Barium Isotopic Compositions in Thirty‐Four Geological Reference Materials Analysed by MC‐ICP‐MS

Measurement of Ba isotope ratios of widely available reference materials is required for interlaboratory comparison of data. Here, we present new Ba isotope data for thirty‐four geological reference materials, including silicates, carbonates, river/marine sediments and soils. These reference materials (RMs) cover a wide range of compositions, with Ba mass fractions ranging from 6.4 to 1900 µg g^?1, SiO₂ from 0.62% to 90.36% m/m and MgO from 0.08% to 41.03% m/m. Accuracy and precision of our data were assessed by the analyses of duplicate samples and USGS rock RMs. Barium isotopic compositions for all RMs were in agreement with each other within uncertainty. The variation of δ^138/134Ba in these RMs was up to 0.7‰. The shale reference sample, affected by a high degree of chemical weathering, had the highest δ^138/134Ba (0.37 ± 0.03‰), while the stream sediment obtained from a tributary draining carbonate rocks was characterised by the lowest δ^138/134Ba (?0.30 ± 0.05‰). Geochemical RMs play a fundamental role in the high‐precision and accurate determination of Ba isotopic compositions for natural samples with similar matrices. Analyses of these RMs could provide universal comparability for Ba isotope data and enable assessment of accuracy for interlaboratory data.     

A Compilation of Silicon,Rare Earth Element and Twenty‐One other Trace Element Concentrations in the Natural River Water Reference Material SLRS‐5 (NRC‐CNRC)

The natural river water certified reference material SLRS‐5 (NRC‐CNRC) was routinely analysed in this study for major and trace elements by ten French laboratories. Most of the measurements were made using ICP‐MS. Because no certified values are assigned by NRC‐CNRC for silicon and 35 trace element concentrations (rare earth elements, Ag, B, Bi, Cs, Ga, Ge, Li, Nb, P, Rb, Rh, Re, S, Sc, Sn, Th, Ti, Tl, W, Y and Zr), or for isotopic ratios, we provide a compilation of the concentrations and related uncertainties obtained by the participating laboratories. Strontium isotopic ratios are also given.     

Lu–Hf and U–Pb isotope systematics of zircons from the Storgangen intrusion, Rogaland Intrusive Complex, SW Norway: implications for the composition and evolution of Precambrian lower crust in the Baltic Shield

The Storgangen orebody is a concordantly layered, sill-like body of ilmenite-rich norite, intruding anorthosites of the Rogaland Intrusive Complex (RIC), SW Norway. 17 zircon grains were separated from ca. 5 kg of sand-size flotation waste collected from the on-site repository from ilmenite mining. These zircons were analysed for major and trace elements by electron microprobe, and for U–Pb and Lu–Hf isotopes by laser ablation microprobe plasma source mass spectrometry. Eight of the zircons define a well-constrained (MSWD=0.37) concordant population with an age of 949±7 Ma, which is significantly older than the 920–930 Ma ages previously reported for zircon inclusions in orthopyroxene megacrysts from the RIC. The remaining zircons, interpreted as inherited grains, show a range of ²⁰⁷Pb/²⁰⁶Pb ages up to 1407±14 Ma, with an upper intercept age at ca. 1520 Ma. The concordant zircons have similar trace element patterns, and a mean initial Hf isotope composition of ¹⁷⁶Hf/¹⁷⁷Hf_{949 Ma}=0.28223±5 (_Hf=+2±2). This is similar to the Hf-isotope composition of zircons in a range of post-tectonic Sveconorwegian granites from South Norway, and slightly more radiogenic than expected for mid-Proterozoic juvenile crust. The older, inherited zircons show Lu–Hf crustal residence ages in the range 1.85–2.04 Ga. One (undated) zircon plots well within the field of Hf isotope evolution of Paleoproterozoic rocks of the Baltic Shield. These findings indicate the presence of Paleoproterozoic components in the deep crust of the Rogaland area, but do not demonstrate that such rocks, or a Sveconorwegian mantle-derived component, contributed significantly to the petrogenesis of the RIC. If the parent magma was derived from a homogeneous, lower crustal mafic granulite source, the lower crustal protolith must be at least 1.5 Ga old, and it must have an elevated Rb/Sr ratio. This component would be indistinguishable in Sr, Nd and Hf isotopes from some intermediate mixtures between Sveconorwegian mantle and Paleoprotoerzoic felsic crust, but it cannot account for the initial ¹⁴³Nd/¹⁴⁴Nd of the most primitive, late Sveconorwegian granite in the region, without the addition of mantle-derived material.     

The δ60/58Ni Values of Twenty‐Six Selected Geological Reference Materials

The high‐precision δ^60/58Ni values of twenty‐six geological reference materials, including igneous rocks, sedimentary rocks, stream sediments, soils and plants are reported. The δ^60/58Ni values of all samples were determined by double‐spike MC‐ICP‐MS (Nu Plasma III). Isotope standard solution (NIST SRM 986) and geological reference materials (BHVO‐2, BCR‐2, JP‐1, PCC‐1, etc.) were used to evaluate the measurement bias and intermediate precision over a period of six months. Our results show that the intermediate precision of Ni isotope determination was 0.05‰ (2s, n = 69) for spiked NIST SRM 986 and typically 0.06‰ for actual samples, and the δ^60/58Ni _{NIST SRM 986} values were in excellent agreement with previous studies. Eighteen high‐precision Ni isotope ratios of geological reference materials are first reported here, and their δ^60/58Ni values varied from ?0.27‰ to 0.52‰, with a mean of 0.13 ± 0.34‰ (2s, n = 18). Additionally, SGR‐1b (0.56 ± 0.04‰, 2s), GSS‐1 (?0.27 ± 0.06‰, 2s), GSS‐7 (?0.11 ± 0.01‰, 2s), GSD‐10 (0.46 ± 0.06‰, 2s) and GSB‐12 (0.52 ± 0.06‰, 2s) could potentially serve as candidate reference materials for Ni isotope fractionation and comparison of Ni isotopic compositions among different laboratories.     

电感耦合等离子体质谱(ICP-MS)技术在地学研究中的应用

简单介绍ICP MS技术应用最新进展。着重对该技术在中国地学研究和多目标地质调查中的应用作一回顾 ,包括ICP MS技术简介和地质样品分析需求 ,稀土稀散等痕量、超痕量多元素分析 ,铂族元素分析 ,卤素等非金属元素分析 ,同位素比值分析等内容。着重对最近几年国内地质样品分析的一些新方法加以介绍。     

Analytical perspective on trace element species of interest in exploration

Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH₂OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH₂OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.     

电感耦合等离子体质谱法同时测定地质样品中痕量碘溴硒砷的研究：Ⅱ.土壤及沉积物标准物质分析

样品用碳酸钠和氧化锌混合熔剂半熔，热水提取，然后用强酸性阳离子交换树脂将阴离子形式存在的分析元素与溶液中大量钠、锌等阳离子分离，采用电感耦合等离子体质谱法直接同时测定溶液中的碘、溴、硒、砷。用0.07mol/L的氨水溶液清洗进样系统，有效减少了碘等元素的记忆效应和清洗时间。方法检出限（10σ，DF=100）溴、碘分别为0.15和0.028μg/g，砷、硒分别为0.04和0.004μg/g。用土壤和沉积物等地质标准物质分析验证了方法的准确度和精密度，绝大多数分析结果在标准值的允许误差范围之内。样品10次测定的RSD为0.8%～2.8%。     

辽东半岛～2．2 Ga 岩浆事件及其地质意义

本文报道了辽东半岛古元古代胶—辽—吉活动带内辽河群变质火山岩和辽吉花岗岩的锆石LA-ICP-MS U-Pb年代学和地球化学数据。变质安山岩的锆石具典型的岩浆振荡环带结构和较高的Th/U值(0.5),锆石U-Pb年龄为(2 182±6)Ma和(2 229±22)Ma,该年龄可代表安山岩的形成年龄。辽吉花岗岩的锆石同样具有典型的岩浆振荡环带结构和较高的Th/U值(0.3),锆石U-Pb年龄为(2 199±10)Ma,代表花岗岩的侵位时代,在误差范围内与辽河群火山岩喷发时代一致,表明辽吉花岗岩并不是辽河群的基底,二者可能为同一次岩浆作用过程的产物。辽东半岛~2.2Ga岩浆事件的识别及性质,对于正确认识古元古代胶—辽—吉活动带的属性至关重要。结合前人有关辽东半岛前寒武纪岩石的研究成果,本文研究认为胶—辽—吉活动带的形成演化可能与弧-陆碰撞有关。     

LA‐ICP‐MS Analysis of Small Samples: Carbonate Reference Materials and Larval Fish Otoliths

This article proposes a methodology to analyse the composition of very small carbonate samples such as larval fish otoliths. The chemical composition of otoliths, which are carbonate structures in the inner ear, is often used to explore population dynamics in fishes. Recent advances in laser ablation‐inductively coupled plasma‐mass spectrometry have suggested its potential application to this field. In this study, analyses were performed using a 193 nm ArF Resonetics LA system, coupled to an Agilent 7700X‐ICP‐MS, with the following ablation parameters: a beam diameter of 5 μm, energy of 3 mJ, 2.7 J cm^?2, laser repetition rate of 10 Hz and translation speed of 2.5 μm s^?1. NIST SRM 610 glass was used as the primary calibration material. Performing this protocol, characterisation of a USGS GP‐4 reference material was achieved with suitable precision and accuracy, but the USGS MACS‐3 reference material appeared more heterogeneous under the ablation conditions tested. Calibration was performed using two different beam diameters (5 and 11 μm). Capelin (Mallotus villosus) otoliths measuring between 10 and 20 μm in diameter were tested. Even though a smaller beam diameter and lower energy were used compared with those normally employed to analyse larger otoliths, the method was successful.     

利用MPI实现多幅点云ICP并行配准

迭代最近点算法（ICP）是一种用于点云精确配准的经典算法。针对多幅点云进行ICP配准存在耗时多、效率低的问题,本文利用消息传递接口MPI对多幅点云进行分批并行配准。首先并行求解相邻两幅点云的相邻变换矩阵,然后计算每幅点云在当前批次的局部变换矩阵,最后获得每幅点云的全局变换矩阵。本文以DELL PowerEdge R730服务器为计算平台,对空间点总规模达四千多万的65幅点云进行了分批并行配准。试验结果表明：利用MPI对多幅点云进行分批处理可显著加快配准速度,最优进程数为计算机的核数时,加速比为5.3。