Accurate Determination of Cobalt in South African Primary and Secondary Geochemical Reference Materials by Cation Exchange Chromatography and Atomic Absorption Spectrometry

Cobalt in the six S.A. primary (NIMROCS) and fourteen secondary reference samples as well as in a phosphate rock has been determined accurately by means of atomic absorption spectrometry. A selective and quantitative ion exchange separation procedure, using a 20 g column of AG50W-X8 cation exchange resin and 0.4 M hydrochloric acid-86% acetone and 1 M hydrochloric acid-80% acetone as eluting agents, is employed for the separation of cobalt from all other elements. The accuracy and precision of the described method are demonstrated by the analysis of synthetic rock solutions containing various amounts of cobalt. Amounts of 1, 10 and 100 μg of cobalt can be determined with a coefficient of variation of 1%, 0.3% and 0.2%. respectively.     

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.     

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.     

地质样品的一次阴离子色谱法Hf分离及其MC-ICP-MS分析

本文建立了适合MC-ICP-MS测试地质样品中Hf同位素的一次阴离子交换化学分离方法。使用常规的阴离子交换树脂就可以完成Hf与干扰元素和基体元素的分离,避免了当前广泛采用的多次离子交换柱的麻烦,也无需使用特效树脂,HF处理样品后,也不必使用HClO_4赶尽HF。Hf的回收率大于90%,过程空白约为50pg。岩石标样的重复分析表明,该方法简单、快速、经济、有效,尤其适合年轻地质样品Hf同位素组成分析。     

Accurate Determination of Copper in South African Primary and Secondary Reference Samples by Cation Exchange Chromatography and Atomic Absorption Spectrometry

Copper in S.A. primary (NIMROCS) and in six secondary reference samples has accurately been determined by means of atomic absorption spectrometry. A selective ion exchange separation procedure, using a 20 g column of AG50W-X8 cation exchange resin and 0.2 M hydrochloric acid and 0.5 M hydrobromic acid, both containing 85% acetone, is employed for the separation of copper from all other elements, except vanadium. Vanadium which can partially accompany copper, however, is separated at the start of the sorption step with 0.01 M nitric acid-0.15% hydrogen peroxide. Accuracy and precision of the described method are demonstrated by the analysis of synthetic rock solutions containing various amounts of copper. Amounts of 10 and 100 μg of copper can be determined with a coefficient of variation of 0.3% and 0.2%, respectively.     

铷—锶年龄测定中样品制备的一种新方法

在铷—锶年龄测定中,制样工作占有重要地位。要从千变万化的岩石、矿物样品中制出能满足质谱测定的Rb、Sr同位素样品,要使Rb~(87)和Sr~(87)这对同量异位素完全分离,就需要有一个简便、完备的方法。国内、外的Rb—Sr同位素实验室大都采用离子交换分离制样法。 为了满足高精度、高灵敏度及高自动化程度的     

Study on the Development Laws of Bed-Separation Under the Hard-Thick Magmatic Rock and its Fracture Disaster-Causing Mechanism

Based on the analysis of dynamic phenomena under the condition of high-located hard-thick (HLHT) stratum of one coal mine, along with the similar material simulation and theoretical analysis, the characteristics of bed separation development and cracks distribution under the HLHT stratum are studied. This paper proposes a discriminating method for overlying strata Three Zones considering the influence of HLHT stratum. The development laws of cracks and disaster-causing mechanism of hard-thick magmatic rock in different strata are respectively analyzed. The studies show that in line with the working face advancing direction, the height of bed separation under the magmatic rock increases in the trend of “Increase–Stability–Decrease”, and the width of bed separation increases linearly. The width of bed separation reaches the maximum before the first breaking of magmatic rock, the bed separation completely closes after the breaking. There are no obvious bed separations during the period migration of magmatic rock. Along the direction of the height of roof, the development of bed separation is characterized by bottom-up jump based on the key strata. The analyzed results of “Three zone” height obtained by the discriminate method of overlying strata Three Zones which is based on the key strata theory and the S–R instability theory are in line with the actual facts. When the hard-thick magmatic rock is in the fractured zone, large amounts of gas and water are easy to accumulate in the bed separation space and “O” ring space around the gob. The first breaking of magmatic rock may induce bed separation gas outburst and water inrush. When the hard-thick magmatic rock is in the sagging zone, the long-term stability of magmatic rock will not cause serious disasters. But with the adjacent working face mining, bed separation gas and water often become a safety hazard.     

岩层及地表移动与冲击地压相关性研究

对岩层及地表移动规律的观测、室内试验和数值计算分析表明,采动覆岩层沉陷运动的不协调性造成裂隙带上部弯曲带岩体中产生大范围的离层空隙。随着工作面的推采,离层空隙周期性悬露垮断构成了上覆岩层及地表移动变形运动的不同特征。根据现场观测,砾岩层运动是矿井冲击地压发生的主要力源,地表下沉速度发生剧烈变化,冲击地压发生的频率较高,地表产生反弹时更为危险,且随着砾岩层的运动,冲击地压发生周期性变化。     

岩石样品中低含量铂族元素和锇同位素比值的高精度测量方法

铂族元素（Os,Ir,Pt,Ru,Rh,Pd)具有强亲铁性和强亲铜性，为一组地球化学性质相近的相容元素，铂族元素包含两个同位素衰变体系（^190Pt-^186Os和^187Re-^187Os)。近年来，铂族元素和Re-Os同位素在研究各类不同地持作用过程中，尤其是在地幔岩石的研究中，作用独特，效果显著。由于地幔岩石的铂族元素含量较低，因此高精度，高灵敏度的分析测试方法的研究就显得十分重要。以往的分析方法（如常规的ICP－MS和中子活化分析方法），对含10^-9-10^012级低含量铂族元素的产品分析精度一般较差（＞15％－100％）。所采用的分析流程通常也无法同时获得样品的铂族元素含量和Os同位素比值。本文采用新的熔样方法（HAP－S高温高压釜酸溶法），新的化学流程（溶剂萃取和阴离子交换树脂柱）和新的分析仪器（多接收等离子体质谱MC－ICPMS和负离子热电离质谱N－TIMS）。用同位素稀释法对低含量地幔橄榄岩样品同时测定的铂族元素含量和Os同位素比值，获得了高精度的分析结果。对所分析的地橄榄样品中的铂族元素分配曲线和Os同位素组成的地质意义进行了初步探讨。     

利用同一化学流程分析地质样品中的铂族元素含量和铼-锇同位素组成

报道了利用一次溶样和同一化学流程分离富集地质样品中铂族元素(Pt、Pd、Os、Ir和Ru)和Re的方法.该化学流程包括以下几个步骤:(1) Carius管溶样法分解岩石样品中富集铂族元素的矿物;(2)四氯化碳萃取法分离出Os;(3)微蒸馏法进一步纯化Os;(4)阳离子交换树脂法将铂族元素(Pt、Pd、Ir和Ru)以及R...     

Determination of Rare Earth Elements and Yttrium in Nine Geochemical Reference Samples Using a Novel Group Separation Procedure Involving Mixed-Acid Elution Ion-Exchange Chromatography

Rare earth data for nine well-known geochemical reference samples were obtained using a rapid and efficient cation exchange chromatographic separation procedure. It involves the use of a mixed-acid eluent (HCI and HNO3) on a 15 x 1 cm column of Bio-Rad AG50–X8 (200–400 mesh) to remove matrix and many trace elements from rock solutions. The rare earth elements are removed from the column using 60 ml 7M HNO3. The pre-concentration procedure described is routinely used in this laboratory for the determination of the rare earth elements by mass spectrometry-isotope dilution, and has been satisfactorily used for their determination using inductively-coupled plasma-source atomic emission spectrometry.     

川西北马脑壳金矿床流体相分离作用及其成矿意义

马脑壳金矿床是近年来在川西北地区发现的一大型微细浸染型矿床。本文通过对流体包裹体系统研究，指出了石英-(白钨矿)-辉锑矿脉型金矿化阶段成矿流体曾发生过较强的相分离作用，并运用热力学原理探讨了流体相分离机制下金的沉淀成矿机理，提出了微细浸染型金矿床形成过程中流体相分离作用与成矿的关系。     

Accurate Determination of Gallium in South African Primary and Secondary Reference Samples by Ion Exchange Chromatography and Atomic Absorption Spectrometry

Results are presented for gallium in six South African primary rock standards (NIMROCS) and in twelve secondary rock standards (SAROCS). A selective ion exchange procedure is used to separate gallium completely from all other elements, except remaining traces of thorium. It is followed by a determination of gallium with flame atomic absorption spectrometry using the nitrous oxide-acetylene flame, after the addition of 2000 ppm lanthanum as ionization suppressor.     

含水层中考虑水—岩间阳离子交换的溶质运移方程

导出了能反映含水层中水—岩间阳离子交换作用的溶质运移方程,并提出了一个新的海水入侵数学模型.模型以交换阳离子Na+和Ca2+作为模拟因子,考虑了海水入侵过程中水—岩间的Na+—Ca2+交换,模型用于模拟山东省龙口市黄河营地区的海水入侵,取得了令人满意的结果,从而证明导出的溶质运移方程是正确的,建立的模型是可靠的.     

General equations for modeling fluid/rock interaction using trace elements and isotopes

General equations for modeling open and closed system fluid/rock interaction using trace elements and isotopes are presented. Taylor's (1977) open system equation for stable isotopes is extended to account for a change in the Δ value between rock and fluid during interaction. It is shown that hydrothermal systems in which fractionation factors vary during fluid/rock interaction will significantly alter the isotopic ratios of rocks compared to equivalent systems with invariant fractionation factors. The equations for modeling trace element exchange are analogous to the stable isotope equations and permit the calculation of fluid/rock ratios using changes in trace element concentrations in the rock. Similarly to stable isotope exchange, the change of the trace element concentration in a rock during infiltration is a function of the trace element concentration in the fluid, the fluid/rock partition coefficient and the fluid/rock ratio rather than simply the concentration of the trace element in the fluid.     

用于多接收器等离子体质谱铜铁锌同位素测定的离子交换分离方法

采用AGMP-1阴离子交换树脂，分别以7mol／L HCl、2mol／L HCl、0．5mol／L HNO3作为淋洗剂，可有效分离Cu、Fe、Zn。介绍了方法的基本原理、化学分离过程及混合标准溶液与地质标样的分离结果。结果表明，Cu、Fe、Zn回收率均接近100％，标准溶液在离子交换分离前后同位素组成一致，可以满足多接收器等离子体质谱对Cu、Fe、Zn同位素高精度分析的要求。     

浙东早白垩世火山岩组合的地球化学及其成因研究

浙东早白垩世含中性岩的火山岩组合和双峰式火山岩组合的主量元素和微量元素特征对比研究表明，中性火山岩的地球化学特征明显受到伴生的基性和酸性火山岩的影响。它们的微量元素协变关系证实：中性火山岩是由基性岩浆和酸性岩浆混合形成的。双峰式火山岩具有与含中性岩的火山岩组合相类似的主量元素特征，但两者的微量元素特征相差较大。根据东南沿海在早白垩世时期的构造背景是由挤压向伸展拉张转变，以及各种元素具有不同的扩散速度，提出了浙东早白垩世火山岩组合的形成模式：若基性岩浆和酸性岩浆仅进行了部分微量元素的交换，没有来得及发生主量元素的交换，就在伸展拉张的构造背景下喷出地表，则形成双峰式火山岩组合；若基性岩浆与酸性岩浆在地壳深处共存的时间较长，发生一定程度的主量元素交换，则形成偏基性和偏酸性的中性岩浆，若进一步发生化学成分的交换，则可形成典型的安山质岩浆，喷出地表就形成含中性岩的火山岩组合。     

A Comprehensive Method for Precise Determination of Re,Os, Ir,Ru, Pt,Pd Concentrations and Os Isotopic Compositions in Geological Samples

A comprehensive method for the precise determination of Re, Os, Ir, Ru, Pt and Pd concentrations as well as Os isotopic compositions in geological samples is presented. Samples were digested by the Carius tube method, and the Os was extracted by conventional CCl₄ method. The Re, Ir, Ru, Pt and Pd were first subgroup separated from the matrix elements into Re‐Ru, Ir‐Pt and Pd by a 2‐ml anion exchange column. Subsequently, the Re‐Ru was further purified by a secondary 0.25 ml anion exchange column or by microdistillation of Ru using CrO₃‐H₂SO₄ as an oxidant followed by a secondary 0.25 ml anion exchange separation of Re. The Pd and Ir‐Pt were further successively purified by an Eichrom‐LN column to completely remove Zr and Hf, respectively. Rhenium, Ir, Ru, Pt and Pd were individually measured by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS), except for Ru after microdistillation purification was analysed by negative‐thermal ionisation mass spectrometry (N‐TIMS). The analytical results for peridotite reference material WPR‐1 agree well with the previously published data. Finally, several mafic rock reference materials including TDB‐1, WGB‐1, BHVO‐2, BCR‐2, BIR‐1a and DNC‐1a were analysed for Re‐Os isotopes and platinum‐group element concentrations to test their suitability for certification.     

On the stress distribution at the bonding interface between rock and bolt

Rock bolt is a major reinforcement technique for roadways in coal mines in China. Generally, separation of the bonding interface between the rock mass and the bolt may lead to collapse of the bolted rock mass due to stress concentration. In order to establish the stress concentration mechanism on the bonding interface, the distribution functions for shear stress and longitudinal force on the interface are derived using Mindlin's model, and a failure criterion for the interface is proposed. In addition, influencing factors for the stress distribution mode are identified. Both analytical study and numerical simulations by ANSYS have shown that, as the elastic modulus of rock increases, both shear stress and the longitudinal force-concentrating zone move towards the outer end of bolt and decrease gradually from the free surface to the rock mass body. Also, there is an optimizing cement thickness which results in relatively uniform distributions of shear stress and longitudinal force on the interface. It is valuable to investigate the bolt invalidity mechanism as well as reinforcement safety estimation in underground rock engineering design.     

Zoning patterns in orthopyroxene and garnet in granulites: implications for geothermometry

Compositional maps of orthopyroxene and garnet of contrasting grain size and in contact with different minerals were made from two paragneiss granulites from the Minto terrane of northern Quebec. The compositional maps provide clear evidence of late exchange of Fe/(Fe + Mg) after Ca in garnet and Al in orthopyroxene had been quenched-in. The extent of late Fe-Mg exchange was controlled by neighbouring minerals, with negligible Fe-Mg gradients against plagioclase and quartz, and substantial gradients against exchangeable Fe-Mg minerals. Cores of grains in contact with exchangeable Fe-Mg neighbours are progressively more reset in Fe/(Fe + Mg) as grain size decreases, whereas cores of even small grains surrounded by only plagioclase and quartz are not significantly different in Fe/(Fe + Mg) than cores of the largest grains. Gradients of Ca in garnet and of Al in orthopyroxene in grains of uniform Fe/(Fe + Mg) preserve a high-temperature retrograde history during which intergranular exchange effected compositional uniformity of mineral rims and intragranular Fe-Mg diffusion in garnet and orthopyroxene was rapid enough to homogenize Fe/(Fe + Mg). The transition from efficient intergranular exchange at relatively high temperatures to local Fe-Mg exchange at lower temperatures may have been controlled by loss of an intergranular exchange medium in the rock, possibly an internally generated dehydration melt phase. Implications for geothermometry of granulites include the following (numerical values are particular to this study): (1) core compositions of garnet and orthopyroxene grains in contact with exchangeable neighbours may be reset in Fe/(Fe + Mg) relative to the most refractory compositions by an amount equivalent to 120d? C; (2) Fe-Mg exchange thermometry using even the most refractory Fe/(Fe + Mg) compositions may not record peak granulite conditions, possibly recording instead the temperature at which an intergranular exchange medium was lost from the rock; and (3) temperature-sensitive net transfer equilibria involving Al solubility in orthopyroxene yield temperatures up to 150d? C higher than maximum Fe-Mg exchange temperatures, even in grains with flat Fe/(Fe - Mg) compositional profiles, making them a better means of estimating peak granulite temperatures than Fe-Mg exchange thermometry.