Determination of Zr and Hf in a Flux-Free Fusion of Whole Rock Samples using Laser Ablation Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) with Isotope Dilution Calibration

Isotope dilution calibration has been applied to the determination of Zr and Hf in whole rocks by laser ablation (LA)-ICP-MS. Enriched isotopes were added during the preparation of flux-free, synthetic whole rock glasses and homogenised through a combination of grinding and fusion. This method avoids problems, such as solution instability and the chemical resistance of minerals such as zircon, inherent in acid digestion sample preparation. The use of isotope dilution removes the need for external calibration using certified reference material glasses such as NIST SRM 612 for which certified Zr and Hf values are not available. The precision of Zr and Hf determinations were found to be < 1% and 3.5% respectively, limited by Poisson counting statistics which contributed to 50% of the final precision of analysis. Measured values correlate closely with compiled literature values.     

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.     

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.     

Experience of the International Association of Geoanalysts as a Certifying Body

Reference materials (RMs) to support geoanalysis have a long history, dating back to the issuance of G-1 and W-1 in 1951. This paper addresses only one aspect of the most recent part of that history, the experience of the International Association of Geoanalysts (IAG) as a certifying body. In 2002, the Certification Committee of the IAG met in Potsdam to discuss becoming a certifying body able to produce RMs for the geoanalytical community. Following that meeting, the IAG developed and published a protocol to assure that IAG RMs would meet International Organization for Standardization (ISO) guidelines to the fullest extent possible. Many practical problems arise in the application of the recommendations of the ISO Guides to any one specific certification project. The recommendations describe the ideal; achievable reality is always somewhat less than that ideal, presenting a significant challenge to the IAG as a certifying body. This paper will summarise experience to date, while focusing on the most challenging issues, deriving uncertainties compliant with the Guide to Uncertainty in Measurement (GUM) and establishing traceability of certified values (CVs).     

Penglai Zircon Megacrysts: A Potential New Working Reference Material for Microbeam Determination of Hf–O Isotopes and U–Pb Age

We introduce a potential new working reference material – natural zircon megacrysts from an Early Pliocene alkaline basalt (from Penglai, northern Hainan Island, southern China) – for the microbeam determination of O and Hf isotopes, and U–Pb age dating. The Penglai zircon megacrysts were found to be fairly homogeneous in Hf and O isotopes based on large numbers of measurements by LA-multiple collector (MC)-ICP-MS and SIMS, respectively. Precise determinations of O isotopes by isotope ratio mass spectrometry (IRMS) and Hf isotopes by solution MC-ICP-MS were in good agreement with the statistical mean of microbeam measurements. The mean δ¹⁸O value of 5.31 ± 0.10‰ (2s) by IRMS and the mean ¹⁷⁶Hf/¹⁷⁷Hf value of 0.282906 ± 0.0000010 (2s) by solution MC-ICP-MS are the best reference values for the Penglai zircons. SIMS and isotope dilution-TIMS measurements yielded consistent ²⁰⁶Pb/²³⁸U ages within analytical uncertainties, and the preferred ²⁰⁶Pb/²³⁸U age was found to be 4.4 ± 0.1 Ma (95% confidence interval). The young age and variably high common Pb content make the Penglai zircons unsuitable as a primary U–Pb age reference material for calibration of unknown samples by microbeam analysis; however, they can be used as a secondary working reference material for quality control of U–Pb age determination for young (particularly < 10 Ma) zircon samples.     

慢太阳风中的小冕洞风和阿尔芬波

慢太阳风的起源是一个困扰空间物理领域多年的问题,一些研究人员认为慢太阳风中阿尔芬度比较高的部分起源于小冕洞或者是冕洞的边界,不过另外一些研究者发现高阿尔芬度慢太阳风在成分上和低阿尔芬度的慢太阳风并无显著差别.最近的一项研究中发现的慢太阳风中的小冕洞风并没有特别高的阿尔芬度.我们利用一个简单的二维太阳风模型计算了阿尔芬波和小冕洞风的传播;计算结果显示,由于阿尔芬波的传播特性,从小冕洞出发的等离子体和阿尔芬波动在传播到1AU的过程中会发生分离,形成了低阿尔芬度的小冕洞风和高阿尔芬度的普通慢风.这个结果定性地解释了慢太阳风中观测到的小冕洞风和高阿尔芬度慢风的特性,也为解开慢太阳风的起源之谜提供了新的思路.

     

Preparation of Four Chromium Ore Reference Materials

The preparation and characterisation of four chromium ore reference materials are described in this paper. The sample material for GCr‐1, GCr‐3 and GCr‐4 was collected from chromite deposits in Tibet, Qinghai province and Inner Mongolia. GCr‐2 is a composite sample from GCr‐1 and GCr‐4. Sample homogeneity was tested by WD‐XRF and the relative standard deviations were < 1.0%. An F‐test showed that all four materials were homogeneous. Thirteen laboratories involved in the inter‐laboratory programme provided 672 determinations (eighteen oxides and elements). Sixteen components were characterised as certified values, of which Cr₂O₃ ranged from 17.59 to 57.80% m/m. The contents of FeO and CO₂ were taken as reference values.     

Synthesis of Fluid Inclusion Reference Materials in the H2O–NaCl–CH4 System

In this study, we detail procedures to synthesise inclusions of fluids of known composition under diagenetic conditions – low temperatures (50–180 °C) and pressures (2–25 MPa) – hosted by quartz. Pre‐existing microcavities in polished quartz chips were used, decrepitated and rinsed before being healed in an autoclave. Each synthesis required around 4 weeks. A range of biphase liquid–vapour inclusions in the H₂O–CH₄–NaCl system, similar to natural ones, were synthesised in quartz, varying the content of all three components. The quartz chips were checked before and after synthesis by optical microscopy, microthermometry and Raman spectroscopy. The method was used to build a series of calibration curves relating methane‐to‐water count ratios to the methane content of aqueous fluid inclusions. Good correlation was obtained between Raman band area ratios and the expected CH₄ solubilities from equations of state. The chosen procedure's main advantages, compared with other published methods, are as follows: quicker healing of the microfractures at lower temperatures, larger inclusions, simple quartz sample preparation, control of fluid inclusion composition and the use of commercial reactors. Such reference material inclusions allow the calibration of Raman microspectrometers with the objective of PTX reconstruction of palaeofluid migration in petroleum reservoirs.     

基于行星际磁场阿尔芬特性的星载磁通门磁强计在轨标定新方法

准确的磁场测量对深入研究空间等离子体环境具有重要意义.星载磁通门磁强计的磁补偿随时间缓慢变化, 因此, 需要对其进行常规的在轨标定.现有的在轨标定方法都依赖于磁扰动或磁结构事件的筛选, 导致标定结果的频次受限于事件的筛选, 且差的事件还会增大计算误差.为此, 本文研发出一种不依赖于磁场事件筛选的在轨标定新方法.根据行星际磁场强度的取值范围, 我们可建构一个磁补偿取值空间.不同的磁补偿值会影响行星际磁场的阿尔芬特性; 于是, 我们通过在磁补偿空间中找到使被调整之后的行星际磁场的阿尔芬特性最强的点作为磁补偿值的最优解.测试结果表明, 我们的新方法可以利用1~4 h时长的行星际磁场数据获得误差小于0.1 nT的标定结果.