Sulfur redox reactions: Hydrocarbons,native sulfur,Mississippi Valley-type deposits,and sulfuric acid karst in the Delaware Basin,New Mexico and Texas

Hydrocarbons, native sulfur, Mississippi Valley-type (MVT) deposits, and sulfuric acid karst in the Delaware Basin, southeastern New Mexico, and west Texas, USA, are all genetically related through a series of sulfur redox reactions. The relationship began with hydrocarbons in the basin that reacted with sulfate ions from evaporite rock to produce isotopically light ( ³⁴S = -22 to -12) H₂S and bioepigenetic limestone (castiles). This light H₂S was then oxidized at the redox interface to produce economic native sulfur deposits ( ³⁴S = -15 to +9) in the castiles, paleokarst, and along graben-boundary faults. This isotopically light H₂S also migrated from the basin into its margins to accumulate in structural (anticlinal) and stratigraphic (Yates siltstone) traps, where it formed MVT deposits within the zone of reduction ( ³⁴S = -15 to +7). Later in time, in th zone of oxidation, this H₂S reacted with oxygenated water to produce sulfuric acid, which dissolved the caves (e.g., Carlsbad Cavern and Lechuguilla Cave, Guadalupe Mountains). Massive gypsum blocks on the floors of the caves ( ³⁴S = -25 to +4) were formed as a result of this reaction. The H₂S also produced istopically light cave sulfur ( ³⁴S = -24 to -15), which is now slowly oxidizing to gypsum in the presence of vadose drip water.     

密西西比河谷型(MVT)铅锌矿床:认识与进展

MVT铅锌矿床作为一种重要的沉积型铅锌矿床类型一直受到人们的重视,近年来取得了许多重要进展,主要体现在6个方面:①MVT铅锌矿床研究范围逐渐扩大,在全世界发现了诸多相关矿床,多归为其亚类;②提出该类矿床主要分布在造山带的前陆盆地、逆冲推覆带等构造挤压环境,少数产于陆内伸展环境,改变了MVT矿床与板块构造无关的观点;③放射性同位素测年和古地磁测年技术广泛应用,获得了大量成矿年龄数据,表明MVT矿床主要形成在显生宙石炭纪—早三叠纪和白垩纪—第三纪两个时期,与地球演化史上全球尺度的板块会聚时间密切相关;④流体包裹体研究揭示了成矿流体温度主要为90~150℃,盐度w(NaCleq)为10%~30%,成矿流体具有盆地卤水特征,卤水源自近地表蒸发海水或围岩蒸发盐,同位素资料反映Pb来自地壳岩石,S来自地壳岩石或沉积物中残留的硫酸盐。成矿流体驱动机制包括构造挤压和重力驱动两种;⑤古地磁和生物化学标志物判定,单期热液活动可能持续几千到几万年,而整个矿床形成可能持续几个到十几个百万年;⑥矿质沉淀机制主要有3种:流体混合、硫酸盐还原和还原硫机制,不同成矿环境可能受不同机制控制。     

Geochemical constraints on the modes of carbonate precipitation in peridotites from the Logatchev Hydrothermal Vent Field and Gakkel Ridge

The ultramafic-hosted Logatchev Hydrothermal Field (LHF) at 15°N on the Mid-Atlantic Ridge and the Arctic Gakkel Ridge (GR) feature carbonate precipitates (aragonite, calcite, and dolomite) in voids and fractures within different types of host rocks. We present chemical and Sr isotopic compositions of these different carbonates to examine the conditions that led to their formation. Our data reveal that different processes have led to the precipitation of carbonates in the various settings. Seawater-like ⁸⁷Sr/⁸⁶Sr ratios for aragonite in serpentinites (0.70909 to 0.70917) from the LHF are similar to those of aragonite from the GR (0.70912 to 0.70917) and indicate aragonite precipitation from seawater at ambient conditions at both sites. Aragonite veins in sulfide breccias from LHF also have seawater-like Sr isotope compositions (0.70909 to 0.70915), however, their rare earth element (REE) patterns show a clear positive europium (Eu) anomaly indicative of a small (< 1%) hydrothermal contribution. In contrast to aragonite, dolomite from the LHF has precipitated at much higher temperatures (~ 100 °C), and yet its ⁸⁷Sr/⁸⁶Sr ratios (0.70896 to 0.70907) are only slightly lower than those of aragonite. Even higher temperatures are calculated for the precipitation of deformed calcite veins in serpentine–talc fault schists form north of the LHF. These calcites show unradiogenic ⁸⁷Sr/⁸⁶Sr ratios (0.70460 to 0.70499) indicative of precipitation from evolved hydrothermal fluids. A simple mixing model based on Sr mass balance and enthalpy conservation indicates strongly variable conditions of fluid mixing and heat transfers involved in carbonate formation. Dolomite precipitated from a mixture of 97% seawater and 3% hydrothermal fluid that should have had a temperature of approximately 14 °C assuming that no heat was transferred. The much higher apparent precipitation temperatures based on oxygen isotopes (~ 100 °C) may be indicative of conductive heating, probably of seawater prior to mixing. The hydrothermal calcite in the fault schist has precipitated from a mixture of 67% hydrothermal fluid and 33% seawater, which should have had an isenthalpic mixing temperature of ~ 250 °C. The significantly lower temperatures calculated from oxygen isotopes are likely due to conductive cooling of hydrothermal fluid discharging along faults. Rare earth element patterns corroborate the results of the mixing model, since the hydrothermal calcite, which formed from waters with the greatest hydrothermal contribution, has REE patterns that closely resemble those of vent fluids from the LHF. Our results demonstrate, for the first time, that (1) precipitation from pure seawater, (2) conductive heating of seawater, and (3) conductive cooling of hydrothermal fluids in the sub-seafloor all can lead to carbonate precipitation within a single ultramafic-hosted hydrothermal system.     

Geochemical constraints on the origin of the Kicking Horse and Monarch Mississippi Valley-type lead-zinc ore deposits, southeast British Columbia, Canada

Two Mississippi Valley-type (MVT) ore deposits, Kicking Horse and Monarch, have been studied with the aim of comparing the ores at the two localities and to characterize the origin of the mineralizing fluids and the ore formation process(es). Both deposits are hosted by the Middle Cambrian Cathedral Formation carbonate host rocks, Kicking Horse on the north and Monarch on the south flank of the Kicking Horse valley near Field (SE British Columbia). The ore bodies are situated at the transition of (western) basinal to (eastern) shallow-water strata of the paleo-Pacific passive margin succession in the Cordilleran Foreland Province of the Western Canada Sedimentary Basin. Both deposits are related spatially to normal faults. In both localities, the ore minerals are dominated by pyrite, sphalerite, and galena. Dolomite, minor quartz, and calcite are also present in close association with the ores. The salinity (21–30 wt% NaCl eq.) and homogenization temperatures (63–182°C) measured in fluid inclusions in carbonate, quartz, and sphalerite lie within the typical range of MVT fluid conditions. The good stoichiometry (50–53 mol% CaCO₃), low δ¹⁸O values (−21 to −14‰ Vienna Peedee belemnite) and relatively high homogenization temperatures (>95°C) of the dolomite suggest the dolomites were formed under burial diagenesis. The ore-forming fluids probably interacted with siliciclastic units, based on elevated Li contents and ⁸⁷Sr/⁸⁶Sr ratios, which are highest in the dolomite type after the main ore stage. We propose that the ores formed from the mixing of a downward-infiltrating, sulfur-bearing halite-dissolution fluid with an upward-migrating, metal-rich evaporated seawater fluid, which had already undergone minor mixing with a dilute fluid.     

特提斯域的密西西比河谷型(MVT)铅锌矿床

特提斯域是全球最重要的密西西比河谷型(MVT)铅锌矿床富集区,矿床广泛地分布在陆-陆碰撞造山带两侧的陆块上,就位于碰撞形成的褶皱-逆冲带和前陆带内,成矿通常发生在碰撞挤压作用晚期或之后、区域处于走滑或伸展的阶段。矿床、矿体的就位与张性断裂密切相关,主要控矿因素有蒸发盐底辟构造、碳酸盐岩溶蚀垮塌构造、蒸发盐溶蚀垮塌构造、高孔隙度白云岩、含重晶石地层等。油气流体在许多矿床和矿集区出现,其主要通过与硫酸盐发生反应为铅锌成矿提供还原硫。陆-陆碰撞的大地构造环境、大量的蒸发盐、丰富的油气流体是特提斯域富集MVT矿床的重要原因,域内寻找MVT矿床的潜力巨大。     

川滇黔地区MVT铅锌矿床分布、特征及成因

位于扬子地台西南缘的川滇黔铅锌多金属成矿区是中国重要的铅、锌、银、锗生产基地,目前在该成矿区已经发现大、中、小型铅锌矿床和矿点400多处。经过对比研究,这些矿床的赋矿围岩为震旦系一二叠系碳酸盐岩,矿体明显受控于断裂构造,并伴随有强烈的白云岩化和方解石化,以低温、低盐度为特征,成矿时代可能为中生代,成矿物质主要来自地层本身。它们为受热对流循环流体经过成矿物质萃取、搬运和卸载而成矿,是大陆边缘造山带东侧伸展带中的产物,属于比较典型的密西西比河谷型铅锌矿床。     

Origin of Ore-Forming Fluids of Mississippi Valley-Type （MVT） Pb-Zn Deposits in Kangdian Area, China

Analyses of fluid-inclusion leachates from ore deposits show that Na/Br ratios are within the range of 75 - 358 and Cl/Br 67 - 394, respectively, and this variation trend coincides with the seawater evaporation trajectory on the basis of the Na/Br and Cl/Br ratios. The average Cl/Br and Na/Br ratios of mineralizing fluids are 185 and 173 respectively, which are very close to the ratios ( 120 and 233 ) of the residual evaporated seawater past the point of halite precipitation. It is suggested that the original mineralizing brine was derived from highly evapo-rated seawater with a high salinity. However, the inclusion fluids have absolute Na values of 69.9—2606.2 mmol kg^-1 and Cl values of 106.7 — 1995.5 mmol kg^-1. Most of the values are much less than those of seawater: Na, 485 mmol kg^-1 and Cl, 566 mmol kg^-1 , respectively; the salinity measured from fluid inclusions of the deposits ranges from 2.47 wt% to 15.78 wt% NaCl equiv. The mineralizing brine has been diluted. The δ ^18O and δD values of ore-forming fluids vary from -8.21‰ to 9.51‰ and from -40.3‰ to -94.3‰, respectively. The δD values of meteoric water in this region varied from - 80‰ to - 100‰ during the Jurassic. This evidenced that the ore-forming fluids are the mixture of seawater and meteoric water. Highly evaporated seawater was responsible for leaching and extracting Pb, Zn and Fe, and mixed with and diluted by descending meteoric water, which resulted in the formation of ores.     

Fluorite deposits at Encantada–Buenavista, Mexico: products of Mississippi Valley type processes

Petroleum and aqueous fluid inclusions from the Encantada–Buenavista fluorite mineralized zone in northern Mexico were analyzed by microthermometry, UV fluorescence, Raman Spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR) and Confocal Scanning Laser Microscopy (CSLM) to evaluate the geochemical evolution of the mineralizing fluids. Two-phase (petroleum or brine+vapor) and three-phase (petroleum+brine+vapor) inclusions are described. Aqueous and petroleum-rich inclusions commonly occur in the same plane. Vapor-decrepitated and stretched fluid inclusions are present. A low-salinity methane-saturated fluid and a high salinity-fluid with highly variable methane contents are recognized. H₂S is not quantified but is always detected in close association with methane. Petroleum inclusions are of two types: a low methane petroleum fluid (20 mol%) with low T_h (60 °C) and a petroleum fluid with a methane of content near 30 mol% and a T_h of 90 °C.Pressure and temperature diagrams for the aqueous and petroleum inclusions show three main intersects that allow P–T–X reconstruction of fluid evolution at La Encantada–Buenavista. A CH₄- and H₂S-rich low-salinity brine was mixed with oil that migrated under hydrostatic conditions with a thermal gradient of 70 °C/km. The arrival and mixing of a high-salinity aqueous fluid produced overpressure to 300 bars. A return to hydrostatic conditions was accompanied by an increase in the thermal gradient.The brine related to the fluorite orebodies appears to have a genetic relationship with the brines reported from the Jurassic petroleum basins located west of the fluorite bodies and similarities with reported fluids from Mississippi Valley type deposits. It is interpreted that the fluorine-rich fluids migrated toward the platform margins during the mid-Tertiary (30 to 32 Ma) using extension zones related to Basin and Range tectonism. Mixing of two different brines was responsible for precipitation and mineralization. Heat from magmas, related to tectonic extension, caused decrepitation and changes in the shape of fluid inclusions near the contact zones.     

胶东金矿床碳酸盐矿物的碳-氧和锶-钕同位素地球化学研究

对胶东四类金矿床(盆地边缘砾岩型、斑岩型-浅成热液型、石英脉型和破碎带蚀变岩型)矿石中的碳酸盐矿物开展了系统的碳-氧同位素和锶-钕同位素地球化学研究。研究结果表明，与宏观的成矿地质条件和矿床地质特征相对应，山东金矿床可能有亲岩浆岩和亲沉积盆地两个不同的成矿系统。前者包括斑岩型-浅成热液型、石英脉型和破碎带蚀变岩型三类金矿床，后者指盆地边缘砾岩型金矿床，二者具有不同的碳-氧和锶-钕同位素地球化学特征。山东亲岩浆岩系列的金矿床，其锶-钕同位素与同时代的幔源岩浆岩一致，碳同位素显示幔源碳和岩浆碳的特征，氧同位素则显示初生水与大气降水不同比例混合的可能性，因此有可能是以CO2为主、富合成矿金属的地幔流体与浅部下渗大气降水相互作用的结果。而与岩浆岩关系不密切、主要受盆地边缘断裂控制的盆地边缘砾岩型金矿床，其碳-氧和锶-钕同位素组成均较分散，可能主要与地壳浅部下渗大气降水对上地壳各种岩石淋滤萃取演化而成的成矿流体有关。     

扬子板块周缘MVT型铅锌矿床闪锌矿微量元素组成特征与指示意义:LA-ICPMS研究

扬子板块周缘铅锌多金属成矿带内分布着数以百计的沉积岩容矿型铅锌矿床,它们不仅是我国主要的铅锌矿产地,同时也是重要的稀散元素(Ge、Ga等)生产基地。本次研究采用LA-ICPMS技术分别测定了扬子板块西南缘的会泽铅锌矿床、金沙厂铅锌矿床、大梁子铅锌矿床,扬子板块北缘的马元铅锌矿床以及扬子板块东南缘的凤凰茶田锌(铅)汞矿床中闪锌矿的微量元素组成,以揭示闪锌矿中微量元素(稀散元素)的富集规律和赋存状态,并为矿床成因类型的厘定及稀散元素矿产资源综合利用提供更多依据。LA-ICPMS微量元素测定结果显示闪锌矿中不同微量元素(稀散元素)分布不均匀,但这些矿床中闪锌矿总体以富集稀散元素Ge、Ga、Cd,贫In、Se、Tl、Te为特征,其Fe、Mn含量要明显低于与岩浆热液有关的高温闪锌矿,指示了扬子板块周缘铅锌矿床可能形成于中-低温成矿流体,而与岩浆热液无直接的成因联系,此外这些矿床中闪锌矿富Ge贫In的特征与其他的密西西比河谷型铅锌矿床(MVT)一致。同时,本次研究综合分析了闪锌矿中不同微量元素(稀散元素)之间的相关关系,并与闪锌矿微量元素LA-ICPMS时间分辨率特征相结合,研究表明:这些铅锌矿床中稀散元素Ge可能主要通过3Zn2+?Ge4++2(Cu+,Ag+)和2Zn2+?Ge4++□(晶体空位)的替代方式进入闪锌矿,Ga在闪锌矿中富集机理主要为2Zn2+?(Cu,Ag)++(Ga,As,Sb)3+。此外,为进一步揭示不同成因类型铅锌矿床中稀散元素的富集规律,本文还系统对比了全球范围内不同类型铅锌矿床闪锌矿的稀散元素(均为LA-ICPMS数据)组成特征,并初步探讨了造成不同成因闪锌矿中稀散元素(Ge、Ga和In)差异性富集的主要控制因素,研究表明:(1) Ge在中低温盆地卤水成矿系统(MVT和SEDEX矿床)和岩浆-火山热液成矿系统(浅成脉状铅锌矿床和VMS矿床)形成的闪锌矿中均可能富集成矿,但中低温浅成脉状矿床中Ge的富集程度要明显高于高温脉状矿床,指示了成矿温度是控制闪锌矿中Ge富集的一个重要因素。(2)铅锌矿床闪锌矿中In主要为岩浆来源,In倾向于在成矿温度较高的岩浆及火山热液成因铅锌矿床中富集成矿,而壳源的MVT和SEDEX型铅锌矿床中闪锌矿均贫In。可见除形成温度外,成矿物质来源是决定闪锌矿是否富In的关键因素。(3)除矽卡岩型铅锌矿床外,其他不同成因类型、不同形成温度的铅锌矿床中闪锌矿均可能富Ga。矽卡岩型铅锌矿床闪锌矿具有明显的贫Ga、Ge的特征,这可能是由于矽卡岩化过程中稀散元素Ga、Ge大量进入早期矽卡岩矿物,进而导致了成矿流体以及随后形成的闪锌矿中Ga、Ge的贫化。综上所述,闪锌矿中稀散元素富集与否和富集程度受成矿物质来源、成矿流体性质以及流体演化过程等多因素的综合控制。(4)扬子板块周缘铅锌矿床闪锌矿的微量元素(稀散元素)组成特征指示了它们形成于中低温成矿环境,稀散元素的富集规律与其它MVT型铅锌矿床类似。     

Evidence for Late-Paleozoic brine migration in Cambrian carbonate rocks of the central and southern Appalachians: Implications for Mississippi Valley-type sulfide mineralization

Many Lower Paleozoic limestones and dolostones in the Valley and Ridge province of the central and southern Appalachians contain 10 to 25 weight percent authigenic potassium feldspar. This was considered to be a product of early diagenesis, however, ${}^{40}\text{Ar}{}^{39}\text{Ar}$ analyses of overgrowths on detrital K-feldspar in Cambrian carbonate rocks from Pennsylvania, Maryland, Virginia, and Tennessee yield Late Carboniferous-Early Permian ages (278–322 Ma). Simple mass balance calculations suggest that the feldspar could not have formed isochemically, but required the flux of multiple pore volumes of fluid through the rocks, reflecting regional fluid migration events during the Late-Paleozoic Alleghanian orogeny.Microthermometric measurements of fluid inclusions in overgrowths on detrital K-feldspar and quartz grains from unmineralized rocks throughout the study area indicate homogenization temperatures from 100° to 200°C and freezing point depressions of −14° to −18.5°C (18–21 wt.% NaCl equiv). The apparent similarity of these fluids to fluid inclusions in ore and gangue minerals of nearby Mississippi Valley-type (MVT) deposits suggests that the regional occurrences of authigenic K-feldspar and MVT mineralization may be genetically related. This hypothesis is supported by the discovery of authigenic K-feldspar intergrown with sphalerite in several mines of the Mascot-Jefferson City District, E. Tennessee. Regional potassic alteration in unmineralized carbonate rocks and localized occurrences of MVT mineralization are both explainable by a gravity-driven flow model, in which deep brines migrate towards the basin margin under a hydraulic gradient established during the Alleghanian orogeny. The authigenic K-feldspar may reflect the loss of K during disequilibrium cooling of the ascending brines. MVT deposits are probably localized manifestations of the same migrating fluids, occurring where the necessary physical and chemical traps are present.     

P-T-X conditions of hydrothermal fluids and precipitation mechanism of stibnite-gold mineralization at the Wiluna lode-gold deposits,Western Australia: conventional and infrared microthermometric constraints

The Wiluna lode-gold deposits are located in the Archean Wiluna greenstone belt, in the northern sector of the Norseman-Wiluna belt in the Yilgarn Craton of Western Australia. They are hosted in subgreenschist facies meta-basalts, and controlled by the Wiluna strike-slip fault system and associated shear veins and breccias. The 13 individual lode-gold deposits have produced around 115 t Au from 1901 to 1946 and 1986 to today. Historically, they also produced 38.3 t As and 3.5 t Sb. Gold formed in two stages: stage 1 gold-pyrite-arsenopyrite is finely disseminated in the wallrock and breccia fragments, whereas stage 2 gold-stibnite is located in massive shear veins and breccia matrix, as fracture-fill and in banded-colloform textured veins. Stibnite-gold orebodies only occur in some of the deposits (e.g., Moonlight and northern part of the West Lode) and also display a restricted vertical extent, being preserved only in the uppermost 200 m of stibnite-bearing lodes.Petrographic, conventional, and infrared microthermometric and laser-Raman analysis on stibnite-bearing quartz veins and breccias reveal that the antimony- and gold-rich hydrothermal fluid was of mixed H₂O-NaCl-CO₂±CH₄ type. Microthermometric measurements reveal maximum homogenization temperatures of 340 °C (average 290±25 °C), and a wide range of salinities between 0.2 and 23 eq. wt% NaCl. Aqueous-carbonic fluid inclusions contain variable X_CO2+CH4 (0.03 to 0.82), with the carbonic phase containing a maximum X_CH4 of 0.21.Combined petrographic and microthermometric evidence suggests that the fluid inclusion properties reflect fluid immiscibility of a low-salinity, medium X_CO2+CH4, homogeneous parent fluid at about 290 °C and pressures between 700 and 1,700 bar. Fluid immiscibility was triggered by cyclic pressure release during fault-zone movement. The decompression (adiabatic cooling) of the hydrothermal fluids shifted the ore fluid to lower temperatures, significantly reduced the degree of stibnite undersaturation, and caused stibnite to precipitate. The deposition of stibnite reduced the ore-fluid H₂S concentration, thereby destabilized gold bisulfide complexes in solution, and caused gold precipitation locally. This mechanism explains the intimate spatial association of stibnite and gold in quartz veins and breccias in the stibnite-gold orebodies at Wiluna.Editorial handling: B. Lehmann     

Storm deposits and storm-generated coarse carbonate breccias on a pelagic outer shelf (South-East Basin, France)

Uppermost Jurassic limestones of the South‐East Basin (France) are organized into four facies associations that were deposited in four distinct zones: (1) peritidal lagoonal limestones; (2) bioclastic and reefal limestones; (3) pelagic lime mudstones; (4) lime mudstones/calcarenites/coarse breccias. Calcarenite deposits of zone 4 exhibit sedimentary structures that are diagnostic of deposition under wave‐induced combined flow. In subzone 4a, both vertical and lateral transitions from lime mudstone/calcarenite to breccia indicate in situ brecciation under wave‐cyclic loading. Breccias were produced by heterogeneous liquefaction of material previously deposited on the sea floor. Deposits in subzone 4a record relatively long periods (>400 kyr) of sedimentation below wave base, alternating with periods of deposition under wave‐induced currents and periods of in situ deformation. In this zone, storm waves were attenuated by wave–sediment interaction, and wave energy was absorbed by the deformation of soft sediment. With reference to present‐day wave attenuation, water depths in this zone ranged between 50 and 80 m. Landwards of the attenuation zone, in zone 3, storm waves were reduced to fair‐weather wave heights. Storm wave base was not horizontal and became shallower landwards. As a consequence, water depth and wave energy were not linearly related. On a small area of the seaward edge of subzone 4a, cobbles were removed by traction currents and redeposited in subzone 4b. There, they formed a 100‐m‐thick wedge, which prograded over 3 km and was built up by the stacking of 5‐ to 20‐m‐thick cross‐stratified sets of coarse breccia. This wedge records the transport and redeposition of cobbles by a high‐velocity unidirectional component of a combined flow. The increase in flow velocity in a restricted area is proposed to result from flow concentration in a channel‐like structure of the downwelling in the gulf formed by the basin. In more distal subzone 4c, the hydrodynamic effect of wave‐induced currents was quasi‐permanent, and brecciation by wave–sediment interaction occurred only episodically. This indicates that, seawards of the attenuation zone, hydrodynamic storm wave base was deeper than mechanical storm wave base. Uppermost Jurassic carbonates were deposited and soft‐sediment deformed on a hurricane‐dominated ramp of very gentle slope and characterized by a zone of storm wave degeneration, located seawards of a zone of sedimentation below wave base.     

海底热水成矿系统中的流体端员与混合过程：来自白银厂和呷村VMS矿床的流体包裹体证据

古今海底热液流体系统是人们关注的重要科学问题,正确识别流体系统中不同来源的流体端员及其混合-分离过程,是深刻理解海底流体系统及火山成因块状硫化物(VMS)矿床成因的关键。本文选择了我国境内两个典型的VMS矿床:甘肃白银厂矿床和四川呷村矿床,分别对上部块状矿带和下部脉状-网脉状矿带进行了系统的流体包裹体研究。研究表明,海底热液成矿流体系统是一个富集CO_2和CH_4的NaCl-H_2O流体系统。在此系统中,至少已鉴别出5种端员流体,即(1)低温 (12wt％NaCl)卤水;(2)高温(>320℃)高盐度(>14.5wt％NaCl)流体和(3)高温(>350℃)中盐度(10～16wt％Nacl)富气流体,以及(4)低温(～100℃)低盐度(2～5wt％NaCl)流体和(5)中温低盐度流体,它们构成了3个相互分离的温度-盐度演变趋势或混合途径。)低温高盐度卤水封存于卤水池中,在呷村矿床,卤水池发育在海底凹陷盆地热液区内,在白银厂矿床,卤水池则发育在海底之下的多孔火山碎屑岩单元及穿透性断裂破碎带内。高温高盐度流体和高温中盐度富气流体均来自矿区下部浅位岩浆房,前者以液态富金属H_2O流体为主,通常与冷海水发生混合;后者以富CO_2和CH_4的气体为主,高温(>450℃)下呈相对独立的气流存在,至到250～260℃才作为液相混入成矿热液流体中。低温低盐度     

碳酸盐岩深覆盖区隐伏岩溶构造的音频大地电磁探测：以云南大关地区为例

碳酸盐岩受水溶蚀易于发育岩溶,形成溶洞、地下河等,常导致油气钻探出现掉钻、卡钻等情况。调查和研究显示,云南大关地区奥陶系五峰—志留系龙马溪组富有机质页岩具有高含气性,是勘探开发的重要领域。然而,该地区分布的二叠系茅口组和栖霞组碳酸盐地层广泛发育岩溶构造,这在很大程度上制约了页岩气的进一步勘探。同时,这两套地层的埋深可能超过1 km,对地球物理方法的探测精度也提出了挑战。本文通过理论模型试算和已有钻孔（D0）的方法试验,明确了音频大地电磁方法识别深部隐伏岩溶的可行性。在预选井位区（D1）开展音频大地电磁探测,并根据电性模型重新部署了调查井（D2）,实际钻井检验了方法的可靠性,并认为不连续分布的高电阻率异常区往往指示岩溶构造的存在,井位布设的有利区可能是高电阻率异常连续分布的块状或带状异常区。因此,音频大地电磁探测不仅对岩溶覆盖区的油气钻井选址具有先导作用,同时也拓宽了该方法的应用范围。

     

重庆中梁山碳酸盐岩溶蚀速率对季节的响应研究

在重庆市中梁山岩溶槽谷,选取林地、园地、耕地和菜地4种不同土地利用类型,通过野外下三叠统嘉陵江组白云质灰岩石试片的溶蚀试验分析不同土地利用方式下溶蚀速率对季节的响应关系。结果表明:不同土地利用方式将造成土壤性质发生不同的变化,进而对岩石的溶蚀速率产生明显的影响。但无论是从夏半年还是从全年来看,试片的溶蚀速率的大小变化均表现为:林地>菜地>耕地>园地。夏半年在全年的试片溶蚀作用过程中贡献较大,其绝对溶蚀量占全年比例都大于50%;除林地、菜地和园地土下50cm试片外,其余试片的夏半年溶蚀速率都大于全年溶蚀速率。究其原因,主要是由于夏半年气温高,降水量大,使土壤中CO2和水分等增加,从而有利于岩溶作用的进行      

Characteristics of Breccias and C-O-Sr-S Isotope Geochemistry of the Duocaima Pb-Zn Deposit in Tuotuohe, Qinghai Province: Implications for the Ore-forming Process

The Duocaima carbonate-hosted Pb-Zn deposit is a newly found large deposit in the southern area of Qinghai Province.In this paper, the characteristics, genesis, significance to Pb-Zn mineralization of the widely developed breccias, and the ore-forming process have been carefully studied based on geological documentation of drilling holes, microscopic observations of petrography and microstructure and some stable isotope measurements.Based on the compositions of the clast and matrix, the breccias can be classified into three types: limestone clasts cemented by marl; limestone clasts with fine-grained calcareous materials; and limestone clasts cemented by hydrothermal calcite.The mineralization in the first type of breccia is weak, whereas it is strong in the latter two types of breccias.According to the locations of occurrence and structural characteristics of the breccias along with the relationship between the breccias and mineralization, part of the limestone clasts that are cemented by marl and outcrop in the contact zone between the Wudaoliang Formation(Nw) and the underlying Jiushidaoban Formation(Pj) are attributed to synsedimentary fault-genetic breccia, whereas the last of the limestone clasts that are cemented by marl and developed in the Jiushidaoban Formation(Pj) are attributed to the breccia generated by karst cave collapse; the limestone clasts with fine-grained calcareous materials and the limestone clasts cemented by hydrothermal calcite are attributed to breccia formed by hydrothermal dissolution.The breccia formed by karst collapse had consistently evolved for a long period of time, while the breccias with other origins were formed around the period of mineralization(i.e., about or slightly later than 20–16 Ma).The breccia generated by karst cave collapse and hydrothermal dissolution are somewhat related; the formation of the breccia from karst cave collapse provided open space for the later mineralization and reaction between hydrothermal fluids and host rocks, and the subsequent strong dissolution by hydrothermal fluids transformed some of the breccia formed earlier by karst cave collapse.Meanwhile, carbonate host rocks with breccias and brecciaed mineralization can be a potential sign of Mississippi Valley Type(MVT) deposits and important indicators for regional mineral exploration.The δ13CV-PDB, δ18OVSMOW, and 87Sr/86 Sr values of hydrothermal calcite in the Duocaima deposit range from 4.3‰ to 7.1‰, 14.9‰ to 20.1‰, and 0.707494 to 0.708185, respectively; the δ13CV-PDB, δ18OV-SMOW, and 87Sr/86 Sr values of the host limestones of the Jiushidaoban Formation range from 3.6‰ to 5.3‰, 18.0‰ to 20.5‰, and 0.707372 to 0.707945, respectively.The δ13CV-PDB and 87Sr/86 Sr values of hydrothermal calcite and limestone are similar, indicating single sources of C and Sr in this deposit, with the likely source being the limestone of the Jiushidaoban Formation.The minor scattering of the δ18OV-SMOW values suggests that different O isotope fluids underwent the isotope exchange reaction.The C-O-Sr isotope characteristics indicate that the host limestones experienced a dissolution and precipitation process during mineralization, which is beneficial to improving the porosity of host rocks and promoting the precipitation of metal sulfides.The δ34SV-CDT value of the breccia-type mineralization sulfides ranges from-30.4‰ to-0.3‰; that is, the δ34SV-CDT value is negative with considerable variation, illustrating that during the breccia-type mineralization process, the bacteriogenic reduction of sulfates provided the vast majority of sulfur, whereas the thermochemical reduction of sulfates was relatively unimportant.The brecciation that occurred as a result of karst cave collapse was mainly generated by the dissolution of groundwater; however, the brecciation related to hydrothermal dissolution and mineralization processes were caused by mixing of different fluids.     

Nonsulfide and sulfide-rich zinc mineralizations in the Vazante, Ambrósia and Fagundes deposits, Minas Gerais, Brazil: Mass balance and stable isotope characteristics of the hydrothermal alterations

The Vazante Group hosts the Vazante nonsulfide zinc deposit, which comprises high-grade zinc silicate ore (ZnSiO₄), and late-diagenetic to epigenetic carbonate-hosted sulfide-rich zinc deposits (e.g. Morro Agudo, Fagundes, and Ambrósia). In the sulfide-rich deposits, hydrothermal alteration involving silicification and dolomitization was related with ground preparation of favorable zones for fluid migration (e.g. Fagundes) or with direct interaction with the metalliferous fluid (e.g. Ambrósia). At Vazante, hydrothermal alteration resulted in silicification and dolomite, siderite, jasper, hematite, and chlorite formation. These processes were accompanied by strong relative gains of SiO₂, Fe₂O_3(T), Rb, Sb, V, U, and La, which are typically associated with the nonsulfide zinc mineralization. All sulfide-rich zinc ores in the district display a similar geochemical signature suggesting a common metal source from the underlying sedimentary sequences.Oxygen and carbon isotope compositions of hydrothermally altered rocks reveal a remarkable alteration halo at the Vazante deposit, which is not a notable feature in the sulfide-rich deposits. This pattern could be attributed to fluid mixing processes involving the metalliferous fluid and channelized meteoric water, which may control the precipitation of the Vazante nonsulfide ore. Sulfide deposition resulted from fluid–rock interaction processes and mixing between the ascending metalliferous fluids and sulfur-rich tectonic brines derived from reduced shale units.     

三峡地区碳酸盐岩化学组分与溶蚀速率的响应关系

文章通过室内静水溶蚀实验测定了三峡地区香溪河流域震旦-三叠系碳酸盐岩的化学溶蚀速率,探讨了碳酸盐岩的化学溶蚀速率对岩石化学组分的响应关系,为区域岩溶量化研究与地层含水性评价等提供了科学依据。研究结果表明:较纯碳酸盐岩的溶蚀速率受到CaO、SrO的促进作用和MgO的抑制作用共同控制,而这三者对纯灰岩的溶蚀速率影响较小;碳酸盐岩中的酸不溶物对化学溶蚀过程呈现出抑制的趋势。碳酸盐岩的化学溶蚀速率受到多化学组分的共同影响,综合决定了碳酸盐岩的可溶性。