Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

Hydrothermal Alteration and Mineralization of Middle Jurassic Dexing Porphyry Cu-Mo Deposit, Southeast China

The Dexing deposit is located in a NE‐trending magmatic belt along the southeastern margin of the Yangtze Craton. It is the largest porphyry copper deposit in China, consisting of three porphyry copper orebodies of Zhushahong, Tongchang and Fujiawu from northwest to southeast. It contains 1168 Mt of ores with 0.5% Cu and 0.01% Mo. The Dexing deposit is hosted by Middle Jurassic granodiorite porphyries and pelitic schist of Proterozoic age. The Tongchang granodiorite porphyry has a medium K cal‐alkaline series, with medium K₂O content (1.94–2.07 wt%), and low K₂O/(Na₂O + K₂O) (0.33–0.84) ratios. They have high large‐ion lithophile elements, high light rare‐earth elements, and low high‐field‐strength elements. The hydrothermal alteration at Tongchang is divided into four alteration mineral assemblages and related vein systems. They are early K‐feldspar alteration and A vein; transitional (chlorite + illite) alteration and B vein; late phyllic (quartz + muscovite) alteration and D vein; and latest carbonate, sulfate and oxide alteration and hematite veins. Primary fluid inclusions in quartz from phyllic alteration assemblage include liquid‐rich (type 1), vapor‐rich (type 2) and halite‐bearing ones (type 3). These provide trapping pressures of 20–400 ´ 10⁵ Pa of fluids responsible for the formation of D veins. Igneous biotite from least altered granochiorite porphyry and hydrothermal muscovite in mineralized granodiorite porphyry possess δ¹⁸O and δD values of 4.6‰ and ?87‰ for biotite and 7.1–8.9‰, ?71 to ?73‰ for muscovite. Stable isotopic composition of the hydrothermal water suggests a magmatic origin. The carbon and oxygen isotope for hydrothermal calcite are ?4.8 to ?6.2‰ and 6.8–18.8‰, respectively. The δ³⁴S of pyrite in quartz vein ranges from ?0.1 to 3‰, whereas δ³⁴S for chalcopyrite in calcite veins ranges from 4 to 5‰. These are similar to the results of previous studies, and suggest a magmatic origin for sulfur. Results from alteration assemblages and vein system observation, as well as geochemical, fluid inclusion, stable isotope studies indicate that the involvement of hydrothermal fluids exsolved from a crystallizing melt are responsible for the formation of Tongchang porphyry Cu‐Mo orebodies in Dexing porphyry deposit.     

Characteristics of Triassic epithermal Au mineralization at the Q prospect,Chatree mining area,Central Thailand

The Chatree deposit is located in the Loei‐Phetchabun‐Nakhon Nayok volcanic belt that extends from Laos in the north through central and eastern Thailand into Cambodia. Gold‐bearing quartz veins at the Q prospect of the Chatree deposit are hosted within polymictic andesitic breccia and volcanic sedimentary breccia. The orebodies of the Chatree deposit consist of veins, veinlets and stockwork. Gold‐bearing quartz veins are composed mainly of quartz, calcite and illite with small amounts of adularia, chlorite and sulfide minerals. The gold‐bearing quartz veins were divided into five stages based on the cross‐cutting relationship and mineral assemblage. Intense gold mineralization occurred in Stages I and IV. The mineral assemblage of Stages I and IV is characterized by quartz–calcite–illite–laumontite–adularia–chlorite–sulfide minerals and electrum. Quartz textures of Stages I and IV are also characterized by microcrystalline and flamboyant textures, respectively. Coexistence of laumontite, illite and chlorite in the gold‐bearing quartz vein of Stage IV suggests that the gold‐bearing quartz veins were formed at approximately 200°C. The flamboyant and brecciated textures of the gold‐bearing quartz vein of Stage IV suggest that gold precipitated with silica minerals from a hydrothermal solution that was supersaturated by boiling. The δ¹⁸O values of quartz in Stages I to V range from +10.4 to +11.6‰ except for the δ¹⁸O value of quartz in Stage IV (+15.0‰). The increase in δ¹⁸O values of quartz at Stage IV is explained by boiling. P_H2O is estimated to be 16 bars at 200°C. The f_CO2 value is estimated to be 1 bar based on the presence of calcite in the mineral assemblage of Stage IV. The total pressure of the hydrothermal solution is approximately 20 bars at 200°C, suggesting that the gold‐bearing quartz veins of the Q prospect formed about 200 m below the paleosurface.     

Geology and geochemistry of the sediment-hosted Cheshmeh-Konan redbed-type copper deposit,NW Iran

The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl₂ equiv.). The range of δ³⁴S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ³⁴S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ¹³C_V-PDB from −8.2 to −5.1‰ and δ¹⁸O_V-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO₃⁻ from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) deposit.     

Characteristic Features of REE and Pb–Zn–Ag Mineralizations in the Na Son Deposit,Northeastern Vietnam

The Na Son deposit is a small‐scale Pb–ZnPb–Zn–Ag deposit in northeast Vietnam and consists of biotite–chlorite schist, reddish altered rocks, quartz veins and syenite. The biotite–chlorite schist is intruded by syenite. Reddish altered rocks occur as an alteration halo between the biotite–allanite‐bearing quartz veins and the biotite–chlorite schist. Allanite occurs in the biotite–allanite‐bearing quartz veins and in the proximal reddish altered rocks. Rare earth element (REE) fluorocarbonate minerals occur along fractures or at rim of allanite crystals. The later horizontal aggregates of sulfide veins and veinlets cut the earlier reddish altered rocks. The earlier Pb–Zn veins consist of a large amount of galena and lesser amounts of sphalerite, pyrite and molybdenite. The later Cu veins cutting the Pb–Zn veins include chalcopyrite and lesser amounts of tetrahedrite and pyrite. The occurrences of two‐phase H₂O–CO₂ fluid inclusions in quartz from biotite–allanite‐bearing quartz veins and REE‐bearing fluorocarbonate minerals in allanite suggest the presence of CO₂ and F in the hydrothermal fluid. The oxygen isotopic ratios of the reddish altered rocks, biotite–chlorite schist, and syenite range from +13.9 to +14.9 ‰, +11.5 to +13.3 ‰, and +10.1 to +11.6 ‰, respectively. Assuming an isotopic equilibrium between quartz (+14.6 to +15.8 ‰) and biotite (+8.6 ‰) in the biotite–allanite‐bearing quartz vein, formation temperature was estimated to be 400°C. At 400°C, δ¹⁸O values of the hydrothermal fluid in equilibrium with quartz and biotite range from +10.5 to +11.7 ‰. These δ¹⁸O values are consistent with fluid that is derived from metamorphism. Assuming an isotopic equilibrium between galena (+1.5 to +1.7 ‰) and chalcopyrite (+3.4 ‰), the formation temperature was estimated to be approximately 300°C. The formation temperature of the Na Son deposit decreased with the progress of mineralization. Based on the geological data, occurrence of REE‐bearing minerals and oxygen isotopic ratios, the REE mineralization is thought to result from interaction between biotite–chlorite schist and REE‐, CO₂‐ and F‐bearing metamorphic fluid at 400°C under a rock‐dominant condition.     

Hydrothermal Alteration of Limestone and Mineral Exploration of Zn-Pb Skarn Deposits in the Sako-nishi Area of the Kamioka Mine, Central Japan

Abstract: Crystalline limestone of the Sako-nishi area in the Kamioka Zn-Pb mine, central Japan, is depleted in ¹⁸O and ¹³C toward the center of mineralization due to interaction with hydrothermal fluids with a dominant meteoric water component. The relationship between isotopic composition and mineral assemblage, texture, the chemical composition of the minerals, and the bulk chemical composition in the limestone was examined. A decrease in the δ¹⁸OSMOW value correlated with: (1) increase of fine-grained calcite which is enriched in Mn and exhibits a bright cathodoluminescence, (2) progressive hy-drothermal alteration of clinopyroxene in the original limestone into tremolite within the weakly-altered zone, and into chlorite and actinolite within the strongly-altered zone, (3) dominance of hydrothermal chlorite in altered limestone having δ¹⁸O values of less than 10%. This chlorite was enriched in Fe compared to mafic minerals in the unaltered limestone. The enrichment of Fe and Mn was more conspicuous in calcite and chlorite in skarn deposits. The occurrence and chemical composition of hydrothermal minerals in the limestone, skarn, and ore indicate that the ¹⁸O–depleted zones were formed in the later stage from fluids, which were responsible for mineralization and skarnization, and for Fe and Mn enrichment. The Al, Mn, and Fe contents, and the ratios of Mg/(Mg+Mn+Fe), Al/Mg, and Mn/Sr in the hydrochloric acid leachate of limestone varied with decreasing δ¹⁸O and δ¹³C values, reflecting increases in high-Mn calcite and high-Fe chlorite. These indexes were useful for the identification of hydrothermally altered limestone. Furthermore, the potential score weighted by each index was more effective and accurate means of detecting promising mineralization zones. An anomalous potential score due to the presence of hydrothermal minerals in the outcropping limestone occurred along the Atotsu–1GO fault. This structure indicates that the skarn deposits of the Sako-nishi area belong to Mozumi-type Zn–Pb skarn deposits, in which fissures and faults served as major passages for the hydrothermal fluid. High-Mn carbonate and high-Fe chlorite widely occur in base-metal vein deposits and Zn-Pb type skarn deposits. Leaching of altered rock with hydrochloric acid in addition to stable isotope composition and cathodoluminescence imaging is effective for geochemical exploration for hydrothermal deposits because it makes possible the detection of the elemental composition of hydrothermal minerals such as chlorite and carbonate and because of the rapidity and convenience of analysis.     

Genesis of the Xiuwenghala Gold Deposit in the Beishan Orogen,Northwest China: Evidence from Geology,Fluid Inclusion,and H–O–S–Pb Isotopes

The Xiuwenghala gold deposit is located in the Beishan Orogen of the southern Central Asian Orogenic Belt. The vein/lenticular gold orebodies are controlled by Northeast‐trending faults and are hosted mainly in the brecciated/altered tuff and rhyolite porphyry of the Lower Carboniferous Baishan Formation. Metallic minerals include mainly pyrite and minor chalcopyrite, arsenopyrite, galena, and sphalerite, whilst nonmetallic minerals include quartz, chalcedony, sericite, chlorite, and calcite. Hydrothermal alterations consist of silicic, sericite, chlorite, and carbonate. Alteration/mineralization processes comprise three stages: pre‐ore silicic alteration (Stage I), syn‐ore quartz‐chalcedony‐polymetallic sulfide mineralization (Stage II), and post‐ore quartz‐calcite veining (Stage III). Fluid inclusions (FIs) in quartz and calcite are dominated by L‐type with minor V‐type and lack any daughter mineral‐bearing or CO₂‐rich/‐bearing inclusions. From Stages I to III, the FIs homogenized at 240–260°C, 220–250°C, and 150–190°C, with corresponding salinities of 2.9–10.9, 3.2–11.1, and 2.9–11.9 wt.% NaCl eqv., respectively. The mineralization depth at Xiuwenghala is estimated to be relatively shallow (<1 km). FI results indicate that the ore‐forming fluids belong to a low to medium‐temperature, low‐salinity, and low‐density NaCl‐H₂O system. The values decrease from Stage I to III (3.7‰, 1.7–2.4‰, and ?1.7 to 0.9‰, respectively), and a similar trend is found for their values (?104 to ?90‰, ?126 to ?86‰, and ?130 to ?106‰, respectively). This indicates that the fluid source gradually evolved from magmatic to meteoric. δ³⁴S values of the hydrothermal pyrites (?3.0 to 0.0‰; avg. ?1.1‰) resemble those of typical magmatic/mantle‐derived sulfides. Pyrite Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.409–18.767, ²⁰⁷Pb/²⁰⁴Pb = 15.600–15.715, ²⁰⁸Pb^/204Pb = 38.173–38.654) are similar to those of the (sub)volcanic ore host, indicating that the origin of ore‐forming material was mainly the upper crustal (sub)volcanic rocks. Integrating evidence from geology, FIs, and H–O–S–Pb isotopes, we suggest that Xiuwenghala is best classified as a low‐sulfidation epithermal gold deposit.     

Origin and evolution of hydrothermal fluids in the Taochong iron deposit,Middle–Lower Yangtze Valley,Eastern China: Evidence from microthermometric and stable isotope analyses of fluid inclusions

The Middle–Lower Yangtze River Valley is one of the most important metallogenic belts in China, hosting numerous Cu–Fe–Au–Mo deposits. The Taochong deposit is located in the northern part of the Fanchang iron ore district of the Middle–Lower Yangtze River metallogenic belt. The Fe-orebody is hosted by Middle Carboniferous to Lower Permian limestones. Skarns and Fe-orebodies occur as tabular bodies along interlayer-gliding faults, at some distance from the inferred granitic intrusions. Field evidence and petrographic observations indicate that the three stages of hydrothermal activity—the skarn, iron oxide (main mineralization stage), and carbonate stages—all contributed to the formation of the Taochong iron deposit. The skarn stage is characterized by the formation of garnet and pyroxene, with high-temperature, hypersaline hydrothermal fluids with isotopic compositions similar to those of typical magmatic fluids. These fluids were probably generated by the separation of brine from a silicate melt instead of the product of aqueous fluid immiscibility. The iron oxide stage coincides with the replacement of garnet and pyroxene by actinolite, chlorite, quartz, calcite and hematite. The hydrothermal fluids at this stage are represented by saline fluid inclusions that coexist with vapor-rich inclusions with anomalously low δD values (− 66‰ to − 94‰). The decrease in ore fluid δ¹⁸O_water with time and decreasing depth is consistent with the decreases in fluid salinity and temperature. The fluid δD values also show a decreasing trend with decreasing depth. Both fluid inclusion and stable isotopic data suggest that the ore fluid during the main period of mineralization was evolved by the boiling of various mixtures of magmatic brine and meteoric water. This process was probably induced by a drop in pressure from lithostatic to hydrostatic. The carbonate stage is represented by calcite veins that cut across the skarn and orebody, locally producing a dense stockwork. This observation indicates the veins formed during the waning stages of hydrothermal activity. The fluids from this stage are mainly represented by a variety of low-salinity fluid inclusions, as well as fewer high-salinity inclusions. These particular fluids have the lowest δ¹⁸O_water values (− 2.2‰ to 0.4‰) and a wide of range of δD values (− 40‰ to − 81‰), which indicate that they were originated from a mixture of residual fluids from the oxide stage, various amounts of meteoric water, and possibly condensed vapor. Low-temperature boiling probably occurred during this stage.We also discuss the reasons behind the anomalously low δD values in fluid inclusion water extracted by thermal decrepitation from quartz at high temperatures, and suggest that calcite data provide a possible benchmark for adjusting low δD values found in quartz intergrown with calcite.     

Geological,mineralogical, and oxygen isotope studies of the Chandmani Uul iron oxide–copper–gold deposit in Dornogobi Province,Southeastern Mongolia

The Chandmani Uul deposit is located in Dornogovi province, Southeastern Mongolia. Iron oxide ores are hosted in the andesitic rocks of the Shar Zeeg Formation of Neoproterozoic to Lower‐Cambrian age. Middle‐ to Upper‐Cambrian bodies of granitic rocks have intruded into the host rocks in the western and southern regions of the deposit. The wall rocks around the iron oxide ore bodies were hydrothermally altered to form potassic, epidote, and sericite–chlorite alteration zones, and calcite and quartz veinlets are ubiquitous in the late stage. Since granitic rocks also underwent potassic alteration, the activity of the granitic rocks must have a genetic relation to the ore deposit. The ore mineral assemblage is dominated by iron oxides such as mushketovite, euhedral magnetite with concentric and/or oscillatory zoning textures, and cauliflower magnetite. Lesser amounts of chalcopyrite and pyrite accompany the iron oxides. Among all these products, mushketovite is dominant and is distributed throughout the deposit. Meanwhile, euhedral magnetite appears in limited amounts at relatively shallow levels in the deposit. By contrast, cauliflower magnetite appears locally in the deeper parts of the deposit, and is associated with green‐colored garnet and calcite. Sulfide minerals are ubiquitously associated with these iron oxides. The oxygen isotope (δ¹⁸O) values of all types of magnetite, quartz, and epidote were found to be ?5.9 to ?2.8‰, 10.5 to 14.9‰, and 3.6 to 6.6‰, respectively. The δ¹⁸O values of quartz–magnetite pairs suggest an equilibrium isotopic temperature near 300°C. The calculated values of δ¹⁸O for the water responsible for magnetite ranged from 2 to 10‰. All the data obtained in this study suggest that the iron oxide deposit at the Chandmani Uul is a typical iron oxide–copper–gold deposit, and that this deposit was formed at an intermediate depth with potassic and sericite–chlorite alteration zones under the oxidized conditions of a hematite‐stable environment. The δ¹⁸O range estimated implies that the ore‐forming fluid was supplied by a crystallizing granodioritic magma exsolving fluids at depth with a significant contribution of meteoric water.     

Mineralogy and Isotope Geochemistry of Active Submarine Hydrothermal Field at Suiyo Seamount, Izu–Bonin Arc, West Pacific Ocean

This report presents mineralogical, geochemical and isotopic data on samples obtained using the Benthic Multi‐coring System (BMS) to drill a submarine hydrothermal deposit developed in a caldera on the summit of the Suiyo Seamount in the Izu–Bonin Island Arc, south of Japan. This deposit is regarded as the first example of Kuroko‐type sulfide mineralization on a volcano at the volcanic front of an island arc. The mineralization and hydrothermal alteration below the 300 × 150‐m area of active venting was investigated to depths of 2–9 m below the sea floor. Drilling beneath the area of active venting recovered a sequence of altered volcanic rocks (dacite lavas, pyroclastic rocks of dacite–rhyolite compositions and pumice) associated with sulfide veining and patches/veins of anhydrite. No massive sulfide was found, however, and the subsea‐floor mineralization to 10 m depth is dominated by anhydrite and clay minerals with some sulfides. Sulfide‐bearing samples contained high Au (up to 42 ppm), Ag (up to 263 ppm), As (up to 1550 ppm), Hg (up to 55 ppm), Sb (up to 772 ppm), and Se (up to 24 ppm). Electron probe microanalyzer indicated that realgar, orpiment, and mimetite were major As‐bearing minerals. The sulfides were also characterized by high Zn (>10%) compared to Cu (<6.3%) and Pb (<0.6%). The δ²⁰²Hg/¹⁹⁸Hg, δ²⁰²Hg/¹⁹⁹Hg and δ²⁰²Hg/²⁰⁰Hg of the sulfide‐bearing dacite samples and a sulfide chimney decreased with increasing Hg/Zn concentration ratio. The variation of the δ²⁰²Hg/¹⁹⁸Hg ranged from ?2.8 to +0.5‰ to relative to S‐HG02027. The large range of these δ²⁰²Hg/¹⁹⁸Hg was greater than might be expected for such a heavy element and may be due to a predominance of kinetic effects. The variation of δ²⁰²Hg/¹⁹⁸Hg of sulfide‐bearing dacite samples suggested that light Hg isotope in the vapor mixed with oxygenated seawater near sea floor during mineralization. Lead isotope ratios of the sulfide were very similar to those of the dacite lava, suggesting that lead is of magmatic origin. The ⁸⁷Sr/⁸⁶Sr ratio (0.70872) of anhydrite was different from that of the dacite lava, and suggests an Sr derivation predominantly from seawater. Hydrothermal alteration of the dacite in the Suiyo hydrothermal field was characterized by Fe‐sulfides, anhydrite, barite, montmorillonite, chlorite/montmorillonite mixed‐layer minerals, mica, and chlorite with little or no feldspar or cristobalite. Hydrothermal clay minerals changed with depth from montmorillonite to chlorite/montmorillonite mixed‐layer minerals to chlorite and mica. Hydrogen isotope ratios of chlorite/montmorillonite and mixed‐layer, mica‐chlorite composites obtained below the active venting sites ranged from ?49 to ?24‰, suggesting seawater as the dominant fluid causing alteration. Oxygen isotope ratios of anhydrite ranged from 9.2 to 10.4‰ and anhydrite formation temperatures were calculated to be 188–207°C. Oxygen isotope ratios ranged from +5.2 to +9.2‰ for montmorillonite, +3.2 to +4.5‰ for chlorite/montmorillonite mixed‐layer minerals, and +2.8 to +3.8‰ in mixtures of chlorite and mica. The formation temperatures of montmorillonite and of the chlorite–mica mixture were 160–250°C and 230–270°C, respectively. The isotope temperatures for clay minerals (220–270°C) and anhydrite (188°C) were significantly lower than the borehole temperature (308.3°C) measured just after the drilling, suggesting that temperature at this site is now higher than when clay minerals and anhydrite were formed.     

Biogenic processes in crystalline bedrock fractures indicated by carbon isotope signatures of secondary calcite

Variation in ¹³C/¹²C-isotope ratios of fracture filling calcite was analyzed in situ to investigate carbon sources and cycling in fractured bedrock. The study was conducted by separating sections of fracture fillings, and analyzing the ¹³C/¹²C-ratios with secondary ion mass spectrometry (SIMS). Specifically, the study was aimed at fillings where previously published sulfur isotope data indicated the occurrence of bacterial sulfate reduction. The results showed that the δ¹³C values of calcite were highly variable, ranging from −53.8‰ to +31.6‰ (VPDB). The analysis also showed high variations within single fillings of up to 39‰. The analyzed calcite fillings were mostly associated with two calcite groups, of which Group 3 represents possible Paleozoic fluid circulation, based on comparison with similar dated coatings within the Baltic Shield and the succeeding Group 1–2 fillings represent late-stage, low temperature mineralization and are possibly late Paleozoic to Quaternary in age. Both generations were associated with pyrite with δ³⁴S values indicative of bacterial sulfate reduction. The δ¹³C values of calcite, however, were indicative of geochemical environments which were distinct for these generations. The δ¹³C values of Group 3 calcite varied from −22.1‰ to +11‰, with a distinct peak at −16‰ to −12‰. Furthermore, there were no observable depth dependent trends in the δ¹³C values of Group 3 calcite. The δ¹³C values of Group 3 calcite were indicative of organic matter degradation and methanogenesis. In contrast to the Group 3 fillings, the δ¹³C values of Group 1–2 calcite were highly variable, ranging from −53.8‰ to +31.6‰ and they showed systematic variation with depth. The near surface environment of <30 m (bsl) was characterized by δ¹³C values indicative of degradation of surface derived organic matter, with δ¹³C values ranging from −30.3‰ to −5.5‰. The intermediate depth of 34–54 m showed evidence of localized methanotrophic activity seen as anomalously ¹³C depleted calcite, having δ¹³C values as low as −53.8‰. At depths of ∼60–400 m, positive δ¹³C values of up to +31.6‰ in late-stage calcite of Group 1–2 indicated methanogenesis. In comparison, high CH₄ concentrations in present day groundwaters are found at depths of >300 m. One sample at a depth of 111 m showed a transition from methanogenetic conditions (calcite bearing methanogenetic signature) to sulfate reducing (precipitation of pyrite on calcite surface), however, the timing of this transition is so far unclear. The results from this study gives indications of the complex nature of sulfur and carbon cycling in fractured crystalline environments and highlights the usefulness of in situ stable isotope analysis.     

Unique Origin of Skarn at the Ohori Base Metal Deposit,Yamagata Prefecture,NE Japan: C,O and S Isotopic Study

The Ohori ore deposit is one of the Cu–Pb–Zn deposits in the Green Tuff region, NE Japan, and consists of skarn‐type (Kaninomata) and vein‐type (Nakanomata) orebodies. The former has a unique origin because its original calcareous rocks were made by hydrothermal precipitation during Miocene submarine volcanism. Carbon and oxygen isotope ratios of skarn calcite and sulfur isotope ratios of sulfides were measured in and around the deposit. Carbon and oxygen isotope ratios of the skarn calcite are δ¹³C = ?15.51 to ?5.1‰, δ¹⁸O = +3.6 to +22.5‰. δ¹³C values are slightly lower than those of the Cretaceous skarn deposits in Japan. These isotope ratios of the Kaninomata skarn show that the original calcareous rocks resemble the present submarine hydrothermal carbonates at the CLAM Site, Okinawa Trough, than Cenozoic limestones, even though some isotopic shifts had occurred during later skarnization. δ³⁴S ratios of the sulfide minerals from the Kaninomata and Nakanomata orebodies are mostly in a narrow range of +4.0 to +7.0‰ and they resemble each other, suggesting the same sulfur origin for the both deposits. The magnetite‐series Tertiary Kaninomatasawa granite is distributed just beneath the skarn layer and has δ³⁴S ratios of +7.5 to 8.1‰. The heavy sulfur isotope ratio of the skarn sulfides may have been affected by the Kaninomatasawa granite.     

Association of Electrum and Calcite and Its Significance to the Genesis of the Hishikari Gold Deposits, Southern Kyushu, Japan

Abstract. Mineral assemblage, precipitation sequence and textures of the gold‐bearing veins from the Hishikari epithermal vein‐type deposits, southern Kyushu, Japan, were examined. In addition, fluid inclusion microthermometry and carbon and oxygen isotopic compositions of calcite were determined. Calcite, and that replaced by quartz, were commonly observed throughout the precipitation sequence of the veins. Thus, calcite must be a more common gangue constituent initially than observed presently. Association of calcite and electrum is observed immediately subsequent to columnar adularia in some vein samples. In addition, close association of electrum with pseudo‐acicular quartz, and electrum with truscottite were observed. The initial coprecipitation of electrum and calcite might be a common phenomenon in the gold‐bearing veins at the Hishikari deposits. The Th (homogenization temperature) data from the Honko‐Sanjin deposits are generally higher than those from the Yamada deposit. Samples that show association of calcite and electrum yielded higher Th (206–217°C, average) than the Th data from calcite associated with low‐grade Au ore or barren (180–204°C, average). The measured Tm (temperature of last melting point of ice) range from ‐0.4 to 0.0°C. The result suggests that the salinity of the hydrothermal solution was low during the precipitation both of calcite associated with Au mineralization and of barren calcite. Fluid inclusion evidence suggestive of boiling of hydrothermal solution for the precipitation of calcite was not recognized in the present work. The δ¹³C and δ¹⁸O values of calcite range from ‐10.8 to —4.7 % and from +3.2 to +15.2 %, respectively. The δ¹³C value of H₂CO₃ and the δ¹⁸O value of H₂O in the hydrothermal fluids calculated assuming isotopic equilibrium with calcite using the temperature obtained by fluid inclusion microthermometry, range from ‐14.4 to ‐9.1 %, and from ‐6.2 to +5.5 %, respectively. Thus, the calculated δ¹⁸O values of H₂O for calcite further confirm the presence of the ¹⁸O‐enriched ore fluids during the mineralization at the Hishikari deposits. The hydrothermal solution isotopically equilibrated with the sedimentary basement rocks was responsible for the gold mineralization associated with calcite.     

Geochemistry of Triassic Carbonates: Exploration Guide to Pb–Zn Mineralization in North Tunisia

The Triassic carbonate rocks in Northern Tunisia (Nappes, Domes, Jurassic Mountains zones), consist of massive carbonates, clays and gypsum with authigenic minerals. These are associated with several Pb–Zn deposits and occurrences. At Jebel Ichkeul, Bechateur and Oum Edeboua, these Triassic carbonates exhibit enrichment in Pb (0.32 to 228 ppm), Zn (17 to 261 ppm), Cd (5 to 6 ppm) and Co (0.3 to 89.5 ppm), with respect to their average contents in crustal carbonates. The enrichment is more pronounced at Oum Edeboua (near the ore zone). Permeability is one of the most effective factors of dispersion of metallic trace elements, causing the development of geochemical halos. The genetic relationship of the Triassic carbonate rocks with the ore deposits was controlled by diapirism and tectonic movements, which favored mineralization along the Triassic‐cover contact as well as the remobilization of metals from the mineralized rocks. Analysis of metallic trace elements in Triassic rocks provides clues to the presence of possible mineral deposits. These could be effectively used for both geochemical interpretation and mineral exploration. Carbon and O‐isotope data (– 9.3‰ < δ¹³C < +3‰; +21.9 < δ¹⁸O < +31‰) suggest that the Triassic carbonates of all study areas have marine carbonates as their origin; some of them show significantly lower δ¹⁸O values indicating some exchange with hydrothermal fluids. Calcites associated with mineralization at Oum Edeboua have δ¹³C of –6.2‰ to –8.22‰ and δ¹⁸O of +24.88‰ to +25‰. The C‐isotope compositions of these calcites are ¹³C depleted, indicating an organic origin.     

Geology and Isotope Geochemistry of the Yinchanggou-Qiluogou Pb-Zn Deposit, Sichuan Province, Southwest China

The Yinchanggou-Qiluogou Pb-Zn deposit,located in the western Yangtze Block,southwest China,is hosted by the Upper Sinian Dengying Formation dolostone.Ore bodies occur in the Qiluogou anticline and the NS-and NNW-trending faults.Sulfide ores mainly consist of sphalerite,pyrite,galena and calcite,with subordinate dolomite and quartz.Seventeen ore bodies have been discovered to date and they have a combined 1.0 million tons of sulfide ores with average grades of 2.27wt%Zn and 6.89wt%Pb.The δD_(H2O-SMOW) and δ~(18)O_(H2O-SMOW) values of fluid inclusions in quartz and calcite samples range from-68.9‰ to-48.7‰ and 7.3‰ to 15.9‰,respectively,suggesting that H_2O in the hydrothermal fluids sourced from metamorphic water.Calcite samples have δ~(13)C_(PDB) values ranging from-6.2‰ to-4.1‰ and δ~(18)O_(SMOW) values ranging from 15.1‰ to 17.4‰,indicating C and O in the hydrothermal fluids likely derived from a mixed source of metamorphic fluids and the host carbonates.The δ~(34)S_(CDT) values of sulfide minerals range from 5.5‰ to 20.3‰,suggesting that thermal chemical reduction of sulfate minerals in evaporates were the most probable source of S in the hydrothermal fluids.The ~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb and ~(208)Pb/~(204)Pb ratios of sulfide minerals fall in the range of 18.11 to 18.40,15.66 to 15.76 and 38.25 to 38.88,respectively.The Pb isotopic data of the studied deposit plot near the upper crust Pb evolution curve and overlap with the age-corrected Proterozoic basement rocks and the Upper Sinian Dengying Formation hosting dolostone.This indicates that the Pb originated from a mixed source of the basement metamorphic rocks and the ore-hosting carbonate rocks.The ore geology and C-H-O-S-Pb isotopic data suggest that the YinchanggouQiluogou deposit is an unusual carbonate-hosted,strata-bound and epigenetic deposit that derived ore-forming materials from a mixed source of the underlying Porterozoic basements and the Sinian hosting carbonates.     

Fluid Inclusions and Hydrogen,Oxygen, Sulfur Isotopes of Nuri Cu‐W‐Mo Deposit in the Southern Gangdese,Tibet

The Nuri Cu‐W‐Mo deposit is located in the southern subzone of the Cenozoic Gangdese Cu‐Mo metallogenic belt. The intrusive rocks exposed in the Nuri ore district consist of quartz diorite, granodiorite, monzogranite, granite porphyry, quartz diorite porphyrite and granodiorite porphyry, all of which intrude in the Cretaceous strata of the Bima Group. Owing to the intense metasomatism and hydrothermal alteration, carbonate rocks of the Bima Group form stratiform skarn and hornfels. The mineralization at the Nuri deposit is dominated by skarn, quartz vein and porphyry type. Ore minerals are chalcopyrite, pyrite, molybdenite, scheelite, bornite and tetrahedrite, etc. The oxidized orebodies contain malachite and covellite on the surface. The mineralization of the Nuri deposit is divided into skarn stage, retrograde stage, oxide stage, quartz‐polymetallic sulfide stage and quartz‐carbonate stage. Detailed petrographic observation on the fluid inclusions in garnet, scheelite and quartz from the different stages shows that there are four types of primary fluid inclusions: two‐phase aqueous inclusions, daughter mineral‐bearing multiphase inclusions, CO₂‐rich inclusions and single‐phase inclusions. The homogenization temperature of the fluid inclusions are 280°C–386°C (skarn stage), 200°C–340°C (oxide stage), 140°C–375°C (quartz‐polymetallic sulfide stage) and 160°C–280°C (quartz‐carbonate stage), showing a temperature decreasing trend from the skarn stage to the quartz‐carbonate stage. The salinity of the corresponding stages are 2.9%–49.7 wt% (NaCl) equiv., 2.1%–7.2 wt% (NaCl) equiv._, 2.6%–55.8 wt% (NaCl) equiv. and 1.2%–15.3 wt% (NaCl) equiv., respectively. The analyses of CO₂‐rich inclusions suggest that the ore‐forming pressures are 22.1 M Pa–50.4 M Pa, corresponding to the depth of 0.9 km–2.2 km. The Laser Raman spectrum of the inclusions shows the fluid compositions are dominated in H₂O, with some CO₂ and very little CH₄, N₂, etc. δD values of garnet are between ?114.4‰ and ?108.7‰ and δ¹⁸O_H2O between 5.9‰ and 6.7‰; δD of scheelite range from ?103.2‰ to ?101.29‰ and δ¹⁸O_H2O values between 2.17‰ and 4.09‰; δD of quartz between ?110.2‰ and ?92.5‰ and δ¹⁸O_H2O between ?3.5‰ and 4.3‰. The results indicate that the fluid came from a deep magmatic hydrothermal system, and the proportion of meteoric water increased during the migration of original fluid. The δ³⁴S values of sulfides, concentrated in a rage between ?0.32‰ to 2.5‰, show that the sulfur has a homogeneous source with characteristics of magmatic sulfur. The characters of fluid inclusions, combined with hydrogen‐oxygen and sulfur isotopes data, show that the ore‐forming fluids of the Nuri deposit formed by a relatively high temperature, high salinity fluid originated from magma, which mixed with low temperature, low salinity meteoric water during the evolution. The fluid flow through wall carbonate rocks resulted in the formation of layered skarn and generated CO₂ or other gases. During the reaction, the ore‐forming fluid boiled and produced fractures when the pressure exceeded the overburden pressure. Themeteoric water mixed with the ore‐forming fluid along the fractures. The boiling changed the pressure and temperature, oxygen fugacity, physical and chemical conditions of the whole mineralization system. The escape of CO₂ from the fluid by boiling resulted in scheelite precipitation. The fluid mixing and boiling reduced the solubility of metal sulfides and led the precipitation of chalcopyrite, molybdenite, pyrite and other sulfide.     

Genesis of the Weiquan Ag–Polymetallic Deposit in East Tianshan, China: Evidence from Zircon U–Pb Geochronology and C–H–O–S–Pb Isotope Systematics

The Weiquan Ag-polymetallic deposit is located on the southern margin of the Central Asian Orogenic Belt and in the western segment of the Aqishan-Yamansu arc belt in East Tianshan,northwestern China. Its orebodies, controlled by faults, occur in the lower Carboniferous volcanosedimentary rocks of the Yamansu Formation as irregular veins and lenses. Four stages of mineralization have been recognized on the basis of mineral assemblages, ore fabrics, and crosscutting relationships among the ore veins. Stage I is the skarn stage(garnet + pyroxene), Stage Ⅱ is the retrograde alteration stage(epidote + chlorite + magnetite ± hematite 士 actinolite ± quartz),Stage Ⅲ is the sulfide stage(Ag and Bi minerals + pyrite + chalcopyrite + galena + sphalerite + quartz ± calcite ± tetrahedrite),and Stage IV is the carbonate stage(quartz + calcite ± pyrite). Skarnization,silicification, carbonatization,epidotization,chloritization, sericitization, and actinolitization are the principal types of hydrothermal alteration. LAICP-MS U-Pb dating yielded ages of 326.5±4.5 and 298.5±1.5 Ma for zircons from the tuff and diorite porphyry, respectively. Given that the tuff is wall rock and that the orebodies are cut by a late diorite porphyry dike, the ages of the tuff and the diorite porphyry provide lower and upper time limits on the age of ore formation. The δ~(13)C values of the calcite samples range from-2.5‰ to 2.3‰, the δ~(18)O_(H2 O) and δD_(VSMOW) values of the sulfide stage(Stage Ⅲ) vary from 1.1‰ to 5.2‰ and-111.7‰ to-66.1‰, respectively,and the δ~(13)C, δ~(18)O_(H2 O) and δD_(V-SMOW) values of calcite in one Stage IV sample are 1.5‰,-0.3‰, and-115.6‰, respectively. Carbon, hydrogen, and oxygen isotopic compositions indicate that the ore-forming fluids evolved gradually from magmatic to meteoric sources. The δ~(34)S_(V-CDT) values of the sulfides have a large range from-6.9‰ to 1.4‰, with an average of-2.2‰, indicating a magmatic source, possibly with sedimentary contributions. The ~(206)Pb/~(204)Pb, ~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of the sulfides are 17.9848-18.2785,15.5188-15.6536, and 37.8125-38.4650, respectively, and one whole-rock sample at Weiquan yields~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of 18.2060, 15.5674, and 38.0511,respectively. Lead isotopic systems suggest that the ore-forming materials of the Weiquan deposit were derived from a mixed source involving mantle and crustal components. Based on geological features, zircon U-Pb dating, and C-H-OS-Pb isotopic data, it can be concluded that the Weiquan polymetallic deposit is a skarn type that formed in a tectonic setting spanning a period from subduction to post-collision. The ore materials were sourced from magmatic ore-forming fluids that mixed with components derived from host rocks during their ascent, and a gradual mixing with meteoric water took place in the later stages.     

Two pulses of mineralization and genesis of the Zhaxikang Sb–Pb–Zn–Ag deposit in southern Tibet: Constraints from Fe–Zn isotopes

Zhaxikang is one large Sb–Pb–Zn–Ag deposit located in the North Himalaya of southern Tibet. To date, the genesis of this deposit still remains controversial. Here, we present new pyrite Fe and sphalerite Zn isotopic data for the first three stages of mineralization, Fe–Zn isotopic data for Mn–Fe carbonate that formed during the first two stages of mineralization, and Zn isotopic data for the slate wall rocks of the Jurassic Ridang Formation to discuss the genesis of the Zhaxikang deposit. The overall δ⁵⁶Fe and δ⁶⁶Zn values range from −0.80‰ to 0.43‰ and from −0.03‰ to 0.38‰, respectively. The δ⁵⁶Fe values of Mn–Fe carbonates are lighter than those of associated pyrite in six mineral pairs, indicating that the iron carbonates are preferentially enriched in light Fe isotopes relative to pyrite. The sphalerite has lighter δ⁶⁶Zn values than associated Mn–Fe carbonates in three mineral pairs.The δ⁵⁶Fe values of pyrite that formed during the first three stages of mineralization gradually increase from stage 1 (−0.33‰ to −0.09‰) through stage 2 (−0.30‰ to 0.19‰) to stage 3 (0.16‰–0.43‰). In comparison, the sphalerite that formed during these stages has δ⁶⁶Zn values that gradually decrease from stage 1 (0.16‰–0.35‰) through stage 2 (0.09‰–0.23‰) to stage 3 (−0.03‰ to 0.22‰). These data, in conjunction with the observations of hand specimens and thin sections, suggest that the deposit was overprinted by a second pulse of mineralization. This overprint would account for these Fe–Zn isotopic variations as well as the kinetic Rayleigh fractionation that occurred during mineralization. The temporally increasing δ⁵⁶Fe and decreasing δ⁶⁶Zn values recorded in the deposit are also coincident with an increase in alteration, again supporting the existence of two pulses of mineralization. The δ⁵⁶Fe values of the first pulse of ore-forming fluid were calculated using theoretical equations, yielding values of −0.54‰ to −0.34‰ that overlap with those of submarine hydrothermal solutions (−1‰ to 0‰). However, the δ⁵⁶Fe values of the stage 3 pyrite are heavier than those of typical submarine hydrothermal solutions, which suggests that the second pulse of mineralization was probably derived from a magmatic hydrothermal fluid. In addition, the second pulse of ore-forming fluid has brought some Fe and taken away parts of Zn, which results the lighter δ⁶⁶Zn values of sphalerite and heavier δ⁵⁶Fe values of pyrite from the second pulse of mineralization. Overall, the Zhaxikang deposit records two pulses of mineralization, and the overprint by the second pulse of mineralization causes the lighter δ⁶⁶Zn values and heavier δ⁵⁶Fe values of modified samples.     

Anatomy of a large Ag–Pb–Zn deposit in the Great Xing'an Range,northeast China: metallogeny associated with Early Cretaceous magmatism

The Bairendaba vein-type Ag–Pb–Zn deposit, hosted in a Carboniferous quartz diorite, is one of the largest polymetallic deposits in the southern Great Xing'an Range. Reserves exceeding 8000 tonnes of Ag and 3 million tonnes of Pb?+?Zn with grades of 30 g/t and 4.5% have been estimated. We identify three distinct mineralization stages in this deposit: a barren pre-ore stage (stage 1), a main-ore stage with economic Ag–Pb–Zn mineralization (stage 2), and a post-ore stage with barren mineralization (stage 3). Stage 1 is characterized by abundant arsenopyrite?+?quartz and minor pyrite. Stage 2 is represented by abundant Fe–Zn–Pb–Ag sulphides and is further subdivided into three substages comprising the calcite–polymetallic sulphide stage (substage 1), the fluorite–polymetallic sulphide stage (substage 2), and the quartz–polymetallic sulphide stage (substage 3). Stage 3 involves an assemblage dominated by calcite with variable pyrite, galena, quartz, fluorite, illite, and chlorite. Fluid inclusion analysis and mineral thermometry indicate that the three stages of mineralization were formed at temperatures of 320–350°C, 200–340°C, and 180–240°C, respectively. Stage 1 early mineralization is characterized by low-salinity fluids (5.86–8.81 wt.% NaCl equiv.) with an isotopic signature of magmatic origin (δ¹⁸O_fluid = 10.45–10.65‰). The main ore minerals of stage 2 precipitated from aqueous–carbonic fluids (4.34–8.81 wt.% NaCl equiv.). The calculated and measured oxygen and hydrogen isotopic compositions of the ore-forming aqueous fluids (δ¹⁸O_fluid = 3.31–8.59‰, δD_fluid?=??132.00‰ to??104.00‰) indicate that they were derived from a magmatic source and mixed with meteoric water. Measured and calculated sulphur isotope compositions of hydrothermal fluids (δ³⁴S_∑S?=??1.2–3.8‰) indicate that the ore sulphur was derived mainly from a magmatic source. The calculated carbon isotope compositions of hydrothermal fluids (δ¹³C_fluid?=??26.52‰ to??25.82‰) suggest a possible contribution of carbon sourced from the basement gneisses. The stage 3 late mineralization is dominated (1.40–8.81 wt.% NaCl equiv.) by aqueous fluids. The fluids show lower δ¹⁸O_fluid (?16.06‰ to??0.70‰) and higher δD_fluid (?90.10‰ to??74.50‰) values, indicating a heated meteoric water signature. The calculated carbon isotope compositions (δ¹³C_fluid?=??12.82‰ to??6.62‰) of the hydrothermal fluids in stage 3 also suggest a possible contribution of gneiss-sourced carbon. The isotopic compositions and fluid chemistry indicate that the ore mineralization in the Bairendaba deposit was related to Early Cretaceous magmatism.     

Sulfur and lead isotopes of Guern Halfaya and Bou Grine deposits (Domes zone,northern Tunisia): Implications for sources of metals and timing of mineralization

The Pb–Zn ore deposits in the Guern Halfaya and Bou Grine areas (northern Tunisia) are hosted mainly by dolostones in the contact zone between Triassic and Upper Cretaceous strata and by Upper Cretaceous limestones. The deposits occur as lenticular, stratiform, vein, disseminations and stockwork ore bodies consisting of sphalerite, galena, pyrite, chalcopyrite and sulfosalt (gray copper). Barite and celestite dominate the gangue, with lesser calcite. The δ³⁴S values of barite and celestite (12.7–15.0‰) at the Oum Edeboua mine are consistent with the reduction of sulfates in Triassic evaporites within the study area (12.8 < δ³⁴S < 14.0‰). The δ³⁴S values in base-metal sulfides from both study areas (2.6–9.5‰) and the presence of bacterial relics suggest involvement of bacterially-mediated sulfate reduction in the mineralization. The present Pb isotope data are homogeneous with ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of 18.723–18.783, 15.667–15.685 and 38.806–38.889, respectively, which suggest a single source reservoir of Pb at depth in the upper crust. The syn-diagenetic mineralization in the Bahloul Formation and the calculated age from the Pb isotopic data suggest an Upper Cretaceous age for the Pb–Zn deposits in the Guern Halfaya and Bou Grine areas. During this period, NE–SW to ENE–WSW trending regional extensional tectonic structures likely favored migration of mineralizing fluids and eventual deposition at Guern Halfaya and Bou Grine.