热液成矿作用地球化学:以金矿为例

文中以金矿为例总结了热液成矿地球化学特征,包括热液蚀变、金在成矿热液中的地球化学行为、富集-沉淀机制以及在硫化物中的存在形式。热液蚀变过程中形成的矿物组合反映了成矿流体的地球化学特征,蚀变模式具有重要的找矿勘探意义。在热液体系中,金主要以Au-Cl或者Au-S络合物的形式进行运移,体系温度、压力、氧逸度以及硫逸度等条件的变化是导致络合物分解、金沉淀的主要机制。在较高压力条件下,金趋向于在热液蒸汽相中富集。As和Sb是金矿热液体系中常见的伴生元素,在较低硫逸度条件下,形成自然砷/自然锑-自然金组合。金从热液中沉淀后主要以显微包裹体或者固溶体金的形式赋存于黄铜矿、毒砂、磁黄铁矿以及黄铁矿等硫化物中,而硫化物中固溶体金的量主要受热液H_2S活动性的控制。     

安徽天井山金矿成矿流体特征及成矿过程初探

本文在矿床地质调研的基础上,通过主要矿石和蚀变岩石的岩矿相、SEM/EDS、流体包裹体岩相学、显微测温和成分分析,对天井山金矿成矿流体特征、流体来源及成矿过程进行了研究.结果表明,金矿化主要发育于石英脉中,少数产于蚀变围岩中,矿区蚀变以硅化、绢云母化最为发育,另发育含铁碳酸盐化、绿泥石化、黄铁矿化、黄铜矿化、方铅矿化、闪锌矿化等.金矿化发生于石英脉形成后的脆性变形阶段,与之相关的蚀变以绢云母化为主,其次为含铁碳酸盐化和硫化物矿化.金主要以自然金的形式与绢云母共生于石英脉的裂隙中或蚀变围岩中.通过与绢云母同期的流体包裹体研究表明,与金矿化有关的成矿流体为富水、含CO2的中高温(286～380℃)、低盐度流体(3.0％～5.1％,NaCleq,质量分数),单个流体包裹体的LA-ICP-MS成分分析表明,成矿流体中富含Pb、Zn、Cu、Bi、Mo、Sb等金属元素.综合流体包裹体中水的H同位素组成和流体成分特征,成矿流体主要为岩浆水的贡献.含CO2的岩浆流体沿活化的先期断裂上升并发生流体沸腾,在流体沸腾过程中CO2进入气相而改变了流体的pH值,造成金和其它金属硫化物的沉淀,同时形成石英裂隙中和围岩中的绢云母化、含铁碳酸盐化等蚀变.     

成矿热液分类兼论岩浆热液的成矿效率

根据流体中H2O、CO2、NaCl三组分的相对含量,结合H2O-NaCl体系临界压力和石盐融化曲线温度,可以将地壳中的成矿流体分为5类：大气降水、海水、盆地卤水、变质流体和岩浆流体。这种基于地壳环境中普遍存在的三元系结合流体临界性和石盐融化温度的分类,对于理解地壳中沿地温地压梯度流动流体的多样性和流体混合与不混溶具有重...     

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.     

Rare-earth element mobility during ore-forming hydrothermal alteration: A case study of Dongping gold deposit Hebei Province,China

REE mobility during hydrothermal ore-forming processes has been extensively investigated in recent years and the potential of REE to provide information about ore forming processes has commonly been recognized.The Dongping gold deposit,which is located in northwestern Hebei Province,China,occurring in the inner contact zone of the Shuiquangou syenite complex,is spatially,and probably genetically,related to the syenite,the deposit was formed under the moderate to high temperature(220℃ to 320℃),weakly acidic to weakly alkaline,rather high fo2(lgfo2=-30～-34)environment.The REE study of the host rocks,altered wall rocks,ores and gangue minerals from the deposit suggests that the REEs have been mobilized and differentiated during K-feldspathization and silicification.The extremely altered syenite enveloping auriferous quartz vein shows positive Ce anomaly and larger LREE/HREE ratio than that of the unaltered syenite.The REE concentrations and patterns of the ores are determined by the ore types and mineral assemblages,LREE/HREE ratios in the gangue quartz and hydrothermal Kfeldspars are relatively low.The most significant observation is that the gangue quartz shows significant positive Eu anomaly,whereas the hydrothermal K-feldspars show less significant or no positive Eu anomaly at all relative to the primary feldspar in the unaltered syenite. It is evident that the REEs are mobile during K-feldspathization and silicification in the ore forming process.Weak to moderate K-feldspathization caused REE mobility without apparent differentiation with the exception of extreme K-feldspathization and silicification which resulted in significant depletion of HREE and Eu and relative enrichment of Ce.The REE,Y,U,Th and Au contents of the syenite decrease as the degrees of K-feldspathization and silicification of the rocks increase towards the auriferous quartz veins.As the ores were deposited under a rather oxidized environment,Ce^4 predominated over Ce^3 .The precipitation of the former in the form of CeO2 or absorpted onto the secondary mineral assemblage resulted in the inconsistent removal of the REE and the relative Ce enrichment in the strongly altered rocks.in contrast,Eu was present mainly in a low valence state (Eu^2 ).The geochemical differences from the other REE^3 and much less sites in the secondary minerals to accommodate the Eu released form the original minerals resulted in the enrichment of Eu in the fluids.The mobility and differentiation of REE and the coherent mobilities of Y,U,Th and Au also support the argument that the syenite is one of the source rocks for gold mineralization.The REE contents and patterns of the altered rocks enveloping the auriferous quartz vein could be used as a guide for locating ore veins in mineral exploration.     

湘西北海相磷块岩中气水溶液铀多金属成矿作用

湘西北地区位于扬子陆块东南缘,在其寒武系纽芬兰统海相磷块岩的微孔隙中发现nm~μm级晶质铀矿。文章通过扫描电镜对铀矿的空间占位进行微区解剖,确定铀以超显微状态(1~4μm)的晶质铀矿形式存在于方硫镍矿中。认为超显微晶质铀矿和辉砷镍矿是同沉积鲕粒状磷块岩在较高的温压条件下,通过海底喷流气水溶液强溶蚀改造并发生结晶时,以超显微包体的形式存在于方硫镍矿中;随着温度、压力的下降,包体中富铀溶液出现过饱和,晶质铀矿从富铀溶液中结晶析出,以独立矿物晶质铀矿的形式呈超显微状态存在于方硫镍矿中。晶质铀矿在中高温热液成矿作用中以超显微状态呈立方体、八面体、立方体与八面体的聚形以及块状体产出,对认识天然条件下晶质铀矿生成的物理化学条件具有重要意义。同时,晶质铀矿呈超显微状态存在的实例对该类型铀矿存在形式的发现和研究具有重要启迪,为揭示扬子陆块东南缘的陆缘裂陷中海底喷流成矿示踪提供了依据。     

团结沟金矿氧氢同位素组成特征与成矿关系的研究

氢氧同位素研究表明团结沟金矿成矿热液水主要为大气降水来源，成矿W／R值较小(0.05～0.15)。通过对东露采区蚀变岩石的系统采样和氧同位素分析，获得氧同位素平面等值线趋势图，指示出矿体与高18O蚀变花岗斑岩有密切关系。利用大气降水二阶段理想演化定性解释了高18O蚀变岩石成因。一个浅钻岩心的氧同位素组成向深部具明显升高趋势，指示金矿主矿体还在深部。     

广东河台金矿成矿物理-化学条件及找矿方向

本文通过对河台金矿流体包裹体的研究,从包裹体一般特征,成矿温度、压力,成矿流体特征、来源等方面系统分析了成矿的物理化学条件,并进一步探讨了成矿流体在不同成矿期、不同成矿阶段的演化以及流体的演化在成矿过程中的意义。通过这些研究,结合成矿地质条件、矿床地质特征以及矿物学等方面的研究成果,提出了本区的找矿方向。     

含金剪切带蚀变特征及其与金成矿的关系——以新疆天格尔金矿带为例

含金剪切带剪切变形过程中构造、流体-岩石相互作用导致系统内组分的迁移和再分配，这些过程控制着含金剪切带内蚀变特征及其金的成矿作用。在含金剪切带脆-韧性变形域内，成矿层次从深到浅矿石类型由蚀变糜棱岩型向石英脉型过渡，矿床成因类型由韧性剪切带型向蚀变破碎带型过渡，是主期剪切成岩成矿过程中不同时空演化阶段的产物。     

松树岗钽铌钨锡矿床石英脉的矿物学研究——云母和黑钨矿成分对热液成矿过程的制约

矿石矿物和脉石矿物的成分演化蕴含了热液成矿过程的详细信息。本文基于岩相学观察,从云母和黑钨矿着手,利用电子探针和LA-ICP-MS分析技术,对赣东北松树岗Ta-Nb-W-Sn矿床的浅部热液成矿过程开展了研究。结果表明,松树岗矿床浅部的钨锡矿体的石英脉,从早到晚,由深至浅,可以划分为黑钨矿石英脉、锡石石英脉、硫化物石英脉和贫矿石英脉。4类石英脉中都含有早期的铁锂云母和晚期的白云母与铁的氧化物集合体,深部早期脉中的云母以铁锂云母为主,而浅部晚期脉中的云母以白云母为主。与早期铁锂云母相比,晚期白云母具有明显较低的Ti、Na、Rb、Cs、W、Nb、Zn、Li_2O含量和明显较高的Pb、Cu、B含量。从深部早期脉到浅部晚期脉,云母成分存在如下演化趋势:Ti、Na、W、Nb含量降低,Pb、Zn、Cu、Li_2O、B含量增高。不同深度的黑钨矿石英脉中含有两种不同成分的黑钨矿,属同一期演化早晚形成。相对于热液流体早期沉淀的黑钨矿,晚期黑钨矿具有明显较低的Nb、Ta、Zr、Hf、Ti、Sn、U、In、Sc含量和明显较高的Mo含量和Fe O/MnO值。云母和黑钨矿主微量元素成分的演化揭示了在松树岗矿床浅部的热液成矿早期以岩浆热液为主,晚期由于水岩反应的加强有较多围岩物质贡献。     

印支晚期冲断-褶皱活动在黔西南中部卡林型金矿成矿中的作用——以地震勘探资料为例

地震勘探资料对黔西南中部卡林型金矿赋存层位上二叠统龙潭组煤系地层、东吴不整合面和广西不整合面显示良好.该地区卡林型金矿主要受古隆起和冲断-褶皱构造的双重控制.根据卡林型金矿在冲断-褶皱构造中的位置,可以将其划分为2类,即断层控制型金矿和断层伴生型金矿.在断层控制型金矿床中,断层“上陡下缓”,为低角度逆冲断层,断层上盘常...     

广西龙头山金矿床多期次成矿及金银元素的分布特征

广西龙头山金矿床在沉积岩或岩浆岩中均普遍发育电气石化,不同的岩石均出现电气石化说明电气石是热液作用的产物;电气石化强烈的地段多发现金矿物说明电气石与金矿物的关系密切。硫化物的互相穿插和交代现象,说明矿床是经过多期次热液叠加的结果。金元素分布在硫化物中较脉石多,银元素在硫化物和脉石中没有太大的变化;金银以较均匀的点相间分布,未形成矿物固溶体相;在出现金矿物的地段,金、银的含量明显上升,铁、硫大大减少。     

安徽铜陵冬瓜山铜(金)矿床成矿流体特征及成矿过程探讨

流体包裹体的研究表明冬瓜山铜（金）矿床原生流体包裹体分为气液两相水溶液包裹体（Ⅰ型）和含子矿物多相水溶液包裹体（Ⅱ型）,以Ⅰ型包裹体为主。同一矿物中多种类型包裹体共存,且均一温度相近、均一方式不同,显示成矿过程中流体可能发生过沸腾作用。流体包裹体均一温度大致可分为318.8~547.5℃、220.1~378.2℃和196.7~263.2℃三个区间,对应流体密度和均一压力分别为0.86~0.98 g/cm³和（219~661）×10⁵ Pa、0.66~1.08 g/cm³ 和（26~190）×10⁵ Pa、0.88~0.96 g/cm³和（17~48）×10⁵ Pa,盐度w（NaCl_eq）峰值为12%~16%和40%~48%。结合成矿流体的演化特征,对成矿过程进行了探讨,认为流体的不混溶是引起成矿物质沉淀富集成矿的重要因素。     

Chemical study of tectonically controlled hydrothermal dolomitization: an example from the Lessini mountains,Italy

In the Central Southern Alps (Feltre, Verona — Italy), a 750 m thick interval of Jurassic and Cretaceous pelagic limestones shows post-depositional partial brecciation and dolomitization. The overlying 500 m thick Tertiary sedimentary sequence is unaffected. Through the Paleogene, mostly submarine, mafic volcanism has been documented in the area. Small-scale extensional features were observed in the limestone near the contact with the dolomitized breccias. Their orientations measured in the field correspond to the tectonic framework of the area and give evidence for the contemporaneousness of the volcanic activity and the brecciation. The distribution and petrologic characteristics of the basalts, combined with the orientation of the extensional features observed in the field, allow a paleotectonic reconstruction. This tectonic scenario can be viewed as a back-arc extension, an eastward prolongation of the spreading that divided Southern France from the Sardinia-Corsica-Calabria block, generating the Ligurian-balearic basin in the Late Oligocene.The dolomite is fine-grained to sucrosic, with a microamygdaloidal porosity, partially filled with ankerite and calcite. The matrix shows a homogeneous, orange-red cathodoluminescence, indicating a single phase of iron-poor dolomite. The carbonate fraction consists of more than 90% dolomite. The dolomite is almost stoichiometric (Ca_0.6Mg_0.4 to Ca_0.5Mg_0.5). The ¹³C values of the dolomite are less than 1%. more negative than the unaffected limestone. The ¹⁸O values are between –5%. to –13%., with a depletion of 2–11%. relative to the undolomitized limestone. The depleted oxygen isotope ratios in the dolomitized rock can be derived either from fluids impoverished in the heavy isotopes (e.g. meteoric water) or high temperatures. The unvaried carbon isotopic ratios make the second interpretation the most acceptable. As the⁸⁷Sr/⁸⁶Sr values increase from a mean of 0.7077 in the unaffected limestones to 0.7085 in the dolomitized limestones, a derivation of the dolomitizing fluids from the volcanic rocks can be excluded. Comparing the obtained data with the Phanerozoic seawater isotope curve, however, the radiogenic Sr may be derived from marine waters of Late Oligocene-Early Miocene age. Microthermometric analyses of the fluid inclusions in the dolomite crystals from the bulk rocks and from the veins suggest a trapping temperature ranging from a minimum of 70°C (dolomite rock) to a maximum of 120°C (dolomite in veins). The solution contained in the inclusions is water with NaCl and MgCl₂ with salinities of 46%. (dolomite bulk rock) and 17%. (dolomite in veins). The pressure correction calculated from the fluid inclusion data is about 250 bars, which roughly correspond to the lithostatic pressure over the Mesozoic limestones in the Early Miocene.These results point to a hydrothermal origin of the dolomitization during the Late Oligocene-Early Miocene, as ascertained from the strontium isotope and fluid inclusion data. The circulation of hot marine water through the brecciated limestones in convective cells, triggered by the geothermal gradient related to the volcanic activity, is the proposed hydrodynamic model. Hydrologie considerations demonstrate that the proposed model is feasible.

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Zusammenfassung In den zentralen Südalpen (Feltre, Verona — Italien) findet sich eine etwa 750 m dicke Abfolge jurassischer und kretazischer pelagischer Kalke, die nach der Ablagerung zum Teil breckziert und dolomitisiert wurde, während die darüberliegenden 500 m mächtigen tertiären Sedimente keine Dolomitisierung zeigen. Im Paläogen ist im Gebiet ein mafischer, überwiegend mariner Vulkanismus dokumentiert. Kleinmaßstäbliche listrische Brüche in Kalken am Kontakt mit der dolomitisierten Breckzie entsprechen geometrisch einem großräumigen extensiven Regime im Paläogen. Sie beweisen die Gleichzeitigkeit der vulkanischen Aktivität und der Breckzierung. Die Verteilung und petrographischen Eigenschaften der Basalte, mit der Geometrie der Extensionsstrukturen, erlauben eine paläotektonische Rekonstruktion. Diese tektonische Situation entspricht einem Back-arc-basin und stellt die östliche Verlängerung des ligurisch-balearischen Beckens dar, das Südfrankreich vom Sardisch-Korsisch-Kalabrischen-Block im späten Oligozän getrennt hat.Die ¹³C Werte der Dolomite sind weniger als 1%. negativer als die entsprechender nicht dolomitisierter Kalke. Die ¹⁸O-Werte (relativ zum PDB Standard) variieren zwischen –5%. und –13%., das ist 2 bis 11%. negativer als die nicht dolomitisierter Kalke. Dies wird auf erhöhte Bildungstemperaturen zurückgeführt. Ein Anstieg der⁸⁷Sr/⁸⁶Sr-Signaturen im Mittel von 0.7077 in den nicht dolomitisierten Kalken auf 0.7085 in den dolomitisierten Kalken schließt eine Herkunft der dolomitisierenden Fluide von den vulkanischen Gesteinen aus. Beim Vergleich der Isotopensignaturen mit der phanerozoischen Meerwasser-Isotopenkurve, könnte aber das radiogene Strontium von spät oligozänem — früh miozänem Meerwasser kommen. Mikrothermometrische Analysen flüssiger Einschlüsse in Dolomitkristallen im Gestein und in Adern deutet auf eine Einschlußtemperatur von 70°C (Dolomitgestein) bzw. 120°C (Dolomit in Adern) hin. Die Lösung in den Einschlüssen ist Wasser mit NaCl und MgCl₂, mit einer Salinität von 46%. (Dolomitgestein) bzw. 17%. (Adern). Die aus den Einschlüssen berechnete Druckkorrektur ist etwa 250 bar. Dies entspricht ungefähr der früh miozänen Gesteinssäule über den mesozoischen Kalken.Aufgrund dieser Daten wird eine hydrothermale Bildung der Dolomite im späten Oligozän - frühen Miozän postuliert. Es wird ein hydrodynamisches Modell vorgeschlagen, in dem aufgeheiztes Meerwasser konvektiv durch die breckzierte mesozoische Abfolge zirkuliert. Als Motor wirkt ein vulkanischer geothermischer Gradient. Dieses Modell läßt sich mit hydrologischen Betrachtungen testen und stützen.

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Résumé Dans la partie sud des Alpes Centrales (Feltre, Verone: Italie) il existe une succession, épaisse de 750 m, de calcaires pélagiques jurassiques et crétacés, qui ont subi après leur sédimentation une bréchification et une dolomitisation partielles. Les sédiments tertiaires surincombants, épais de 500 m, ne sont pas affectés par ces phénomènes. Un volcanisme paléogène mafique, essentiellement sousmarin, a été reconnu dans la région. Dans les calcaires, au contact de la brèche dolomitisée, existent des cassures listriques de petite échelle dont la géométrie témoigne d'un régime extensif général au Paléogène. Leurs orientations, mesurées sur le terrain, indiquent la contemporanéité de l'activité volcanique et de la bréchification. La distribution et les caractères pétrologiques des basaltes, combinés à la géometrie des structures extensives, permet une reconstitution paléotectonique. Celle-ci montre une extension dans un bassin d'arrière-arc, prolongement oriental de l'expansion qui, à l'Oligocène supérieur, a séparé du sud de la France le bloc corsico-sardo-calabrais en créant le bassin liguro-baléare.La dolomie, finement grenue à saccharoïde, possède une porosité à vides micro-amygdaloïdes, partiellement occupés par de l'ankérite et de la calcite. La matrice présente une cathodoluminescence homogène rouge-orange, indiquant la présence d'une seule phase constituée de dolomite pauvre en Fe. La fraction carbonatée consiste en dolomite pour plus de 90%. Cette dolomite est à peu près stoechiométrique (Ca_0,6Mg_0,4 à Ca_0,5Mg_0,5). Les rapports ¹³C de la dolomie sont inférieurs de moins de 1%. à ceux du calcaire intact. Les rapports ¹⁸O sont compris entre –5%. et –13%., soit 2 à 11%. inférieurs à ceux du calcaire non dolomitisé. Cette baisse du rapport isotopique peut provenir soit de fluides appauvris en isotopes lourds (p. ex. l'eau météorique), soit d'une température élevée; la constance des rapports isotopiques du C rend cette deuxième explication la plus plausible. Le rapport⁸⁷Sr/⁸⁶Sr passe d'une valeur moyenne de 0,7077 dans les calcaires non affectés à 0,7085 dans les calcaires dolomitisés; cet accroissement exclut une origine volcanique pour les fluides dolomitisants. En comparant ces valeurs à la courbe isotopique du Sr de l'eau de mer au Phanérozoïque, on peut déduire que le Sr radiogénique est dérivé d'eaux marines d'âge oligocène tardif à miocène inférieur. L'analyse microthermométrique des inclusions fluides contenues dans les cristaux de dolomite suggère une température de formation qui va de 70°C (dans la roche) à 120° (dans les veines). Le contenu de ces inclusions est une solution aqueuse de NaCl et MgCl₂ avec une salinité de 44%. (dans la roche) et de 17%. (dans les veines). La correction de pression calculée à partir des inclusions fluides est d'environ 250 bars, ce qui correspond grosso modo à la pression lithostatique qui s'exerçait au Miocène inférieur sur les calcaires mésozoïques.Sur la base de ces données, on conclut à une origine hydrothermale de la dolomie au cours de l'Oligocène supérieur - Miocène inférieur. Le modèle hydrodynamique proposé fait appel à la circulation convective, à travers le calcaire bréchié, d'eau marine échauffée grâce au gradient géothermique élevé dû à l'activité volcanique. Ce modèle est en accord avec des considérations hydrologiques.

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Thermodynamic model of ore-forming processes in a submarine island-arc hydrothermal system

A thermodynamic model suggested for ore-forming processes in a hydrothermal system (HS) in an island arc is based on the technique suggested earlier in [1] for simulating ore-forming hydrothermal systems in mid-oceanic ridges. This technique make use of the principle of flow-through multistep reactor and encompasses (a) the region where hydrothermal solutions are generated when seawater interacts with rocks (descending convection branch); (b) the region where material is transported with the solution at decreasing pressure (feeder channel); and (c) the region where the ore material is deposited (orebody). Hydrothermal systems in island arcs exhibit the following distinctive features taken into account in the model: (1) the composition of the host crustal rocks (rocks of mafic-acid composition instead of basalt and serpentinite) and (2) possible significant involvement of magmatic gases in the feeding of the hydrothermal system. The naturally occurring prototype of the simulated system is the hydrothermal system in the caldera of a submarine volcano in an island arc. The model is simulated in a number of variants in which the hydrothermal fluid is exogenic (heated seawater convecting through hot volcanic rocks), magmatic, or mixed (magmatic plus exogenic) is involved. The simulations were carried out using the HCh version 4.3 [2] program package for the multisystem H-O-K-Na-Ca-Mg-Fe-Al-Si-C-S-Cl-Cu-Zn-Pb-As-Sb-Ag-Au at temperatures of 25?C370°C and pressures of 10?C500 bar. The multisystem included 88 possible solid phases and aqueous solution with 95 species. The thermodynamic properties of compounds were calculated using the UNITHERM databank. The model is underlain by the principle of multiwave flow-through multistep reactor (MFTMR) with a starting rock/water (R/W) ratio of 1: 1. As progressively more solution portions passed through the rocks, the participation of fresh rock in the interaction accordingly diminished because the rock material was gradually exhausted in the system. The magmatic fluid had a composition selected based on data on fumaroles at Kudryavyi volcano [3] with a correction for the degassing pressure. The evolution of ore deposition was simulated in compliance with the scheme described in [4], which was implemented using the technology of ??openness from above?? [3]. The model was simulated with various compositions of the host rocks (basalts, andesites, dacites, and rhyolites) and the origin of the fluid (magmatic fluid alone, seawater alone, and variable proportions of both). Our simulation results indicate that the metallogeny (relative enrichment in Pb, As, Sb, or Ag) of island-arc ore deposits is controlled by the abundances of metals in the host rocks predominant in the hydrothermal system. The mineralogy and geochemistry of ores generated in arc hydrothermal systems are predetermined by the effective transport of metalloids (S, As, and Sb) that have a high migration capacity in these systems. Magmatic gases introduced in the hydrothermal systems play dualistic roles in the ore-forming processes. If the hydrothermal fluid in a hydrothermal system is dominated by magmatic components, deposits of native sulfur are formed, and the precipitation of base metal is thereby suppressed because of the high acidity of the generated hydrothermal solutions. The involvement of magmatic gases in an amount of a few percent in a hydrothermal system enhances the overall oregenerating potential of the system in terms of sulfide ores.     

Thio complexes of gold and the transport of gold in hydrothermal ore solutions

The solubility of gold in aqueous sulphide solutions has been determined from pH_20°C ≈ 4 to pH_20°C ≈ 9.5 in the presence of a pyrite-pyrrhotite redox buffer at temperatures from 160 to 300°C and 1000 bar pressure. Maximum solubilities were obtained in the neutral region of pH as, for example, with m_NaHS = 0.15 m, pH_20°C = 5.96, T = 309°C, P = 1000 bar where a gold solubility of 225 mg/kg was obtained. It was concluded that three thio gold complexes contributed to the solubility. The complex Au₂(HS)₂S^2? predominated in alkaline solution, the Au(HS)₂^? complex occurred in the neutral pH region, and in the acid pH region, it was concluded with less certainty that the Au(HS)° complex was present. Formation constants calculated forAu₂(HS)₂S^2? and Au (HS)₂^? emphasize their high stability. In the temperature range from 175 to 250°C, values of pβ for Au₂(HS)₂S^2? vary from ?53.0 to 47.9 (±1.6) and from ?23.1 to ?19.5 ( ± 1.5) for Au(HS)₂^?. Equilibrium constante for the dissolution reactions, $\text{Au° + H}{}_2\text{S + HS}{}^{\mathrm{?}}\text{? Au(HS)}{}_2{}^{\mathrm{?}}\text{+}\text{1}\text{2}\text{H}{}_2$ and 2Au° + H₂S + 2H8^? ? Au(HS)₂^? + H₂ vary from pK_m = +2.4 to +2.55 (±0.10) for Au₂(HS)₂S^2? and from pK_n = + 1.29 to + 1.19 (±0.10) for Au(HS)₂^? over the temperature range 175 to 250°C. Enthalpies of these dissolution reactions were calculated to be ΔH_m° = ?5.2 ±2.0 kcal/mol and ΔH_n° = +1.7 ±2.0 kcal/mol respectively. It was concluded that gold is probably transported in hydrothermal ore solutions as both thio and chloro complexes and may be deposited in response to changes in temperature, pressure, pH, oxidation potential of the system and total sulphur concentration.