含金络合离子[Au（Sb2S4）]^—在高岭石表面吸附的量子化学研究

用离散变分Xa量子化学计算方法，研究了络合离子[Au(Sb2S4)]^-吸附在粘土矿物高岭石晶体边缘时，它们之间的化学键性质。根据所选用的络合离子[Au(Sb2S4)]^-处于基面及侧面不同位置的10个模型的计算结果，表明当络合离子[Au(Sb2S4)]^-位于高岭石晶片的侧面时，比其位于基面时更为稳定，而且与高岭石晶片侧面中的O形成共价键。     

含金络合离子-在高岭石表面吸附的量子化学研究

用离散变分X-α量子化学计算方法,研究了络合离子-吸附在粘土矿物高岭石晶体边缘时,它们之间的化学键性质.根据所选用的络合离子-处于基面及侧面不同位置的10个模型的计算结果,表明当络合离子-位于高岭石晶片的侧面时,比其位于基面时更为稳定,而且与高岭石晶片侧面中的O形成共价键.     

43～17ka川东北石笋234U/238U变化及其意义初探

铀(U)是自然界中最重的天然元素.U的价态随氧化-还原条件的变化而变化:在还原环境下多形成难溶于水的+4价铀离子沉淀[2]而在氧化环境中多形成易溶于水的+6价铀酰离子[UO2]2+随溶液迁移[2],并易与碳酸根离子(CO32-)、磷酸根离子(PO43-)和氟离子(F-)形成络合离子[1].岩溶地下水由于具有较高的CO2分压(pCO2)和pH值,铀酰离子主要以碳酸根离子络合态的形式存在[2.3].在表生环境下,土壤氧化还原状态(Eh)与土壤水分含量密切相关,水分含量降低有利于氧化环境形成和土壤Eh上升,因而有利于U的迁移.     

小秦岭西南段金矿床的地球化学研究

本文简要叙述了金成矿的地质条件和地球化学特征 ,主要阐述了金的来源、迁移和沉淀机制及矿床成因。研究表明 ,金大部分来源于周围变质岩层 ,小部分由燕山期花岗岩和基性岩脉提供 ;成矿介质热液以岩浆期后热液为主 ,还有少量的大气降水的加入 (或变质岩的粒间溶液 ) ;矿化剂如 Cl-,CO2 ,S2 -多数来源于基性岩脉或上地幔汁 ,少数由地层本身提供。金在成矿早阶段几乎都呈 [Au Cl2 ]-形式迁移 ;在成矿中阶段主要呈 [Au(HS) 2 ]-形式迁移 ;在成矿晚阶段大部分呈 [Au2 (HS) 2 S]2 -形式迁移。金主要是由于含金热液在从封闭系统转化为开放系统时降压沸腾而沉淀富集的     

大兴安岭北段三道湾子碲金型矿床的原生晕分带及意义

三道湾子金矿位于大兴安岭燕山期成矿带东南部,属于典型的富碲贫硫石英脉型金矿。以此为例,研究了该类矿床矿床原生晕的分布特征,并采用格里戈良分带指数的改进方法计算了原生晕轴向分带序列和分带指数,目的是揭示该类矿床的勘查地球化学特征,并为该矿区进一步找矿指明方向。研究结果表明,原生晕轴向分带序列为:Mo-Sb-Pb-As-Bi-W-Zn-Ag-Cu-Hg-Te-Au。[w(As)·w(Sb)]/[w(Au)·w(Zn)]、[w(Sb)·w(Mo)]/[w(Au)·w(Zn)]、[w(As)·w(Sb)·w(Mo)]/[w(Au)·w(Cu)·w(Zn)]等分带性指数指示主成矿元素Au、Ag在130中段下方异常形态尚未封闭,Ⅰ号矿体深部仍有找矿的潜力,矿石品位会有所降低。     

黝铜矿-砷黝铜矿矿物学研究进展

黝铜矿-砷黝铜矿系列矿物(Tetrahedrite -Tennantite Series Mineral,TTSM)作为含Cu、Ag、S、Sb、As、Hg及少量Au、Fe、Zn、Cd、Bi、Te、Se的硫盐矿物广泛存在于世界各地的Cu、Ag、Au、Pb、Zn多金属矿床中.为了能够更好的认识该系列矿物,提高矿物中有用元素的回收率,扩大黝铜矿型铜矿床的经济效益,本文对TTSM的化学组成和类质同象置换规律,晶胞参数和晶体结构的形变,矿物人工合成和有用元素的浸出试验等研究进展进行了综述.天然TTSM矿物一般化学式为:(Cu,Ag)6 Cu4 (Fe,Zn,Cu,Hg,Ag,Cd)2 (Sb,As,Bi,Te)4 (S,Se)13,其中S-Se、Sb-As-Bi-Te、Ag-Cu、Cu-Hg-Fe-Pb-Zn-Cd的类质同象置换相当普遍;TTSM晶体结构中不同结构位置离子置换规律更多的受限于离子价键,而同一结构位置不同离子的置换除受限于离子价键还受限于该位置空间大小,晶胞参数与离子置换类型和数量密切相关;人工合成实验证实形成TTSM矿物的温度范围为350～540℃,浸出试验证明随反应温度增高、浸出浓度增大、矿物颗粒减小时,TTSM中有用元素的浸出速率增大.     

Study on the evolution of ore-formation fluids for Au-Sb ore deposits and the mechanism of Au-Sb paragenesis and differentiation in the southwestern part of Guizhou Province, China

Ore deposits (occurrences) of Au, As, Sb, Hg, etc. distributed in Southwest Guizhou constitute the important portion of the low-temperature metallogenic domain covering a large area in Southwest China, with the Carlin-type Au and Sb deposits being the most typical ones. In this paper the Au and Sb ore deposits are taken as the objects of study. Through the petrographic analysis, microthermomitric measurement and Raman spectrophic analysis of fluid inclusions in gangue minerals and research on the S and C isotopic compositions in the gold ore deposits we can reveal the sources of ore-forming materials and ore-forming fluids and the rules of ore fluid evolution. Ore deposits of Au, Sb, etc. are regionally classified as the products of ore fluid evolution, and their ore-forming materials and ore fluids were probably derived mainly from the deep interior of the Earth. Fluid inclusion studies have shown that the temperatures of Au mineralization are within the range of 170-361℃,the salinities are 0.35 wt%-8 wt% NaCl eq.; the temperatures of Sb mineralization are 129.4-214℃ and the salinities are 0.18 wt%- 3.23 wt% NaCl eq.; the ore-forming fluid temperatures and salinities tend to decrease progressively. In the early stage (Au metallogenic stage) the ore-forming fluids contained large amounts of volatile components such as CO2, CH4, N2 and H2S, belonging to the H2O-CO2-NaCl fluid system; in the late stage (Sb metallogenic stage) the ore-forming fluids belong to the Sb-bearing H2O-NaCl system. The primitive ore-forming fluids may have experienced at least two processes of immiscibility: (1) when early ore-bearing hydrothermal solutions passed through rock strata of larger porosity or fault broken zones, CO2, CH4, N2 would escape from them, followed by the release of pressure, resulting in pressure release and boiling of primitive homogenous fluids, thereafter giving rise to their phase separation, thus leading to Au unloading and mineralization; and (2) in the late stage (Sb metallogenic stage ) a large volume of meteoric water was involved in the ore-forming fluids, leading to fluid boiling as a result of their encounter, followed by the drop of fluid temperature. As a result, the dissolubility of Sb decreased so greatly that Sb was enriched and precipitated as ores. Due to differences in physic-chemical conditions between Au and Sb precipitates, Au and Sb were respectively precipitated in different structural positions, thus creating such a phenomenon of Au/Sb paragenesis and differentiation in space.     

贵州三都苗龙金-锑矿床金赋存状态初步探讨

采用电子探针和扫描电镜分析,通过对贵州苗龙卡林型金-锑矿床矿石中不同成矿阶段载金矿物的Au、As、S、Fe和Sb等元素含量及其分布规律的详细研究,确定了含砷环带黄铁矿和毒砂是最重要的载金矿物。成岩期黄铁矿S、Fe含量与理论值接近,成矿期早阶段黄铁矿和主阶段S1亚阶段环带黄铁矿核心S含量与理论值接近,Fe含量具弱亏损的特点;环带黄铁矿外环S、Fe具有弱亏损的特点。沉积成岩期黄铁矿为草莓状,不含As和Sb,金含量低,平均为59×10-6;热液成矿期早阶段黄铁矿颗粒较粗(≥100μm),其As、Sb和Au含量较低,As、Au平均分别为0.205%和275×10-6;热液成矿期主阶段S1亚阶段环带黄铁矿粒度较细(50μm,10~20μm为主),外环As和Au含量高,外环As含量为0.1961%~7.897%,平均为1.4668%;Au含量为40×10-6~905×10-6,平均为429×10-6;Sb含量为0.01%~0.035%,平均为0.0233%。S2亚阶段毒砂具有富硫亏砷等低温热液毒砂特征,Au含量为230×10-6~1400×10-6,平均为643×10-6;Sb含量为0.019%~0.50%,平均为0.087%。晚阶段辉锑矿Au含量较低,平均为237×10-6。Au含量从成岩沉积期一成矿早阶段一成矿主阶段一晚阶段呈低或不含→低→高→低的特点分布。金可能以类质同象形式(固溶体形式)存在于毒砂和黄铁矿晶格中。     

矿物吸附金的实验研究及其在红土型金矿形成中的意义

Au(Ⅲ）－氯化物和Au(Ⅰ)－硫代硫酸盐被蒙脱石、高岭石、伊利石、针铁矿、褐铁矿及黄铁矿的吸附实验研究结果表明，各种矿物对AuCl4^-的吸附作用显著大于Au(S2O3)2^3-，粘土矿物对金的吸附能力，蒙脱石＞高岭石＞伊利石；含铁矿物中，黄铁矿＞针铁矿＞褐铁矿。矿物对金的吸附作用与矿物结构和金的存在形式有关，即受矿物表面基、金组分的稳定性和位阻的影响；天然雨水中所含微量H2O2是Au、黄铁矿等不同矿物氧化－还原的催化剂，可加速地表岩（矿）石的风化氧化过程和Au的溶解与迁移。雨水对红土中的Au具有一定的淋滤浸取能力。红土型金矿形成于富Cl^-、SO4^2-的酸性、氧化的水化学环境，含金黄铁矿等硫化物的氧化不仅直接导致了Au的溶解和酸的释放，而且其反应产物Fe^3 、S2O3^2-等为Au的氧化、溶解和迁移提供了氧化剂和络合剂，并促进Au的溶解和迁移；Au主要以硫代硫酸络合物、氯化络合物及其水合物的形式进行迁移；硫代硫酸根的氧化和风化壳下部的还原作用是导致金络合物失稳、Au被其他矿物吸附和沉淀富集的主要因素。矿物对金的吸附在红土型金矿的形成过程中起了重要作用。     

高岭石对重金属离子的吸附机理及其溶液的pH条件

高岭石对Cu^2+,Pb^2+离子的吸附实验及高岭石的溶解实验表明,高岭石对重金属离子的吸附有别于石英单一表面配位模式,离子交换和表面配位模式并存,并随溶液pH由酸性往碱性的变化发生规律性的演替：pH<6.5时主要表现为外圈层配位的离子交换吸附,且在pH<4时由于受到高岭石表层中铝的高溶出及溶液中较高离子强度的影响,高岭石对Cu^2+,Pb^2+离子的吸附率较低,pH为5～6时由于高岭石端面的荷电性为近中性,吸附率则有明显的提升并且表现为一个吸附平台;pH>6.5时离子交换和表面配位均为重要吸附机制,pH再升高时沉淀机制则起着重要作用。研究表明,pH调控高岭石-水界面溶解与质子化-去质子化反应过程,并影响着Cu^2+,Pb^2+离子的吸附行为。最后采用Sverjensky(1993)表面配位的物理模型对吸附结果作了描述。     

Antimony adsorption on kaolinite in the presence of competitive anions

Antimony (Sb) emissions to the environment are increasing, and there is a dearth of knowledge regarding Sb fate and behavior in natural systems. In natural systems, the presence of competitive anions may compete with Sb for adsorption sites on mineral surfaces, hence increasing its potential bioavailability. Accordingly, the adsorption of Sb(III) on kaolinite was investigated in the presence of competitive anions. Kinetic studies suggest that adsorption reaction of Sb(III) on kaolinite is rapid initially and becoming slow after 12 h both in binary Sb(III)–kaolinite system and in ternary Sb(III)-competitive anion–kaolinite system. The presence of PO₄ ^3? has a much stronger and more obvious promotive effect on the adsorption of Sb(III) on kaolinite compared with the other two anions. The adsorption data of Sb(III) on kaolinite in the absence and presence of competitive anions at three temperatures were successfully modeled using Langmuir (r ² > 0.95) and Freundlich (r ² > 0.95) isotherms. Accompanied the adsorption of Sb(III) on kaolinite, significant oxidation of Sb(III) to Sb(V) had occurred under the experimental conditions used in this study. The presence of kaolinite which has a larger specific surface area could increase the contact area between the adsorbed Sb(III) and oxygen in the bulk solution, which promoted the oxidation rate of Sb(III) to Sb(V).     

Dualistic distribution coefficients of elements in the system mineral-hydrothermal solution. II. Gold in magnetite

The system magnetite-Au-hydrothermal solution was employed to continue studying the distribution coefficients of trace elements in system with real crystals. The role of surface nonautonomous phase (NP) is elucidated. The distribution coefficient of an Au structural admixture between magnetite and hydrothermal solution at the experimental conditions [450°C, 1 kbar (100 MPa), and fluid sampling by a trap] is, according to the most representative data, 1.0 ± 0.3, and Au is thus not an incompatible element in magnetite, in contrast to pyrite and arsenopyrite [1], minerals for which this coefficient is much lower than one. The NP is enriched in Au with respect to the rest of the crystal by a factor of more than 4000, and this results in an one order of magnitude increase in the bulk distribution coefficient. Similar to pyrite, the reason for the dualistic nature of the distribution coefficient is the presence of an NP, which contains ∼2000 ± 500 ppm Au. The NP occupies the approximately 330-nm surface layer of the crystal, and the chemically bound Au [Au(III), according to XPS data] admixture is evenly distributed with depth within the layer, which is the reason for the strongly determinate dependences of the concentrations of the evenly distributed Au admixture on the size and specific surface area of the crystal. The occurrence of an NP is controlled by the chemistry of the system. The partial substitution of Fe for Mn and the synthesis of a phase close to jacobsite MnFe₂O₄ results in the disappearance of both the NP itself and the size dependence of the Au concentration. The XPS spectra of O 1s and Fe 2p are used to analyze two models: (i) a single goethite-like (O²⁻/OH⁻∼ 1) phase of variable composition and Fe in more than one valence state and (ii) a heterogeneous structure of alternating domains of wuestite- and goethite-like NP. The reason for the “excess” admixture in the former instance can be vacancies at Fe sites, whereas that in the latter one is the interaction of the admixture with nanometer-in-size nanometer in-size strained domains on the surface of the crystal.     

副硫锑钴矿(CoSbS)的晶体结构

副硫锑钴矿是硫锑钴矿(CoSbS)的一个同质多象变体。1970年由卡布里(L. J. Cabri)等人发现于加拿大安大略州,他们对该矿物进行了化学分析及X射线粉晶分析等研究。测得该矿物属斜方晶系,a=5.764,b=5.952,c=11.635,空间群为Pbca,Z=8。     

胶东西北部仓上金矿床上盘围岩蚀变和黄铁矿标型特征研究

上盘围岩是矿床钻探过程中首先遇到的围岩,研究其蚀变特征具有重要的找矿指导意义。对胶东西北部露天开采的仓上金矿床的详细研究表明,上盘围岩蚀变以绿泥石化为主,蚀变分带自远矿端到近矿端依次为方解石绿泥石化带、赤铁矿绿泥石化带、绿帘石化带和绢英岩化带。黄铁矿的形态、成分和热电性标型显示,成矿过程中上盘围岩提供了丰富的Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｐｂ、Ｚｎ和Ａｕ、Ｐｔ等。上盘围岩的近矿标志是绢英岩化增强,黄铁矿的｛１００｝＋｛２１０｝增多,Ｓ、Ｃｕ、Ｐｂ、Ｚｎ和Ａｕ、Ｐｔ增高,Ｓ／Ｆｅ离子比和ｗ（Ｃｏ＋Ｎｉ）／ｗ（Ａｓ＋Ｓｂ）降低,Ｐ型黄铁矿出现率增高,蚀变岩的金含量增高。     

黄铁矿与石英含金机理探讨

从晶体结构化学角度出发，分析了金的电子结构及性质、黄铁矿晶体结构特点、二氧化硅的电子结构特点和石英晶体表面特征；探讨了Au^＋和Au^－离子形式分别替代Fe^2 离子和S^2-离子的形成机理以及以可见金方式在黄铁矿中的赋存机制；认为金在黄铁矿中的富集主要与其晶体结构有关，特别是与黄铁矿中Fe-S，S-S，Au-S和Fe-Au键的电子结构特点有关；应用稳定配合物的18电子规则和晶体生长的界面相模型探讨了石英含金机理；研究表明，石英含金不仅与石英表面的结构、内部缺陷和表面特征有关，还与石英生长的环境有关，尤其是与石英表面键的电子结构特点有关，并主要受石英晶体生长过程中的界面相的控制。     

红土型金矿的成矿机理与成矿模式

对红土型金矿的地质特征，主要控矿因素，金的溶解迁移与沉淀富集机理进行了分析。红土型金矿风化壳剖面具有分带性，金矿体主要呈层状，似层状产于铁（硅铝）质硬壳层，杂色粘土层中。金以自然金为主，主要呈显微，次显微状被褐铁矿，蒙脱石，高岭石及伊利石等矿物所吸附，金的成色较高。红土型金矿的形成受干，湿交替的热带，亚热带气候控制，并与基底构造（特别是断裂构造0密切相关。金主要以AuCl4^-,Au(S2O3)2^3-等络合的溶解和迁移,还原作用是金沉淀富集的重要因素。建立了红土型金矿的综合成矿模式。     

The iron-nickel-phosphorus system: Effects on the distribution of trace elements during the evolution of iron meteorites

To better understand the partitioning behavior of elements during the formation and evolution of iron meteorites, two sets of experiments were conducted at 1 atm in the Fe-Ni-P system. The first set examined the effect of P on solid metal/liquid metal partitioning behavior of 22 elements, while the other set explored the effect of the crystal structures of body-centered cubic (α)- and face-centered cubic (γ)-solid Fe alloys on partitioning behavior. Overall, the effect of P on the partition coefficients for the majority of the elements was minimal. As, Au, Ga, Ge, Ir, Os, Pt, Re, and Sb showed slightly increasing partition coefficients with increasing P-content of the metallic liquid. Co, Cu, Pd, and Sn showed constant partition coefficients. Rh, Ru, W, and Mo showed phosphorophile (P-loving) tendencies. Parameterization models were applied to solid metal/liquid metal results for 12 elements. As, Au, Pt, and Re failed to match previous parameterization models, requiring the determination of separate parameters for the Fe-Ni-S and Fe-Ni-P systems.Experiments with coexisting α and γ Fe alloy solids produced partitioning ratios close to unity, indicating that an α versus γ Fe alloy crystal structure has only a minor influence on the partitioning behaviors of the trace element studied. A simple relationship between an element’s natural crystal structure and its α/γ partitioning ratio was not observed. If an iron meteorite crystallizes from a single metallic liquid that contains both S and P, the effect of P on the distribution of elements between the crystallizing solids and the residual liquid will be minor in comparison to the effect of S. This indicates that to a first order, fractional crystallization models of the Fe-Ni-S-P system that do not take into account P are appropriate for interpreting the evolution of iron meteorites if the effects of S are appropriately included in the effort.