辽吉成矿带热液型铅锌矿床矿物组合共生分异的热力学制约——以岫岩红旗铅锌矿床为例

辽吉成矿带上广泛分布着热液型铅锌矿床,对于该类型矿床中矿物共生组合特征和成矿物质迁移沉淀机制的研究是矿床学研究的核心问题之一。通过共生矿物热力学平衡的相关计算,绘制热力学lg[Cu2+]-pH、lg[HS−]-pH和Eh-pH相图,可以有效地诠释成矿流体中成矿元素在迁移、沉淀过程中的物理化学条件。本文以辽吉成矿带上典型的热液型铅锌矿床——岫岩红旗铅锌矿床为例,在对该矿床进行镜下典型矿物共生组合研究的基础上,选取了黄铁矿、黄铜矿、方铅矿和闪锌矿四种矿物进行热力学平衡的相关计算,选取473 K、549 K、648 K三个温度截面绘制了热力学lg[Cu2+]-pH、lg[HS−]-pH和Eh-pH相图,结果显示成矿流体中矿物迁移沉淀机制和矿物共生组合的形成主要受成矿流体的温度、离子活度、pH、Eh多因素制约。此研究对于解释辽吉成矿带上典型热液型铅锌矿床的运移沉淀机制和矿物组合特征具有重要的指导意义。     

碳酸盐岩型铅锌矿床成矿流体中铅锌元素运移与沉淀机制研究综述

成矿流体中金属元素的运移、沉淀机制历来是矿床学研究的重要问题之一。本文总结了近半个世纪以来碳酸盐岩型铅锌矿床成矿流体中铅锌运移与沉淀机制的研究成果。概括来说,针对MVT型铅锌矿床前人提出了3种运移沉淀模式和4种流体运移驱动模式,这些模式各有特色,适用于不同的矿床;铅锌溶解度的实验研究为运移沉淀机制研究提供了大量的基础数据,热力学相图和计算机模拟为铅锌迁移、沉淀的物理化学条件提供了半定量数据。对于元素迁移形式,在大型—超大型的碳酸盐岩容矿的铅锌矿床中,铅锌于酸性流体中主要以能携带大量金属的氯络合物形式运移,而其沉淀机制研究,除冷却与温度有关外,稀释、沸腾、水岩反应、氧化还原作用均可产生沉淀,均是因为这些作用能使流体的pH升高,上述机制综合作用的混合是大型—超大型碳酸盐岩容矿的铅锌矿床形成的最有可能机制,其本质是pH升高使H_2S分子更易离解成HS~-使沉淀反应得以进行。     

滇东北茂租热液型铅锌矿床矿物组合共生分异的热力学Eh—pH相图

滇东北地区广泛分布的热液型铅锌矿床具有普遍的矿物组合分带特征,研究矿床矿物组合的共生分异特征,是了解该类型矿床的成矿流体在演化过程中,成矿元素迁移和沉淀的核心问题之一,通过共生矿物的热力学Eh—pH相图可以有效的诠释成矿流体中成矿元素在迁移、沉淀过程中的物理化学条件。本文以滇东北茂租铅锌矿床为例,对滇东北热液型铅锌矿床的金属矿物共生组合在时间、空间分带特征进行热力学相图分析,选取373K、423K、473K、523K四个温度截面对金属矿物共生组合稳定存在的Eh—pH范围进行计算,相图显示成矿流体中矿物迁移、沉淀机制主要是由于成矿流体的Eh、p H值双重制约:Eh值的变化控制着硫化物沉淀的时间分带,成矿流体从深部向浅部运移,Eh值将会逐渐增大,主要矿物从黄铁矿→方铅矿→闪锌矿依次开始析出;p H值控制硫化物的空间分带,随着p H值的增大,成矿元素从离子的形式转变为硫酸盐矿物进行迁移。研究表明,控制成矿流体中硫化物迁移、沉淀的物理化学条件除了温度、压力、金属离子浓度及流体的氧硫逸度之外,流体的酸碱度及氧化还原电位同样是控制矿物组合共生分异的重要影响因素,此研究对该类型矿床的成矿流体的演化和成矿机制提供了一定的理论依据。     

钴矿床类型划分初探及其对特提斯钴矿带的指示意义

作为一种战略性关键金属,钴的现有矿床类型划分方案存在标准不统一等问题。文章从矿床成因角度提出新的划分方案,认为钴矿床主要有岩浆型、热液型、风化型和化学沉积型4种基本矿床类型。热液型可细分为岩浆热液矿床和盆地流体有关矿床2个亚类型。这一新划分方案对于理解钴矿床成矿作用和指导找矿勘查等方面具有重要启示意义。研究发现热液过程对钴富集成矿具有重要作用,而高盐度流体是钴迁移富集的关键所在。根据盆地流体有关热液钴矿床时空分布规律分析,提出欧亚大陆南缘存在一条上万公里长的特提斯碰撞钴矿带。该带具有得天独厚的金属源区、流体运移和金属沉淀等成矿条件,成矿潜力巨大。     

与花岗岩有关锡矿成岩成矿作用研究若干问题讨论

文章基于近年来大量典型锡矿床和成矿区带成岩成矿作用及高温高压实验研究成果,对锡矿成矿年代学、成矿花岗岩类型、物质来源、源区物质的熔融条件及锡在岩浆中的存在形式、熔体-流体相间分配行为及热液流体中的存在形式等方面的研究进展及存在问题进行了系统综述,指出:①锡石原位U-Pb测年已成为直接测定锡成矿年龄的有效手段,近年来发展起来的多种矿石矿物U-Pb测年方法与传统蚀变矿物测年方法的结合,将为研究锡多金属矿床多期次成矿作用叠加、矿集区内不同类型矿床成因联系及区域矿床组合模型的建立提供关键的年代学依据;②锡的富集成矿不仅与花岗质岩浆的高程度的结晶分异密切相关,而且受源区组成及部分熔融条件的制约;③全球锡多金属矿床的不均匀分布、与准铝质花岗岩有关锡矿的富集成矿机制以及各类复杂的锡-钨-铜-钼-铅-锌银多金属矿种组合差异及其金属元素富集机制亟待查明;④已有的关于锡在花岗质熔体、热液流体相中的存在形式及两相间的分配行为的高温高压实验结果受锡与贵金属容器间合金效应的影响,人工合成流体包裹体等新的实验方法的开发及XAS同步辐射和激光拉曼等原位分析技术的应用,将为研究花岗岩浆-热液过程锡的迁移、富集及沉淀成矿机制提供更为直接、可靠的实验依据。     

成矿金属元素的气相运移研究进展

尽管早在360余年前就有人提出了金属元素气相运移的概念,但在近代矿床学和矿床地球化学研究中却一直没有予以充分的重视。现代陆上和海底火山喷气中金属元素的分析表明很多金属元素在火山气中的含量相当高,具有直接形成金属矿床的潜力。随着现代分析技术的发展,特别是同步加速器-XRF、PIXE、LAM-ICP-MS等的出现,使得我们可以直接测定流体包裹体的微量元素组成,取得了富气相的流体包体中Au、Cu、Mo等元素的含量显著的高于液相包体的重要发现。熔融包体的研究结果也表明岩浆沸腾作用在热液矿床的成矿过程中可能起着重要的作用,在岩浆的结晶过程中可能有高达65%的挥发份逸出,而Cu、Au等金属元素强烈的选择性进入气相而非熔体相,说明岩浆演化早期的去气过程对斑岩等热液矿床的形成可能具有重要的控制。气相对金属元素溶解度的实验研究亦表明,气相对金属的溶解和迁移能力比人们想象的要高得多。所以,气相运移可能在一些热液矿床(特别是在蒸气相占重要地位的高温热液矿床)的成矿过程中可能起着重要的作用。     

●●以下文章网络预出版（在线出版）于2022年12月20日，预计刊于《地质论评》2023年第69卷第1期(2023年1月15日发行纸质版）或2023年第69卷第2期（2023年3月15日发行纸质版）

元素富集机制的研究是重现成矿过程和查明成矿机制的基础,有助于深化对矿床的认识,为找矿提供理论依据。本文总结了近年来关于铅锌元素的迁移与沉淀机制的研究及其应用,包括3种铅锌迁移沉淀模式,4种含铅锌流体驱动模式,铅锌的迁移形式及其沉淀机制;同时简述了我国高温高压实验的发展历程以及4种高温高压模拟实验方法。重点介绍了4种高温高压实验模拟方法及其研究现状：① 高压釜实验;② 热液金刚石压腔—激光拉曼实验;③ 熔融毛细硅管—激光拉曼实验;④ 计算机模拟实验。从封闭—平衡—静止到（半）开放—非平衡—流动、淬火分析到原位观察,应是今后高温高压实验的发展方向。以地质特征为基础,采用高温高压成岩成矿模拟实验结合计算机模拟,精细刻画成矿过程并揭示元素富集机制不仅是解决实际地质问题的有效手段,更是很长一段时间内要为之努力的方向。     

铅锌富集机制实验研究方法综述

元素富集机制的研究是重现成矿过程和查明成矿机制的基础,有助于深化对矿床的认识,为找矿提供理论依据。本文总结了近年来关于铅锌元素的迁移与沉淀机制的研究及其应用,包括3种铅锌迁移沉淀模式,4种含铅锌流体驱动模式,铅锌的迁移形式及其沉淀机制;同时简述了我国高温高压实验的发展历程以及4种高温高压模拟实验方法。重点介绍了4种高温高压实验模拟方法及其研究现状：(1)高压釜实验;(2)热液金刚石压腔—激光拉曼实验;(3)熔融毛细硅管—激光拉曼实验;(4)计算机模拟实验。从封闭—平衡—静止到(半)开放—非平衡—流动、淬火分析到原位观察,应是今后高温高压实验的发展方向。以地质特征为基础,采用高温高压成岩成矿模拟实验结合计算机模拟,精细刻画成矿过程并揭示元素富集机制不仅是解决实际地质问题的有效手段,更是很长一段时间内要为之努力的方向。     

成矿流体中金的沉淀机理研究述评

成矿流体中金的沉淀机理是金地球化学的一个重要研究领域。建立在现代实验地球化学和络合物化学等理论基础上，热液成矿流体中金的迁移形式研究已经取得很大进展。结合矿床地球化学、流体包裹体地球化学等的研究，对金的沉淀机理已提出了许多假说，如沸腾作用、不同流体的混合作用、流体不混溶作用、热液蚀变等等。一方面，受成矿地质环境的制约，不同矿床类型和不同成矿环境，金的沉淀机理可能不同；另一方面，不同沉淀机理还有各自不完善之处，需要更深入地研究。而成矿实验地球化学、计算机模拟等可以发挥重要作用。     

金氯配合物高温热力学常数研究现状

金氯配合物高温热力学常数研究现状张生，柳少波（中国科学院广州地球化学研究所，广州５１０６４０）关键词金氯配合物，溶解度实验，平衡常数金的溶解度实验提示，在富还原硫和氯的热液中金分别形成硫氢配合物和氯配合物，二者为理解和分析金在热液成矿过程中的迁移沉淀...     

西太平洋岛弧-弧后盆地热液活动及成矿作用

岛弧-弧后盆地是海底热液硫化物发育的重要环境。本文总结了近几十年对西太平洋地区岛弧-弧后盆地热液活动调查及研究的成果,阐述了岛弧-弧后盆地热液活动的分布规律、构造环境、热液喷口水深和流体温度变化关系、相分离过程以及热液硫化物的金属元素组成特征,分析了成矿元素富集规律和控矿因素。研究认为,随着岛弧-弧后盆地热液喷口所处水深的增加,其最高喷口流体温度也相应增加,这与相分离过程有关;岛弧-弧后盆地热液硫化物与洋中脊硫化物不同,以Fe-Zn-Pb型硫化物为主,显著富集Zn、Pb、Au、Ag等金属元素;热液成矿作用主要受到岛弧及弧后扩张处的岩浆作用、相分离、基岩、弧后扩张速率、沉积物盖层等5类因素的制约。     

Metal mobility during hydrothermal breakdown of Fe-Ti oxides: Insights from Sb-Au mineralizing event (Variscan Armorican Massif,France)

Hydrothermal alteration related to Sb-Au mineralization is widespread in the Variscan Armorican Massif, but mineral replacement reactions are not well characterized, in particular the hydrothermal breakdown of ilmenite-titanohematite. Based on petrography, electron probe micro-analyzer and laser ablation-inductively coupled plasma-mass spectrometer analyses, we document mineralogical change at rock- and mineral-scale and the redistribution of Sb and others trace elements during the recrystallization of ilmenite-titanohematite to hydrothermal rutile. Hydrothermal alteration is mainly potassic with associated carbonation. The replacement mechanism is interpreted to be an interface-coupled dissolution-reprecipitation process. Results show that Mn, Zn, Co, Ni, Sn, Mo and U are released during hydrothermal alteration, whereas Sb and W are incorporated in newly-formed hydrothermal rutile from the hydrothermal fluid. Furthermore, the concentration of Sb evolves through time suggesting a change in fluid composition likely related to an enrichment of fluid in Sb during rutile crystallization. Considering that Fe-Ti oxides breakdown during hydrothermal alteration is common within epithermal and mesothermal/orogenic Au-Sb mineralizing systems, results report in this study yield important constraints about metal mobility and exchanges in hydrothermal gold systems.     

Hydrothermal Gold Mineralization at the Rodnikovoe Deposit in South Kamchatka, Russia

Abstract. The Rodnikovoe gold deposit situated in a presently active hydrothermal system located north of the Mutnovsko-Asachinskaya geothermal area in southern Kamchatka, Far Eastern Russia, consists of typical low-sulfidation quartz-adularia veins in a host rock of diorite. The age of the mineralization was dated by the K-Ar method as 0.9 to 1.1 Ma based on adular-ia collected from the veins. Representative ore minerals in the deposit are electrum, argentite, aguilarite, polybasite, pearceite and lenaite. Dominant alteration minerals are adularia, α-cristobalite, chlorite, illite and kaolinite. Hydrothermal solutions of neutral pH were responsible for the mineralization, which is divided into six stages defined by tectonic boundaries. Gold mineralization occurred in stages I and III. Hydrothermal brecciation occurred during stages III, IV and VI. Stages II, IV, V and VI were barren. The estimated ore formation temperature based on a fluid inclusion study is 150 to 250 °C at a depth of approximately 170 m below the paleo-water table. Boiling of hydrothermal fluids is hypothesized as the cause of the intermittent deposition of gold ore. The sulfur and oxygen fugacities during the deposition of anhydrite prior to the hydrothermal brecciation were higher than those during the gold mineralization stages. The occurrence in the hydrothermal breccia of fragments of high grade Au-Ag and polymetallic ores suggests that higher grade mineralization of these metal ores might have occurred in a deeper portion of the deposit.     

Lincang superlarge germanium deposit in Yunnan Province,China: Sedimentation,diagenesis,hydrothermal process and mineralization

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Function of metal distribution in ores,as genetic characteristics of mineralization process

The process of ore deposition is examined, using the function of metal distribution in ores as the most important energy characteristic and demonstrating the geochernical importance of these functions. The Process of hydrothermal mineralization during a single stage is assumed to proceed as a continuous stationary process Of the Markov type. The resulting concentration of metal is controlled by a distribution function, a most important genetic characteristic reflecting the speed of the process of mineralization and the thermodynamic function of its state. The Pearson group of curves can be considered the most common type representing the distribution of metal in ores. These distribution functions are affected by the size of samples and may be used for comparative study of various types of ore and ore bodies, and in solving other problems, provided their sampling was correct and performed according to a uniform method. — P.A. Alexandrov     

临沧超大型锗矿床的沉积环境、成岩过程和热液作用与锗的富集

临沧超大型锗矿庆的形成与其沉积、成岩和热液作用有密切联系。详细研究了矿床煤岩产出特征、煤岩组成、无机矿物、微量元素、腐殖体反射率,认为该矿床中的锗主要源于盆地西缘的白云母花岗岩的风化作用。在沉积作用阶段,锗被湖水中的低等生物和腐殖酸富集,为形成矿化煤打下基础。临沧褐煤经历了泥炭化阶段、早期成岩阶段和热液改造阶段。泥炭化阶段,沉积物中锗被凝胶体吸附和配合。早期成岩阶段,与腐残酸结合的锗,在碱性还原条     

Thermodynamic Calculation of Solubility of Na2SO4/K2SO4 in Hydrothermal Fluids

Sulfate fluids are common fluids in nature, and their salinity studies can provide important information for the evolution of ore-forming fluids, migration and enrichment of ore-forming elements, and the classification of deposit types. Considerable research has been carried out to investigate the solubility of Na₂SO₄ and K₂SO₄ in hydrothermal fluids, however most of the literature reported experimental data were under saturated vapor pressure or the water supercritical region. A few data have been reported for the low temperature hydrothermal mineralization region. Thermodynamic model is a useful method to study the properties of hydrothermal geofluids, especially for mineral solubility. Pitzer interaction model is one of the most widely used model to calculate the thermodynamic properties of hydrothermal fluids, but few work have ever been carried out to calculate the solubility of sulfate at high temperature and pressure. With Pitzer specific interaction model, using the literature reported density data of Na₂SO₄ and K₂SO₄ solutions at high temperature and pressure, the pressure effect on Pitzer activity coefficient of sulfate and the standard partial molar volume change during sulfate dissolution process were evaluated and related parameters were obtained. The standard partial molar volumes of Na₂SO₄ and K₂SO₄ calculated with these parameters agreed well with those reported in the literature. Combined with the relevant parameters in the literature under saturated vapor pressure, a thermodynamic model for Na₂SO₄ and K₂SO₄ solubility calculation with temperature up to 250 ℃ and pressure up to 40 MPa was developed. The model gave very good agreement with the experimental solubility data. With this model, Na₂SO₄ and K₂SO₄ solubility was calculated at high temperature and pressure. The calculation results showed that pressure had a positive effect on both the average activity coefficient and solubility product of Na₂SO₄ and K₂SO₄, but the solubility of Na₂SO₄ and K₂SO₄ decreased with pressure due to the larger change of the average activity coefficient with pressure. And as the temperature increased, the degree of such reduction became larger. The results herein can provide instructions for the compositional analysis of sulfate fluid inclusions.     

Gas mixing with aqueous solution in the ore-forming hydrothermal process: an example of gold

The mixing of gas and aqueous fluid in hydrothermal ore-forming processes is discussed with reference to gold deposits to demonstrate that this phenomenon may affect ore deposition. Data on fluid inclusions in samples from the Sukhoi Log and Olimpiadinskoe deposits in Russia are utilized to demonstrate possible implications of gas mixing with hydrothermal solution when gold ores are formed. A simplified thermodynamic model is suggested to show how interaction between aqueous saline solutions with pure carbon dioxide or carbon dioxide—methane mixture may affect gold solubility. Further studying such processes may provide interesting information for understanding the genesis of ore mineralization.     

鄂西地区铅锌矿基本特征与找矿方向

鄂西地区铅锌矿床的成因类型主要有两种:沉积型和热液型.沉积型铅锌矿主要形成于晚震旦世-寒武纪;热液型铅锌矿床主要形成于燕山中晚期,与区域性伸展构造事件密切相关,矿化主要集中于青峰强变形带、神农架断穹西部、黄陵断穹北部及咸丰背斜和长阳走马坪背斜等次级褶皱中.近年来的找矿勘查实践表明,区内铅锌成矿地质条件十分有利,找矿前景良好.