钨的气态迁移与岩浆-热液成矿作用:实验研究及其成矿学意义

低密度的水热蒸气和超临界似气流体广泛存在于中地壳至地球表面的各种地质环境中, 是成矿金属搬运和富集的重要介质。火山喷气凝结水、火山结壳和升华物、矿床的流体包裹体气相中均存在具有地质意义的W含量或含钨矿物, 表明W同样可在含水气相中溶解和迁移。本文在350 ℃~400 ℃和压力为60~200 bar的实验条件下, 测定了WO₃-H₂O体系中W在水蒸气和似气流体中的溶解度, 考察了水蒸气压力对W溶解度的影响。结果显示, W在水蒸气中的逸度(或含量)远高于依据无水体系中固体WO₃挥发性数据计算的蒸气压力, 证明气态溶质W与溶剂水蒸气之间存在促进W溶解的水合作用。经热力学方法分析, 认为可能形成了WO₃·nH₂O(g)形式的水合气体物种, 其水合数n在350 ℃、370 ℃和400 ℃时分别为1.4、1.6和2.9。因此WO₃·3H₂O(g)或H₂WO₄·2H₂O(g)及H₆WO₆(g)在温压较高的岩浆-热液或气成-热液成矿环境中(如斑岩系统)对W的气态迁移和浓集可能具有重要作用, 而在温压较低的水热蒸气条件下, W的迁移形式可能以水合数较小的WO₃·H₂O(g)(或H₂WO₄)和WO₃·2H₂O(g)(或H₂WO₄·H₂O)物种为主, 其含量或比例随水蒸气的压力而改变。某些斑岩型和脉型钨(钼)矿床常存在富气体包裹体, 伴随酸性岩浆结晶出溶的以低盐度含水蒸气占优势的岩浆流体对斑岩系统中W、Mo在高温阶段的气态迁移和矿质在花岗岩体顶部和上覆岩层的聚集具有重要意义, 之后蒸气冷凝可产生高盐度的含矿卤水或与渗流地下水混合形成低-中等盐度的成矿流体, 流体的减压沸腾(相分离)和对围岩的交代蚀变导致W、Mo等金属在不同阶段和构造-岩性部位沉淀富集。     

内蒙古额尔古纳市虎拉林金矿床成矿流体包裹体研究

通过矿床流体包裹体岩相学、显微测温学和激光拉曼光谱成分分析,研究成矿流体性质,探讨了矿床成因类型.研究结果表明,流体包裹体以气液两相包裹体为主,少量含CO₂三相、含子矿物三相和纯气相包裹体等.成矿流体均一温度为320~360℃,盐度为19.2%~21.8%,密度为0.73~0.90 g/cm³,估算成矿压力为92.1~129.1 MPa,成矿深度为3.07~4.3km.成矿流体气相成分以H₂O为主,其次为CO₂、CH₄和N₂,微量的C₆H₆、C₂H₆和C₃H₈等,总体属H₂O-CO₂-NaCl体系.成矿流体是一种不混溶流体,主要来源于深部岩浆,并可能有幔源组分参与.金主要是以金氯配合物的形式迁移.矿床的地质-地球化学特征与隐爆角砾岩型金矿类似,应属隐爆角砾岩型金矿床.     

辽东地区后仙峪及翁泉沟硼矿床流体包裹体特征研究

对后仙峪硼矿区热水喷流沉积成因的电英岩中石英及翁泉沟硼矿区后生热液成因的石英脉中的原生流体包裹体进行了对比研究。结果表明：后仙峪电英岩石英中只发育气液两相包裹体,测温结果显示流体包裹体均一温度为146~249 ℃,盐度为15.9%~18.4%,密度为0.96~1.04 g/cm³,计算出成矿压力为43.95~68.43 MPa,由此估算出热水喷流沉积时的古海水深度为4.40~6.84 km;包裹体成分分析结果显示气相成分以H₂O、CH₄为主,含CO₂和N₂及少量的H₂S和H₂。翁泉沟石英脉中则发育气液两相包裹体及含CO₂三相包裹体两种类型,测温结果显示流体包裹体均一温度为142~377 ℃,盐度为12.7%~14.5%,密度为0.96~1.01 g/cm³,计算出压力为43.48~65.86 MPa,推算出后生成因石英脉的形成深度为5.23~6.55 km;包裹体成分分析结果显示气相成分以H₂O、CO₂为主,含CO、N₂和H₂,并含少量的CH₄、H₂S和微量的C₂H₆。矿床地质特征与硼同位素特征显示这两个矿床均为热水喷流沉积矿床,并经历了区域变质作用改造及后期热液交代蚀变作用。流体包裹体特征表明,热水喷流沉积成矿作用发生在相对还原的海底条件;而后期叠加的热液活动发生在相对氧化的环境下。     

西藏恰功矽卡岩铁矿床成矿流体特征及演化:对Fe-Pb矿化的约束

目前关于恰功矽卡岩型铁矿床的流体演化过程及成矿机制,尤其是铁-铅矿体的成矿作用尚缺研究.对不同阶段的主要矿物进行包裹体均一温度-盐度、激光拉曼光谱分析以及H-O同位素测试.进矽卡岩阶段包裹体均一温度为400~550℃;盐度为15.5%~20.9% NaCl_eqv,其中S型盐度高达56.5% NaCl_eqv;气液相成分均为H₂O.退化蚀变阶段包裹体均一温度为350~420℃;盐度集中于14.1%~16.6% NaCl_eqv,少量为2%~8% NaCl_eqv,而S型包裹体盐度亦高达55.8% NaCl_eqv;气液相成分均为H₂O,液相富含HCO₃-和CO₃2-.石英-方铅矿阶段包裹体均一温度范围为238~343℃,对应盐度为3.1~13.9% NaCl_eqv,其中含CO₂三相包裹体完全均一温度集中在290~310℃,盐度为1.6%~11.2% NaCl_eqv.石英-方解石阶段包裹体均一温度与盐度分别为242~360℃和1.7%~11.8% NaCl_eqv,气液相成分均为H₂O.H-O同位素显示:进矽卡岩阶段δD_H2O为-106.4‰~-113.2‰,δ18O_H2O为6.2‰~8.0‰;退化蚀变阶段δD_H2O为-84.8‰~-130.1‰,δ18O_H2O为2.7‰~5.5‰,退化蚀变阶段δ18O_H2O值相对进矽卡岩阶段低;石英-方铅矿阶段δD_H2O为-95.3‰~-103.8‰,δ18O_H2O为-1.6‰~-0.7‰;石英-方解石阶段δD_H2O为-67.4‰~-101.0‰,δ18O_H2O为-0.8‰~0.6‰.结果表明流体整体具有从高温、中-高盐度逐渐向低温、低盐度演化的特征,矽卡岩期成矿流体来源于岩浆出溶;矽卡岩期流体的不混溶作用并与围岩发生反应是磁铁矿沉淀的重要机制,石英-方铅矿阶段流体温压下降是方铅矿沉淀的根本原因.      

山东谢家沟金矿流体包裹体研究及其地质意义

山东谢家沟金矿是新发现的产于玲珑型花岗岩中的蚀变岩型金矿。对3个成矿阶段含矿流体的温度、压力和成分分析表明,矿床属于浅成中温热液矿床。含矿流体的演化是从高温向低温、从低盐度、低密度向高盐度、高密度的转变。Ⅰ成矿阶段流体包裹体均一温度为320~350 ℃,盐度为2.7%~6.6%,密度为0.498~0.886 g/cm³;Ⅱ成矿阶段包裹体均一温度为270~330 ℃,盐度为3.6%~8.4%,密度为0.571~0.959 g/cm³;Ⅲ成矿阶段包裹体均一温度为250~290 ℃,盐度为5.8%~10.6%,密度为0.724~1.158 g/cm³。流体成分以CO₂和H₂O为主,尚有CO、CH₄、H₂S、SO₂、N₂等,流体中CO2含量与矿石金品位正相关。据不同类型包裹体共生组合及流体演化特征,认为流体的不混溶性是导致大量金沉淀的主要原因。     

黑龙江省逊克县坤得气南山金矿床流体包裹体研究

坤得气南山金矿床产出于小兴安岭-张广才岭多金属成矿带北缘,矿体赋存于光华组硅化长石砂岩、细砂岩中.金矿化包括石英-黄铁矿、石英-多金属硫化物和石英-方解石3个成矿阶段.前两个阶段矿石硅化石英细脉中的石英矿物的流体包裹体,包括气液两相包裹体、富气相包裹体和含子矿物三相包裹体3种类型,并以气液两相包裹体为主.流体包裹体的均一温度变化范围在234.8~420.5℃之间,盐度（NaCl当量质量分数）变化在2.6%~33.6%之间,可分为高温低盐度、中高温中低盐度和中高温中高盐度类.流体包裹体气相成分主要为H₂O、CO₂;液相成分也以H₂O、CO₂为主,含有Na⁺、K⁺、Ca²⁺、Mg²⁺离子;子矿物主要为石盐.3类包裹体在同一矿物颗粒中同时共生发育,表明捕获流体为不均匀流体状态,显示成矿过程中存在一定程度的溶体不混溶作用.根据流体包裹体研究结果,确定矿床为浅成热液成因,而且矿床深部具有找寻斑岩型矿化的潜力.     

均匀流体和不均匀流体的形成机制: 来自合成流体包裹体的证据

为详细了解流体的形成机制, 对系统的流体包裹体合成实验进行研究.研究表明, 在合成流体包裹体实验中, 广泛存在流体的均一化和沸腾作用; 流体的均匀与否, 与流体p-t轨迹在TP (H₂O)-CP(H₂O)-CP(NaCl-H₂O) 曲线的部位有密切的关系.p-t轨迹在曲线上部的流体为均匀流体, 反之则为沸腾流体.但也有例外, 如在溶解曲线上被主矿物捕获的流体.这为本次研究一定条件下流体的形成机制、探讨成矿作用提供了理论依据.      

西南天山阿沙哇义金矿床流体包裹体和H-O同位素地球化学特征与造山型金矿成因

【研究目的】阿沙哇义金矿位于西南天山,处在“亚洲金腰带”的中南缘,是最近几年新探明、中型规模的金矿,矿床基础研究程度较低。【研究方法】通过野外地质调查,室内开展流体包裹体岩相学、成分分析、测温、H-O同位素等研究。【研究结果】提出矿床的含矿地层为上石炭统喀拉治尔加组,矿体产于NEE走向逆冲推覆构造系统的次级断裂内;成矿可分为3阶段,早—中阶段发育H₂O溶液型、CO₂-H₂O型及纯CO₂型三种流体包裹体,但晚期仅发育纯H₂O溶液型包裹体。其中早期均一温度236～386℃,盐度1.6%～9.7%Na Cl eqv.;中期均一温度225～301℃,盐度1.4%～12.5%Na Cl eqv.;晚期均一温度139～222℃,盐度1.4%～7.3%Na Cl eqv.;流体包裹体激光拉曼图谱显示液体成分为H₂O和CO₂,含CH₄和N₂;表明成矿流体具中低温、富CO₂、含CH     

基于DFT方法的注热蒸汽开采CH4吸附机理

为探究不同煤阶煤吸附CH₄和H₂O吸附机理,采用量子化学方法中的密度泛函理论（DFT）,在B3LYP/6-31G基组上计算了不同煤阶煤的大分子稳定构型及煤分别吸附CH₄、H₂O及CH₄与H₂O共存条件下的吸附能和电荷转移情况。研究结果表明:煤吸附CH₄为物理吸附,随着煤阶升高,煤吸附CH₄能力增强;吸附H₂O时以氢键形式作用,其中煤中含氧官能团为氢键供体,H₂O中-OH为氢键受体,随着煤阶升高,吸附H₂O能力减弱;当H₂O与CH₄共存时,H₂O抢占CH₄吸附位,导致煤优先吸附H₂O,使吸附态CH₄减少,游离态CH₄增多。从分子水平完善了煤吸附甲烷和H₂O的吸附机理,为注热蒸汽开发煤层气奠定了吸附理论基础。      

金是通过什么方式搬运与沉淀的

数十年来,金在不同的地质作用过程中的迁移与沉淀机理一直是许多矿床地质学家和地球化学家们争论的焦点。根据最近的地质与地球化学研究,对如下几个问题进行了探讨:(1)什么样的含水络合物最有利于金的迁移与搬运;(2)为什么金富集在脉型矿床中;(3)在什么样的物理-化学条件下,金的含水络合物可以得到充分溶解;(4)为什么绝大多数金矿床的形成范围集中在340℃~400℃.在热液成矿流体中,金可能是以AuHS(H₂S)₃⁰形式进行迁移,温度的降低会使溶液中90%的金沉淀,这能够解释这些含金石英脉为什么形成在一个很窄的温度范围内.     

A Preliminary Study of the Solubility of Copper in Water Vapor at Elevated Temperatures and Pressures

INTRODUCTIONAs early as 1644 , Ren啨Descartes proposed thatsilver-,gold-,and lead-bearing veins were producedby the condensation of vapors emanating from theearth' s interior ( Williams-Jones et al ., 2002) . Butthe solubility of many metals is higher in liquid thanin vapor andtherefore the focus of research on hydro-thermal ore deposits was placed on hydrothermal sys-tems (Barnes ,1997) ,considering the fact that ore-forming elements may exist as complexes in hydro-thermal solutions . T…     

The exsolution of magmatic hydrosaline chloride liquids

Hydrosaline liquid represents the most Cl-enriched volatile phase that occurs in magmas, and the exsolution of this phase has important consequences for processes of hydrothermal mineralization and for volcanic emission of Cl to the atmosphere. To understand the exsolution of hydrosaline liquids in felsic to mafic magmas, the volatile abundances and (Cl/H₂O) ratios of more than 1000 silicate melt inclusions (MI) have been compared with predicted and experimentally determined solubilities of Cl and H₂O and associated (Cl/H₂O) ratios of silicate melts that were saturated in hydrosaline chloride liquid with or without aqueous vapor in hydrothermal experiments. This approach identifies the minimum volatile contents and the values of (Cl/H₂O) at which a hydrosaline chloride liquid exsolves from any CO₂- or SO₂-poor silicate melt. Chlorine solubility is a strong function of melt composition, so it follows that Cl solubility in magmas varies with melt evolution. Computations show that the (Cl/H₂O) ratio of residual melt in evolving silicate magmas either remains constant or increases to a small extent with fractional crystallization. Consequently, the initial (Cl/H₂O) in melt that is established early during partial melting has important consequences for the exsolution of vapor, vapor plus hydrosaline liquid, or hydrosaline liquid later during the final stages of melt ascent, emplacement, and crystallization or eruption. It is demonstrated that the melt (Cl/H₂O) controls the type of volatile phase that exsolves, whereas the volatile abundances in melt control the relative timing of volatile phase exsolution (i.e., the time of earliest volatile exsolution relative to the rate of magma ascent and crystallization history).

Comparing melt inclusion compositions with experimentally determined (Cl/H₂O) ratios and corresponding volatile solubilities of hydrosaline liquid-saturated silicate melts suggests that some fractions of the eruptive, calc-alkaline dacitic magmas of the Bonnin and Izu arcs should have saturated in and exsolved hydrosaline liquid at pressures of 2000 bars. Application of these same melt inclusion data to the predicted volatile solubilities of Cu-, Au-, and Mo-mineralized, calc-alkaline porphyritic magmas suggests that the chemical evolution of dioritic magmas to more-evolved quartz monzonite compositions involves a dramatic reduction in Cl solubility that increases the probability of hydrosaline liquid exsolution. The prediction that quartz monzonite magmas should exsolve a hydrosaline chloride liquid, that is potentially mineralizing, is consistent with the general observation of metal-enriched, hypersaline fluid inclusions in the more felsic plutons of numerous porphyry copper systems. Moreover, comparing the volatile contents of melt inclusions from the potassic, alkaline magmas of Mt. Somma-Vesuvius with the predicted (Cl/H₂O) ratios of hydrosaline liquid-saturated melts having compositions similar to those of the volatile-rich, alkaline magmas associated with the orthomagmatic gold–tellurium deposits of Cripple Creek, Colorado, suggests that hydrosaline chloride liquid should have exsolved at Cripple Creek as the magmas evolved to phonolite compositions. This prediction is consistent with the well-documented role of Cl-enriched, mineralizing hydrothermal fluids at this major gold-mining district.     

Experimental abiotic synthesis of methanol in seafloor hydrothermal systems during diking events

The abiotic synthesis of organic compounds in seafloor hydrothermal systems is one mechanism through which the subsurface environment could be supplied with reduced carbon. A flow-through, fixed-bed laboratory reactor vessel, the Catalytic Reactor Vessel (CRV) system, has been developed to investigate mineral–surface promoted organic synthesis at temperatures up to 400°C and pressures up to 30 MPa, conditions relevant to seafloor hydrothermal systems. Here we present evidence that metastable methanol can be directly synthesized from a gas-rich CO₂–H₂–H₂O mixture in the presence of a mineral substrate. Experiments have been performed without a substrate, with quartz, and with a mixture of quartz and magnetite. Temperatures and pressures in the experiments ranged from 200°C to 350°C and from 15 to 18 MPa, respectively. Maximum conversion of 5.8×10⁻⁴% CO₂ to CH₃OH per hour was measured using a mixture of magnetite and quartz in the reactor. After passivation of the stainless steel reactor vessel, experiments demonstrate that methanol is formed at temperatures up to 350°C in the presence of magnetite, and that the formation rate decreases over time. The experiments also show a loss of surface reactivity at 310°C and a regeneration of surface reactivity with increased temperature up to 350°C. Concentrations of CO₂ and H₂ used in the experiments simulate periodic, localized and dynamic conditions occurring within the seafloor during and immediately following magmatic diking events. High concentrations of CO₂ and H₂ may be generated by dike injection accompanied by exsolution of CO₂ and reaction of dissolved H₂O with FeO in the magma to form H₂. The experiments described here examine how the ephemeral formation of an H₂–CO₂-rich vapor phase within seafloor hydrothermal systems may supply reactants for abiotic organic synthesis reactions. These experiments show that the presence of specific minerals can promote the abiotic synthesis of simple organic molecules from common inorganic reactants such H₂O, CO₂ and H₂ under geologically realistic conditions.     

The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.     

冷冻条件下天然包裹体中流体水分子氢键的拉曼光谱特征

水的拉曼图谱实际就是带氢键作用的OH伸缩振动峰(包括对称伸缩振动峰和反对称伸缩振动峰)和不带氢键作用的OH对称伸缩振动峰(包括对称伸缩振动峰和反对称伸缩振动峰)的叠加包络线,通过对流体中水的拉曼图谱的分析可以反映流体中氢键作用的强弱.因此,用Renishaw MK1-1000型显微激光拉曼探针原位分析了冷冻条件下天然的流体包裹体腔内流体水分子的氢键作用.研究表明,在冷冻条件下,水分子运动以带氢键作用的伸缩振动为主,同时还有微弱的非氢键作用的伸缩振动;随着温度的降低,流体中水分子的氢键作用不断地增强;在-130~-180 ℃区间氢键作用增强的趋势明显加大,暗示流体性质在此温度区间可能发生了突变.      

河南祁雨沟金矿临界-超临界包裹体特征及成矿流体演化

河南省祁雨沟金矿床位于华北地块南部熊耳地体东北缘,是我国典型的角砾岩型金矿。该矿床临界-超临界流体包裹体的发现对研究成矿流体演化及成矿机制有重要意义。包裹体岩相学、显微测温以及激光拉曼显微探针（LRM）研究显示,祁雨沟J4角砾岩筒中发育临界状态均一的包裹体富含CO₂,这些包裹体出现在第Ⅰ、Ⅱ成矿阶段,并且在金品位最高的400-460中段出现最为集中,对成矿有明显的指示作用。临界-超临界流体来自富含挥发分的高氧化状态岩浆的出溶作用。流体演化先后经历了高氧化状态的岩浆-流体体系→临界-超临界流体体系→H₂O-NaCl和CO₂-H₂O流体体系→低盐度的H₂O-NaCl流体体系→H₂O流体体系。临界―超临界流体体系在383.7~387.2 ℃发生了沸腾作用,沸腾作用可能是祁雨沟金矿J4岩筒中成矿物质沉淀的重要原因之一。     

吉林安图海沟金矿成矿流体特征及成矿机制

海沟金矿流体包裹体为3种类型：富CO₂三相、气液两相和纯气相。流体盐度集中在7.44％～8．67％NaCleqv,8.54％～8.94％NaCleqv和9.84％～10.87％NaCleqv三个区间;流体密度为0.54～0.88 g/cm3;成矿温度主要集中在298.4℃～313.5℃和258.2℃～264.6℃。研究表明成矿早期阶段流体为低盐度、富CO₂的高温流体,且富CO₂型和富气相包裹体共存。成矿中晚期阶段流体盐度和温度明显降低,CO₂、H₂O等气体能够大量逃逸,流体体系由封闭状态转化为较开放状态,大气降水、层间水等大量进入与岩浆流体发生混合,并引起流体内金络合物的溶解度减小而直接导致金和金属矿物的沉淀和富集。成矿压力范围为110～146 MPa,成矿深度为8.7～10.1 km。通过与典型的造山型金矿特征对比,该矿床成因类型为中成造山型金矿,动力学背景为早一中侏罗世华北板块与西伯利亚板块碰撞的持续汇聚力和古太平洋板块俯冲欧亚大陆的作用力引起的远程效应联合作用的结果。     

CO2流体对含片钠铝石砂岩改造作用的实验研究

不同温度（100℃,200℃和300℃）下CO_{2流体对含片钠铝石砂岩的改造作用研究显示:随着温度的升高,砂岩的溶蚀、溶解程度逐渐增强,样品中片钠铝石的稳定性逐渐减弱。同时,各温度下样品表面均有一水软铝石放射状集合体沉淀。200℃时,随着片钠铝石的溶解有自生菱铁矿生成,300℃时样品局部有绿泥石沉淀。100℃下片钠铝石的微弱溶解及200℃下菱铁矿的形成表明,在地层条件下以碳酸盐矿物形式捕获的CO2,不会由于CO2的二次注入而重新释放。}