黔西南微细浸染型金矿带中金锑共生分异的物理化学条件研究

黔西南微细浸染型金矿带成矿热液中金可能主要以Au(HS) ₂^-形式迁移,锑则主要以Sb(OH)₃⁰形式迁移。随着成矿热液系统物理化学条件的改变,从成矿前阶段、热液主成矿阶段至晚成矿阶段,金、锑络合物在热液中的沉淀经历了共生、初始分异至分异的富集演化阶段。物理化学条件改变是导致金、锑共生分异的重要因素。     

陕西省桐峪金矿床成矿流体研究

桐峪金矿床位于华北地台南缘小秦岭金矿带的西段。矿体多呈薄板状、脉状和透镜状产出。赋矿围岩为太古代太华群变质岩系。围岩蚀变主要有绢云母化、硅化、碳酸盐化等。文章对该矿床的流体包裹体进行了岩相学研究,并开展了显微测温、流体成分及氢、氧同位素测试,模拟估算了密度、压力、深度。结果表明,第Ⅰ、Ⅱ、Ⅲ阶段流体包裹体的均一温度、盐度分别为:280~360℃,3%~11%;190~330℃,3%~15%;150~290℃,1%~11%。包裹体液相成分中阳离子以Na⁺、K⁺、Ca²⁺为主,阴离子以Cl^-为主,SO₄^2-次之;气相成分以H₂O、CO₂和N₂为主,含少量O₂、CH₄。流体为弱还原性。成矿温度属中(高)温,低盐度,成矿压力为78~220 MPa,成矿深度大约为3~8 km。包裹体水的δD_V-SMOW值为-44.4‰~-81.8‰,δ¹⁸O_水值为0.01‰~6.65‰。成矿流体成矿初期为岩浆水或者混有少量变质水的混合水,成矿后期有大气降水的混入。Au在成矿流体中主要是以Au(HS)₂^-的形式进行迁移,其次为Au₂S(HS)₂^2-。     

黔西南丫他金矿矿化过程中元素迁移特征研究

黔西南册亨县丫他金矿是扬子地块西南缘右江盆地中的重要卡林型金矿之一,产于三叠系巨厚的裂陷槽盆相复理石建造碎屑岩相区中。矿体受控于褶皱断裂带,其形态、规模、产状受高角度断裂带控制。根据典型矿物蚀变组合,可划分三个成矿阶段：铁白云石-黄铁矿阶段、白云石-黄铁矿-似碧玉岩-多金属矿物阶段以及毒砂-雌雄黄-方解石-石英阶段。本文为探究丫他金矿成矿过程中元素的迁移特征,通过采集不同矿化程度的样品,采用Isocon图解法对元素质量平衡进行了定量计算,结果显示在成矿作用过程中,伴随着持续的SiO₂含量升高以及CaO含量的降低,指示硅化与去碳酸盐化与成矿关系密切;K₂O和TFe₂O₃含量虽有变化但过程中有所波动,表现为载金矿物黄铁矿与黏土矿物的沉淀;TiO₂和Al₂O₃含量在各个阶段岩石中变化不大,且显示出较高的平均值。与金矿化密切相关的微量元素是As、Sb、W、Hg、Ag、Cu、Zn、Tl,随着成矿流体通过与围岩的相互作用成矿过程中发生迁移,在金以Au(HS)⁰或是Au(HS)^2-络合物形式进入含砷黄铁矿晶格中的同时沉淀黄铜矿、闪锌矿、硫砷锑汞矿等其他金属矿物。     

四川东北寨微细浸染型金矿床成矿物理化学条件和成矿过程分析

东北寨金矿床是产于碳酸盐岩一碎屑岩建造中的微细浸染型（卡林型）金矿床。矿化严格受控于垮石崖断裂下盘富含有机质和成岩黄铁矿的黑色岩系地层。包裹体研究和热力学计算表明，成矿温度为220—120℃，压力为4.05×10⁷—3.04 ×10⁷pa，形成深度小于2km。成矿流体具弱酸一弱碱性、还原性较强和Cl-活度较低等特点。矿源层中的金以硫氢络合物Au(HS)₂^-形式活化进入溶液，促使金沉淀富集的机制是溶液中总硫活度的降低、氧逸度的下降和有机质的还原吸附作用等。矿床形成包括四个阶段。     

广东省顺德肝癌多发区病因探讨

根据顺德肝癌病多发区与周边正常区土壤、水地球化学特征对比,结合病区人文景观探讨顺德肝癌病因,分析认为病区水中NH₄⁺, NO₂^-, NO₃-的显著异常(高含量)是主要病因。     

贵阳市区地表/地下水化学与锶同位素研究

贵阳市及邻近地区地表和地下水的化学与Sr同位素组成变化反映了典型喀斯特地区地表/地下水文系统的水-岩反应和城市污染特征:水体中的化学溶解物质主要来源于碳酸盐岩(石灰岩和白云岩)的风化作用和膏岩层的溶解,其次为人为污染物的输入;污染物以K⁺,Na⁺,Cl^-,SO^2-₄,NO^-₃为主,枯水期因大气降水补给小而受人为活动影响较大;丰水期和枯水期地表/地下水的化学组成变化说明地表/地下水交换活跃,地下水环境容易受到人为活动影响。     

滇西老王寨金矿床黄铁矿形貌特征与化学组成

老王寨金矿床是三江特提斯成矿域中已探明规模最大的造山型金矿床,黄铁矿是其最主要的载金矿物,依据矿(化)脉切割关系、矿石结构构造及矿物共生组合,该矿床成岩-成矿期共发育5个世代黄铁矿。沉积-成岩期草莓状黄铁矿含Pb、Zn、Mn、Co、Ni和Bi。热液金成矿期可划分为:Ⅰ石英-绢云母-黄铁矿、Ⅱ石英-多金属硫化物、Ⅲ方解石-石英-毒砂-黄铁矿和Ⅳ方解石-石英-辉锑矿-黄铁矿四个阶段,其黄铁矿分别以粗粒他形、立方体、五角十二面体和立方体为主,总体继承了沉积-成岩期黄铁矿含Pb、Zn、Mn、Co、Ni和Bi的特征,Au、As、Sb和Cu也有不同程度富集,显示成矿流体成分复杂。Ⅲ阶段为金的主成矿阶段,以发育五角十二面体黄铁矿为特征,富集Au、As、Sb、Pb、Zn、Cu、Co、Ni和Bi,其中,Au与As构成 [Au, As]^2-和[Au(As, S₃)]^2-等络合物以类质同象的形式替代[S²]^2-而进入到黄铁矿中,两者呈正相关,成矿系统处于中-低温、流体过饱和度(硫逸度)高,且缓慢冷却,矿质来源充足的环境。     

对下庄矿田沥青铀矿形成机理的认识

本文在分析下庄矿田成矿地质背景的基础上,对该矿田成矿热水溶液中铀的存在形式、铀酰络合物的氧化还原临界电位值和水-铀比电位值进行了计算。计算结果表明,成矿热液中,铀的迁移形式为UO₂(CO₃)₂^2-、UO₂F^3-和UO₂F₄^2-,其Ehcu和Ehw,u值分别为-0.18 ~0.46 V和-0.44~ -0.5 eV。CO₂和F^-, 是铀成矿的主要矿化剂。沥青铀矿是在地壳处于拉张环境,水-铀比电位值小于零的条件下形成的。     

吉林省海沟石英脉型金矿床流体包裹体特征及地质意义

海沟金矿床地处夹皮沟-海沟成矿带东南端,为典型的石英脉型金矿。该矿床产于海西期花岗杂岩体中,由多条含金石英脉组成。成矿过程可分为4个阶段:Ⅰ. 钾长石-石英脉阶段;II. 乳白色石英-(少)黄铁矿-(少)金阶段;III. 多金属硫化物-石英-金阶段;IV. 碳酸盐-石英-黄铁矿阶段。流体包裹体研究表明,海沟金矿各阶段流体包裹体存在一定差异,早期成矿阶段(第Ⅱ阶段)以H₂O-NaCl包裹体(Ⅰ类)为主,偶见含子晶包裹体(Ⅳ类);主成矿阶段(第Ⅲ阶段)以CO₂-H₂O-NaCl包裹体(II类)为主,并含有少量纯CO₂包裹体(III类);成矿后阶段(第Ⅳ阶段)以H₂O-NaCl包裹体(Ⅰ类)为主。早期成矿阶段、主成矿阶段、成矿后阶段均一温度范围分别为227~497℃、189~427℃、130~267℃,对应盐度分别为0.53%~10.23% NaCleqv、0.35%~9.23% NaCleqv、0.18%~3.27% NaCleqv。早期成矿阶段和主成矿阶段包裹体均一温度、盐度相对较高,成矿后阶段包裹体均一温度、盐度明显降低;在空间上,主成矿阶段矿床深部包裹体的盐度较矿床浅部偏高。拉曼和气相色谱结果显示,包裹体气相成分以H₂O、CO₂、N₂、CH₄、C₂H₆为主,并含有少量H₂S,成矿流体为低盐度的H₂O-CO₂-NaCl±CH₄流体;包裹体液相离子成分主要为Na⁺、K⁺、Ca²⁺、Cl^-,个别包裹体中含有少量Mg²⁺、F^-离子。主成矿阶段不同类型、不同相比包裹体均一温度相近,显示不混溶特征。流体减压引起的不混溶作用可能是海沟金矿金沉淀的主要原因。     

5 12矿床成矿的地球化学条件分析

通过对伊犁512矿床成矿的物理化学条件分析,可知蚀源区的各类火山岩及盆地侏罗系砂岩和灰黑色泥岩是本矿床的铀源,含铀地下水是层间氧化带型铀矿床的成矿流体。由PHREEQC l.5地球化学模式程序计算得知,成矿流体中铀主要以UO_{2 (CO3);、UO2 ( CO3)3^4-的形式迁移,而有机质、黄铁矿对铀的还原沉淀作用及水解产物高岭土、伊利百对铀的吸附沉淀作用导致铀矿体产于层间氧化带的氧化还原过渡亚带。形成层间氧化带型铀矿床的决定性因素不是水中铀的含量,而是成矿时的地球化学条件。}     

中国微细浸染型金矿矿质迁移沉淀机制

本文在分析矿源和成矿物化条件基础上,化理论计算和研究,提出中国微细浸染型金矿中金是呈Ａｕ（ＨＳ）２＾－形式存在阀迁移的,矿质沉淀的主要机理为温度下降和因硫化物沉淀而引起的决硫（及还原硫）活度下降,其次为压力的下降和有机质的还原吸附作用。     

A spectrophotometric study of aqueous Au(III) halide-hydroxide complexes at 25-80 °C

The mobility and transport of gold in low-temperature waters and brines is affected by the aqueous speciation of gold, which is sensitive in particular to pH, oxidation and halide concentrations. In this study, we use UV-Vis spectrophotometry to identify and measure the thermodynamic properties of Au(III) aqueous complexes with chloride, bromide and hydroxide. Au(III) forms stable square planar complexes with hydroxide and halide ligands. Based on systematic changes in the absorption spectra of solutions in three binary systems NaCl-NaBr, NaCl-NaOH and NaBr-NaOH at 25 °C, we derived log dissociation constants for the following mixed and end-member halide and hydroxide complexes: [AuCl₃Br]⁻, [AuCl₂Br₂]⁻, [AuBr₃Cl]⁻ and [AuBr₄]⁻; [AuCl₃(OH)]⁻, [AuCl₂(OH)₂]⁻, [AuCl(OH)₃]⁻ and [Au(OH)₄]⁻; and [AuBr₃(OH)]⁻, [AuBr₂(OH)₂]⁻ and [AuBr(OH)₃]⁻. These are the first reported results for the mixed chloride-bromide complexes. Increasing temperature to 80 °C resulted in an increase in the stability of the mixed chloride-bromide complexes, relative to the end-member chloride and bromide complexes. For the [AuCl_(4−n)(OH)_n]⁻ series of complexes (n = 0-4), there is an excellent agreement between our spectrophotometric results and previous electrochemical results of Chateau et al. [Chateau et al. (1966)]. In other experiments, the iodide ion (I⁻) was found to be unstable in the presence of Au(III), oxidizing rapidly to I₂(g) and causing Au to precipitate. Predicted Au(III) speciation indicates that Au(III) chloride-bromide complexes can be important in transporting gold in brines with high bromide-chloride ratios (e.g., >0.05), under oxidizing (atmospheric), acidic (pH < 5) conditions. Native gold solubility under atmospheric oxygen conditions is predicted to increase with decreasing pH in acidic conditions, increasing pH in alkaline conditions, increasing chloride, especially at acid pH, and increasing bromide for bromide/chloride ratios greater than 0.05. The results of our study increase the understanding of gold aqueous geochemistry, with the potential to lead to new methods for mineral exploration, hydrometallurgy and medicine.     

Speciation of gold in hydrosulphide-rich ore-forming fluids: Insights from first-principles molecular dynamics simulations

To shed light on gold speciation in sulfur-containing ore-forming fluids, we perform first principles molecular dynamics (FPMD) simulations to investigate gold-hydrosulphide complexing under representative geological conditions. With this advanced technique, the electronic structures of solutes and solvents are calculated with density functional theory and the thermal motions are sampled with molecular dynamics. The molecular structures, solvated structures and stabilities of possible complexes are characterized in detail and the following insights have been gained. (1) The previously hypothesized species Au(HS)(H₂S)₃ and Au(HS) are found unstable under ore-forming conditions. Au(HS)(H₂S)₃ would dissociate to LAu(HS) (L = H₂S or H₂O) and free H₂S molecules spontaneously. Au(HS) is highly reactive and tends to capture a second ligand to form a double-coordinated complex. (2) In the thin vapor-like phases of low pressures, the stable complexes include Au(HS)(H₂O), Au(HS)(H₂S) and Au(HS)₂⁻ and their relative stability is Au(HS)₂⁻ > Au(HS)(H₂S) > Au(HS)(H₂O). In dense aqueous phases of high pressures, Au(HS)(H₂S) would spontaneously deprotonate to Au(HS)₂⁻ and thus Au(HS)(H₂O) and Au(HS)₂⁻ are the stable forms. All of these complexes can retain to the upper-limit of ore-forming temperatures. (3) The gold ions in the complexes do not favor coordinating more molecules and therefore the solvations happen mainly through H-bonding interactions between the ligands and environmental waters. H-bonds are found in vapor, liquid, and dense supercritical phases, whereas in the thin supercritical phase the hydration is very weak. These results provide quantitative and microscopic basis for understanding the speciation of gold in hydrothermal fluids.     

新疆南天山阿沙哇义金矿床的成因与找矿启示:来自流体和硫化物成分的限定

阿沙哇义金矿位于中国新疆南天山造山带,属于著名的中亚南天山锑-汞-金成矿带的东延部分。该矿床严格受断裂所控制,以浸染状黄铁矿化、毒砂化为特征。矿化可分为三个阶段:早期无矿或贫矿石英阶段,中期石英多金属硫化物阶段,晚期石英-碳酸盐阶段。其中,中期是主要成矿阶段。成矿流体气相成分以H_2O为主,摩尔含量为75%～93%,其次为CO_2,摩尔含量为6%～25%,其余为CH_4、C_2H_6、H_2S、N_2和Ar;液相成分阳离子以Na~+为主,含少量K~+、Ca~(2+)离子,阴离子以Cl~-为主,SO~(2-)次之;矿石的Au含量与其流体的CO_2含量呈反相关,与K~+含量呈正相关。硫化物成分分析结果表明:(1)围岩地层和矿石中的黄铁矿和毒砂是重要的载金矿物,黄铁矿Au含量为0～0. 09%,平均值0. 03%;毒砂Au含量为0～0. 28%,平均值0. 07%;(2)黄铁矿和毒砂Au含量与其自形程度没有明显的相关性;(3)环带状黄铁矿较均质结构黄铁矿具有更高的Au含量;(4)岩体中的黄铁矿几乎不含Au。在成矿构造环境、成矿流体特征及演化、金矿富集机制、成矿温压条件等方面,该矿床与世界上大多数造山型金矿显示出一致性,成矿类型应属于剥蚀程度较浅的造山型金矿。断层阀作用控制的断层愈合-破裂导致的流体不混溶作用是本区金富集、沉淀的最重要机制,但流体混合机制对金的富集沉淀也发挥了作用。黄铁矿、毒砂发育及较多的含炭物质三者共存是本区寻找富矿的关键标志。     

Transport and Concentration of Gold in Metamorphic—hosted Reworked Gold Deposits,China

Calculations based on the available thermodynamic data of AuCl ₂ ⁻ and Au (HS) ₂ ⁻ indicate that AuCl ₂ ⁻ is responsible for the transport and enrichment of gold during the stage of pre-concentration in the source bed while Au (HS) ₂ ⁻ is the main gold species involved in the formation of gold deposits in response to hydrothermal reworking. Acid chloride solutions witha _Cl ⁻ > 10° and sulfur-rich solutions with a_Σs in excess of 10⁻² are held as important criteria for gold enrichment in the source bed and for the formation of gold deposits by subsequent hydrothermal event, respectively.     

Thermodynamic study of the association and separation of copper and gold in the Shizishan ore field, Tongling, Anhui Province, China

The Shizishan ore field is the largest gold–copper ore field in the Tongling ore district of Anhui Province, China. Copper and gold deposits in the district are present as one-commodity deposits or as deposits with both commodities. Copper and gold mineralization are either cogenetic or are temporally and spatially distinct. We present the results of systematic geochemical analysis of fluid inclusions from typical Au–Cu deposits in the Shizishan ore field; these data are used to determine the solubility of Cu and Au in the ore-forming fluids and to ascertain the mechanisms and factors that controlled variations in the association and separation of copper and gold mineralization. Our results indicate that copper in the ore-forming fluids was transported as CuCl₂⁻ and CuCl⁰ complexes and that the solubility of copper was controlled by variations in Cl⁻ concentration. In addition, the precipitation of copper was controlled by changes in temperature, pH, fO₂, and fO₂. In comparison, gold in the ore-forming fluids was transported as Au(HS)₂⁻ and Au₂S(HS)₂²⁻ complexes, and the solubility of gold was controlled by variations in total sulfur concentration; the precipitation of gold was controlled by temperature, pH, fO₂, and fO₂. These differences between the two elements meant that copper and gold in the ore-forming fluids responded in different ways to changes in physicochemical conditions. Copper precipitated under relatively acidic conditions at high temperatures, while gold precipitated under weakly alkaline conditions at relatively low temperatures; this dissociation resulted in the temporal and spatial separation and zonation of copper and gold mineralization in the Shizishan ore field.     

Arsenic as an indicator element for gold exploration in the region of the Xiangxi Au–Sb–W deposit, NW Hunan, PR China

The Xiangxi Au–Sb–W deposit, the largest of its type in northwestern Hunan, China, is a sulfide-dominated ore body hosted by low grade metamorphic red slates of the Neoproterozoic Madiyi Formation. Three stages of mineralization, quartz–scheelite, quartz–gold–pyrite, quartz–gold–stibnite, and one metal-barren stage of veining, quartz–calcite, are recognized. Arsenopyrite occurs only as a minor mineral phase in the second stage. Analyses for 21 trace elements show that the enrichment factors of As in the metal deposit (EC [=element concentration of sample/average content of an element in the upper crust]: 190; 43 samples) in ore veins and in the Guanzhuang and Yuershan reference sections (3.7 km and 2.7 km away from the Xiangxi mine, EC: 3.5; 96 samples) are much smaller than those of Sb (52855 [in ore veins], 117 [in the sections]), W (5665, 7.5) and Au (2727, 5.3). The background concentrations of Au and As in the two sections were 1.4 ppb and 1.4 ppm, respectively. Arsenic (with an anomaly coefficient [AC = number of anomalous samples/total number of samples] of 76%) forms a larger geochemical halo than W (AC: 8%) and Au (AC: 32%). Gold and As in the deposit were transported mainly as metal complexes such as Au(HS)⁻₂, H_nAs₃S⁻⁽³⁻ⁿ⁾₆ (n=1, 2 or 3) and HAsS⁰₂. Au(HS)⁻₂ is rapidly precipitated by a geochemical oxidation barrier — the red slates of the Madiyi Formation. As–S complexes in the stratigraphic horizon can be transformed into As–O complexes (e.g., H₃AsO⁰₃) under oxidizing conditions, and are continuously transported. Therefore, they can be widely distributed in the red slate units, thus forming extensive geochemical haloes, so that As can be used as an indicator element for Au exploration in the Xiangxi region.     

Mineralogy and geochemistry of gold-bearing arsenian pyrite from the Shuiyindong Carlin-type gold deposit, Guizhou, China: implications for gold depositional processes

Arsenian pyrite in the Shuiyindong Carlin-type gold deposit in Guizhou, China, is the major host for gold with 300 to 4,000 ppm Au and 0.65 to 14.1 wt.% As. Electron miroprobe data show a negative correlation of As and S in arsenian pyrite, which is consistent with the substitution of As for S in the pyrite structure. The relatively homogeneous distribution of gold in arsenian pyrite and a positive correlation of As and Au, with Au/As ratios below the solubility limit of gold in arsenian pyrite, suggest that invisible gold is likely present as Au¹⁺ in a structurally bound Au complex in arsenian pyrite. Geochemical modeling using the laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) analysis of fluid inclusions for the major ore forming stage shows that the dominant Au species were Au(HS)₂⁻ (77%) and AuHS_(aq)⁰ (23%). Gold-hydroxyl and Gold-chloride complexes were negligible. The ore fluid was undersaturated with respect to native Au, with a saturation index of −3.8. The predominant As species was H₃AsO₃⁰ _(aq). Pyrite in the Shuiyindong deposit shows chemical zonation with rims richer in As and Au than cores, reflecting the chemical evolution of the ore-bearing fluids. The early ore fluids had relatively high activities of As and Au, to deposit unzoned and zoned arsenian pyrite that host most gold in the deposit. The ore fluids then became depleted in Au and As and formed As-poor pyrite overgrowth rims on gold-bearing arsenian pyrite. Arsenopyrite overgrowth aggregates on arsenian pyrite indicate a late fluid with relatively high activity of As. The lack of evidence of boiling and the low iron content of fluid inclusions in quartz, suggest that iron in arsenian pyrite was most likely derived from dissolution of ferroan minerals in the host rocks, with sulfidation of the dissolved iron by H₂S-rich ore fluids being the most important mechanism of gold deposition in the Shuiyindong Carlin-type deposit.