Hydrothermal mixing,carbonate dissolution and sulfide precipitation in Mississippi Valley-type deposits

A large number of Mississippi Valley-Type (MVT) deposits are located within dissolution zones in carbonate host rocks. Some genetic models propose the existence of cavities generated by an earlier event such as a shallow karstification, that were subsequently filled with hydrothermal minerals. Alternative models propose carbonate dissolution caused by the simultaneous precipitation of sulfides. These models fail to explain either the deep geological setting of the cavities, or the observational features which suggest that the dissolution of carbonates and the precipitation of minerals filling the cavities are not strictly coeval. We present a genetic model inspired by the textural characteristics of MVT deposits that accounts for both the dissolution of carbonate and precipitation of sulfides and later carbonates in variable volumes. The model is based on the mixing of two hydrothermal fluids with a different chemistry. Depending on the proportion of the end members, the mixture dissolves and precipitates carbonates even though the two mixing solutions are both independently saturated in carbonates. We perform reactive transport simulations of mixing of a regional groundwater and brine ascending through a fracture, both saturated in calcite, but with different overall chemistries (Ca and carbonate concentrations, pH, etc). As a result of the intrinsic effects of chemical mixing, a carbonate dissolution zone, which is enhanced by acid brines, appears above the fracture, and another zone of calcite precipitation builds up between the cavity and the surrounding rock. Sulfide forms near the fracture and occupies a volume smaller than the cavity. A decline of the fluid flux in the fracture would cause the precipitation of calcite within the previously formed cavities. Therefore, dissolution of carbonate host rock, sulfide precipitation within the forming cavity, and later filling by carbonates may be part of the same overall process of mixing of fluids in the carbonate host rock.Editorial handling: C. Everett     

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。     

The possible role of thiosulfate in the precipitation of 34S-rich barite in some Mississippi Valley-type deposits

The precipitation of extremely ³⁴S-rich barite in the late stage of mineralization in the Mississippi Valleytype deposits of the Illinois-Kentucky district (U.S.A.) may be explained by reactions involving thiosulfate (S₂O ₃ ⁼ ). Inorganic processes are known to concentrate ³⁴S in the sulfonate site of thiosulfate and ³²S in the sulfate site. In the mineralizing solution, these inorganic processes may have fractionated sulfur between the two sites by about 40 per mil. At the low temperatures of the late barite stage of mineralization, bacteria are known to metabolize thiosulfate by various reactions. In one of these, dissimilatory reduction, hydrogen sulfide and sulfite are produced. Isotopically light sulfite is preferentially reduced to sulfide by bacteria to leave a residual sulfite enriched in ³⁴S. Part of the residual sulfite may be oxidized to form isotopically heavy sulfate; part may recombine with hydrogen sulfide to form thiosulfate. The recombination also enriches the sulfonate site in ³⁴S and the sulfane site in ³²S. Recycling the newly formed thiosulfate through the above steps further enriches sulfite and sulfate from oxidation of sulfite in ³⁴S. During genesis of the ores, the aggregate effect of these reactions may have been the precipitation of extremely ³⁴S-rich barite. The sequence of reactions suggested above requires the presence of organic matter. Previously proposed reactions to account for the precipitation of sulfide minerals and fluorite and for the carbonate paragenesis also require the presence of organic matter. Thus, organic matter in the host rocks may cause the various ore-zone reactions and account for the localization of the ores.     

A palaeoenvironmental interpretation of the Early Proterozoic Malmani dolomite from Zwartkops,South Africa

The Malmani Subgroup northwest of Johannesburg consists of dolomite and chert with only minor clastic sediments.A precise upper intertidal to marginal supratidal analogy and the associated relationship of varied structures suggest that much of the succession represents a tidal flat to intertidal complex formed within differing semiprotected to protected conditions. The dolomites from these environments are recrystallized, reflecting a meteoric influence, and the cherts which are commonly developed within them are also related to prevailing lower pH's. This dolomitization is considered to have been enhanced by the influx of meteoric waters which however resulted in the dolomites having undersaturated iron-manganese ratios. Rare colour-banded dolomites containing columnar stromatolites are thought to represent more steeply shelving intertidal conditions than are normally encountered in the epeiric sea. These dolomites contain quartz crystals rather than chert, suggestive of a lower concentration of silica in the original alkaline solutions. The exposure is part of a very widespread carbonate unit, dated at ca. 2.250 m.y.Subtidal conditions in which large elongate stromatolitic domes developed can be related to a marine transgression across a basal clastic beach sand; and secondly to a progradational tidal flat seawards of which a talus breccia developed on a steepened slope leading down to the subtidal regime. These dolomites formed by interaction with marine waters saturated with respect to iron and manganese, while the absence of chert reflects persisting alkaline conditions.A dark chert-free dolomitic facies with high iron and manganese contents of saturated ratios is considered to have developed in an alkaline lagoonal environment behind a subaqueous bar that is now represented by an overlying thick oolitic unit.The succession contains numerous chert breccias with which shales are associated. The breccias represent subaerial exposure phenomena related to regressions which were followed by periods of short-lived terrigenous influx.     

The early proterozoic greenstone belt of the Northern Guiana Shield,South America

A large part of the northern Guiana Shield is underlain by metavolcanic and metasedimentary sequences steeply folded and metamorphosed in the greenschist facies during the 2000 Ma old Trans-Amazonian orogeny. It is suggested that this extensive early Proterozoic belt represents a back-arc basin environment marginal to a supercontinent; that is to say, this belt was possibly intercratonic with respect to existing Archaean basements, whereas elsewhere in the interior of the continent, as in Brazil, fold belts of identical age were intracratonic. The formation of the volcano-sedimentary pile and subsequent orogeny to which the Guiana belt was subjected are ascribed to plate convergence and subduction. This interpretation is supported by the nature of the volcanic pile and the presence of a possible fossil suture in northern Guiana.     

新太古界Campbellrand亚群白云岩岩溶系统对南非Postmasburg锰矿田的影响

为分析新太古界Campbellrand亚群白云岩基底形成的岩溶系统对南非Postmasburg锰矿田发育和分布的影响,笔者等利用XRF和偏光显微镜鉴定技术,结合野外地质调查和岩芯钻探,对矿石的矿物成分、矿体中的Mn、Fe空间分布、Doornfontein砾岩的结构特征、白云岩容矿构造的形态进行了研究。结果表明：Maremane穹隆上的Campbellrand亚群白云岩遭受了两次大规模的溶蚀。溶蚀构造引起沉积物分异,沉积建造底部Mn质最为富集,向外、向上逐渐由Fe质主导,形成褐锰矿—方铁锰矿—赤铁矿的序列,顶部则演变为铝土质岩。沉积序列中Mn+Fe质和Al质含量呈现出较强的负相关性。溶坑的特殊形态导致矿体受层控,但并不呈现规则的层状形态。东矿带的Wolhaarkop硅质角砾岩与白云岩中的燧石和硅质白云岩密切相关,而混合带和西矿带普遍发育的Doornfontein砾岩则是岩溶作用影响下锰质的成岩作用被推迟所形成,它们都是成矿期岩溶系统发育的间接产物。溶坑底部的锰土混合物揭示了成矿后期溶蚀作用的发生和沉积序列的坍塌破碎,小型的断层也造成了矿体的严重破碎和顶板地层的褶曲。Gamagara低山脊...     

Sphalerite-bearing detrital ‘sand’ bodies in Mississippi Valley-type zinc deposits Mascot-Jefferson City district,Tennessee

The Mississippi Valley-type sphalerite mineralization in the Mascot-Jefferson City zinc district of East Tennessee occurs as open-space fillings in breccia bodies within the upper part of the Knox Group (Lower Ordovician) which is truncated by a regional unconformity. A lower age limit of mineralization is constrained by the formation of solution-collapse breccia bodies, which are believed to be related to the post-Knox unconformity. The breccias contain irregularly distributed “sand” bodies that represent cavities filled with well-laminated and size-graded, sphalerite-bearing, detrital, internal sediments. The texture, composition, and fluid inclusion characteristics of the sphalerite, are consistent with its local derivation from the wallrocks as detrital grains. The conformability between the laminations in the sediments and the bedding planes of the host carbonate rocks suggests that the sand bodies formed prior to the regional deformation event (Alleghenian orogeny). The stylolitization of carbonate and sphalerite clasts in the internal sediments as well as the deformation of the sphalerite are also consistent with a pre-Alleghenian age for the emplacement of the main-stage sphalerite mineralization in the Mascot-Jefferson City district and, by analogy, in other Lower Ordovician-hosted Mississippi Valley-type districts of the southern Appalachians.     

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.     

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.     

Vanished evaporites and carbonate formation in the Neoarchaean Kogelbeen and Gamohaan formations of the Campbellrand Subgroup,South Africa

Field, petrographic and stable isotopic evidence indicate the former presence of widespread evaporites in the Neoarchaean Campbellrand Subgroup of South Africa. Calcitization of the vanished but once laterally-extensive evaporites was apparently driven by bacterial sulphate reduction of solid sulphate in association with organic diagenesis and pyrite precipitation within platform-wide microbialites and sapropels. This counters current interpretations that much of the calcite was precipitated directly on the seafloor or in primary voids in open marine conditions controlled by regional seawater chemistry. Rather, large-scale microbial mediation of ambient waters across a shallow to emergent platform raised carbonate alkalinity and removed kinetic inhibitors to carbonate formation.The low preservation potential of Precambrian solid sulphate is related in part to bacterial sulphate reduction within the microbially-dominated ecosystems of which cyanobacteria were a major component. Evidence for the former presence of solid sulphate in shallow Neoarchaean seas includes pseudomorphs after selenite, also recorded from the contemporaneous Carawine Dolomite of Australia, together with rock fabrics and textures typical of evaporite dissolution. Importantly, sulphur isotopes of pyrite samples from the Cambellrand carbonates show a wide range of values indicating biogenic fractionation of sulphate, a signature also seen in the Neoarchaean Belingwe Greenstone Belt of Zimbabwe, and the Mt McRae and Jeerinah shales of Western Australia.Mass microbial colonization across extensive Neoarchaean epeiric seas witnessed the microbiogeochemical transformation of the Earth’s hydrosphere, atmosphere and biosphere. The consequences for a reducing ocean would be the progressive oxidation of the major dissolved species in surface seawater, most notably of reduced sulphur and iron. Cyanobacterial photosynthetic oxidation of surface seawater drove formation of aqueous sulphate and permitted the precipitation of extensive evaporites in restricted basins, perhaps beginning the process of ridding the oceans of reduced sulphur. The first dramatic explosion of carbonate precipitation can be related to intense bacterial sulphate reduction in association with anoxic organic diagenesis and pyrite formation within the decaying interiors of microbialites and in sapropels.     

新太古界Campbellrand亚群白云岩岩溶系统对南非Postmasburg锰矿田的影响

为分析新太古界Campbellrand亚群白云岩基底形成的岩溶系统对南非Postmasburg锰矿田发育和分布的影响,利用XRF和偏光显微镜鉴定技术,结合野外地质调查和岩芯钻探,对矿石的矿物成分、矿体中的Mn、Fe空间分布、Doornfontein砾岩的结构特征、白云岩容矿构造的形态进行了研究。结果表明：Maremane穹隆上的Campbellrand亚群白云岩遭受了两次大规模的溶蚀。溶蚀构造引起沉积物分异,沉积建造底部Mn质最为富集,向外、向上逐渐由Fe质主导,形成褐锰矿—方铁锰矿—赤铁矿的序列,顶部则演变为铝土质岩。沉积序列中Mn+Fe质和Al质含量呈现出较强的负相关性。溶坑的特殊形态导致矿体受层控,但并不呈现规则的层状形态。东矿带的Wolhaarkop硅质角砾岩与白云岩中的燧石和硅质白云岩密切相关,而混合带和西矿带普遍发育的Doornfontein砾岩则是岩溶作用影响下锰质的成岩作用被推迟所形成,它们都是成矿期岩溶系统发育的间接产物。溶坑底部的锰土混合物揭示了成矿后期溶蚀作用的发生和沉积序列的坍塌破碎,小型的断层也造成了矿体的严重破碎和顶板地层的褶曲。Gamagara低山脊两侧分布的小型堆积型矿体也与后期地表岩溶系统长期的发育有关。     

The Mississippi Valley-type Lead-zinc Deposits along the Southwest Margin of the Yangtze Block, China

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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.     

The copper deposits of the O'okiep District,South Africa: New data and concepts

The copper deposits of the O'okiep District rank amongst the top three S. African producers, with an annual output of 3 million metric tons grading 1.65% Cu on average. They occur in what is now considered the S. extension of the 1200 m. y. Kibaran orogenic belt. Copper mineralization is linked to cross-cutting bodies of "noritoid" R_O=0.7126–0.7250) which have been emplaced into the granulite facies metamorphic country rocks 1100 m. y. ago. The results of 150 electron probe analyses show that orthopyroxene in the non-ore-bearing noritoids is En_51–52, in the ore-bearing noritoids En_60–65. There is a concomitant variation in the composition of phlogopitic mica which carries higher Fe in non-ore-bearing noritoids. The Ticontents of magnetite are below 0.1%; there are significant chromium values. Spinel exsolution lamellae contain up to 14% ZnO. The copper sulphides occur as granular aggregates with silicates, on grain boundaries and on cleavage planes of hypersthene and mica; they also replace altered Fe-Ti-oxides. Pyrite (up to 1.4% Co) and pentlandite (up to 5% Co) are not widespread. The possible derivation of the noritoids from a reservoir of basic magma at depth is considered. A source-bed model, involving generation of noritoid "magma" from Cu-bearing members of the stratigraphic sequence, during the peak of metamorphism (800–1000 °C, 6–8 kb) is tentatively proposed. Stratabound base metal concentrations (Aggeneys, Gamsberg) in lower grade (amphibolite facies) metamorphic terrains to the East have not been mobilized.formerly, Mineralogisch-Petrographisches Institut, Universität Hamburg     

The Karoo Basin of South Africa: type basin for the coal-bearing deposits of southern Africa

The coal-bearing sediments and coal seams of the Karoo Basin, Southern Africa are described and discussed. The Karoo Basin is bounded on its southern margin by the Cape Fold Belt, onlaps onto the Kaapvaal Craton in the north and is classified as a foreland basin. Coal seams are present within the Early Permian Vryheid Formation and the Triassic Molteno Formation.The peats of the Vryheid Formation accumulated within swamps in a cool temperate climatic regime. Lower and upper delta plain, back-barrier and fluvial environments were associated with peat formation. Thick, laterally extensive coal seams have preferentially accumulated in fluvial environments. The coals are in general inertinite-rich and high in ash. However, increasing vitrinite and decreasing ash contents within seams occur from west to east across the coalfields. The Triassic Molteno coal seams accumulated with aerially restricted swamps in fluvial environments. These Molteno coals are thin, laterally impersistent, vitrinite-rich and shaly, and formed under a warm temperate climatic regime.Palaeoclimate, depositional systems, differential subsidence and basin tectonics influence to varying degrees, the maceral content, thickness and lateral extent of coal seams. However, the geographic position of peat-forming swamps within a foreland basin, coupled with basin tectonics and differential subsidence are envisaged as the primary controls on coal parameters. The Permian coals are situated in proximal positions on the passive margin of the foreland basin. Here, subsidence was limited which enhanced oxidation of organic matter and hence the formation of inertinitic coals. The coals in this tectonic setting are thick and laterally extensive. The Triassci coals are situated within the tectonically active foreland basin margin. Rapid subsidence and sedimentation rates occurred during peat formation which resulted in the preservation of thin, laterally impersistent, high ash, vitrinite-rich, shaly coals.     

The chemistry and origin of zincian spinel associated with the Aggeneys Cu-Pb-Zn-Ag deposits,Namaqualand, South Africa

Zincian spinel or gahnite [(Zn,Fe,Mg)Al₂O₄] occurs in metamorphosed sulphide-rich rocks, garnet quartzites, quartz-magnetite rocks, aluminous metasediments, barite-magnetite rocks, quartz veins, and pegmatites associated with the Aggeneys base metal deposits, Namaqualand, South Africa. Zincian spinel in, sulphide-bearing rocks, is considered to have formed predominantly by desulphurization reactions involving a member of the system Fe-S-O and sphalerite with sillimanite or garnet. Gahnite in sulphide-free garnet quartzites, quartz-magnetite rocks and barite-magnetite rocks probably formed from Zn and Al that were hydrothermally derived whereas gahnite in aluminous metasediments was derived from the metamorphism of metalliferous shales, in which Zn may originally have been linked to organic material. Gahnite is Zn-rich in sulphide-bearing rock, but is Fe-rich in sulphide-free garnet quartzites and quartz-magnetite rocks. Although Zn-rich spinels represent guides to ore in the Aggeneys area and elsewhere in the Namaqualand Metamorphic Complex, Fe-rich spinels should not be discounted because Zn-rich and Fe-rich spinels occur within metres of sulphides at Aggeneys.     

Volcanic-hosted massive sulfide deposits in the Murchison greenstone belt, South Africa

The Archean Murchison greenstone belt, Limpopo Province, South Africa, represents a rifted epicontinental arc sequence containing the largest volcanic-hosted massive sulfide (VMS) district in Southern Africa. The so-called Cu–Zn line is host to 12 deposits of massive sulfide mineralization including: Maranda J, LCZ, Romotshidi, Mon Desir, Solomons, and Mashawa with a total tonnage of three million metric tons of very high grade Zn, subordinate Cu, and variable Pb and Au ore. The deposits developed during initial phases of highly evolved felsic volcanism between 2,974.8 ± 3.6 and 2,963.2 ± 6.4 Ma and are closely associated with quartz porphyritic rhyolite domes. Elevated heat supply ensured regional hydrothermal convection along the entire rift. Recurrent volcanism resulted in frequent disruption of hydrothermal discharge and relative short-lived episodes of hydrothermal activity, probably responsible for the small size of the deposits. Stable thermal conditions led to the development of mature hydrothermal vent fields from focused fluid discharge and sulfide precipitation within thin layers of felsic volcaniclastic rocks. Two main ore suites occur in the massive sulfide deposits of the “Cu–Zn line”: (1) a low-temperature venting, polymetallic assemblage of Zn, Pb, Sb, As, Cd, Te, Bi, Sn, ±In, ±Au, ±Mo occurring in the pyrite- and sphalerite-dominated ore types and (2) a higher temperature suite of Cu, Ag, Au, Se, In, Co, Ni is associated with chalcopyrite-bearing ores. Sphalerite ore, mineralogy, and geochemical composition attest to hydrothermal activity at relatively low temperatures of ≤250 °C for the entire rift, with short-lived pulses of higher temperature upflow, reflected by proportions of Zn-rich versus Cu-rich deposits. Major- and trace-metal composition of the deposits and Pb isotope signatures reflect the highly evolved felsic source rock composition. Geological setting, host rock composition, and metallogenesis share many similarities not only with Archean VMS districts in Canada and Australia but also with recent arc–back-arc systems on the modern seafloor where fragments of continental crust and areas of elevated heat flow are involved in petrogenetic and associated metallogenic processes.     

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。     

Sedimentation and palaeoenvironments of Late Cretaceous crater-lake deposits in Bushmanland, South Africa

A large diameter borehole core from an epiclastic kimberlite remnant on the farm Stompoor in the Prieska district, Cape Province, contains a continuous 76 m section of fossiliferous sediments interpreted as having accumulated within a crater-lake during the Late Cretaceous. Three distinct facies associations reflect depositional processes that prevailed in offshore areas of the original lake. Facies Association A: matrix-supported pebble conglomerates comprising a chaotic assemblage of pyroclastic, basement and country rocks set in a fine-grained matrix. Flat, non-erosional basal surfaces with ‘frozen’ rip-up clasts, the protrusion of matrix-supported clasts above the upper surfaces and a direct relationship between maximum clast size and bed thickness suggest deposition from debris flows that originated subaerially on pyroclastic talus cones surrounding the crater. Facies Association B: alternating thin beds of matrix-supported granule conglomerate, structureless fine-grained sandstone and parallel laminated mudrock. Small fining-upward sequences within these beds are comparable to turbidite Bouma Tade, Tde. Numerous partings display petrified fish and frog skeletons, as well as bivalve, gastropod and ostracode shells, leaf impressions, insect wings and a possible bird bone. These beds were deposited by thin debris-flows and turbidity underflows interspersed with periods of ‘pelagic’ sedimentation. Facies Association C: microlaminated mudstone beds containing scattered ‘dropstone lapilli’. The lamination is imparted by alternating Ca-rich/Ca-poor layers which may reflect climatic seasonality. They are interpreted as the result of seasonally influenced suspension settling through a thermally stratified water column. Short-term periodicities in conglomerate bed thicknesses are interpreted as the result of successive block caving of a slump scar giving rise to several debris flows from the same source area. Seismic shock from nearby volcanism may have simultaneously triggered slumps on both subaerial and subaqueous slopes. Dropstone lapilli in Type C beds and the preponderance of load casting in Type B beds support this interpretation. An estimate of the time span involved in accumulating 76 m of crater lake sediments based on the possible seasonal imprint of Type C beds gives a figure of some 220,000 yr.