SIMULTANEOUS DETERMINATION OF THIRTY-SEVEN TRACE ELEMENTS IN TWENTY-EIGHT INTERNATIONAL ROCK STANDARDS BY ICP-MS

Thirty-seven trace elements, including rare-earth elements, have been determined by ICP-MS in twenty-eight international rock standards using routine sample preparation techniques. Samples were decomposed by either pressurized HF-HCIO₄-aqua regia attack, or by lithium borate fusion. Generally, the ICP-MS data for geological rock standards presented here agree well with certified values. However, the results for light rare earth elements appear to be systematically low in comparison with the published working values.     

Ion Exchange Chromatography Applied to the Separation and Accurate Determination Of Some Trace Elements in Rocks

Ion exchange chromatography is extremely well suited for the complete or partial separation of trace and ultra-trace elements from rooks and minerals. Selective methods are described for the separation of traces of lithium, beryllium, vanadium, uranium, strontium, barium, sodium, potassium and rare earth elements, and their determination in rook samples. The methods are especially useful for accurate standardization work. Some typical elution curves and results for the concentration of these trace elements in the six South African NIM-rock standards and some international standard rocks are presented.     

Dissolved trace elements and heavy metals in the Danjiangkou Reservoir,China

Concentrations of trace elements and heavy metals (Al, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Se, Sr, V and Zn) in the Danjiangkou Reservoir, the water source area of the Middle Route of China’s interbasin South to North Water Transfer Project, were analyzed using an Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES) and compared with the national and international standards for drinking water. The results indicated that concentrations of As, Pb, Sb and Se in the Reservoir exceeded the standards and they would pose health risk for residents in the region and the water receiving areas of the interbasin water transfer project. Spatial and temporal variability of the trace elements and heavy metals in the Reservoir implies their mixed sources of natural processing and anthropogenic activities in the upper drainage of the Reservoir. The research results would help develop water resource management and conservation strategy for the interbasin water transfer project.     

Application of an Ion-Selective Electrode Method to the Determination of Chloride in 41 International Geochemical Reference Materials

Determinations of trace amounts (with one exception) of chloride are reported for 41 international geochemical reference standards, 12 of which have no previously reported literature values. All determinations were made by the chloride-specific ion-selective electrode method of Aruscavage and Campbell with certain refinements. Chlorine is separated from most other elements in geologic materials by acid-dissolution in a gas diffusion cell, and is subsequently determined as the chloride ion in basic solution. A statistical F-test was applied to 19 of the standards for which three bottles of each were analyzed in triplicate with no failures. All these standards, plus the other 22 for which six analyses were performed on a single bottle, exhibited a relative standard deviation of 1-6% for concentrations of chloride >50 ppm. For most samples chloride values agree well both with available, reported experimental values and with recommended or consensus values.     

SIMS测定玻璃固化样品中铀分布的分析方法研究

玻璃固化是一种常用的高放废液固化方法,其优点在于具有较高的抗化学介质侵蚀的能力和很好的辐照稳定性、热稳定性和机械稳定性,其不足之处在于抗水浸出等性能有所下降而使其安全性需要进一步通过抗浸出实验来进行衡量和确认。使用二次离子质谱(SIMS)分析玻璃固化体中的放射性成分(如铀元素)的分布及浸出行为等各项指标,是一种评估玻璃固化体抗浸出性能的分析手段。本文应用SIMS测试模拟玻璃固化体,以碳作为镀膜材料通过真空蒸发镀碳的方法优化样品制备条件,有效地解决了样品导电性差的问题,~(235)U/~(238)U同位素测定结果约为7.9‰±0.395‰,基本符合制作模拟样品时所使用的天然铀的同位素特征(~(235)U/~(238)U参考值约7.3‰)。研究表明,建立的方法实现了铀元素同位素丰度的测量,能直接显示铀的分布情况,该方法可为研究玻璃固化体中放射性元素的浸出行为提供一定的技术支持。     

归一化定量技术在激光烧蚀-等离子体质谱测定石榴子石多元素中有关问题的讨论

讨论了采用相对灵敏度系数进行多外标归一校正的可行性。该校正方法应用于激光烧蚀-等离子体质谱同时分析了未知石榴子石样品中主、次、痕量共43个元素,并与内标法结果进行对比,其一致性令人满意。探讨了激光线扫描和单点剥蚀两种取样方式下,相对灵敏度系数间的变化关系,结果表明,在剥蚀深度基本一致的情况下,取样方式对相对灵敏度系数没有显著影响。     

Trace Element Data on Geostandards by Mass Spectrometric Isotope Dilution Technique

The stable isotope dilution technique using solid source mass spectrometry is described. The method is capable of high sensitivity, and can yield accurate determinations of elements in trace quantities. The method enjoys freedom from interference effects and systematic errors, and because of its high absolute accuracy it is ideal for the determination of trace elements in geochemical reference samples. A compilation of isotope dilution analyses on ten trace elements in a number of international standard rock samples carried out at the Western Australian Institute of Technology is presented.     

不同检测方法对氢氧同位素分馏的影响

氢氧同位素的检测方法由最初的离线双路进样同位素比质谱法(Dual-inlet IRMS),发展到自动化程度较高的连续流水平衡法(Gasbench-IRMS)检测方法以及现阶段正在研究使用的热转换元素分析同位素比质谱法(TC/EA-IRMS)。为了探讨不同检测方法对氢氧同位素分馏的影响以及各方法的优缺点,文章应用Dual-inlet IRMS、GasbenchⅡ-IRMS、TC/EA-IRMS三种检测方法对四种不同水样的氢氧同位素进行检测,并用国际标准和国家标准对检测结果进行校正。结果表明,Dual-inlet IRMS法检测氢同位素的精密度高,重现性好;Gasbench-IRMS法检测氢同位素的结果重现性较差;Dual-inlet IRMS和Gasbench-IRMS法检测氧同位素要比TC/EA-IRMS法的精密度高,重现性好。用TC/EA-IRMS法检测氢氧同位素,分别用国际标准和国家标准校正,δD值的最大绝对偏差为1.13‰,δ18O值的最大绝对偏差为0.27‰。测定不同水样的氢氧同位素时,连续流GasbenchⅡ-IRMS测定氧同位素较有优势,而TC/EA-IRMS测定氢同位素比较有优势。样品测试过程中选用的校正标准不同,检测结果也存在一定的误差。     

Abundance of Boron in International Geochemical Standards by Prompt-Gamma Neutron Activation Analysis

Eighteen international reference standards, mostly geochemical standards, have been analysed for boron using prompt-gamma neutron activation analysis (PGNAA). There is good agreement between the results for samples with high boron abundances and the few published values using PGNAA and other methods. However, correlation is poor at low boron abundances, especially in those standards with low boron/sodium ratios. Corrections for sodium interference on boron have been critically evaluated and the data corrected using two different methods.     

Report (1968–1978) on Two Mica Reference Samples: Biotite Mica-Fe and Phlogopite Mica-Mg

Since 1967–68, two mica reference samples, Biotite Mica-Fe and Phlogopite Mica-Mg, were made available to several geochemical laboratories. The analytical data reported during the past ten years by 142 geoanalysts belonging to 74 international laboratories are presented and assessed for deriving preferred values. Reaomrmended or proposed values are assigned for major, minor and several trace elements. The biotite Mica-Fe is better characterized for its chemical composition than the Phlogopite Mica-Mg. Both the samples are also proposed as geochronological standards. Because very few mica reference samples have been processed in large quantities, the international geochemiaal community is invited to contribute further useful data.     

Determination of some trace elements in geochemical standards by X-ray fluorescence

The following trace elements Cr, Cu, Nb, Ni, Pb, Rb, Sr, Y, Zn, and Zr were determined by X-ray fluorescence in some geochemical standards from Japan and France. The internal standard method was applied using a Philips PW 1410 X-ray spectrometer. The results were compared with the published data.     

地质样品中40个微量、痕量、超痕量元素的ICP-MS分析研究

以基体匹配的混合标准溶液为外标校正溶液, 采用115In - 10 3 Rh双内标校正系统, 通过单个元素Ca, Cr, Ti, Ba, La, Ce, Pr的氧化物、氢氧化物产率的测定, 计算其等效干扰离子浓度, 并进行校正, 从而有效地抑制了分析信号的漂移、基体效应及多原子离子干扰.针对不同岩性的地质样品, 分别采用酸消解、碱熔融样品制备体系, 在POEMSⅢ上建立了等离子体质谱法同时测定微量、痕量、超痕量元素的分析方法.用于国际地质标样AGV - 1 (安山岩), BH VO - 2 (玄武岩), GSR - 3 (玄武岩), DNC - 1 (橄榄岩), RGM - 1 (流纹岩), G - 2 (花岗岩), JG- 2 (花岗岩) 的分析, 结果令人满意.      

刍议相关规范中关于单桩承载力计算的几点疑惑

国内相关规范中单桩抗压承载力设计计算方法分为特征值法及极限值法两类,单桩承载力均通过桩侧阻力与桩端阻力直接相加的方法得到,在概念及理论上均存在着不完善之处,主要原因是桩侧阻力与桩端阻力的力学特性及对变形的要求不同、不能同步发挥所致。相对来说,极限值设计法更直接、更可靠、更准确,概念更明确,且易于与国际接轨,建议规范优先采用。不同规范根据抗拔试验结果求取单桩抗拔承载力的计算方法存在矛盾,建议求取时桩的自重按天然重度计算、不考虑水的浮力。建议相关规范对以下两种现象进行深入研究：桩长超过有效长度后,单位长度侧摩阻力将会降低;部分工程中得到的抗拔桩的抗拔系数远小于相关规范推荐值,尤其是桩长较长时。     

微量磷灰石中磷酸根氧同位素分析方法

生物磷灰石壳体的磷酸根氧同位素组成是重建古温度理想指标之一,在古环境研究中具有重要意义.针对牙形石等磷灰石量极少的情况,稳定可靠的前处理方法是分析其δ18O_PO4的重要保障,目前仅有少数国外实验室已建立了相关提取分析方法.结合这些方法的优缺点对分析步骤进行改进优化,建立了微量磷灰石的磷酸根氧同位素分析方法,通过硝酸消解磷灰石并除去非磷酸根氧,利用KF溶液沉淀法分离Ca2+,采用氨缓冲溶液形式调节pH,并加入AgNO₃溶液以氨挥发法将PO₄3-转化成Ag₃PO₄结晶分离,气体稳定同位素质谱仪在线测定Ag₃PO₄氧同位素组成.结果表明,方法全流程未产生明显的氧同位素分馏,样品最低仅需0.2 mg,标准偏差小于0.2‰（1σ）,与目前国际报道的分析精度一致.      

Determination of Cobalt in South African Primary and Secondary Reference Samples by Ion Exchange Chromatography and electrothermal Atomic Absorption Spectrophotometry

Results are presented for the determination of trace quantities of cobalt in three South African primary rock standards and in four secondary rock standards. Cohalt is separated from all other elements using a selective ion exchange separation procedure and determined by electrothermal atomic absorption spectrophotometry.     

TRACE ELEMENT ANALYSIS OF TEN U.S. GEOLOGICAL SURVEY ROCK STANDARDS BY NEUTRON ACTIVATION USING A LOW FLUX REACTOR

Ten U.S. Geological Survey rock standards have been analyzed for trace elements by instrumental neutron activation using a low flux reactor and Ge detectors. Results compare favorably with the current working values for all elements except Mo. REE values that have been determined are generally slightly lower than accepted values. Data obtained for rocks that have very low trace element concentrations (e.g., BIR-1) will aid in refining the working values for these standards.     

Simultaneous determinations of U–Pb age,Hf isotopes and trace element compositions of zircon by excimer laser-ablation quadrupole and multiple-collector ICP-MS

We describe an in situ method for simultaneous measurement of U–Pb–Hf isotopes and trace element compositions of zircons using a quadrupole and multiple-collector inductively-coupled-plasma mass spectrometer (Q-ICP-MS and MC-ICP-MS, respectively) connected to a single excimer laser-ablation system. A laser-generated zircon aerosol was split behind the ablation cell into two transport tubes via a Y-shaped connector and simultaneously introduced into the two mass spectrometers. Hafnium isotopes were measured on the MC-ICP-MS instrument, while U–Pb ages and trace element compositions were determined using the Q-ICP-MS. The precision and accuracy of this method was evaluated using six well-known and widely used zircon standards (91500, Temora-2, GJ-1, Mud Tank, BR266 and Monastery). Analyses were carried out using spot sizes of 32, 44 and 60 μm. For the 44 and 60 μm spot, the resulting U–Pb ages, Hf isotopic and rare earth element (REE) compositions of these six zircons agree with recommended/reported values within 2σ error. The difference in relative standard deviations (RSD) of ²⁰⁶Pb/²³⁸U ages between split-flow measurements and those obtained separately on the Q-ICP-MS is within ～ 20% for 91500, Temora-2 and GJ-1, and ～ 60% for Mud Tank (due to its lower U and Pb concentrations). Our method provides a precise approach for determining the U–Pb age and the Hf isotopic and trace element compositions of zircon within a single ablation event. This is in particular important for analysis of zircons that are small or contain complicated zoning patterns. Finally, the REE composition of zircon BR266 is more homogeneous than other zircons and could be a suitable standard by which to benchmark new standards for microprobe analyses of zircons.     

An evaluation of trace element release associated with acid mine drainage

The determination of trace element release from geologic materials, such as oil shale and coal overburden, is important for proper solid waste management planning. The objective of this study was to determine a correlation between trace element residency and concentration to trace element release using the following methods: (1) sequential selective dissolution for determining trace element residencies, (2) toxicity characteristic leaching procedure (TCLP), and (3) humidity cell weathering study simulating maximum trace element release. Two eastern oil shales were used, a New albany shale that contains 4.6 percent pyrite, and a Chattanooga shale that contains 1.5 percent pyrite. Each shale was analyzed for elemental concentrations by soluble, adsorbed, organic, carbonate, and sulfide phases. All leachates were analyzed to determine total trace element concentrations. The results of the selective dissolution studies show that each trace element has a unique distribution between the various phases. Thus, it is possible to predict trace element release based on trace element residency. The TCLP results show that this method is suitable for assessing soluble trace element release but does not realistically assess potential hazards. The results of the humidity cell studies do demonstrate a more reasonable method for predicting trace element release and potential water quality hazards. The humidity cell methods, however, require months to obtain the required data with a large number of analytical measurements. When the selective dissolution data are compared to the trace element concentrations in the TCLP and humidity cell leachates, it is shown that leachate concentrations are predicted by the selective dissolution data. Therefore, selective dissolution may represent a rapid method to assess trace element release associated with acid mine drainage.     

Determination of Gallium at the ppb Level in South African Primary and Secondary Reference Samples by Ion Exchange Chromatography and Electrothermal Atomic Absorption Spectrophotometry

Results are presented for the determination of trace amounts of gallium in two South African primary rock standards (MIMROCS) and in four secondary rock standards (SAROCS). Gallium is separated from all other elements, except traces of thorium, using a selective ion exchange separation procedure (1) and determined by electro-thermal atomic absorption spectrophotometry.     

Trace Element Analysis by Neutron Activation With a Low Flux Reactor (Slowpoke - II): Results for International Reference Rocks

A low-flux reactor (SLOWPOKE II) may be used to determine a large number of trace elements by neutron activation. Details of this technique are given along with results for 22 elements in 22 international reference rocks. Our results are compared with published "best values"; the agreement is favourable in most cases.