on the geochron is significantly larger than that defined by analytical error. This indicates that in terms of Pb at least two different magma compositions were present. The composition of the least radiogenic magma was approximated by that of the contemporaneous BSE with μ (²³⁸U/²⁰⁴Pb) and ω (²³²Th/²⁰⁴Pb) values of ≈9.0 and 35, respectively, suggesting a mantle derivation with little or no involvement of the continental crust, while the second magma possessed a Pb isotopic composition similar to the upper crust with μ ≈ 9.6.Compared to plagioclase, sulfides generally possess slightly higher ²⁰⁶Pb/²⁰⁴Pb ratios for equivalent ²⁰⁷Pb/²⁰⁴Pb ratios such that their compositions fall between the 2.06 and 1.86 Ga geochrons. The latter age is much younger than the cooling age. The data are interpreted to mean that the Bushveld Complex remained buried in the crust at temperatures of several hundred °C for about 200 Ma after solidification, and that any sulfides accessible to fluid continued to re-equilibrated during this time with more radiogenic Pb. The sulfide Pb may have been transported into the Bushveld Complex by fluids from an external reservoir when the rocks were still partially molten and thus permeable. Alternatively, the sulfide Pb may have originated mainly from radiogenic decay of U and Th present in minerals other than the sulfides in the immediately surrounding Bushveld rocks, followed by local redistribution of Pb by whatever fluid was present. Indeed, some sulfides are characterized by ²⁰⁸Pb/²⁰⁴Pb ratios sufficiently high that an external source is unlikely. This observation and the fact that the sulfides display small-scale heterogeneity suggest that most, if not all, of the radiogenic sulfide Pb was locally derived. It also implies that during the post-solidification, re-equilibration period there was no large-scale fluid-flow through the microfracture network because otherwise the isotopic heterogeneities would not have been preserved. The minerals in 2 of the 19 samples studied contain young Pb, presumably introduced by meteoric waters that permeated the macrofracture network.