橄榄石、单斜辉石和斜方辉石锂、氧同位素原位微区分析标准物质及其微量元素特征

随着分析技术的发展,锂、氧同位素原位微区分析已成为地球科学研究的重要发展方向。本文介绍了可同时作为锂、氧同位素原位微区分析标准物质的橄榄石(Mg~#=896～942)、单斜辉石(Mg~#=90～919)和斜方辉石(Mg~#=901～921)的化学组成并对其微量元素进行了报道。三种标准物质的主量成分均一,在其Mg#值范围内,SIMS氧同位素分析基体效应均不显著,而橄榄石的Mg#值对SIMS锂同位素分析基体效应为1‰。橄榄石标准物质Ni、Co和Zn含量较高,约为原始地幔值的1～15倍;大离子亲石元素和稀土元素含量较低。单斜辉石微量元素中除个别元素外,SN-ICP-MS和LA-ICP-MS的分析结果误差范围内一致,具有成为原位微区分析标准物质的潜力;在原始地幔标准化配分曲线中,V、Sc、Cr和Ga相对其他过渡族元素显著富集;大离子亲石元素Rb和Ba相对Th和U显著亏损,轻稀土相对重稀土元素略富集。斜方辉石过渡族元素Cr、V和Sc接近原始地幔值,大离子亲石元素和轻稀土元素含量较低,在不同仪器分析中误差较大。     

正交最小二乘法及其在分析化学中的应用

介绍了一种线性模型参数回归分析方法-正交最小二乘法，并以电子探针微区分析技术分析环境样品的数据为例，对正交最小二乘法和经典最小二乘法的结果进行了详细比较。数据处理结果表明，当变自量和因变量都同时存在测量误差时（或自变量的测量误差与因变量的测量误差相比不能忽略时），正交最小二乘法获得的回归系数优于经典最小二乘法。对正交最小二乘法中的线性模型能解释的方差与经典最小二乘法中的相关系数的关系也进行了讨论。     

太原市灰霾期间黑碳气溶胶形貌与成分分析

为掌握太原市冬季灰霾发生期间黑碳气溶胶形貌特征和化学成分变化特点,分别于2011-12-30T08:00至2012-01-01 T 04:00和2018-11-25 T 08:00至2018-11-27 T 04:00灰霾发生期间在山西大学环境与资源学院楼顶使用MAY七级冲击式颗粒采样器每隔4h采集空气动力学直径分别为0.25～0.5μm、0.5～1.0μm以及1～2μm的大气单颗粒分析样品,运用带超薄窗口能谱仪的扫描电镜(JEOL JSM-6390)测定了样品中4330个颗粒的二次电子像及X射线能谱,通过基于蒙特卡罗模拟程序的定量电子探针微区分析技术对每个颗粒的元素原子浓度进行了计算,并对颗粒进行了分类与计数。共检测到6类颗粒,分别是矿物尘、碳质颗粒、钠盐颗粒、二次颗粒、富铁颗粒和其他,其中黑碳气溶胶数量相对丰度在2011和2018年样品中平均为26.8%和34.2%。按照伸长率(E)、纵横比(R)、是否与其他物质结合等将其分为伸展型、支链型、嵌入或粘附型和团聚型4种,反映了黑碳颗粒不同的老化过程。2011年样品中团聚型和支链型数量较多,而2018年样品中伸展型和嵌入型多于团聚型和支...     

环境扫描电子显微镜工作原理及其气象学应用

大气颗粒物具有吸附性、吸湿性以及对光的吸收和散射性等特性,对环境、气候和人类健康造成许多不利影响。扫描电子显微镜和能谱分析技术,可在观测大气组成的微小颗粒的微观结构的同时,实现对微结构元素组分分析的目的,为气象学中开展微观物理化学研究提供一个有效的手段。文章简要介绍了环境扫描电子显微镜(ESEM)的基本工作原理及特点,指出环境扫描电子显微镜在气象科学研究中的独特作用、适用领域,并通过对人工影响天气焰剂产生的大气颗粒的物理化学性质研究的实例来说明其应用。     

Itrax μ-XRF core scanning for rapid tephrostratigraphic analysis: a case study from the Auckland Volcanic Field maar lakes

Itrax micro X-ray fluorescence (μ-XRF) core scanning is a non-destructive, rapid approach to measuring elemental concentrations and their variability in sediment cores. As such, it records elemental signatures of tephra layers, which serve as correlation tie points and chronological markers for these sedimentary archives of past climatic changes. The traditional tephra identification approach using electron microprobe-based geochemical fingerprinting of glass shards is a slow and invasive process, whilst μ-XRF scanning of rhyolite tephra in sediment cores from Auckland (New Zealand) could provide a faster, non-invasive approach to aid the recognition of tephra layers. This study highlights the potential and pitfalls in this novel approach: changes in most scanning parameters, and the use of two different Itrax core scanners, still led to similar chemical characterizations of the tephra layers. Changes in other scanning parameters have a biasing influence on the chemical characterization of the tephra, which would lead to misidentification of unknown layers. We demonstrate that μ-XRF core scanning provides a faster and non-invasive approach to correlation of sediment sequences using chemically distinct, visually pure tephra layers if a strict scanning protocol is followed. Nevertheless, an extensive database of μ-XRF-scanned rhyolite tephra is required for recognition of unknown tephra units using this approach.     

A Practical Method for Accurate Measurement of Trace Level Fluorine in Mg‐ and Fe‐Bearing Minerals and Glasses Using Electron Probe Microanalysis

Fluorine plays an important role in magmatic and hydrothermal processes, but due to its low abundance in geological samples determining F is difficult by electron probe microanalysis. By using a W‐Si multi‐layered pseudocrystal as the diffraction crystal instead of thallium acid phthalate (TAP), count rates were considerably higher, which however introduced spectral interferences between FKα and FeLα and MgKβ lines when normal integral mode is applied. In this study, we developed a protocol using a W‐Si multi‐layered pseudocrystal for measuring accurately trace level F in both minerals and glasses. First, we used differential mode with an optimised PHA (pulse height analysis) setting in signal processing, instead of normal integral mode, which completely eliminated the second‐order MgKβ line. Second, the overlap of the first‐order FeLα on FKα peak, which cannot be filtered by modifying the PHA setting, was calibrated quantitatively using F‐free minerals and silicate glasses. Applying this two‐step method, F was determined in a number of reference glasses, as well as in glasses synthesised from powders of the rock reference materials AC‐E, GS‐N and DR‐N. Our data are consistent within error with F concentrations determined by other methods, demonstrating the reliability of this method.     

透射电子显微镜在关键矿产成因机制研究中的应用进展

关键矿产的元素赋存形式对矿产超常富集机制和资源综合利用有着至关重要的作用。然而,关键矿产的元素赋存形式大多以细小矿物、吸附或类质同象的方式存在,不易于直接观察分析,在一定程度上增加了对其进一步认识和综合利用的难度,而透射电子显微镜(Transmission Electron Microscopy,TEM)可以在微纳米尺度上从结构和成分方面提供有效的解决途径。文章扼要地介绍了TEM的基本原理、工作模式、样品制备的方法及工作流程,并根据国内关键矿产的类型与元素赋存形式综述了TEM在关键性稀有金属、稀土金属、稀散金属、稀贵金属、能源金属以及黑色和有色金属等6类矿产中成因机制研究的应用进展情况,指出了限制TEM广泛应用的瓶颈问题,并提出了几点浅显的意见和建议。     

含金磷酸盐矿物的发现及其地质意义 ——以山东牟平腊子沟金矿为例

山东牟平腊子沟金矿位于华北板块苏鲁造山带胶南-威海隆起区,牟平-乳山金矿成矿带中段,区内岩浆活动频繁,构造活动强烈,成矿地质条件优越。本文通过镜下显微结构观察、电子探针测试分析对腊子沟金矿载金矿物的组成、成分及金的赋存状态进行了研究,首次在该矿区发现含金独居石和含金磷灰石,金含量达到0.283%～0.456%,推测金可能通过类质同象形式替代磷灰石中的Ca2+或独居石中的稀土元素(Ce2+、 La2+)以晶格金的形式存在。前人研究认为成矿流体中金主要以Au[HS]2－和AuCl2－络合物形式进行迁移,本次含金磷酸盐矿物的发现表明：可能部分金以磷酸根络合物形式进行迁移。     

Columbite SN3: A New Potential Reference Material for U-Pb Dating by LA-ICP-MS

Columbite-tantalite LA-ICP-MS U-Pb dating is a fast and useful method to determine the age of rare-metal deposits and fingerprint the provenance of columbite-tantalite ore concentrates. Accurate LA-ICP-MS U-Pb dating requires matrix-matched reference materials. We analysed three columbite-tantalite samples (SN3, HND and RL2) from China using ID-TIMS and LA-ICP-MS to assess their potential as reference materials for in situ U-Pb dating. Coltan 139 and these three columbite-tantalite samples with variable compositions yielded internally consistent LA-ICP-MS U-Pb ages when using each other for calibration and the weighted mean ²⁰⁶Pb/²³⁸U ages are comparable to respective ID-TIMS ages. Composition-dependent U-Pb fractionation seems to be insignificant under the LA-ICP-MS conditions used. Sample SN3 has a low percentage of heterogeneity for ²⁰⁶Pb/²³⁸U ages (4%) with low common Pb contributions (f₂₀₆ < 1%) and shows a good potential in calibrating unknown samples as primary reference material for LA-ICP-MS analysis. Samples RL2 and HND have altered sections characterised by high LREE contents, flat LREE patterns and old ²⁰⁶Pb/²³⁸U apparent ages, and are not suited as reference materials. The low ²⁰⁷Pb/²⁰⁶Pb intercepts for samples RL2 and HND lack geological meaning but provide strong evidence that the disturbed U-Pb systematics with anomalous apparent ²⁰⁶Pb/²³⁸U ages is a secondary feature.     

赣东北朱溪钨(铜)矿床两期石榴石研究及其对成矿作用的指示

本文对朱溪超大型钨(铜)矿床中两类与白钨矿密切相关的石榴石进行了研究。研究表明,这两类共存的石榴石与夕卡岩型矿床中常见的同期热液在不同阶段形成的两种石榴石不同。早期石榴石相对更加富Fe(Ad_37.17~41.84Gr_54.83~59.57Sp_3.10~4.62),而晚期石榴石更加富Al(Ad_12.69~14.42Gr_77.56~79.03Sp_0.44~0.92),成分上更接近钙铝榴石端员,具有更低的Sn含量,更高的U含量,并在稀土配分曲线中显示出更明显的正Eu异常,表明晚期石榴石形成时的氧逸度明显低于早期石榴石形成时的氧逸度。晚期石榴石相对于早期石榴石具有更高的Cu、Pb、Zn、Li、Be、B、Rb、Cs、Sr含量和更低的W、Mo、Ga、Ge含量,并且与成矿相关岩体具有相似的稀土配分模式曲线,表明晚期石榴石与朱溪矿床的成矿相关岩浆演化而形成的残余岩浆热液流体具有更加密切的相关性。本文研究的两类共存的石榴石可能是两期成矿热液流体作用的产物,暗示朱溪矿床的成矿作用可能与多期岩浆活动有关。