Primary diagenetic copper carbonate at the Malbunka copper deposit,Amadeus Basin,Northern Territory,Australia

The Malbunka copper deposit, located about 220 km west of Alice Springs, in the Northern Territory of Australia, may be a rare example of primary formation of copper carbonate mineralization. This deposit consists of unusual azurite disks up to 25 cm diameter, and lesser amounts of secondary azurite crystals and malachite. Carbon isotope values of the copper carbonate minerals are consistent with formation from groundwater-dissolved inorganic carbon. Oxygen isotope thermometry formation temperature estimates are 5–16 °C above ambient temperatures, suggesting the copper carbonates formed at a depth between 0.3 and 1.6 km in the Amadeus Basin. Azurite fluid inclusion waters are rich in boron, chlorine, and other elements suggestive of dilute oil basin formation fluids. In addition, presence of euhedral tourmaline with strong chemical zonation suggest that this was a low temperature diagenetic setting. The strong correlation of structures associated with hydraulic fracturing and rich copper carbonate mineralization suggest a strongly compartmentalized overpressure environment. It is proposed that copper carbonates of the Malbunka deposit formed when deep, copper-rich formation fluids were released upward by overpressure-induced failure of basin sediments, permitting mixing with carbonate-rich fluids above. This work bears directly upon exploration for a new type of primary copper deposit, through understanding of the conditions of genesis.     

Thermodynamic properties of synthetic calcium-free carbonate cancrinite

Calcium-free carbonate cancrinite with formula unit Na_8.28[Al_5.93Si_6.07O₂₄](CO₃)_0.93(OH)_0.49·3.64H₂O (CAN) has been synthesized under hydrothermal conditions. The product has been characterized by the methods of scanning electronic microscopy and energy dispersive X-ray analysis, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis with FTIR of evolved gases (TGA–FTIR), and X-ray powder diffraction. The heat capacity of CAN has been measured from 6 to 259 K via low-temperature adiabatic calorimetry. A linear combination of Einstein functions has been used to approximate the obtained data on the heat capacity. The thermal contributions to the entropy and enthalpy of CAN in the temperature range 0–300 K have been calculated from these data. The heat capacity and third-law absolute entropy of CAN at 298.15 K are 1,047 ± 30 and 1,057 ± 35 J mol^?1 K^?1, respectively. High-temperature oxide-melt solution calorimetry has been used to determine the enthalpy of formation from elements of CAN at 298.15 K; the value equals ?14,684 ± 50 kJ mol^?1. The Gibbs energy of formation from elements at 298.15 K has been calculated and totaled ?13,690 ± 51 kJ mol^?1.     

Thermodynamic projection and extrapolation of high-variance mineral assemblages

A procedure is described whereby the effect of extra components on the plotting positions of minerals in projected phase diagrams may be accounted for rigorously. The method employs the equilibrium constraints of the mineral assemblage to extrapolate the compositions of the minerals to where the values of the extra components approach 0. The same procedure may also be used to extrapolate the compositions of natural assemblages over isothermal, isobaric composition diagrams or polythermal, polybaric diagrams.Examples from typical garnet-bearing pelite assemblages indicate that the extra components MnO and CaO dramatically shift the compositions of coexisting phases to lower Fe/Mg, even where the phase itself (e.g. chlorite or biotite) does not contain appreciable quantities of the extra component. Recognition of, and correction for, this effect is critical if projected phase diagrams are to be compared with experimentally calibrated phase diagrams in the chemical subsystem.     

Effects of groundwater flow on mineral diagenesis, with emphasis on carbonate aquifers

 This article provides a critical synopsis of the effects of groundwater flow on mineral diagenesis. Emphasis is placed on those aspects and processes that change porosity and permeability in carbonate aquifers, because they are of particular importance to human societies as sources of supplies of water for human consumption (drinking, irrigation) and of crude oil and natural gas. Diagenetic settings in carbonates as well as clastics are generally ill defined. This paper proposes a new comprehensive classification of diagenetic settings into near-surface, shallow-, intermediate-, and deep-burial diagenetic settings; hydrocarbon-contaminated plumes; and fractures. These settings are defined on the basis of mineralogy, petroleum, hydrogeochemistry, and hydrogeology. This classification is applicable to all sedimentary basins. Diagenesis is governed by various intrinsic and extrinsic factors that include thermodynamic and kinetic constraints, as well as microstructural factors that may override the others. These factors govern diagenetic processes, such as dissolution, compaction, recrystallization, replacement, and sulfate–hydrocarbon redox-reactions. Processes such as cementation, dissolution, and dolomitization require significant flow of groundwater driven by an externally imposed hydraulic gradient. Other processes, such as stylolitization and thermochemical sulfate reduction, commonly take place without significant groundwater flow in hydrologically nearly or completely stagnant systems that are geochemically "closed." Two major effects of groundwater flow on mineral diagenesis are enhancement and reduction of porosity and permeability, although groundwater flow can also leave these rock properties essentially unchanged. In extreme cases, an aquifer or hydrocarbon reservoir rock can have highly enhanced porosity and permeability due to extensive mineral dissolution, or it can be plugged up due to extensive mineral precipitation. Received, April 1998 · Revised, July 1998 · Accepted, September 1998     

Hydrogen bonding in basic copper salts: a spectroscopic study of malachite,Cu2(OH)2CO3, and brochantite,Cu4(OH)6SO4

Infrared and Raman spectra of the basic copper salts malachite, Cu₂(OH)₂CO₃, and brochantite, Cu₄(OH)₆SO₄, as well as of deuterated and ¹³C substituted samples are presented and discussed in terms of group theory and the hydrogen bonds present. The main results are that (i) the hydrogen donor strengths of the OH^? ions are strongly increased due to the very great synergetic effect of the copper ions, (ii) the acceptor strengths of the H-bond acceptor groups (SO₄ ^2-, CO₃ ^2-, and OH^? ions) are significantly modified by the linkage and coordination of the acceptor atoms — this complicates true assignment of the OH bands observed to the two and six different OH^? ions present in malachite and brochantite, respectively -, and (iii) the Cu — O stretching modes at 430–590 cm^?1 and 420–520 cm^?1 for malachite and brochantite, respectively, exhibit strong, partially covalent Cu — O bonding.     

矿产预测基础数据库的数据检查

21世纪的矿产资源预测评价是在GIS平台下,通过建立地质、物探、化探、遥感等信息的空间数据库,并对各数据库进行空间分析和信息转换、提取,最终圈定综合异常的。这项工作的前提是具有高质量的空间数据库。要提高空间数据库的质量,确保入库数据的正确性和完备性是关键,因此数据检查是一个不可回避的难题。矿产预测评价基础空间数据库具有数据量庞大、数据结构复杂、数据类型多样等特点,因此,提出通过元数据技术检查和控制数据的完备性和时效性,通过数据字典技术确保数据的属性精度,借助质量规则控制数据的逻辑一致性和位置精度的数据检查策略,并运用到全国重要成矿区带的基础空间数据库数据检查中．取得了良好的效果。     

Biogeochemical studies at the Khetri copper deposits of Rajasthan,India

Several plants of the Khetri Copper Deposits of Rajasthan (India) accumulate very high levels of copper. The maximum concentration namely 394 ,μg/g (dry wt.) was found in the leaves of Talinum portulacifolium. Some other copper accumulators with the concentration of the metal in μg/g are: Tephrosia villosa (288), Rhus mysorensis (234) and Bouchea morubifolia (147). The respective biological absorption coefficients (copper in dried plant divided by copper in soil) for these four plants were 0.07, 1.35, 0.13 and 0.26, respectively. Leaves were found to be richer in copper than the stems. Copper levels in the leaves of Tephrosia villosa, Aerua tomentosa and Bouchea morubifolia showed a significant (linear) plant/soil relationship. Rhus mysorensis and Talinum protulacifolium showed absorption barriers at high soil copper concentrations, indicating limits to uptake in these two species.     

便携式短波红外矿物分析仪(PIMA)在西藏墨竹工卡县驱龙铜矿区矿物填图中的应用

介绍了应用国内近两年新引进的便携式短波红外矿物分析仪(Portable Infrared Mineral Analyser，简称PIMA)在西藏驱龙铜矿区所做的矿物填图的工作情况，以及依据PIMA测试所获得的光谱数据进行矿物识别的初步研究成果。通过野外对探槽TC0701和TC1101系统采样和对应的光谱测试分析，识别出了与矿化和矿体有直接关系的蚀变指示矿物硬石膏(anhydrite)。在矿物识别过程中，提取到了可以作为矿区标准光谱的白云母等矿物的纯光谱曲线，并且在野外验证过程中确认了航天图像(Hyperion)上解译的零星分布的蚀变矿物绿泥石的存在。     

Thermodynamic properties and phase stability of wadsleyite II

The thermodynamical stability of a newly observed wadsleyite II phase in the Mg₂SiO₄ system is studied by the density functional theory. The wadsleyite II equation of state has been derived. The phase boundaries of Mg₂SiO₄ polymorphs: wadsleyite, wadsleyite II and ringwoodite are studied using the quasi-harmonic approximation at high external pressures. Clapeyron slopes determined for wadsleyite II–ringwoodite and wadsleyite–wadsleyite II boundaries are 0.0047 and 0.0058 GPa/K, respectively. It is shown that the wadsleyite II phase is not thermodynamically preferred in the pure Mg₂SiO₄ system and will probably not occur between wadsleyite and ringwoodite phases.     

滇西北香格里拉市格咱铜多金属矿集区地质演化与成矿作用

格咱矿集区位于义敦-沙鲁里岛弧与盐源-丽江被动陆缘结合部位,长期的地质演化,形成了具有特色的成岩成矿岩石(矿物)组合。该矿集区产出铜钼金等多金属矿床50余处,是我国的铜资源基地之一。本文综合香格里拉市格咱地区沉积、岩浆、变质、构造对矿床分布等制约因素,综述该地区成矿作用与地质演化的关系。格咱矿集区多金属矿成矿作用主要与二叠纪至三叠纪古特提斯俯冲封闭及三叠纪至古近纪陆内造山演化有关,即二叠纪—晚三叠世洋-陆转换(P-T₃)和晚三叠世末期—古近纪的陆内发展演化(J-K-E)两个时期,进一步可细分为甘孜-理塘洋盆的发展演化(P-T₂)、甘孜-理塘洋盆的俯冲消减及碰撞造山(T₃)、白垩纪板内伸展(K)、古近纪碰撞后板内伸展走滑(E)四个阶段。印支晚期(221～199 Ma)、燕山晚期(88～77 Ma)、喜马拉雅早期(50～28Ma)的三期岩浆活动直接导致格咱地区多金属富集。已知矿床(点)深部及三期浅成斑(玢)岩体外围尚有较大找矿潜力,是区内今后勘查的重点方向。     

中条山铜矿峪矿深部段矿石铜矿物粒度查定分析

通过对铜矿物嵌布料度特征的查定，预测选矿效果，确定合理选矿指标，合理配矿及指导深部中段开采方案设计，提供科学的地质依据。     

辽宁省草河掌—桓仁地区铜矿资源量地球化学定量预测

矿产资源地球化学模型建立与定量预测研究以成矿成晕地质、地球化学理论为指导,以各尺度勘查地球化学数据为基础,以现代GIS信息技术为手段,通过研究总结典型矿田(矿集区)、矿床的异常特征,建立成矿带内典型矿床地球化学找矿模型,为预测区的地球化学定量预测提供类比依据,从而进行资源量预测。在资源量预测过程中加入了相似度、剥蚀程度、衬值等要素,有效地加大了预测靶区遴选的可信度,通过类比法与面金属量法两种预测方法的加权平均,使预测资源量合理。文章对草河掌—桓仁地区铜矿资源量进行了估算,共新增预测铜资源量21 812.9t。     

安徽铜陵狮子山矿田铜、金共生与分离的热力学研究

狮子山矿田是安徽铜陵矿集区内最具代表性的大型铜金多金属矿田.矿田内铜、金矿床或矿体既各自独立产出,义相互共生或伴生,铜矿化和金矿化在时间上和空间上存在既共生又分离的现象.本文选择矿田内代表性铜矿床和金矿床开展系统的流体包裹体地球化学研究,并进行成矿流体中铜、金溶解度的热力学理论计算和1分析,探索铜、金共生与分离的机制和...     

Influence of ferric iron on the stability of mineral assemblages

Ferric iron is present in all metamorphic rocks and has the ability to significantly affect their phase relations. However, the influence of ferric iron has commonly been ignored, or at least not been considered quantitatively, mainly because its abundance in rocks and minerals is not determined by routine analytical techniques. Mineral equilibria calculations that explicitly account for ferric iron can be used to examine its effect on the phase relations in rocks and, in principle, allow the estimation of the oxidation state of rocks. This is illustrated with calculated pseudosections in NCKFMASHTO for mafic and pelitic rock compositions. In addition, it is shown that ferric iron has the capacity to significantly increase the stability of the corundum + quartz assemblage, making it possible for this assemblage to exist at crustal P–T conditions in oxidized rocks of appropriate composition.     

The partitioning of Fe and Mg between olivine and carbonate and the stability of carbonate under mantle conditions

We have investigated the effect of Fe on the stabilities of carbonate (carb) in lherzolite assemblages by determining the partitioning of Fe and Mg between silicate (olivine; ol) and carbonates (magnesite, dolomite, magnesian calcite) at high pressures and temperatures. Fe enters olivine preferentially relative to magnesite and ordered dolomite, but Fe and Mg partition almost equally between disordered calcic carbonate and olivine. Measurement of K _d (X _Fe ^carb X _Mg ^ol /X _Fe ^ol X _Mg ^carb ) as a function of Fe/ Mg ratio indicates that Fe–Mg carbonates deviate only slightly from ideality. Using the regular solution parameter for olivine W _FeMg ^ol of 3.7±0.8 kJ/mol (Wiser and Wood 1991) we obtain for (FeMg)CO₃ a W _FeMg ^carb of 3.05±1.50 kJ/mol. The effect of Ca–Mg–Fe disordering is to raise K _d substantially enabling us to calculate W _CaMg ^carb -W _CaFe ^carb of 5.3±2.2 kJ/mol. The activity-composition relationships and partitioning data have been used to calculate the effect of Fe/Mg ratio on mantle decarbonation and exchange reactions. We find that carbonate (dolomite and magnesian calcite) is stable to slightly lower pressures (by 1 kbar) in mantle lherzolitic assemblages than in the CaO–MgO–SiO₂(CMS)–CO₂ system. The high pressure breakdown of dolomite + orthopyroxene to magnesite + clinopyroxene is displaced to higher pressures (by 2 kbar) in natural compositions relative to CMS. CO₂. We also find a stability field of magnesian calcite in lherzolite at 15–25 kbar and 750–1000°C.     

苏北盆地建湖隆起碳酸盐岩储层中的硫酸盐型热矿水成因

碳酸盐岩储层中的硫酸盐型热矿水是宝贵的旅游疗养资源。我国苏北盆地北部分布有丰富的热矿水,其中,盱眙县的一口热水井的单井流量达到3 616t·d-1,矿化度(TDS)达到4g·L-1,温度为53.5℃,为优质硫酸盐型热矿水。采用水化学和同位素方法,结合钻孔地质资料,研究了其形成机理。该地区热矿水的SO2-4离子含量较高,部分热矿水的阴离子中SO2-4离子占主导,成为硫酸盐型水。热水的氢氧稳定同位素(δ2 H、δ18 O)值证明了其来源于大气降水。建湖隆起存在石膏层,主要分布在白垩系浦口组,该组属盐湖相沉积,发育大范围的含膏质泥岩,其中石膏、硬石膏含量较多。根据水样的Sr/Ca摩尔比,该区热水中的硫酸盐来源于石膏的溶解。基于碳酸盐岩热水的pH值和SI值、14 C含量等数据的分析,排除了硫酸盐型热矿水的形成与金属矿的风化或氧化的关系,认为是石膏或硬石膏溶解形成。     

Thermodynamic stability of CoOOH and its coprecipitation with manganese

A precipitate of cobalt oxyhydroxides formed by bubbling oxygen through a dilute solution of Co(NO₃)₂ held at pH 9.0 and 25°C was aged for 23 months in contact with the original solution, with access to atmospheric oxygen. Co₃O₄ and CoOOH were identified in the precipitate by X-ray diffraction. Chemical equilibria involving these solids were evaluated by measurements of solution pH and Co²⁺ activities and by redox potential measurements and gave a $\text{ΔG}{}_{\mathrm{coOOH}}{}^0$ of $\text{?92.3 ± 0.5 kcal/mole}$. This value and other thermodynamic data show relative feasibility of hypothetical reaction steps and changes in reaction paths during automated coprecipitation titrations and subsequent aging of a precipitate that finally contained βMnOOH, MnO₂ (birnessite) and CoOOH.