热液矿床稳定同位素体系理论模式及其地球化学意义

热液矿床稳定同位素体系理论模式及其地球化学意义郑永飞（中国科学技术大学地球和空间科学系，合肥２３００２６）关键词理论模式，地球化学，稳定同位素，热液矿床同位素地球化学示踪已经成为现代地球科学研究的重要手段之一，因为它能够为我们认识地壳和地幔的形成和演...     

浅成环境中岩浆流体的演化：稳定同位素透视

根据矿床地质背景、热液蚀变组合、流体包裹体和稳定同位素地球化学，特别是根据浅成岩浆热液环境中特征矿物明矾石的稳定同位素组成，研究岩浆成矿流体的来源、动态与化成矿机理，获得了许多新认识；根据δ＾１４Ｓ和δ＾１８Ｏ可将明矾石划分出两种不同的成因类型；岩浆成矿热液在时间上从早期的气相流体向主成矿期的液相流体演化，而岩浆热液矿床在空间上主要定位于脆性－延性过渡带。     

热液金矿中辉锑矿矿物学研究综述

辉锑矿是热液金矿化体系中较为重要的矿物。辉锑矿矿物学研究是热液金矿床成矿机制研究不可或缺的一部分。辉锑矿的矿物学特征主要包括物理结构和化学成分特征,笔者综述了热液金矿中辉锑矿的形态、晶胞参数、红外光谱、电子顺磁共振谱等物理特征以及稀土微量元素、硫同位素地球化学特征以及锑同位素的应用、热液金矿辉锑矿的含金性等多方面内容。     

江西德兴银山多金属矿床稳定同位素地球化学特征

江西德兴银山多金属矿床稳定同位素地球化学特征＠吴志军￥中国科学院地球化学研究所银山多金属矿床,稳定同位素,成矿模式江西德兴银山多金属矿床稳定同位素地球化学特征吴志军（中国科学院地球化学研究所,贵阳５５０００２）关键词银山多金属矿床稳定同位素成矿模式银山多金...     

Li同位素在矿床学中的应用:现状与展望

矿床的形成受制于多种复杂的地质作用,包括全球尺度的板块构造运动、岩浆活动、变质沉积改造等过程,并普遍伴随热液活动、流体迁移、水-岩相互作用、元素分异及同位素分馏等一系列局部区域地质和地球化学过程.在过去的矿床学研究中,地球化学方法主要围绕在主、微量元素和传统的稳定同位素等手段,解决了很多矿床成因问题.但仍存在不少的多解和难解问题,比如许多矿床在矿化类型、蚀变分带与金属矿物组合方面具有诸多相似之处,常规地球化学指标难以区分.随着测试精度的提高和自然储库组成的完善,Li同位素近些年来已成为新兴的稳定同位素体系.Li同位素在自然界过程中高达80‰的同位素分馏使其具有更好的辨识能力,同时兼有直接和间接指示作用,有潜力成为研究各种复杂成矿过程的良好示踪剂.本文总结了近年来有关矿床学中Li同位素的研究和应用进展,以俯冲带成矿为主,阐述了斑岩型-热液矿床、伟晶岩型矿床和沉积矿床等类型矿床的Li同位素地球化学特征,并探究新的Li同位素方法在矿床中的应用前景.基于Li同位素体系在各类矿床的应用实例,我们认为Li同位素体系将为矿床学研究提供更多的指示信息和依据.      

碳,硫同位素储库效应的定量理论模式

根据矿物沉淀作用与瑞利蒸馏过程的一级近似,导出了碳酸盐矿物沉淀时热液的碳同位素储库效应理论模式的定量方程,并在Zheng等的研究基础上给出了硫同位素储库效应的一般化理论模式以及模式参数R与物理化学参量的定量关系。180℃、热液的初始δ~(13)C为-2‰时,沉淀方解石和残余热液δ~(13)C值总体呈下降趋势。当热液以氧化碳为主时,储库效应不明显;若热液含较多还原碳,沉淀方解石的δ~(13)C可从早期较大的正值(5‰-35‰)演化为晚期较大的负值(-15‰--30‰)。封闭体系的同位素储库效应模式至少可为预     

阿西金矿床流体成矿的地球化学示踪研究

依据阿西金矿床Ｈ、Ｏ同位素组成特点对成矿流体的来源进行了示踪研究,并且研究了矿床的水岩交换作用,讨论了水－岩作用与金成矿的关系。根据矿床中典型热液矿物和岩矿石的稀土元素地球化学特征对成矿流体作用过程进行了示踪研究,与同位素地球化学示踪研究取得了基本一致的结果。根据成矿流体活动踪迹建立找矿标志,是进行矿产资源预测的新思路。     

独山锑矿稳定同位素地球化学研究

通过氧、硫、氢、碳、铅等稳定同位素和矿物包裹体地球化学的研究;指出独山锑矿成矿温度低(1OO～200℃).成矿流体主要为大气降水,成矿物质主要来自地层;成矿作用以构造裂隙充填型为主;系大气降水低温热液型矿床.该类矿化是地洼区构造活化成矿的一种典型成因类型.     

桂东龙水金矿床地质特征及成因

龙水金矿是赋存于大宁花岗闪长岩体外接触带的破碎蚀变岩型金矿。从矿床地质、矿石物质成分及金的赋存状态、围岩蚀变、矿物流体包裹体、稳定同位素等不同方面阐明金矿床的地球化学特征,认为龙水金矿的形成是在变质热液成矿的基础上叠加后期岩浆热液成矿作用的复合成因金矿床。矿区外围还具有找矿远景。     

贵州铅锌矿的地球化学特征

贵州铅锌矿的分布受断控盆地的控制,主要铅锌矿带沿断控盆地边缘分布,盆地的充填序列—层序对铅锌矿的分布和矿床的地球化学特征有明显的制约作用。由此可在贵州划出索克上部含矿层等多个铅锌矿的含矿层序。同一含矿层序的铅锌矿即使相距很远,其地球化学特征也颇为相似:不同含矿层序的铅锌矿即使近在咫尺,其地球化学特征也迥然不同,表明不同含矿层序有不同矿质来源。根据对矿石铅和岩石中微量铅(岩铅)铅同位素组成特征,以及地层中Pb、Zn等元素背景含量的研究,各含矿层序的矿质主要来源于层序下部的细碎屑岩,个别亦可能来自上下层序紧邻层位的细碎屑岩。铅同位素研究还表明黔东铅锌成矿带形成在加里东晚期,黔西北铅锌成矿区形成在印支期之后。 对铅同位素和稳定同位素地球化学特征的研究表明,贵州铅锌矿多属盆源热液矿床,硫主要来源于含矿层序中的硫酸盐,在成矿过程中存在两种热液:盆源热液和下渗热液,成矿和它们的掺混有一定关系。硫同位素研究还揭示了成矿过程中的pH值变化和成矿体系对硫酸盐的开放程度。     

Iron isotope fractionation during hydrothermal ore deposition and alteration

Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (<100 °C). Measured iron isotope compositions are variable and cover a range in δ⁵⁶Fe between −2.3‰ and +1.3‰. Primary hematite (δ⁵⁶Fe: −0.5‰ to +0.5‰) precipitated by mixing oxidizing surface waters with a hydrothermal fluid that contained moderately light Fe (δ⁵⁶Fe: −0.5‰) leached from the crystalline basement. Occasional input of CO₂-rich waters resulted in precipitation of isotopically light siderite (δ⁵⁶Fe: −1.4 to −0.7‰). The difference between hematite and siderite is compatible with published Fe isotope fractionation factors. The observed range in isotopic compositions can be accounted for by variable fractions of Fe precipitating from the fluid. Therefore, both fluid processes and mass balance can be inferred from Fe isotopes. Supergene weathering of siderite by oxidizing surface waters led to replacement of isotopically light primary siderite by similarly light secondary hematite and goethite, respectively. Because this replacement entails quantitative transfer of iron from precursor mineral to product, no significant isotope fractionation is produced. Hence, Fe isotopes potentially serve to identify precursors in ore alteration products. Goethites from oolitic sedimentary iron ores were also analyzed. Their compositional range appears to indicate oxidative precipitation from relatively uniform Fe dissolved in coastal water. This comprehensive iron isotope study illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.     

流体包裹体在矿床研究中的作用

流体包裹体分析是现代矿床学研究的一个重要手段,对矿床类型的划分及成矿流体成分、温度、压力的研究有着重要的作用.在矿质沉淀的主要机制中,流体相分离及流体混合的主要证据来自流体包裹体;对金属在气相中的搬运的认识,也主要来自包裹体研究.成矿流体成分对认识金属在热液中的搬运方式起着重要作用,流体温度和压力数据是成矿流体动力学模式的重要制约.     

甘肃中秦岭成矿带成矿规律及找矿远景

文章在全面揭示甘肃中秦岭成矿带23种矿产成矿规律的基础上,圈定找矿远景区。通过成矿地质背景和成矿过程研究,建立主要矿床类型的成矿模式;以主要地质事件和成矿作用为主线,归纳矿床的时空分布规律和矿床成矿系列;通过矿床成矿系列与成矿模式相结合的方法预测找矿远景区。结果表明,浅成中-低温热液型铅锌矿由有地幔流体和岩浆流体参与的变质流体和建造水混合或沸腾形成;岩浆热液型金矿由源于下地壳的岩浆热液与大气水混合和沸腾形成,或由源于中地壳的岩浆热液与变质水混合后再与建造水或大气水混合形成;研究区存在7个矿床成矿系列。结论认为,中秦岭华力西期—印支期含矿流体矿床成矿系列分布区中,夏河-两当弧形断裂与近东西向断裂的交汇部位是该矿床成矿系列的成矿有利部位,中秦岭华力西期—印支期岩浆相关矿床成矿系列分布区中,中酸性岩体与近东西向断裂耦合部位是该成矿系列的成矿有利部位。文章圈定找矿远景区12处。     

青海省都兰县双庆铁矿床流体包裹体及稳定同位素地球化学特征

青海省祁漫塔格-都兰成矿带是以铁铜多金属为主的成矿带,其矿产丰富但研究程度较低。双庆铁矿床是该成矿带上的典型矿床,目前尚未系统开展流体包裹体及稳定同位素地球化学研究。本文通过流体包裹体显微测温和稳定同位素分析测试研究表明,该矿床自含磁铁矿石英脉到石英硫化物阶段,流体性质略有改变。均一温度变化范围为213.7℃～327.8℃,盐度变化范围为0.53％～6.14％,密度变化范围为0.703～0.888g/cm³,属于中高温、低盐度、低密度流体; 从变化可知, 随着成矿作用继续进行,成矿均一温度与流体盐度有一定程度降低。磁铁矿的δ¹⁸O_V-SMOW 变化范围为4.4‰～10.8‰,表明磁铁矿的成矿物质来源于幔源;热液硫化物的δ³⁴S_V-CDT 值分别为0.9‰和-0.1‰,平均值为0.4‰,具陨石硫特征,反映了火成硫和深源硫的来源特点;热液方解石的δ¹³C_V-PDB 变化范围为-6.3‰～-5.2‰,表明其碳质来源于深源花岗岩浆,结合δ¹⁸O_V-SMOW 的-33.8‰～-18.3‰变化范围,通过碳氧同位素研究结果推测其碳质可能主要来自花岗岩浆,后期受大气降水影响明显。石英中δD-δ¹⁸O_H2O 结果表明,双庆铁矿床早期成矿流体以岩浆热液为主, 晚期有大量大气降水的加入, 即成矿流体为岩浆水与大气降水的混合流体。     

酒泉盆地青西凹陷下沟组湖相热水沉积岩锶同位素地球化学特征

以地质背景、物质组分和岩石组构分析为基础,对酒泉盆地青西凹陷下沟组湖相热水沉积钠长石—铁白云石岩进行了Sr同位素地球化学研究。结果表明,热水沉积岩87Sr／86Sr比值变化范围为0.712 25～0.717 81,平均值0.715 61,远高于同期海水和下沟组玄武岩,略高于代表早白垩世湖水锶同位素组成的藻灰岩,但低于基底壳源硅铝质岩,反映热流体不可能为单纯的湖水或幔源岩浆水;其中直接化学结晶沉淀的纹层状泥微晶热水沉积岩锶同位素比值变化范围较小,可代表均一化的热卤水池流体锶同位素组成特征;指示不同喷流口位置的“水爆角砾岩”锶同位素组成变化较大,但同一位置的热水角砾与胶结物锶同位素组成基本一致,说明两者应属于具相同成因意义的同期热水喷流沉积产物;综合青西凹陷下沟组湖相热水沉积岩锶同位素地球化学特征,初步推测早白垩世湖底热流体可能为富集硅铝质基底岩石高放射成因Sr的深循环下渗湖水与少量上升幔源岩浆水构成的混合热流体,可为青西凹陷早白垩世湖底热流体性质的确定以及热流体循环动力学模型和热水沉积模式的建立奠定基础。     

Metal sources of the Navan carbonate-hosted base metal deposit, Ireland: Nd and Sr isotope evidence for deep hydrothermal convection

Nd and Sr isotope analyses are presented for gangue mineral samples from the giant carbonate-hosted Navan Zn–Pb deposit, Ireland, and for rocks from which Navan metals may have been derived. Analysis of gangue minerals spanning the Navan paragenetic sequence reveals systematic evolution in the composition of the mineralising fluid. Early fluid represented by replacive dolomite exhibits the lowest initial ⁸⁷Sr/⁸⁶Sr ratio (0.7083–0.7086), closest to that of the host limestone and to Lower Carboniferous seawater, and the highest ¹⁴³Nd/¹⁴⁴Nd ratio (0.51161–0.51176). Later generations of dolomite, barite and calcite, which encompass sulphide precipitation, have higher initial ⁸⁷Sr/⁸⁶Sr ratios (maximum 0.7105) and lower initial ¹⁴³Nd/¹⁴⁴Nd ratios (minimum 0.51157). All samples have initial Nd isotope ratios that are too low to have been acquired only from the host limestone. Drill core samples of presumed Ordovician volcanic and sedimentary rocks from beneath the Navan orebody have ¹⁴³Nd/¹⁴⁴Nd and ⁸⁷Sr/⁸⁶Sr ratios at the time of mineralisation of 0.51184–0.51217 and 0.7086–0.7138, respectively. The data are interpreted to indicate mixing of sulphide-rich, limestone-buffered brine, with a metal-bearing hydrothermal fluid, which had passed through sub-Carboniferous rocks, consistent with published fluid inclusion and S isotope data. The ¹⁴³Nd/¹⁴⁴Nd ratio of this basement-derived fluid is too low to have been imparted by flow through the Devonian Old Red Sandstone, as required in models of regional fluid flow in response to Hercynian uplift. Irrespective of whether such regional fluid flow occurred, the hydrothermal Nd must have been derived from sub-Devonian rocks. These conclusions broadly support the hydrothermal convection cell model in which brines, ultimately of surface origin, penetrated to a depth of several kilometres, leaching metals from the rocks through which they passed. The data also support increasing depth of penetration of convection cells with time. Metals were subsequently precipitated in carbonate rocks at sites of mixing with cooler, sulphide-rich fluids. However, comparison of the Navan hydrothermal gangue Nd–Sr isotope data with data from Lower Palaeozoic rocks strongly suggests that the latter cannot alone account for the “basement” signature. As the Navan deposit lies immediately north of the Iapetus Suture, this suggests that the Laurentian margin includes Precambrian basement.     

广东河台金矿成矿流体特征

通过对矿石中石英包裹体的气、液相成分和氢、氧同位素分析,结果表明,河台金矿床成矿流体具多来源的特性,即为变质热液、大气降水和岩浆热液的混合流体.高村和云西矿床不同中段石英包裹体测温等温线图表明,成矿流体是自下而上,自北东向南西方向运移的,矿液运移方向与矿体侧伏方向一致.成矿的物理化学条件分析表明,成矿的环境属于中高温弱碱性还原环境.     

新疆哈密小白石头钨钼矿床流体包裹体及矿床成因

新疆哈密小白石头钨钼矿床位于中天山地块,是北疆代表性的钨钼矿床,但人们对其成矿流体性质和矿床成因类型了解得很少.矿床地质研究表明,矿体主要产于三叠纪黑云母花岗岩与蓟县系卡瓦布拉克群碳酸盐岩接触带,根据穿插关系和矿物组合,成矿阶段可划分为干矽卡岩、湿矽卡岩、氧化物、硫化物和碳酸盐5个阶段,白钨矿和辉钼矿分别形成于氧化物和硫化物阶段.流体包裹体显微测温结果表明,成矿早期（干矽卡岩阶段）流体为中高温、中高盐度的NaCl-H₂O-CO₂体系,成矿晚期（碳酸盐阶段）演变为低温、低盐度的NaCl-H₂O体系.小白石头矿床为矽卡岩型钨钼矿床,流体包裹体特征指示流体混合及降温可能是矿质沉淀的主要机制.      

Interpretation of Mineral Zoning in Submarine Hydrothermal Ore Deposits in Terms of Coupled Fluid Flow‐Precipitation Kinetics Model

Major minerals (sulfates, sulfides, quartz) are distributed in different parts of submarine hydrothermal ore deposits. For instance, the abundance of barite increases stratigraphically upwards in the massive orebodies of the Kuroko deposits (black and yellow ores), while quartz is abundant in the lower parts (siliceous ore). The different distribution of barite and quartz in the Kuroko deposits can not be accounted for by thermochemical equilibrium calculations based on the precipitation due to mixing of ascending hydrothermal solutions with ambient cold seawater. In the present study, a coupled fluid flow‐precipitation kinetics model was used to calculate the amounts of quartz, barite, and anhydrite precipitated from a hydrothermal solution mixed with seawater, assuming reasonable values for temperature, precipitation rate, fluid flow velocity, mineral surface area/fluid mass ratio (A/M), and initial concentrations of hydrothermal solution and seawater before mixing occurred. The results indicate that barite precipitates more efficiently than quartz from discharging fluids with relatively higher flow velocity, lower temperatures and under the condition of lower A/M ratios on the seafloor (black ore), whereas quartz precipitates more effectively from solutions with lower flow velocity, higher temperatures and higher A/M ratios beneath the seafloor (siliceous ore) and in the orebody (barite ore, ferruginous chert ore). Anhydrite precipitates in shallow sub‐seafloor environments with lower precipitation rates and higher A/M ratios than barite and higher precipitation rates and lower A/M ratios than quartz. These results explain the observed occurrences of barite, anhydrite, and quartz in the Kuroko deposits. Namely, barite is abundant in black ore and barite ore which formed above the seafloor, anhydrite formed in high‐permeability tuff breccias, and quartz formed in low permeability dacite intrusive bodies in the sub‐seafloor environment.     

Quantification of mixing processes in ore-forming hydrothermal systems by combination of stable isotope and fluid inclusion analyses

In the Schwarzwald area, southwest Germany, more than 400 hydrothermal veins hosting different gangue and ore mineral assemblages cross-cut the crystalline basement rocks. Many of the post-Variscan fluorite-barite-quartz veins are considered to have precipitated through mixing of a deep saline brine with meteoric, low salinity waters. This hypothesis was tested using carbon, sulfur, and oxygen isotope data of sulfides, sulfates and calcite, coupled with fluid inclusion studies. Primary hydrothermal calcites from the deposits show a positive correlation of their δ¹³C (V-PDB) and δ¹⁸O (V-SMOW) values, which range from −12 to −3‰ and from 12 to 18.5‰, respectively. Carbon and oxygen isotope compositions of paragenetically young, remobilized calcite types are shifted towards higher values and range from −12 to −1‰ and from 20 to 25‰, respectively. We developed an improved calculation procedure for modeling the covariation of carbon and oxygen isotopes in calcite resulting from mixing of two fluids with different isotopic compositions and total carbon concentrations. In our model, the carbon speciation in the two model fluid end-members and the fluid mixtures are calculated using a speciation and reaction path code. The carbon and oxygen isotope covariation of primary Schwarzwald calcites can effectively be modeled by a mixing trend of a deep saline brine and a meteoric, low salinity water. Sulfur isotope data of barites from 44 hydrothermal fluorite-barite-quartz veins vary from 9 to 18‰ (CDT), sulfide ore minerals show δ³⁴S values between −14.4 and 2.9‰. Calculated sulfide-sulfate equilibrium temperatures are in the range between 300 and 350 °C. These temperatures differ significantly from the formation temperatures of 150 to 200 °C of most of the deposits as estimated from fluid inclusions, and are interpreted as preserved paleotemperatures of the deep aquifer. This assumption has been carefully checked against possible contamination of an equilibrated sulfide-sulfate system from the deep aquifer with sulfate from surface-derived sources, considering also the kinetics of the sulfide-sulfate isotope exchange. A combination of the S isotopic results with microthermometric fluid inclusion data and constraints on the temperature of the meteoric water was used to calculate mixing ratios of the two fluid end-members. The results indicate that mass fractions of the deep saline brine in the mixed fluid were between 0.5 and 0.75. Considering all geologic, geochemical and isotopic information, we propose that the majority of the post-Variscan hydrothermal veins in the Schwarzwald area were precipitated by district-scale mixing of a homogeneous deep saline brine with meteoric waters.