An experimental study on felsic rock–artificial seawater interaction: implications for hydrothermal alteration and sulfate formation in the Kuroko mining area of Japan

Experimental studies on the interactions between artificial seawater (ASW) and fresh rhyolite, perlite and weakly altered dacitic tuff containing a small amount of smectite suggest changing cation transfer during smectite-forming processes. Initially, dissolution of K from the rocks accompanies incorporation of Mg and Ca from ASW during both earlier (devitrification stage) and later smectite formation, whereas Ca incorporated with early smectite formation redissolves with progressive reaction. Barium mobility increases toward the later smectite-forming reactions. Therefore, the large amounts of barite, anhydrite and gypsum in Kuroko ore deposits are considered to have precipitated from hydrothermal solutions derived from the interaction with previously altered felsic rocks during late smectite formation, rather than by the reaction with fresh felsic rocks.Editorial handling: D. Lentz     

Mechanisms for anhydrite and gypsum formation in the Kuroko massive sulfide–sulfate deposits,north Japan

The Sr, Ba, and rare earth elements (REEs) concentrations and Sr isotopic composition of anhydrite and gypsum have been determined for samples from the Matsumine, Shakanai, and Hanaoka Kuroko-type massive sulfide–sulfate deposits of northern Japan to evaluate the mechanisms of sekko (anhydrite and gypsum) ore formation. The Sr isotopic compositions of the samples fall in the range of 0.7077–0.7087, intermediate between that for middle Miocene (13–15 Ma) seawater (0.7088) (Peterman et al., Geochim Cosmochim Acta, 34:105–120, 1970) and that for country rocks (e.g., 0.7030–0.7050) (Shuto, Assn Geol Collab Japan Monograph 18:91–105, 1974). The Kuroko anhydrite samples exhibit two types of chondrite-normalized REE patterns: one with a decrease from light REEs (LREEs) to heavy REEs (HREEs) (type I), and another with a LREE-depleted pattern (type II). Based on the Sr content and isotopic ratio (assuming an Sr/Ca (mM/M) of 8.7 for seawater), anhydrite is considered to have formed by mixing of preheated seawater with a hydrothermal solution of Sr/Ca (mM/M) = ca. 0.59–1.36 under the condition in which the partition coefficient (Kd) ranges between ca. 0.5 and 0.7. This results in the formation of anhydrite with higher Sr content with an Sr isotopic value close to that of seawater under seawater-dominant conditions. Larger crystals of type II anhydrite are partly replaced by smaller ones, indicating that anhydrite dissolution and recrystallization occurred after or during the formation of sekko ore. Gypsum, which partially replaces anhydrite in the Kuroko deposits, also exhibits two distinct chondrite-normalized REE patterns. Because LREEs are likely to be more readily mobilized during dissolution and recrystallization, it is hypothesized that LREEs are leached from type I anhydrite, resulting in the formation of type II anhydrite with LREE-depleted profiles.     

Sulfur and lead isotope geochemistry of hypogene mineralization at the Barite Hill Gold Deposit, Carolina Slate Belt, southeastern United States: a window into and through regional metamorphism

The Barite Hill gold deposit, at the southwestern end of the Carolina slate belt in the southeastern United States, is one of four gold deposits in the region that have a combined yield of 110 metric tons of gold over the past 10 years. At Barite Hill, production has dominantly come from oxidized ores. Sulfur isotope data from hypogene portions of the Barite Hill gold deposit vary systematically with pyrite–barite associations and provide insights into both the pre-metamorphic Late Proterozoic hydrothermal and the Paleozoic regional metamorphic histories of the deposit. The δ³⁴S values of massive barite cluster tightly between 25.0 and 28.0‰, which closely match the published values for Late Proterozoic seawater and thus support a seafloor hydrothermal origin. The δ³⁴S values of massive sulfide range from 1.0 to 5.3‰ and fall within the range of values observed for modern and ancient seafloor hydrothermal sulfide deposits. In contrast, δ³⁴S values for finer-grained, intergrown pyrite (5.1–6.8‰) and barite (21.0–23.9‰) are higher and lower than their massive counterparts, respectively. Calculated sulfur isotope temperatures for the latter barite–pyrite pairs (Δ=15.9–17.1‰) range from 332–355 °C and probably reflect post-depositional equilibration at greenschist-facies regional metamorphic conditions. Thus, pyrite and barite occurring separately from one another provide pre-metamorphic information about the hydrothermal origin of the deposit, whereas pyrite and barite occurring together equilibrated to record the metamorphic conditions. Preliminary fluid inclusion data from sphalerite are consistent with a modified seawater source for the mineralizing fluids, but data from quartz and barite may reflect later metamorphic and (or) more recent meteoric water input. Lead isotope values from pyrites range for ²⁰⁶Pb/²⁰⁴Pb from 18.005–18.294, for ²⁰⁷Pb/²⁰⁴Pb from 15.567–15.645, and for ²⁰⁸Pb/²⁰⁴Pb from 37.555–38.015. The data indicate derivation of the ore leads from the country rocks, which themselves show evidence for contributions from relatively unradiogenic, mantle-like lead, and more evolved or crustal lead. Geological relationships, and stable and radiogenic isotopic data, suggest that the Barite Hill gold deposit formed on the Late Proterozoic seafloor through exhalative hydrothermal processes similar to those that were responsible for the massive sulfide deposits of the Kuroko district, Japan. On the basis of similarities with other gold-rich massive sulfide deposits and modern seafloor hydrothermal systems, the gold at Barite Hill was probably introduced as an integral part of the formation of the massive sulfide deposit. Received: 17 August 1998 / Accepted: 12 October 2000     

Diverse Range of Mineralization Induced by Phase Separation of Hydrothermal Fluid: Case Study of the Yonaguni Knoll IV Hydrothermal Field in the Okinawa Trough Back-Arc Basin

The Yonaguni Knoll IV hydrothermal vent field (24°51′N, 122°42′E) is located at water depths of 1370–1385 m near the western edge of the southern Okinawa Trough. During the YK03–05 and YK04–05 expeditions using the submersible Shinkai 6500, both hydrothermal precipitates (sulfide/sulfate/carbonate) and high temperature fluids (Tmax = 328°C) presently venting from chimney‐mound structures were extensively sampled. The collected venting fluids had a wide range of chemistry (Cl concentration 376–635 mmol kg^?1), which is considered as evidence for sub‐seafloor phase separation. While the Cl‐enriched smoky black fluids were venting from two adjacent chimney‐mound structures in the hydrothermal center, the clear transparent fluids sometimes containing CO₂ droplet were found in the peripheral area of the field. This distribution pattern could be explained by migration of the vapor‐rich hydrothermal fluid within a porous sediment layer after the sub‐seafloor phase separation. The collected hydrothermal precipitates demonstrated a diverse range of mineralization, which can be classified into five groups: (i) anhydrite‐rich chimneys, immature precipitates including sulfide disseminations in anhydrite; (ii) massive Zn‐Pb‐Cu sulfides, consisting of sphalerite, wurtzite, galena, chalcopyrite, pyrite, and marcasite; (iii) Ba‐As chimneys, composed of barite with sulfide disseminations, sometimes associated with realgar and orpiment overgrowth; (iv) Mn‐rich chimneys, consisting of carbonates (calcite and magnesite) and sulfides (sphalerite, galena, chalcopyrite, alabandite, and minor amount of tennantite and enargite); and (v) pavement, silicified sediment including abundant native sulfur or barite. Sulfide/sulfate mineralization (groups i–iii) was found in the chimney–mound structure associated with vapor‐loss (Cl‐enriched) fluid venting. In contrast, the sulfide/carbonate mineralization (group iv) was specifically found in the chimneys where vapor‐rich (Cl‐depleted) fluid venting is expected, and the pavement (group v) was associated with diffusive venting from the seafloor sediment. This correspondence strongly suggests that the subseafloor phase separation plays an important role in the diverse range of mineralization in the Yonaguni IV field. The observed sulfide mineral assemblage was consistent with the sulfur fugacity calculated from the FeS content in sphalerite/wurtzite and the fluid temperature for each site, which suggests that the shift of the sulfur fugacity due to participation of volatile species during phase separation is an important factor to induce diverse mineralization. In contrast, carbonate mineralization is attributed to the significant mixing of vapor‐rich hydrothermal fluid and seawater. A submarine hydrothermal system within a back‐arc basin in the continental margin may be considered as developed in a geologic setting favorable to a diverse range of mineralization, where relatively shallow water depth induces sub‐seafloor phase separation of hydrothermal fluid, and sediment accumulation could enhance migration of the vapor‐rich hydrothermal fluid.     

Insights to magmatic-hydrothermal processes in the Manus back-arc basin as recorded by anhydrite

Microchemical analyses of rare earth element (REE) concentrations and Sr and S isotope ratios of anhydrite are used to identify sub-seafloor processes governing the formation of hydrothermal fluids in the convergent margin Manus Basin, Papua New Guinea. Samples comprise drill-core vein anhydrite and seafloor massive anhydrite from the PACMANUS (Roman Ruins, Snowcap and Fenway) and SuSu Knolls (North Su) active hydrothermal fields. Chondrite-normalized REE patterns in anhydrite show remarkable heterogeneity on the scale of individual grains, different from the near uniform REE_N patterns measured in anhydrite from mid-ocean ridge deposits. The REE_N patterns in anhydrite are correlated with REE distributions measured in hydrothermal fluids venting at the seafloor at these vent fields and are interpreted to record episodes of hydrothermal fluid formation affected by magmatic volatile degassing. ⁸⁷Sr/⁸⁶Sr ratios vary dramatically within individual grains between that of contemporary seawater and that of endmember hydrothermal fluid. Anhydrite was precipitated from a highly variable mixture of the two. The intra-grain heterogeneity implies that anhydrite preserves periods of contrasting hydrothermal versus seawater dominant near-seafloor fluid circulation. Most sulfate δ³⁴S values of anhydrite cluster around that of contemporary seawater, consistent with anhydrite precipitating from hydrothermal fluid mixed with locally entrained seawater. Sulfate δ³⁴S isotope ratios in some anhydrites are, however, lighter than that of seawater, which are interpreted as recording a source of sulfate derived from magmatic SO₂ degassed from underlying felsic magmas in the Manus Basin. The range of elemental and isotopic signatures observed in anhydrite records a range of sub-seafloor processes including high-temperature hydrothermal fluid circulation, varying extents of magmatic volatile degassing, seawater entrainment and fluid mixing. The chemical and isotopic heterogeneity recorded in anhydrite at the inter- and intra-grain scale captures the dynamics of hydrothermal fluid formation and sub-seafloor circulation that is highly variable both spatially and temporally on timescales over which hydrothermal deposits are formed. Microchemical analysis of hydrothermal minerals can provide information about the temporal history of submarine hydrothermal systems that are variable over time and cannot necessarily be inferred only from the study of vent fluids.     

Benthic Foraminifera in Siliceous Black Ore from the Ezuri Kuroko Deposit, Hokuroku District, Japan

Abstract: Abundant benthic foraminifera have been identified in thin sections of the siliceous black ore in the Ezuri Kuroko deposit, Hokuroku, Japan. By treating samples with conventional hydrofluoric acid digestion techniques, sponge spicules and radiolaria have also been recognized in the residue. Under microscopic observations, 94 individual foraminiferal specimens have been detected. However, as it is difficult to identify species or genera by means of microscope observations alone, only a small number of genera have been identified based on morphology. The foraminiferal assemblage is composed predominantly of agglutinated species (83%) with subordinate calcareous species (17%), and is assigned to the Cyclammina Assemblage based on the preponderance of Cyclammina (57%). The foraminifera are generally well preserved within micro‐crystalline to cryptocrystalline quartz, and exhibit no obvious features related to compaction or secondary deformation. Textural observations suggest that the siliceous component of this rock was not derived from an allochthonous block but instead constitutes autochthonous proto‐Kuroko sediment. The Cyclammina Assemblage in the ore is different from recently described foraminiferal assemblages in the vicinity of present deep‐sea hydrothermal vents, but is identical to those found in black shales of the Onnagawa to Funakawa stages in the Green Tuff region. The proto‐Kuroko sediment is assumed to have been deposited in an oxygen‐deficient environment within a closed, deep‐seated basin. The existence of siliceous microfossils suggests that the silica in the siliceous ore did not originate from silica sinter deposits produced by submarine hydrothermal activities, but from a biogenic siliceous ooze, probably composed of diatoms. Sulfide mineralization in the interstices of some of the microfossils is inferred to relate primarily to bacterial sulfate reduction associated with the decomposition of organic matter. The later sulfide mineralization associated with larger crystals (which contain fluid inclusions with homogenization temperatures of approximately 250C) cuts across the siliceous masses and foraminiferal septa, and may have been formed after consolidation of the siliceous ooze, accompanying the formation of acidic intrusive rocks during the late Onnagawa stage.     

Formation of massive sulfide deposits on oceanic ridge crests: Incremental reaction models for mixing between hydrothermal solutions and seawater

Equilibrium path calculations have been used to model mixing between hot (350°C) hydrothermal solutions and ambient seawater, in an attempt to simulate mineral precipitation at seafloor vents. These calculations predict temperatures of precipitation, paragenetic sequence of minerals, and chemical composition of chimney deposits associated with vents on the seafloor at 21°N, EPR. Assuming sulfate-sulfide disequilibrium during mixing, the paragenetic sequence revealed is: chalcopyrite, anhydrite, pyrrhotite, pyrite, sphalerite, graphite, and barite. When sulfate-sulfide equilibria is permitted during mixing, however, reduction of small amounts of sulfate results in early precipitation of pyrite and a sequence of Cu-rich sulfide minerals (chalcopyrite-bornite-chalcocite-covellite). This sequence is analogous to that observed in thin chimney walls. The calculations indicate that sulfide mineral precipitation occurs in response to both cooling and change in composition of the hydrothermal solutions as a result of mixing. Varying the amount of mixing with respect to temperature, simulating conductive heating of seawater prior to mixing, results in only minor variations in the sequence and abundance of precipitated phases.Anhydrite precipitation during mixing occurs early, which is consistent with formation of an anhydrite leading edge of chimney structures. Similarly, extrapolation of warm spring data from Galapagos to zero SO₄ concentration suggests anhydrite formation due to mixing with seawater beneath the seafloor, most likely below the level of reactive calcareous sediments. Subsequent interaction of the mixed hydrothermal solution with those sediments results in elevated and variable Ca concentrations estimated for end-member solutions from the Galapagos.Precipitation of Mg hydroxide sulfate hydrate in the walls of the vent chimneys at 21°N, EPR, occurs as a result of conductive heating of ambient seawater with only very minor amounts of mixing. In contrast, precipitation of amorphous silica in the vents must be due to conductive cooling of the hydrothermal solutions.Thus, incremental reaction calculations demonstrate that reactions occurring in and associated with venting ridge crest hydrothermal solutions can be effectively modeled using the thermodynamic data and reaction modeling codes available today. Departures from equilibrium required to accurately model the mixing process are easily accommodated and consistent with data from the vents and vent forming materials.     

"Brown Ore" from the Fukasawa Kuroko Deposits, Northeast Japan: Its Characteristics and Formation Process

Abstract: Brown–colored sulfide ore (brown ore) occurs in the easternmost part of the Tsunokakezawa No. 1 orebody of the Fukasawa kuroko-type deposits, northern Honshu, Japan. As this type of ores also occur in the marginal or uppermost part of several other kuroko deposits in Japan, the formation of brown ore appears to be repeated in the process of kuroko formation. The brown ore is characterized by its higher Ag concentration (up to around 2000 g/t) than ordinary black ore (Zn–Pb ore) of volcanogenic massive sulfide deposits. The brown ore from the Fukasawa deposits can be divided into following three ore types based on its texture and mineral composition: pyritic brown ore, principal brown ore and “diseased” brown ore. Primary precipitation textures such as framboidal– and colloform-textures and compositional zoning within sulfide grains are significant in the brown ores. This seems to be due to lack of overprinting high temperature mineralization resulting in preservation of primary features. The Ag-Au mineralization is widely observed within the brown ores. Silver and gold are especially concentrated in the barite veinlets in the principal brown ore, which are supposed to be fillings of conduit of hydrothermal solution precipitated in the latest stage of hydrothermal activity. This mineralization seems to occur at waning stage of brown ore formation by ore solution at a lower temperature (around 250°C) than that of main part of brown ore (around 270°C). Relatively low fluid temperature and contribution of oxic ambient seawater may be responsible for the development of the Ag-Au mineralization in the brown ore. The occurrence of framboidal-rich pyritic brown ore having negative δ³⁴S values (less than –10%) and filamentous texture of sphalerite, seeming remnant of bacteria, indicate the presence of intensive microbial activity in the hydrothermal area for brown ore formation. Formation environment of each ore type of the brown ore is supposed to be as follows: Pyritic brown ore is likely to have formed on the sea-floor around redox boundary at temperature (around 240°C) lower than ordinary black ore. Principal brown ore seems to have been formed beneath the shell of the pyritic brown ore at temperature around 270°C. Footwall of the brown ore is disseminated tuff breccia corresponding to feeder zone of hydrothermal fluid. Overprinting chalcopyrite mineralization is not observed in the brown ore except in limited part of “diseased” ore, which occurs just above the disseminated tuff breccia. Based on the features distinct from the ordinary black ore, the brown ore can be regarded as a product in the marginal part of submarine hydrothermal system, where temperature and flow rate of hydrothermal solution was relatively low and microbial activity was intensive. The brown ore seems to well preserve its primary features after its deposition and might show the initial feature of some part of the ordinary stratiform black ore.     

四川呷村V HMS矿床：从野外观察到成矿模型

呷村矿床是一个与晚三叠世海相钙碱性酸性火山岩系有关的典型块状硫化物（VHMS）矿床。热水流体系统和贱金属成矿作用发育于义敦岛弧碰撞造山带上的弧间裂谷盆地内,并受其内部的一系列局限盆地及SN向基底断裂－裂缝系统控制。含矿岩系为双峰岩石组合,具火山碎屑岩－矿体－喷气岩“三位一体”特征。硫化物矿床具有“块状矿席＋层控网脉状矿带”式三维结构特征。块状矿席发育多旋回的硫化物－硫酸盐韵律型式,揭示热水流体在海底的幕式排泄以及硫化物－硫酸盐在卤水池内的韵律式化学淀积和滑塌堆积过程。层控网脉状矿带产出于流纹质火山岩系,与上覆的块状矿席平行展布,揭示高渗透性碎屑岩层和多条同级别断层或断裂共同约束海底下部热水流体,并诱导其“弥散式”排泄和侧向流动交代。热水流体的传导冷凝过程导致硫化物沉积、热水流体与冷海水的简单混合导致硅质岩或／重晶石淀积,传导冷凝与海水混合的联合作用导致含硫化物重晶石、硅质岩和红碧玉形成。     

黑矿型矿床成矿物质来源：日本上向黑矿铼—锇和氦同位素证据

上向黑矿（Uwamuki Kuroko)是日本最典型的黑矿型矿床，它形成于日本岛弧中新世矢折岛弧裂谷环境，产于双峰式岩石组合的长英质火山岩系中。矿床由下部筒状硅矿带和上部块状黑矿带构成，后者显示典型的上黑（黑矿）下黄（黄矿）金属分带。为探索研究长期争议的成矿物质来源，系统测定了矿石和主岩的Os,He同位素组成。含矿流纹岩系的R／RA值介于0．93－1．14间，证实该岩浆可能主要来源于陆壳重熔。上向黑矿的上部块状黑矿矿石具较高的^187Os/^188Os值（2．246－7．608），反映矿石Os主体来源于壳源沉积物或矿区基底岩系；下部脉状－网脉状硅矿、块状黄矿和少量黑矿则具低^187Os/^188Os值（0．423－0．793），证实矿石Os具两源性，估计幔源物质贡献约57％－89％，壳源物质贡献约11％－43％。此外，在上部块状黑矿带内部，矿石 ^187Os/^188O显示清楚的垂向韵律性变化，揭示了成矿流体及成矿物质的周期性混合，据此，本文提出了一个新的两阶段成矿模式。     

Quartz precipitation and fluid inclusion characteristics in sub-seafloor hydrothermal systems associated with volcanogenic massive sulfide deposits

Results of a numerical modeling study of quartz dissolution and precipitation in a sub-seafloor hydrothermal system have been used to predict where in the system quartz could be deposited and potentially trap fluid inclusions. The spatial distribution of zones of quartz dissolution and precipitation is complex, owing to the fact that quartz solubility depends on many inter-related factors, including temperature, fluid salinity and fluid immiscibility, and is further complicated by the fact that quartz exhibits both prograde and retrograde solubility behavior, depending on the fluid temperature and salinity. Using the PVTX properties of H₂O-NaCl, the petrographic and microthermometric properties of fluid inclusions trapped at various locations within the hydrothermal system have been predicted. Vapor-rich inclusions are trapped as a result of the retrograde temperature-dependence of quartz solubility as the convecting fluid is heated in the vicinity of the magmatic heat source. Coexisting liquid-rich and vapor-rich inclusions are also trapped in this region when quartz precipitates as a result of fluid immiscibility that lowers the overall bulk quartz solubility in the system. Fluid inclusions trapped in the shallow subsurface near the seafloor vents and in the underlying stockwork are liquid-rich with homogenization temperatures of 200?C400°C and salinities close to that of seawater. Volcanogenic massive sulfide (VMS) deposits represent the uplifted and partially eroded remnants of fossil submarine hydrothermal systems, and the relationship between fluid-inclusion properties and location within the hydrothermal system described here can be used in exploration for VMS deposits to infer the direction towards potential massive sulfide ore.     

Multiple Sources of Metals of Mineralization in Lower Cambrian Black Shales of South China: Evidence from Geochemical and Petrographic Study

Black shales of the Lower Cambrian Niutitang Formation in southern China (Huangjiawan mine, Zunyi region, northern part of the Guizhou Province) host regionally distributed stratiform polymetallic Ni‐Mo‐platinum group elements (PGE)‐Au phosphate‐ and sulfide‐rich ores. These are confined to a ≥0.2‐m thick ore horizon composed of mineralized bodies of algal onkolites, phosphate nodules, and sulfide and shale clasts in a mineralized phosphate‐ and organic matter‐rich matrix. Compared to footwall and hanging wall shales, the ore bed is strongly enriched in Ni (up to 100‐fold), As (up to 97‐fold), Mo (up to 95‐fold), Sb (up to 67‐fold), Rh (up to 49‐fold), Cu (up to 37‐fold), Pd (up to 33‐fold), Ru (up to 24‐fold), Zn (up to 23‐fold), Pt (up to 21‐fold), Ir (up to 15‐fold), Co (up to 14‐fold), and Pb (up to 13‐fold). Even footwall and hanging wall black shales are significantly enriched by Mo (21‐fold) and Ni (12‐fold) but depleted in Cr in comparison to average Cambrian black shale. Organic matter is represented by separate accumulations dispersed in the rock matrix or as biotic bitumen droplets and veinlets in ore clasts. Similar organic carbon (C_org) values in an ore bed and enclosing footwall and hanging wall shales of little mineralization indicate that metal accumulation was not controlled only by biogenic productivity and organic matter accumulation rate. Evaporitic conditions during sedimentation of the basal part of the Niutitang Formation were documented by an occurrence of preserved Ni‐, V‐, Cr‐, and Cu‐enriched phosphate‐rich hardground with halite and anhydrite pseudomorphs on the paleosurface of the underlying Neoproterozoic carbonates. Neoproterozoic black shales of the Doushantuo Formation are characterized by increased metal concentrations. Comparison of metal abundances in both hardground and Doushantuo black shales indicate that black shales could have become a source of metal‐rich hardground during weathering. The polymetallic Ni‐Mo‐PGE sulfide‐rich ore bed is interpreted to represent a remnant of shallow‐water hardground horizon rich in metals, which originated in a sediment‐starved, semi‐restricted, seawater environment. During the Early Cambrian transgression an influx of fresh seawater and intensive evaporation, together with the hydrothermal enrichment of seawater in a semi‐restricted basin, resulted in the formation of dense metalliferous brines; co‐precipitation of metals together with phosphates and sulfides occurred at or above the oxic–anoxic sediment interface. Metal‐enriched hardground was disintegrated by the action of waves or bottom currents and deposited in a deeper part of the anoxic basin. Contemporaneously with the formation of a polymetallic Ni‐Mo‐PGE‐Au sulfide ore bed, economic sedimentary exhalative (SEDEX)‐type barite deposits were forming in a stratigraphically and geotectonically similar setting. The results of geochemical study at the Shang Gongtang SEDEX‐type Ba deposit indicate that concentrations of Ag, As, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V, Zn and other metals decrease from top of the barite body toward the hanging wall black shale. Lower Cambrian black shales of the Niutitang Formation above the barite body also display similar element abundances as Neoproterozoic black shales of the Doushantuo Formation, developed in the footwall of the barite body. But the geochemical composition of the sulfide layer is different from the Ni‐Mo ore bed, showing only elevated Pb, Cu, Ni and Mo values. It is suggested that hydrothermal brines at Shang Gongtang might have leached metals from footwall Neoproterozoic sequences and became, after mixing with normal seawater, an additional source of Ag, Cr, Cu, Pb, Sb, Zn, Ni, PGE, V and other metals.     

Mineralogical and Genetical Aspects of the Doyashiki Kuroko Deposits, Hokuroku Basin, Japan

Abstract. A detail investigation of ore and gangue minerals was performed on the Doyashiki Kuroko deposits, Hokuroku basin, Japan for the first time. Main ore minerals are sphalerite, galena, pyrite, chalcopyrite, tetrahedrite-tennantite and digen-ite. Small amounts of enargite, wittichenite, electrum, covellite, bornite, marcasite and hematite are also observed. Quartz, barite and gypsum are common gangue minerals. Homogenization temperatures and salinities of fluid inclusions in quartz, sphalerite and barite range from 190 to 240C and 3.0 to 5.5 wt% NaCl equivalent, respectively. The FeS contents of sphalerite and Ag contents of electrum were 0.12 to 0.18 mol %, 39.0 to 39.6 atom %, respectively. The chemical composition of digenite as a primary mineral shows high sulfur contents.
These data indicate that ore fluid responsible for digenite and associated ore minerals was characterized by a range of high sulfur fugacity with a moderate formation temperature. This is concordant with the mineral assemblage of bornite-pyrite and chalcopyrite, which shows high sulfur fugacity conditions. It seems that the mineralization closely associated with acidic volcanism has occurred around 13 Ma of Middle Miocene on the seafloor at the depth of about 1500 m.     

Exploration Indices and Mineral Potential Map of the Kuroko Deposits in Northeast Japan

Abstract. Recent discoveries of seafloor hydrothermal mineralization in submarine volcanic centers of felsic magma in western Pacific island arcs are regarded as modern analogues of Kuroko type deposits. Studies of these deposits and their surrounding geology raised question whether the exploration activity for the Kuroko deposits on land which peaked in the 1960's was adequate or not. However, such an evaluation is not easy because the exploration data are about to be lost as a result of the closure of all the Kuroko mines in the area since 1994.
The Metal Mining Agency of Japan (MMAJ), therefore, decided to compile existing data on about 180 Kuroko deposits and related mineral occurrences in northeast Japan as a new Kuroko database.
This study extends a concept called "exploration indices" which was developed based on a case study of the thoroughly surveyed Hokuroku district to draw a potential map of the Kuroko occurrences for the entire northeast Japan quantitatively with a Geographical Information System (GIS). Effective exploration indices include: 1) distribution of dacitic-rhy-olitic submarine volcanic rocks of the Nishikurosawa and Onnagawa stages, 2) distribution of intrusive rocks of pre- and post-Kuroko horizon, 3) low aeromagnetic anomaly caused by hydrothermal alteration of magnetite, 4) low gravity anomaly which suggests depressions in the basement rocks such as a tectonic basin and/or caldera, and 5) nearby existence of vein type deposits. It is concluded that about 33 % of known Kuroko deposits fall within the high potential zone (score=4 and 5) that occupies only 4 % of the entire northeast Japan arc. The Kuroko potential map is, therefore, useful for limiting the target area for Kuroko type deposits in an island arc setting.     

陕西紫阳下寒武统黑色岩系地球化学特征及成因研究

通过野外研究发现陕西紫阳下寒武统黑色岩系富含多种矿产且成因复杂,主要由硅质岩、灰岩、碳质硅质灰岩、碳硅质页岩四类组成。据此进行了系统的元素地球化学分析,结果显示研究区黑色岩系富含V、Mo、As、Ba等元素,不同岩性稀土模式曲线总体特征相似指示成因联系密切。四类岩性样品各自的MnO/TiO₂均值接近或小于0.5、V/（V+Ni）均值大于0.57、V/Cr均值大于4.2等特征表明该套黑色岩系形成于浅海—半深海相缺氧还原环境。另外,As和Sb的富集、Zn?Co?Ni图解中投点大部分位于热液矿床区域、Sr/Ba小于1、La/Ce均值接近2.8、北美页岩标准化配分图解的Eu负异常—弱正异常均指示了热液参与下的正常海水沉积环境。研究区地层夹含的硅质岩和重晶石等热水沉积岩反映了同沉积时的热液活动。据此推断沉积环境是海水、热液和生物的共同作用下形成的浅海—半深海相缺氧的还原环境。     

Geology,mineralogy, and sulfur isotope geochemistry of the Sargaz Cu–Zn volcanogenic massive sulfide deposit,Sanandaj–Sirjan Zone,Iran

The Sargaz Cu–Zn massive sulfide deposit is situated in the southeastern part of Kerman Province, in the southern Sanandaj–Sirjan Zone of Iran. The stratigraphic footwall of the Sargaz deposit is Upper Triassic to Lower Jurassic (?) pillowed basalt, whereas the stratigraphic hanging wall is andesite. Mafic volcanic rocks are overlain by andesitic volcaniclastics and volcanic breccias and locally by heterogeneous debris flows. Rhyodacitic flows and volcaniclastics overlie the sequence of basaltic and andesitic rocks. Based on the bimodal nature of volcanism, the regional geologic setting and petrochemistry of the volcanic rocks, we suggest massive sulfide mineralization in the Sargaz formed in a nascent ensialic back-arc basin. The current reserves (after ancient mining) of the Sargaz deposit are 3 Mt at 1.34% Cu, 0.38% Zn, 0.08%Pb, 0.24 g/t Au, and 7 g/t Ag. The structurally dismembered massive sulfide lens is zoned from a pyrite-rich base, to a pyrite?±?chalcopyrite-rich central part, and a sphalerite–chalcopyrite-rich upper part, with a sphalerite-rich zone lateral to the upper part. The main sulfide mineral is pyrite, with lesser chalcopyrite and sphalerite. The feeder zone, comprised of a vein stockwork consists of quartz–sulfide–sericite pesudobreccia and, in the deepest part, chlorite–quartz–pyrite pesudobreccia. Footwall hydrothermal alteration extends at least 70–80 m below the massive sulfide lens and more than a hundred meters along strike from the massive sulfide lens. Jasper and Fe–Mn bearing chert horizons lateral to the sulfide deposit represent low-temperature hydrothermal precipitates of the evolving hydrothermal system. Based on mineral textures and paragenetic relationships, the growth history of the Sargaz deposit is complex and includes: (1) early precipitation of sulfides (protore) on the seafloor as precipitation of fine-grained anhedral pyrite, sphalerite, quartz, and barite; (2) anhydrite precipitation in open spaces and mineral interstices within the sulfide mound followed by its subsequent dissolution, formation of breccia textures, and mound clasts and precipitation of coarse-grained pyrite, sphalerite, tetrahedrite–tennantite, galena and barite; (3) replacement of pre-existing sulfides by chalcopyrite precipitated at higher temperatures (zone refining); (4) continued “refining” led to the dissolution of stage 3 chalcopyrite and formation of a base-metal-depleted pyrite body in the lowermost part of the massive sulfide lens; (5) carbonate veins were emplaced into the sulfide lens, replacing stage 2 barite. The δ³⁴S composition of the sulfides ranges from +2.8‰ to +8.5‰ (average, +5.6‰) with a general increase of δ³⁴S ratios with depth within the massive sulfide lens and underlying stockwork zone. The heavier values indicate that some of the sulfur was derived from seawater sulfate that was ultimately thermochemically reduced in deep hydrothermal reaction zones.     

南秦岭地区下寒武统水沟口组黑色岩系成因及其沉积环境

早寒武世全球广泛发育的黑色岩系记录了重要海洋环境信息。为了解决该时期黑色岩系成因模式和沉积环境问题,本文选取南秦岭淅川—内乡地区下寒武统水沟口组黑色岩系为研究对象,通过剖面详测、薄片鉴定、电子探针和主微量元素等岩石学-地球化学分析方法,对其物质来源、形成机制和沉积环境进行分析。研究表明:水沟口组黑色岩系普遍具有海相硅质岩典型特征—微晶石英结构,并具有与海水一致的稀土标准化曲线和低的总稀土值,指示其形成于海水环境;电子探针下发现黑色岩系富含与热液有关的重晶石、萤石矿物,和与生物相关的磷灰石、黄铁矿矿物,同时黑色岩系成因判别图解中绝大部分样品落入生物成因区域,少数落入热液成因内,指示硅质来源以生物成因硅为主并含少量热液硅;样品高V/(V+Ni)、Ni/Co比值和氧化还原敏感元素(Mo、U、V等)不同程度富集指示较强的还原环境,结合黑色岩系形成环境判别图得出该套岩系形成于大陆边缘—深海盆地区域内还原—缺氧的滞流水体环境。综上得出水沟口组黑色岩系形成时洋底热液活动频繁,深部流体上涌带来大量营养物质使得浅海生物繁盛,海水中硅在生物作用和热液影响下促使硅质胶体颗粒化学沉淀,并随洋流在远离热液中心的大陆边缘位置沉积成岩。早寒武世还原—缺氧性质海水和微生态系统有助于硅质沉淀,而微生物富硅作用促进了黑色岩系形成。     

Petrology,Geochemistry, and Fluid Inclusion Microthermometry of Sphalerite from the Laloki and Federal Flag Strata‐Bound Massive Sulfide Deposits,Papua New Guinea: Implications for Gold Mineralization

The Laloki and Federal Flag deposits are two of the many (over 45) polymetallic massive sulfide deposits that occur in the Astrolabe Mineral Field, Papua New Guinea. New data of the mineralogical compositions, mineral textures, and fluid inclusion studies on sphalerite from Laloki and Federal Flag deposits were investigated to clarify physiochemical conditions of the mineralization at both deposits. The two deposits are located about 2 km apart and they are stratigraphically hosted by siliceous to carbonaceous claystone and rare gray chert of Paleocene–Eocene age. Massive sulfide ore and host rock samples were collected from each deposit for mineralogical, geochemical, and fluid inclusion studies. Mineralization at the Laloki deposit consists of early‐stage massive sulfide mineralization (sphalerite‐barite, chalcopyrite, and pyrite–marcasite) and late‐stage brecciation and remobilization of early‐stage massive sulfides that was accompanied by late‐stage sphalerite mineralization. Occurrence of native gold blebs in early‐stage massive pyrite–marcasite‐chalcopyrite ore with the association of pyrrhotite‐hematite and abundant planktonic foraminifera remnants was due to reduction of hydrothermal fluids by the reaction with organic‐rich sediments and seawater mixing. Precipitation of fine‐grained gold blebs in late‐stage Fe‐rich sphalerite resulted from low temperature and higher salinity ore fluids in sulfur reducing conditions. In contrast, the massive sulfide ores from the Federal Flag deposit contain Fe‐rich sphalerite and subordinate sulfarsenides. Native gold blebs occur as inclusions in Fe‐rich sphalerite, along sphalerite grain boundaries, and in the siliceous‐hematitic matrix. Such occurrences of native gold suggest that gold was initially precipitated from high‐temperature, moderate to highly reduced, low‐sulfur ore fluids. Concentrations of Au and Ag from both Laloki and Federal Flag deposits were within the range (<10 ppm Au and <100 ppm Ag) of massive sulfides at a mid‐ocean ridge setting rather than typical arc‐type massive sulfides. The complex relationship between FeS contents in sphalerite and gold grades of both deposits is probably due to the initial deposition of gold on the seafloor that may have been controlled by factors such as Au complexes, pH, and fO₂ in combination with temperature and sulfur fugacity.     

贵州镇宁重晶石矿中硅质岩稀土元素地球化学研究

通过对镇宁泥盆系重晶石矿中硅质岩稀土元素地球化学特征研究,发现硅质岩稀土总量较低,轻稀土富集,δCe呈弱的负异常,δEu呈负异常到正异常,{La/Sm}N和{Gd/Yb}N值表明轻稀土分异强;通过∑REE、Ce/Ce＊、Eu/Eu＊、{La/Ce}N和{La/Lu}N参数综合分析,硅质岩沉积成岩过程中有明显的热水参与,...     

Formation of volcanogenic massive sulfide deposits: The Kuroko perspective

The main objective of this paper is to identify the geochemical, hydrological, igneous and tectonic processes that led to the variations in the physical (size, geometry) and chemical (mineralogy, metal ratios and zoning) characteristics of volcanogenic massive sulfide deposits with respect to space (from a scale of mining district size area to a global scale) and time (from a < 10 000 year time scale to a geologic time scale).All volcanogenic massive sulfide deposits (VMSDs) appear to have formed in extensional tectonic settings, such as at mid ocean spreading centers, backarc spreading centers, and intracontinental rifts (and failed rifts). All VMSDs appear to have formed in submarine depressions by seawater that became ore-forming fluids through interactions with the heated upper crustal rocks. Submarine depressions, especially those created by submarine caldera formation and/or by large-scale tectonic activities (e.g., rifting), become most favorable sites for the formation of large VMSDs because of hydrological, physical and chemical reasons.The fundamental processes leading to the formation of VMSDs include the following six processes:

1. (1) Intrusion of a heat source (typically a 10³ km size pluton) into an oceanic crust or a submarine continental crust causes deep convective circulation of seawater around the pluton. The radius of a circulation cell is typically 5 km. The temperature of fluids that discharge on the seafloor increases with time from the ambient temperature to a typical maximum of 350°C, and then decreases gradually to the ambient temperatures in a time scale of 100 to 10 000 years. The majority of sulfide and sulfate mineralization occurs during the waxing stage of hydrothermal activity.

2. (2) Reactions between low temperature (T < 150°C) country rocks with downward percolating seawater cause to precipitate seawater SO²⁻₄ as disseminated gypsum and anhydrite in the country rocks.

3. (3) Reactions of the “modified” seawater with higher-temperature rocks at depths during the waxing stage cause the transformation of the “seawater” to metal- and H₂S-rich ore-forming fluids. The metals and sulfide sulfur are leached from the county rocks; the previously formed gypsum and anhydrite are reduced by Fe²⁺-bearing minerals and organic matter, providing additional H₂S. The mass of high temperature rocks that provide the metals and reduced sulfur is typically 10¹¹ tons ( 40 km³ in volume). The roles of magmatic fluids or gases are minor in most massive sulfide systems, except for SO₂ to produce acid-type alteration in some systems.

4. (4) Reactions between the ore-forming fluids and cooler rocks in the discharge zone cause alteration of rocks and precipitation of some ore minerals in the stockwork ores.

5. (5) Mixing of the ore-forming fluids with local seawater within unconsolidated sediments and/or on the seafloor causes precipitation of “primitive ores” with the black ore mineralogy (sphalerite + galena + pyrite + barite + anhydrite).

6. (6) Reactions between the “primitive ores” with later and hotter hydrothermal fluids cause transformation of “primitive ores” to “matured ores” that are enriched in chalcopyrite and pyrite.

Variations in the mineralogical and elemental characteristics, the geometry, and the size of submarine hydrothermal deposits are controlled by the following four parameters:

1. (A) The chemical and physical characteristics of seawater (composition, temperature, density), which depend largely on the geographical settings (e.g., equatorial evaporating basins),

2. (B) The chemical and physical characteristics of the plumbing system (lithology, fractures),

3. (C) The thermal structure of the plumbing system, which is determined largely by the ambient geothermal gradient, and the size and temperature of the intrusive, and

4. (D) The physical characteristics of the seafloor (depth, basin topography).

For example, the submarine hydrothermal deposits developed in basaltic plumbing systems are generally poor in Pb and Ba compared to those developed in felsic plumbing systems. The lower temperature systems are generally poorer in sulfides, but richer in iron oxides and sulfates. The higher temperature and larger hydrothermal systems tend to produce chalcopyrite and pyrite rich ores. Contrasts in the metal ratios between the Noranda-type Archean VMSDs and the younger VMSDs reflect the differences in the geothermal gradient of the plumbing systems. The submarine hydrothermal deposits developed in the near equatorial regions tend to form large continuous bedded type ores because of the likeliness of creating large stratified basins.The basic processes of submarine hydrothermal mineralization have remained essentially the same throughout the geologic history, from at least 3.5 billion year ago to the present.