电感耦合等离子体发射光谱法同时测定碳酸盐岩石中19个元素

使用ＪＹ７０Ｐ 电感耦合等离子体发射光谱仪,分别考察了一些主要基体对待测元素的各种干扰。综合各种干扰因素,采用干扰系数校正法消除综合干扰,拟定了适用于包括碳酸盐岩石的区域化探样品中１９ 个元素的电感耦合等离子体原子发射光谱同时测定方法。１９ 个元素的测定限在０ ．２０ ～８ ．０ μｇ／ｇ 。对碳酸盐岩石国家一级标准物质ＧＢＷ０７１０８ 进行检测,各元素的结果与标准值吻合,相对标准偏差（ｎ ＝ １１） 在１ ．２ ％ ～５ ．３ ％ 。     

介形类壳体中Sr/Ca及Mg/Ca比值的ICP-AES测定

沉积物中介形类壳体的Ｓｒ／Ｃａ和Ｍｇ／Ｃａ比值可用于湖泊古盐度和古温度的重建。本文从双通道顺序扫描式ＩＣＰ－ＡＥＳ的特点出发,对μｇ级介形类样品中的低含量元素Ｓｒ和Ｍｇ选择最灵敏谱线和最佳通道,对各项条件进行最优化。Ｓｒ和Ｍｇ的检测限分别为１．１μｇ／Ｌ和１．４μｇ／Ｌ。本文以此法准确测定了介形类样品中Ｓｒ／Ｃａ比值和Ｍｇ／Ｃａ比值,回收率实验结果令人满意。     

Measurement of the Isotopic Composition of Molybdenum in Geological Samples by MC‐ICP‐MS using a Novel Chromatographic Extraction Technique

A novel preconcentration method is presented for the determination of Mo isotope ratios by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS) in geological samples. The method is based on the separation of Mo by extraction chromatography using N‐benzoyl‐N‐phenylhydroxylamine (BPHA) supported on a microporous acrylic ester polymeric resin (Amberlite CG‐71). By optimising the procedure, Mo could be simply and effectively separated from virtually all matrix elements with a single pass through a small volume of BPHA resin (0.5 ml). This technique for separation and enrichment of Mo is characterised by high selectivity, column efficiency and recovery (~ 100%), and low total procedural blank (~ 0.18 ng). A ¹⁰⁰Mo‐⁹⁷Mo double spike was mixed with samples before digestion and column separation, which enabled natural mass‐dependent isotopic fractionation to be determined with a measurement reproducibility of  < 0.09‰ (δ^98/95Mo, 2s) by MC‐ICP‐MS. The mean δ^98/95Mo_{SRM 3134} (NIST SRM 3134 Mo reference material; Lot No. 891307) composition of the IAPSO seawater reference material measured in this study was 2.00 ± 0.03‰ (2s, n = 3), which is consistent with previously published values. The described procedure facilitated efficient and rapid Mo isotopic determination in various types of geological samples.     

New Thorium Isotope Ratio Measurements in Silicate Reference Materials: A‐THO,AGV‐2, BCR‐2, BE‐N,BHVO‐2 and BIR‐1

A two‐step Th isolation protocol, involving micro‐columns of TRU‐Spec extraction chromatography material and AG1 resin, was evaluated. The MC‐ICP‐MS procedure included ²³²Th tailing characterisation and correction, and calibrator bracketing using an in‐house standard solution (ThS1) to correct for instrumental mass bias and Faraday cup to secondary electron multiplier relative gain. Repeated analyses of reference solutions (UCSC Th ‘A’, WUN, OU Th ‘U’, IRMM‐36) were consistent with published data. Six reference materials (A‐THO, BCR‐2, AGV‐2, BHVO‐2, BE‐N and BIR‐1) were processed. The average ²³⁰Th/²³²Th values obtained for these samples are in excellent agreement with published data. In addition, we report the first ²³⁰Th/²³²Th values for BE‐N and BIR‐1. The intermediate precisions for rock samples ranged from ± 0.24 to ± 0.49% (2 RSD) and were similar to those achieved for synthetic solutions, thereby supporting the overall validity of the chemical separation, data acquisition and reduction procedures. Counting statistics on the ²³⁰Th isotope was the most significant source of uncertainty. The intermediate precision of the mean ²³⁰Th/²³²Th for the Th‐depleted BIR‐1 (5.64 × 10^?6 ± 0.27%, 2 RSD) is in the range of the analyses of other reference materials analysed in this study.     

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.     

基于综合改进ICP算法的三维激光扫描技术在露天矿边坡测绘中的应用

以先后发生过两次大规模滑坡的中煤平朔公司东露天矿边坡为研究背景,利用三维激光扫描技术测绘速度快、测量精度高、数据量大的特点,对该露天矿边坡进行三维激光扫描,尤其是对发生过滑坡的两个重点区域进行精细扫描。基于综合改进ICP算法,将扫描得到的多站点云数据进行拼接处理,完成了长约2 km的露天矿边坡三维模型重建。研究结果表明,三维激光扫描结果符合工程实际特征,是一种快速建立矿山边坡数字模型的有效手段。      

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。     

内蒙古锡林浩特毛登牧场早石炭世花岗岩锆石U Pb年龄、地球化学特征及其地质意义

通过对内蒙古锡林浩特毛登牧场早石炭世花岗岩体进行野外观察、LA ICP MS锆石U Pb测年以及地球化学测试,讨论其构造环境,进一步为研究古亚洲洋闭合时限提供依据。测年结果表明：花岗闪长岩为(3306±18) Ma,二长花岗岩为(3277±26) Ma,成岩时代为早石炭世。岩石地球化学分析表明:花岗闪长岩为强过铝质、钙碱性系列岩石,具有活动大陆边缘的亲缘性特征。微量元素特征指示花岗闪长岩具有典型下地壳来源特征并伴有部分幔源岩浆混合作用,为弧岩浆岩。二长花岗岩为具高硅、富碱、相对低铝特征的高钾钙碱性系列岩石。两类差异明显的岩石稀土配分曲线表明二长花岗岩具有下地壳岩浆重熔的演化特征。微量元素特征指示样品为大陆弧环境下壳源重熔的成熟弧花岗岩。构造判别图显示花岗闪长岩为代表活动大陆边缘环境的I型花岗岩,而二长花岗岩则为指示活动大陆边缘弧后伸展环境的A2型花岗岩,二者构成I－A型复合岩体,说明研究区在早石炭世仍存在古亚洲洋向西伯利亚板块的俯冲作用,推测古亚洲洋此时尚未闭合。     

Niobium and Tantalum Concentrations in NIST SRM 610 Revisited

Niobium and Ta concentrations in MPI‐DING and USGS (BCR‐2G, BHVO‐2G, BIR‐1G) silicate rock glasses and the NIST SRM 610–614 synthetic soda‐lime glasses were determined by 193 nm ArF excimer laser ablation and quadrupole ICP‐MS. Measured Nb and Ta values of MPI‐DING glasses were found to be consistently lower than the recommended values by about 15% and 25%, respectively, if calibration was undertaken using commonly accepted values of NIST SRM 610 given by Pearce et al. Analytical precision, as given by the 1 s relative standard deviation (% RSD) was less than 10% for Nb and Ta at concentrations higher than 0.1 μg g^?1. A significant negative correlation was found between logarithmic concentration and logarithmic RSD, with correlation coefficients of ‐0.94 for Nb and ‐0.96 for Ta. This trend indicates that the analytical precision follows counting statistics and thus most of the measurement uncertainty was analytical in origin and not due to chemical heterogeneities. Large differences between measured and expected Nb and Ta in glasses GOR128‐G and GOR132‐G are likely to have been caused by the high RSDs associated with their very low concentrations. However, this cannot explain the large differences between measured and expected Nb and Ta in other MPI‐DING glasses, since the differences are normally higher than RSD by a factor of 3. Count rates for Nb and Ta, normalised to Ca sensitivity, for the MPI‐DING, USGS and NIST SRM 612–614 glasses were used to construct calibration curves for determining NIST SRM 610 concentrations at crater diameters ranging from 16 (im to 60 μm. The excellent correlation between the Nb/Ca_1μgg‐1 signal (Nb represents the Nb signal intensity; Ca_{1μg g‐1} represents the Ca sensitivity) and Nb concentration, and between the Ta/Ca_{1μg g‐1} signal (where Ta represents the Ta signal intensity; Ca_{1μg g‐1} represents the Ca sensitivity) and Ta concentration (R²= 0.9992–1.00) in the various glass matrices suggests that matrix‐dependent fractionation for Nb, Ta and Ca was insignificant under the given instrumental conditions. The results confirm that calibration reference values of Nb and Ta in NIST SRM 610 given by Pearce et al. are about 16% and 28% lower, respectively. We thus propose a revision of the preferred value for Nb from 419.4 ± 57.6 μg g^?1 to 485 ± 5 μg g^?1 (1 s) and for Ta from 376.6 ± 77.6 μg g^?1 to 482 ± 4 μg g^?1 (Is) in NIST SRM 610. Using these revised values for external calibration, most of the determined average values of MPI‐DING, USGS and NIST SRM 612–614 reference glasses agree within 3% with the calculated means of reported reference values. Bulk analysis of NIST SRM 610 by standard additions using membrane desolvation ICP‐MS gave Nb = 479 ± 6 μg g^?1 (1 s) and Ta = 468 ± 7 μg g^?1 (1 s), which agree with the above revised values within 3%.