The Preparation and Preliminary Characterisation of Three Synthetic Andesite Reference Glass Materials (ARM‐1, ARM‐2, ARM‐3) for In Situ Microanalysis

Three synthetic reference glasses were prepared by directly fusing and stirring 3.8 kg of high‐purity oxide powders to provide reference materials for microanalytical work. These glasses have andesitic major compositions and are doped with fifty‐four trace elements in nearly identical abundance (500, 50, 5 µg g^?1) using oxide powders or element solutions, and are named ARM‐1, 2 and 3, respectively. We further document that sector‐field (SF) ICP‐MS (Element 2 or Element XR) is capable of sweeping seventy‐seven isotopes (from ⁷Li to ²³⁸U, a total of sixty‐eight elements) in 1 s and, thus, is able to quantify up to sixty‐eight elements by laser sampling. Micro‐ and bulk analyses indicate that the glasses are homogeneous with respect to major and trace elements. This paper provides preliminary data for the ARM glasses using a variety of analytical techniques (EPMA, XRF, ICP‐OES, ICP‐MS, LA‐Q‐ICP‐MS and LA‐SF‐ICP‐MS) performed in ten laboratories. Discrepancies in the data of V, Cr, Ni and Tl exist, mainly caused by analytical limitations. Preliminary reference and information values for fifty‐six elements were calculated with uncertainties [2 relative standard error (RSE)] estimated in the range of 1–20%.     

Separation and Precise Measurement of Lithium Isotopes in Three Reference Materials Using Multi Collector‐Inductively Coupled Plasma Mass Spectrometry

Lithium separation technique for three reference materials has been established together with precise determination of lithium isotope using a Neptune multi collector-inductively coupled plasma mass spectrometry (MC-ICP-MS). The solutions of lithium element standard reference materials, potassium, calcium, sodium, magnesium and iron single element, were used to evaluate analytical methods applied. Three separate stages of ion-exchange chromatography were carried out using organic cation-exchange resin (AG 50W-X8). Lithium was enriched for the three stages using different eluants, which are 2.8 M HCl, 0.15 M HCl and 0.5 M HCl in 30% ethanol, respectively. The columns for the first and second stages are made of polypropylene, and those for the third stage are made of quartz. Total reagent volume for the entire chemical process was 35 mL for three reference materials. The recovery yielded for the three stages is 98.9–101.2% with an average of 100.0%, 97.6–101.9% with an average of 99.9%, and 99.8–103.3% with an average of 100.6%, respectively. The precision of this technique is conservatively estimated to be ±0.72–1.04‰ (2σ population), which is similar to the precision obtained by different authors in different laboratories with MC-ICP-MS. The δ7Li values (7Li/6Li relative to the IRMM-016 standard) determined for andesite (AGV-2) and basalt (BHVO-2) are 5.68‰ (n=18), 4.33‰ (n=18), respectively. The δ7Li value (7Li/6Li relative to the L-SVEC standard) determined for IRMM-016 is –0.01‰ (n=15). All these analytical results are in good agreement with those previously reported. In addition, the results for the same kinds of samples analyzed at the MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, are consistent with those obtained at the Plasma Laboratory, University of Maryland, within analytical uncertainty. According to these experiment results, it is concluded that this proposed procedure is a suitable method for determining the lithium isotopic composition of natural samples.     

基于U Pb定年和单颗粒锆石粒径分析示踪 中国黄土高原黄土和红粘土物源

中国黄土高原的风成沉积蕴含着丰富的大陆古气候和大气环流变化信息,但关于黄土和红粘土物源是否有变化目前仍存在着争论。近些年,锆石的LA-ICP-MS定年被广泛用于追踪沉积物来源,本文把碎屑锆石的UPb定年运用到红粘土中,并结合前人的数据和碎屑锆石粒径分析对黄土和红粘土物源进行了重新的讨论,认为黄土高原黄土碎屑锆石主要来源于黄土高原北部戈壁沙漠和附近的沙漠,极少量锆石来源于青藏高原北部,而不是主要来源于青藏高原北部和柴达木盆地,红粘土的锆石物源受近缘的基岩影响较大,朝那6.2~3.6Ma红粘土锆石碎屑部分来源于附近的六盘山。而且在0.12 Ma、0.86 Ma、1.25 Ma之间,黄土碎屑锆石物源较稳定,存在少量变化,在2.6 Ma和3.6 Ma前后,黄土、红粘土碎屑锆石物源存在明显变化,这可能和全球变冷导致近地面冬季风增强有关。     

Determination of Boron Concentration in Geochemical Reference Materials Extracted by Pyrohydrolysis and Measured by ICP‐MS

This article presents new boron concentrations for nine geochemical reference materials (GS‐N, FK‐N, GL‐O, BX‐N, DT‐N, AN‐G, GH, Mica‐Fe, Mica‐Mg). After extraction by a modified pyrohydrolysis technique, boron concentrations were measured by ICP‐MS. The blank levels for the whole procedure were 0.091 ± 0.020 ng ml^?1 or 14 ± 5 ng of boron in total. The method was first validated by measuring nine reference materials with known boron concentrations. The determined boron concentrations are all within the range of recommended or published values, which means that the yields were 100%, and show precisions below 10% for samples containing over 2 μg g^?1 of boron.     

A Comparison of In Situ Analytical Methods for Trace Element Measurement in Gold Samples from Various South African Gold Deposits

Trace element concentrations in gold grains from various geological units in South Africa were measured in situ by field emission‐electron probe microanalysis (FE‐EPMA), laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) and synchrotron micro X‐ray fluorescence spectroscopy (SR‐μ‐XRF). This study assesses the accuracy, precision and detection limits of these mostly non‐destructive analytical methods using certified reference materials and discusses their application in natural sample measurement. FE‐EPMA point analyses yielded reproducible and discernible concentrations for Au and trace concentrations of S, Cu, Ti, Hg, Fe and Ni, with detection limits well below the actual concentrations in the gold. LA‐ICP‐MS analyses required larger gold particles (> 60 μm) to avoid contamination during measurement. Elements that measured above detection limits included Ag, Cu, Ti, Fe, Pt, Pd, Mn, Cr, Ni, Sn, Hg, Pb, As and Te, which can be used for geochemical characterisation and gold fingerprinting. Although LA‐ICP‐MS measurements had lower detection limits, precision was lower than FE‐EPMA and SR‐μ‐XRF. The higher variability in absolute values measured by LA‐ICP‐MS, possibly due to micro‐inclusions, had to be critically assessed. Non‐destructive point analyses of gold alloys by SR‐μ‐XRF revealed Ag, Fe, Cu, Ni, Pb, Ti, Sb, U, Cr, Co, As, Y and Zr in the various gold samples. Detection limits were mostly lower than those for elements measured by FE‐EPMA, but higher than those for elements measured by LA‐ICP‐MS.     

A Triple‐Stack Column Procedure for Rapid Separation of Cu and Zn from Geological Samples

We present a new procedure for the separation and purification of Cu and Zn from geological samples. Our procedure employed a single pass, triple‐stack column set‐up. The first column, filled with TRU resin (TrisKem International), quantitatively removed Fe and Ti from sample matrices. A second column, filled with pre‐filter resin (TrisKem International), removed organic compounds. Finally, a third column, filled with anion exchange resin (AG1‐X8, 200–400 mesh, Bio‐Rad), was used to separate Cu and Zn from the remaining matrix. Our procedure required about 50% less acid volume than previously reported methods for Cu and Zn separation, thereby minimising analytical blanks and column running times. Copper and Zn stable isotope ratios were determined by a Thermo Neptune Plus MC‐ICP‐MS using Zn and Cu external normalisation, respectively, in addition to sample‐standard bracketing to correct for instrumental mass bias. We explore the inter‐calibration of Cu and Zn isotope fractionation coefficients during analysis by measuring mixed Cu–Zn solutions with enhanced mass bias variation generated by varying sample gas flow rates. Our results demonstrate that this procedure is useful when variation in instrumental mass bias throughout analytical sequences is insufficient to inter‐calibrate Cu and Zn fractionation coefficients.     

Automated Analyte Separation by Ion Chromatography Using a Cobot Applied to Geological Reference Materials for Li Isotope Composition

The demand for large and reliable data sets on isotopic composition has increased in geochemistry and environmental sciences over recent years. We present an automated ion chromatographic separation method using a robotic pipetting arm, termed ‘ChemCobOne’, to reduce sample separation time. Its performance was tested for lithium isotope separation in geological reference materials using a single‐step separation with HCl (0.2 mol l^?1) and a 2 ml resin volume. This refined lithium purification method does not forfeit precision, accuracy or purity compared with manual sample processing. In addition, a δ⁷Li value for NASS‐6 of 30.99 ± 0.50‰ (2s) (95% CI = 0.14‰, n = 44) was determined and the first δ⁷Li values for the granite rock reference material GS‐N (?0.57 ± 0.25‰ (2s), 95% CI = 0.15‰, n = 15), and for the soil reference material NIST SRM 2709a (?0.37 ± 0.67‰ (2s), 95% CI = 0.15‰, n = 63) are proposed.     

西昆仑库地北依莎克群玄武岩锆石U-Pb年龄、地球化学特征及构造意义

西昆仑山分为北昆仑古生代复合沟弧带和南昆仑地块,依莎克群的形成时代和构造归属一直存在争议,库地蛇绿岩的形成时代亦无定论。本文运用电子探针微区成分分析和锆石U-Pb测年方法,对库地北西奴山依莎克群底部玄武岩中锆石进行了分析。获得依莎克群玄武岩中锆石LA-ICP-MS U-Pb年龄为519.5±1.2Ma,说明依莎克群玄武岩形成时代为中寒武世。与库地蛇绿岩构造环境和形成时代对比表明依莎克群玄武岩是库地蛇绿岩的组成部分,是原特提斯洋俯冲消减作用的产物。综合前人的年代学资料和本文成果表明库地蛇绿岩形成时代为中寒武世—晚寒武世。     

海洋沉积物中多元素分析测定方法

介绍了海洋沉积物消化及多元素分析的测定方法。分析测定过程中 ,应选用国家标准溶液。标准溶液的蒸发次数、加酸量、稀释倍数等对样品测定结果的准确性均有一定影响。消化过程中 ,过多的蒸发次数对微量元素 Cr、V的测定结果有明显影响 ,蒸发的次数越多 ,元素的损失量越大 ,因此 ,为了获得更准确的测定结果 ,应尽可能减少蒸发次数 ,并减少加酸量 ;测定常量元素时 ,样品较大的稀释倍数使获得数据的可靠性增大 ,通常 0 .2 5 g样品应稀释至 5 0m L,0 .5 g样品应稀释至 1 0 0 m L。     

激光扫描数据的多站配准方法

介绍了激光扫描数据多站配准的目的,详细阐述了固定球公共点转换法、ICP算法和测量设备绝对定位法的原理以及实现方法,并分析了3种方法的优缺点。对激光扫描仪数据处理以及逆向工程、曲面质量检测和虚拟现实等领域的相关问题具有一定参考。