电子探针定量分析测定FeO和Fe2O3含量常用方法的评定

直接测氧法测定矿物中FeO和Fe2O3含量，在其众多影响因素中，经测量不确定度评定发现，超轻元素氧的影响显著。一方面受电子探针仪器因素和基体校正精度的限制，氧的电子探针定量分析值的准确度很低；另一方面氧对FeO和Fe2O3含量的不确定度灵敏系数分别为8．981、9．981，将氧的测量不确定度再扩大近10倍。可见直接测氧法测定FeO和Fe2O3含量，仅因超轻元素氧的测量不确定度传递就会使其误差范围过大，效果不是很理想。而利用Fe的Lα、Lβ谱线强度比的价态效应推测矿物中FeO和Fe2O3含量，由于Lβ/Lα强度比与Fe^2＋／Fe^3＋比值之间关系曲线的确定，需要对矿物进行大量的系统性研究，甚至是否必然存在这种对应都还缺乏理论依据，可见此法也并不可靠。相对而言，常用的电价差值法和剩余氧计算法仍为优选方案。     

滇西南翁孔坝铜多金属矿床绿泥石特征及其地质意义

翁孔坝铜多金属矿床位于云县-景洪火山弧带北段,是该带典型的铜多金属矿床之一,具有良好的成矿条件和找矿潜力。绿泥石化是该矿床最重要的蚀变类型之一。文章在详细的野外工作基础上,通过对该矿床岩(矿)石样品的岩相学研究,利用电子探针和扫描电镜分析绿泥石的化学成分和形态特征,进而揭示绿泥石的形成环境,探讨绿泥石化与多金属矿化之间的关系。结果显示,该矿床中绿泥石主要有3种类型：包括沿裂隙和孔洞中充填的Chl-Ⅰ类绿泥石、铁镁质矿物蚀变形成且与斑铜矿-辉铜矿矿脉共生的Chl-Ⅱ_1-2类绿泥石以及与方铅矿一起充填杏仁体的Chl-Ⅱ3类绿泥石。从Chl-Ⅰ类绿泥石→Chl-Ⅱ_1-2类绿泥石→Chl-Ⅱ₃类绿泥石,其氧逸度和硫逸度呈现出逐渐降低的演化规律,温度为188～297℃,反映出它们形成于中等硫逸度、低氧逸度、中低温的热液环境。该矿床绿泥石属于密绿泥石和铁斜绿泥石,其主要阳离子与Mg之间具有较强的相关性,为多期热液蚀变的产物,物质来源于矿区发育的一套中-基性火山岩,其形成机制为溶蚀-结晶和溶蚀-迁移-沉淀。绿泥石化的形成促进了铜、铅锌...     

Quantifying Isotopic Heterogeneity of Candidate Reference Materials at the Picogram Sampling Scale

We propose a method for quantifying the in situ heterogeneity of solid materials at the picogram test portion scale, illustrating its use by investigating the oxygen isotope ratio (¹⁸O^?/¹⁶O^?) of four quartz samples. Using secondary ion mass spectrometry, we could estimate the intrinsic heterogeneity using a large number (~ 100) of closely spaced duplicated measurements. An analysis of variance was then applied to these large data sets to extract the measurement repeatability (typically 0.10–0.15‰, 1s) from the total variability, thereby revealing a variability ranging from 0.18‰ to 2.3‰, which can be attributed to the genuine isotope ratio heterogeneities. A small proportion of outlying values were either rejected manually after inspection, or were accommodated using robust statistics. We also evaluated two distinct approaches for estimating and correcting instrumental drift; the use of a sub‐area of the test material (if shown to have sufficiently low heterogeneity) is judged to be preferable to using a piece of unrelated silicate glass that we believe to be homogeneous. We also compared three approaches for estimating measurement repeatability, from which we show that the ‘duplicate method’ applied to the reference material is preferable to using other methods based either on the drift monitoring material or on assessing residuals of the drift monitoring material after drift correction. Finally, here we propose a strategy for predicting the number of measurements on individual fragments of a material that would be required to achieve a specified target uncertainty.     

Electron Probe Microanalysis of Variable Oxidation State Oxides: Protocol and Pitfalls

Electron probe microanalysis of geological oxide materials relies on stoichiometric considerations to estimate the content of undetermined oxygen and thus calculate ZAF (atomic number, absorption, fluorescence) matrix correction factors, requiring the valences of cations in the corresponding software to be unambiguously defined. However, stoichiometric ZAF corrections may be problematic in the presence of other undetermined elements or variable valence state cations. Herein, we analyse several oxides containing such cations, that is magnetite (Fe₃O₄), haematite (Fe₂O₃), hausmannite (Mn₃O₄) and cuprite (Cu₂O). We compare data re‐calculated for incorrect valence states ( Method 1 ) with reference values, revealing incorrect results, due to an incorrect amount of oxygen used in the matrix correction. Some solid‐solution series of haematite and magnetite were also modelled in CalcZAF program to prove the relative errors when the incorrect oxygen is used. To resolve these issues, we describe two accurate methods. Method 2 uses the true valence states of analysed elements. In Method 3, all cations are analysed as metals, with the content of undetermined oxygen determined by difference. As EPMA software does not allow the use of non‐integer valences, Method 3 is applicable to cations with non‐integer or dubious valences in cases where these non‐integer valences cannot be defined.     

Characterisation of a Natural Quartz Crystal as a Reference Material for Microanalytical Determination of Ti,Al, Li,Fe, Mn,Ga and Ge

A natural smoky quartz crystal from Shandong province, China, was characterised by laser ablation ICP‐MS, electron probe microanalysis (EPMA) and solution ICP‐MS to determine the concentration of twenty‐four trace and ultra trace elements. Our main focus was on Ti quantification because of the increased use of this element for titanium‐in‐quartz (TitaniQ) thermobarometry. Pieces of a uniform growth zone of 9 mm thickness within the quartz crystal were analysed in four different LA‐ICP‐MS laboratories, three EPMA laboratories and one solution‐ICP‐MS laboratory. The results reveal reproducible concentrations of Ti (57 ± 4 μg g^?1), Al (154 ± 15 μg g^?1), Li (30 ± 2 μg g^?1), Fe (2.2 ± 0.3 μg g^?1), Mn (0.34 ± 0.04 μg g^?1), Ge (1.7 ± 0.2 μg g^?1) and Ga (0.020 ± 0.002 μg g^?1) and detectable, but less reproducible, concentrations of Be, B, Na, Cu, Zr, Sn and Pb. Concentrations of K, Ca, Sr, Mo, Ag, Sb, Ba and Au were below the limits of detection of all three techniques. The uncertainties on the average concentration determinations by multiple techniques and laboratories for Ti, Al, Li, Fe, Mn, Ga and Ge are low; hence, this quartz can serve as a reference material or a secondary reference material for microanalytical applications involving the quantification of trace elements in quartz.     

Electron Microprobe/SIMS Determinations of Al in Olivine: Applications to Solar Wind,Pallasites and Trace Element Measurements

Electron probe microanalyser measurements of trace elements with high accuracy are challenging. Accurate Al measurements in olivine are required to calibrate SIMS implant reference materials for measurement of Al in the solar wind. We adopt a combined EPMA/SIMS approach that is useful for producing SIMS reference materials as well as for EPMA at the ~ 100 µg g^?1 level. Even for mounts not polished with alumina photoelectron spectroscopy shows high levels of Al surface contamination. In order to minimise electron beam current density, a rastered 50 × 100 µm electron beam was adequate and minimised sensitivity to small Al‐rich contaminants. Reproducible analyses of eleven SIMS‐cleaned spots on San Carlos olivine agreed at 69.3 ± 1.0 µg g^?1. The known Al mass fraction was used to calibrate an Al implant into San Carlos. Accurate measurements of Al were made for olivines in the pallasites: Imilac, Eagle Station and Springwater. Our focus was on Al in olivine, but our technique could be refined to give accurate electron probe measurements for other contamination‐sensitive trace elements. For solar wind, it is projected that the Al/Mg abundance ratio can be determined to 6%, a factor of 2 more precise than the solar spectroscopic ratio.     

矿物微区原位分析与同位素地球化学分析技术在地学中应用

微区原位分析以高空间分辨率和微量分析为核心,结合同位素地球化学的分析技术,满足了地质过程描述中对时间、物质来源、成因环境的识别需求。该文介绍了微区原位分析技术特点及同位素地球化学应用的基本原理。以锆石U-Pb定年为例,回顾U-Pb同位素测年的技术发展,介绍了SHRIMP技术的发展。在此基础上,结合地学研究的需求,提出了未来微区分析技术的发展趋势。     

碳酸岩型稀土矿床成矿流体演化机制研究现状及展望

与碱性岩有关的碳酸岩型内生稀土矿床在中国乃至世界上轻稀土资源储量中占有极为重要的地位,诸如我国内蒙古的白云鄂博稀土矿床、川西冕宁—德昌稀土成矿带中的牦牛坪、大陆槽等稀土矿床、山东微山县郗山稀土矿床以及美国的Mountain Pass稀土矿床等都属于这种类型的稀土矿床.当前,对于这类稀土矿床的成矿流体演化机制,学界主要存...     

Geostandards and Geoanalytical Research Bibliographic Review 2019

This bibliographic review gives an outline of publications in 2019 focusing on reference materials (RMs) used in geochemistry and related fields, such as palaeoclimate and environmental research.     

GGR Biennial Critical Review: Analytical Developments Since 2010

Advances in the chemical and isotopic characterisation of geological and environmental materials can often be ascribed to technological improvements in analytical hardware. Equally, the creation of novel methods of data acquisition and interpretation, including access to better reference materials, can also be crucial components enabling important breakthroughs. This biennial review highlights key advances in either instrumentation or data acquisition and treatment, which have appeared since January 2010. This review is based on the assessments by scientists prominent in each of the given analytical fields; it is not intended as an exhaustive summary, but rather provides insight from experts of the most significant advances and trends in their given field of expertise. In contrast to earlier reviews, this presentation has been formulated into a unified work, providing a single source covering a broad spectrum of geoanalytical techniques. Additionally, some themes that were not previously emphasised, in particular thermal ionisation mass spectrometry, accelerator‐based methods and vibrational spectroscopy, are also presented in detail.