Geochemical constraints on the origin and environment of Lower Cambrian,selenium-rich siliceous sedimentary rocks in the Ziyang area,Daba region,central China

The Ziyang area is one of the two major regions of central China subjected to selenium (Se) poisoning. Systematic studies of Se contents of different lithologies from this area indicate that Lower Cambrian, carbonaceous, and siliceous strata host the highest Se contents (with Se contents of up to 278 ppm). We have investigated their geochemical characteristics (major and trace elements, and Si and O isotopes), origin, and sedimentary environment of formation. The siliceous rocks are characterized by a wide range in major elements, and are enriched in Se, Ba, Cu, Ni, V, As, Sb, and U relative to average continental crust. They are also enriched in light rare earth elements relative to heavy rare earth elements (La_N/Yb_N?=?1.64–35.7) and show weak or moderate negative Ce anomalies and strong positive Eu anomalies. δ³⁰Si_NBS-28 and δ¹⁸O_V-SMOW values range from –0.3‰ to 0.6‰ and 16.1‰ to 21.7‰, respectively. The homogenization temperatures of inclusions within the studied samples range from 113°C to 319°C, and their salinities from 1.2 to 13.7 wt.% NaCl equivalent. Our results suggest that the studied siliceous rocks resulted from hydrothermal sedimentation in a relatively anoxic semi-deep sea sedimentary environment. The hydrothermal fluid responsible for Se-mineralization involved the mixing of low-temperature high-salinity fluid, low-temperature low-salinity fluid, and a high-temperature low-salinity basinal fluid in the NaCl–(KCl)–H₂O system.     

Geochemistry and Si–O–Fe isotope constraints on the origin of banded iron formations of the Yuanjiacun Formation,Lvliang Group,Shanxi, China

Banded iron formations (BIFs) within the Lvliang region of Shanxi Province, China, are hosted by sediments of the Yuanjiacun Formation, part of the Paleoproterozoic Lvliang Group. These BIFs are located in a zone where sedimentation changed from clastic to chemical deposition, indicating that these are Superior-type BIFs. Here, we present new major, trace, and rare earth element (REE) data, along with Fe, Si, and O isotope data for the BIFs in the Yuanjiacun within the Fe deposits at Yuanjiacun, Jianshan, and Hugushan. When compared with Post Archean Australian Shale (PAAS), these BIFs are dominated by iron oxides and quartz, contain low concentrations of Al₂O₃, TiO₂, trace elements, and the REE, and are light rare earth element (LREE) depleted and heavy rare earth element (HREE) enriched. The BIFs also display positive La, Y, and Eu anomalies, high Y/Ho ratios, and contain ³⁰Si depleted quartz, with high δ¹⁸O values that are similar to quartz within siliceous units formed during hydrothermal activity. These data indicate that the BIFs within the Yuanjiacun Formation were precipitated from submarine hydrothermal fluids, with only negligible detrital contribution. None of the BIF samples analyzed during this study have negative Ce anomalies, although a few have a positive Ce anomaly that may indicate that the BIFs within the Yuanjiacun Formation formed during the Great Oxidation Event (GOE) within a redox stratified ocean. The positive Ce anomalies associated with some of these BIFs are a consequence of oxidization and the formation of surficial manganese oxide that have preferentially adsorbed Ho, LREE, and Ce^4 +; these deposits formed during reductive dissolution at the oxidation–reduction transition zone or in deeper-level reducing seawater. The loss of Ce, LREE, and Ho to seawater and the deposition of these elements with iron hydroxides caused the positive Ce anomalies observed in some of the BIF samples, although the limited oxidizing ability of surface seawater at this time meant that Y/Ho and LREE/HREE ratios were not substantially modified, unlike similar situations within stratified ocean water during the Late Paleoproterozoic. Magnetite and hematite within the BIFs in the study area contain heavy Fe isotopes (⁵⁶Fe values of 0.24–1.27‰) resulting from the partial oxidation and precipitation of Fe^2 + to Fe^3 + in seawater. In addition, mass-independent fractionation of sulfur isotopes within pyrite indicates that these BIFs were deposited within an oxygen-deficient ocean associated with a similarly oxygen-deficient atmosphere, even though the BIFs within the Yuanjiacun Formation formed after initiation of the GOE.     

Geochemistry and origin of the Neoproterozoic Dahongliutan banded iron formation (BIF) in the Western Kunlun orogenic belt,Xinjiang (NW China)

The Neoproterozoic (593–532 Ma) Dahongliutan banded iron formation (BIF), located in the Tianshuihai terrane (Western Kunlun orogenic belt), is hosted in the Tianshuihai Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Iron oxide (hematite), carbonate (siderite, ankerite, dolomite and calcite) and silicate (muscovite) facies are all present within the iron-rich layers. There are three distinctive sedimentary facies BIFs, the oxide, silicate–carbonate–oxide and carbonate (being subdivided into ankerite and siderite facies BIFs) in the Dahongliutan BIF. They demonstrate lateral and vertical zonation from south to north and from bottom to top: the carbonate facies BIF through a majority of the oxide facies BIF into the silicate–carbonate–oxide facies BIF and a small proportion of the oxide facies BIF.The positive correlations between Al₂O₃ and TiO₂, Sc, V, Cr, Rb, Cs, Th and ∑REE (total rare earth element) for various facies of BIFs indicate these chemical sediments incorporate terrigenous detrital components. Low contents of Al₂O₃ (<3 wt%), TiO₂ (<0.15 wt%), ∑REE (5.06–39.6 ppm) and incompatible HFSEs (high field strength elements, e.g., Zr, Hf, Th and Sc) (<10 ppm), and high Fe/Ti ratios (254–4115) for a majority of the oxide and carbonate facies BIFs suggest a small clastic input (<20% clastic materials) admixtured with their original chemical precipitates. The higher abundances of Al₂O₃ (>3 wt%), TiO₂, Zr, Th, Cs, Sc, Cr and ∑REE (31.2–62.9 ppm), and low Fe/Ti ratios (95.2–236) of the silicate–carbonate–oxide facies BIF are consistent with incorporation of higher amounts of clastic components (20%–40% clastic materials). The HREE (heavy rare earth element) enrichment pattern in PAAS-normalized REE diagrams exhibited by a majority of the oxide and carbonate facies BIFs shows a modern seawater REE signature overprinted by high-T (temperature) hydrothermal fluids marked by strong positive Eu anomalies (Eu/Eu¹_PAAS = 2.37–5.23). The low Eu/Sm ratios, small positive Eu anomaly (Eu/Eu¹_PAAS = 1.10–1.58) and slightly MREE (middle rare earth element) enrichment relative to HREE in the silicate–carbonate–oxide facies BIF and some oxide and carbonate facies BIFs indicate higher contributions from low-T hydrothermal sources. The absence of negative Ce anomalies and the high Fe³⁺/(Fe³⁺/Fe²⁺) ratios (0.98–1.00) for the oxide and silicate–carbonate–oxide BIFs do not support ocean anoxia. The δ¹³C_V-PDB (−4.0‰ to −6.6‰) and δ¹⁸O_V-PDB (−14.0‰ to −11.5‰) values for siderite and ankerite in the carbonate facies BIF are, on average, ∼6‰ and ∼5‰ lower than those (δ¹³C_V-PDB = −0.8‰ to + 3.1‰ and δ¹⁸O_V-PDB = −8.2‰ to −6.3‰) of Ca–Mg carbonates from the silicate–carbonate–oxide facies BIF. This feature, coupled with the negative correlations between FeO, Eu/Eu¹_PAAS and δ¹³C_V-PDB, imply that a water column stratified with regard to the isotopic omposition of total dissolved CO₂, with the deeper water, from which the carbonate facies BIF formed, depleted in δ¹³C that may have been derive from hydrothermal activity.Integration of petrographic, geochemical, and isotopic data indicates that the silicate–carbonate–oxide facies BIF and part of the oxide facies BIF precipitated in a near-shore, oxic and shallow water environment, whereas a majority of the oxide and carbonate facies BIFs deposited in anoxic but Fe²⁺-rich deeper waters, closer to submarine hydrothermal vents. High-T hydrothermal solutions, with infusions of some low-T hydrothermal fluids, brought Fe and Si onto a shallow marine, variably mixed with detrital components from seawaters and fresh waters carrying continental landmass and finally led to the alternating deposition of the Dahongliutan BIF during regression–transgression cycles.The Dahongliutan BIF is more akin to Superior-type rather than Algoma-type and Rapitan-type BIF, and constitutes an additional line of evidence for the widespread return of BIFs in the Cryogenian and Ediacaran reflecting the recurrence of anoxic ferruginous deep sea and anoxia/reoxygenation cycles in the Neoproterozoic. In combination with previous studies on other Fe deposits in the Tianshuihai terrane, we propose that a Fe²⁺-rich anoxic basin or deep sea probably existed from the Neoproterozoic to the Early Cambrian in this area.     

Geochemistry and genesis of the banded iron formations of the Cauê Formation,Quadrilátero Ferrífero,Minas Gerais,Brazil

The Cauê Formation of the Paleoproterozoic Minas Supergroup hosts banded iron formations (BIFs), locally called itabirites, deposited in shallow marine passive margin settings. Two major compositional types of itabirite, dolomitic and quartz itabirites, are found in the northwestern part of QF. The former consists of alternating dolomite-rich and hematite-rich bands, whereas the latter is formed with alternating quartz-rich and hematite-rich bands. Accessory minerals are chlorite, sericite, and apatite in both types.Dolomitic and quartz itabirites have a very simple chemical composition. In the dolomitic itabirite, Fe₂O₃ plus CaO, MgO, and LOI range from 95.8 to 97.8%, while in the quartz itabirite, Fe₂O₃ plus SiO₂ range from 94.4 to 99.6%. Both itabirites are highly oxidized and present Fe³⁺/(Fe²⁺ + Fe³⁺) ratios higher than 0.98, by far superior than the average ratios of Paleoproterozoic BIFs. Trace element concentrations in itabirites are very low, ranging from <10 to 55 ppm. Dolomite shows negative δ¹³C values varying from −2.5 to −0.8‰ versus PDB, while the oxygen isotope data display δ¹⁸O values varying from −12.4 to −8.5‰ versus PDB. The δ¹³C values of the dolomitic itabirite are in the same range of those of the overlying stromatolitic dolomites of the Gandarela Formation. C and O isotopes, REE signatures, and Y/Ho ratios suggest a marine origin for the sediments of the Cauê Formation. The HREE enrichment pattern exhibited by the itabirites shows a modern seawater REE signature overprinted by a hydrothermal pattern marked by positive Eu anomalies. Very low contents of Al₂O₃ and TiO₂ and a strong positive correlation between them indicate a minor terrigenous component in the chemically-precipitated marine sediments of the Cauê Formation. Differences in the HREE signatures of itabirites suggest that dolomitic itabirite precipitated in shallower waters receiving sediments from the continent, while quartz itabirite precipitated in deeper waters. Sea-level fluctuations caused by marine transgression–regressions possibly contributed to changes in the composition and varied input of the terrigenous sediments. These changes are expressed by the co-existence of dolomitic, quartz, and amphibolitic itabirites in the Cauê Formation, which represent lateral and vertical facies transitions of dolomitic, cherty, and shaly BIFs, respectively.     

Depositional age and tectonic environment of the Gouap banded iron formations from the Nyong group,SW Cameroon:Insights from isotopic,geochemical and geochronological studies of drillcore samples

The discovery of the Gouap banded iron formations(BIFs)-hosted iron mineralization in the northwestern of the Nyong Group(Ntem Complex)in southwestern Cameroon provides unique insights into the geology of this region.In this contribution,we firstly report detailed study of geochemistry,isotopic and geochronology of well preserved samples of the Gouap BIFs collected from diamond drillcores.The Gouap BIFs consist mainly of amphibole BIFs and amphibole-pyrite BIFs characterized by dominant Fe₂O₃+SiO₂contents and variable contents of CaO,MgO and SO₃,consistent with the presence of amphibole,chlorite,epidote and pyrite,formed during amphibolite facies metamorphism and overprinted hydrothermal event.The amphibole–pyrite BIFs are typically enriched in trace and rare earth elements(REE)compared to the amphibole BIFs,suggesting the influence of detrital materials as well as secondary hydrothermal alteration.The Post Archean Australian Shale(PAAS)-normalized REE–Y profiles of the Gouap BIFs display positive La,Eu anomalies,weak negative Ce anomalies,indicating a mixture of low-temperature hydrothermal fluids and relatively oxic conditions probably under relative shallow seawater.We present here the first isotopic data of BIFs within the Ntem Complex.Theδ³⁰Si_NBS28values of the quartz from the Gouap BIFs vary from-1.5‰to-0.3‰and from-0.8‰to-0.9‰for the amphibole BIFs and amphibole–pyrite BIFs,respectively.The quartz hasδ¹⁸OV-SMOW values of 6.8‰–9.5‰(amphibole BIFs)and 9.2‰–10.6‰(amphibole–pyrite BIFs).The magnetite from the Gouap BIFs showsδ¹⁸O values ranging from-3.5‰to-1.8‰and from-3‰to-1.7‰for the amphibole BIFs and amphibole–pyrite BIFs,respectively.Moreover,the pyrite grains in the amphibole–pyrite BIFs displayδ34S values of 1.1‰–1.8‰.All isotopic data of the Gouap BIFs confirm that they might have precipitated from low-temperature hydrothermal fluids with detrital input distant from the volcanic activity.According to their geochemical and isotopic characteristics,we propose that the Gouap BIFs belong to the Superior type.In situ U–Pb zircon dating of BIFs was conducted to assess the BIF depositional age based on strong evidence of zircon in thin section.The Gouap BIFs were probably deposited at 2422±50 Ma in a region where sediments extended from continental shelf to deep-water environments along craton margins like the Caue Formation of the Minas Supergroup,Brazil.The studied BIFs have experienced regional hydrothermal activity and metamorphism at 2089±8.3 Ma during the Eburnean–Transamazonian orogeny.These findings suggest a physical continuity between the protocratonic masses of both Sao Francisco and Congo continents in the Rhyacian Period.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

Geochemical and isotopic evidence for a magmatic-hydrothermal origin of the polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen,South China

Polymetallic vein-type Zn-Pb deposits are located in the Xiangxi–Qiandong zinc-lead metallogenic belt (XQMB) of the northwestern margin of the Jiangnan Orogen, South China. Ores are mainly found in fault-bounded quartz veins hosted in the upper part of the Banxi Group that consists of low-grade metamorphic sandstone, siltstone with minor tuff interbeds. The Zn-Pb deposits primarily contain sphalerite, galena, chalcopyrite and pyrite, accompanied by quartz and minor calcite. Zinc, lead, copper, indium and gallium are enriched in these ores. Investigation of the ore fluid reveals low temperature (87–262 °C) with scattered salinity (range from 2.73 to 26.64 wt% NaCl_eqv.). Hydrogen and oxygen isotopic compositions of fluid inclusions in quartz indicate mixing of magmatic hydrothermal fluid and meteoric water (δ¹⁸O_{H2O SMOW} = 0.2‰ to 4.2‰; δD_{H2O SMOW} = −126‰ to −80‰). Carbon and oxygen isotopic composition of carbonate samples indicate the magmatic hydrothermal origin of CO₃²⁻ or CO₂ in ore-forming fluid (δ¹³C_PDB = −6.9‰ to −5.7‰, δ¹⁸O_SMOW = 11.3‰ to 12.7‰). Sulfur and lead isotopic compositions (δ³⁴S_VCDT = 8.8–14.2‰ and ²⁰⁶Pb/²⁰⁴Pb = 17.156–17.209, ²⁰⁷Pb/²⁰⁴Pb = 15.532–15.508, ²⁰⁸Pb/²⁰⁴Pb = 37.282–37.546) demonstrate that sulfur sources were relatively uniform, and low radiogenic lead isotopic compositions indicate that ore metals were derived from a relatively unradiogenic source, probably by mixing of mantle with crust. Therefore, polymetallic vein-type Zn-Pb mineralization in this area probably arose from a magmatic-related hydrothermal system, and the deposition of sulfides occurred in response to cooling and boiling of magmatic hydrothermal fluids (high salinity, high δ¹⁸O_H2O and δD_H2O and metal-bearing), and is mainly the result of emplacement into open space and mixing with meteoric water (low salinity, low δ¹⁸O_H2O and δD_H2O). This study provides direct evidence that magmatism was involved in the ore-forming processes of the low temperature metallogenic district, South China, and it raises awareness about the presence of polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen and their potential as a source of zinc, copper, indium and gallium.     

Oxygen isotope ratio of quartz veins from the auriferous Ramagiri–Penakacherla schist belt and surrounding granitoids in the Eastern Dharwar craton: A case for a possible link between gold mineralization and granite magmatism

In the Eastern Dharwar craton, among the many shear zone-hosted lode gold deposits, those at Ramagiri and Penakacherla are located near the western margin of the craton. Mineralized quartz (± sulfide ± carbonate) veins are hosted by the schistose (metavolcanic and carbonaceous metasedimentary) rocks, in close spatial association with granitoids having quartz and quartzofeldspathic veins representing hydrothermal activities associated with them. Mineralized quartz veins from the ore zones (in Ramagiri and Penakacherla regions) and quartz (or pegmatitic) veins from the surrounding granitic terrane were chosen for δ¹⁸O analysis. Samples from the schistose and granitic domains show δ¹⁸O_quartz values in the range of 10.4–14.9 and 9.3–10.9‰ respectively. The ore-zone fluids from the Ramagiri and Penakacherla regions give δ¹⁸O values of 7.9 ± 1.5 and 5.1 ± 0.8‰, calculated at pressure-corrected temperatures obtained from fluid inclusion microthermometry. The late-magmatic fluid is relatively ¹⁸O-poor with δ¹⁸O values estimated at 4.5 ± 0.7‰ and the value is closer to what is obtained for the ore zones. Based on the δ¹⁸O values reported and a possible magmatic contribution to ore fluid deciphered from fluid inclusion characteristics, a genetic relationship between granitic magmatism and gold mineralization is surmised. The observed increase in the ¹⁸O/¹⁶O ratio from the magmatic fluid to ore fluid in the shear zone is attributed to interaction of the magmatic fluid with host metasediments, that agrees well with the variation in the CO₂/CH₄ ratio of carbonic component in such fluids.     

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.     

The origin of the Dapingzhang volcanogenic Cu–Pb–Zn ore deposit,Yunnan province,SW China: Constraints from host rock geochemistry and ore Os–Pb–S–C–O–H isotopes

The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive ε_Nd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ³⁴S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.310–18.656, ²⁰⁷Pb/²⁰⁴Pb = 15.489–15.643 and ²⁰⁸Pb/²⁰⁴Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ¹³C_PDB and δ¹⁸O_SMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ¹³C_PDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ¹⁸O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks.     

Geochronology and fluid inclusion study of the Yinjiagou porphyry–skarn Mo–Cu–pyrite deposit in the East Qinling orogenic belt,China

The Yinjiagou Mo–Cu–pyrite deposit of Henan Province is located in the Huaxiong block on the southern margin of the North China craton. It differs from other Mo deposits in the East Qingling area because of its large pyrite resource and complex associated elements. The deposit’s mineralization process can be divided into skarn, sulfide, and supergene episodes with five stages, marking formation of magnetite in the skarn episode, quartz–molybdenite, quartz–calcite–pyrite–chalcopyrite–bornite–sphalerite, and calcite–galena–sphalerite in the sulfide episode, and chalcedony–limonite in the supergene episode. Re–Os and ⁴⁰Ar–³⁹Ar dating indicates that both the skarn-type and porphyry-type orebodies of the Yinjiagou deposit formed approximately 143 Ma ago during the Early Cretaceous. Four types of fluid inclusions (FIs) have been distinguished in quartz phenocryst, various quartz veins, and calcite vein. Based on petrographic observations and microthermometric criteria the FIs include liquid-rich, gas-rich, H₂O–CO₂, and daughter mineral-bearing inclusions. The homogenization temperature of FIs in quartz phenocrysts of K-feldspar granite porphyry ranges from 341 °C to >550 °C, and the salinity is 0.4–44.0 wt% NaCl eqv. The homogenization temperature of FIs in quartz–molybdenite veins is 382–416 °C, and the salinity is 3.6–40.8 wt% NaCl eqv. The homogenization temperature of FIs in quartz–calcite–pyrite–chalcopyrite–bornite–sphalerite ranges from 318 °C to 436 °C, and the salinity is 5.6–42.4 wt% NaCl eqv. The homogenization temperature of FIs in quartz–molybdenite stockworks is in a range of 321–411 °C, and the salinity is 6.3–16.4 wt% NaCl eqv. The homogenization temperature of FIs in quartz–sericite–pyrite is in a range of 326–419 °C, and the salinity is 4.7–49.4 wt% NaCl eqv. The ore-forming fluids of the Yinjiagou deposit are mainly high-temperature, high-salinity fluids, generally with affinities to an H₂O–NaCl–KCl ± CO₂ system. The δ¹⁸O_H2O values of ore-forming hydrothermal fluids are 4.0–8.6‰, and the δD_V-SMOW values are between −64‰ and −52‰, indicating that the ore-forming fluids were primarily magmatic. The δ³⁴S_V-CDT values of sulfides range between −0.2‰ and 6.3‰ with a mean of 1.6‰, sharing similar features with deeply sourced sulfur, implying that the sulfur mainly came from the lower crust composed of poorly differentiated igneous materials, but part of the heavy sulfur came from the Guandaokou Group dolostone. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb values of sulfides are in the range of 17.331–18.043, 15.444–15.575, and 37.783–38.236, respectively, which is generally consistent with the Pb isotopic signature of the Yinjiagou intrusion, suggesting that the Pb chiefly originated from the felsic–intermediate intrusive rocks in the mine area, with a small amount of lead from strata. The Yinjiagou deposit is a porphyry–skarn deposit formed during the Mesozoic transition of a tectonic regime that is EW-trending to NNE-trending, and the multiepisode boiling of ore-forming fluids was the primary mechanism for mineral deposition.     

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.     

Hydrothermalism in the Tyrrhenian Sea: Inorganic and microbial sulfur cycling as revealed by geochemical and multiple sulfur isotope data

The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry.Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ³⁴S range between ?29.8 and + 10.2‰ and Δ³³S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ³⁴S_CRS with less negative values between ?11.3 and ?1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea.Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ³⁴S and Δ³³S values for pyrite between ?32.8 and ?1.1‰ and between ?0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ³⁴S and Δ³³S values between ?26.7 and ?2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ³⁴S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro.Although a magmatic SO₂ contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface.     

The origin of the Maozu carbonate-hosted Pb–Zn deposit,southwest China: Constrained by C–O–S–Pb isotopic compositions and Sm–Nd isotopic age

The Maozu Pb–Zn deposit, located on the western margin of the Yangtze Block, southwest China, is a typical carbonate-hosted deposit in the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province with Pb + Zn reserves of about 2.0 million tonnes grading 4.15 wt.% Pb and 7.25 wt.% Zn. Its ore bodies are hosted in Sinian (635–541 Ma) Dengying Formation dolostone and show stratiform, vein and irregular textures. Ores are composed of sphalerite, galena, pyrite, calcite, dolomite, quartz and fluorite with massive, banded, disseminated and veined structures. The C–O–Sm–Nd isotopic compositions of hydrothermal calcites and S–Pb isotopic compositions of sulfides were analyzed to constrain the origin of the Maozu deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcites range from −3.7‰ to −2.0‰ and +13.8‰ to +17.5‰, respectively, and plot near the marine carbonate rocks field in a plot of δ¹³C_PDB vs. δ¹⁸O_SMOW, with a negative correlation. It suggests that CO₂ in the hydrothermal fluids was mainly originated from marine carbonate rocks, with limited influence from sedimentary organic matter. δ³⁴S_CDT values of sulfides range from +9.9‰ to +19.2‰, similar to that of Cambrian to Triassic seawater sulfate (+15‰ to +35‰) and evaporate (+15‰ to +30‰) in the Cambrian to Triassic sedimentary strata. It suggests that reduced sulfur was derived from evaporate in sedimentary strata by thermo chemical sulfate reduction. Sulfides have low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.129–18.375, ²⁰⁷Pb/²⁰⁴Pb = 15.640–15.686 and ²⁰⁸Pb/²⁰⁴Pb = 38.220–38.577) that plot in the field between upper crust and the orogenic belt evolution curve in the plot of ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb, and similar to that of age corrected Proterozoic basement rocks (Dongchuan and Kunyang Groups). This indicates that ore-forming metals were mainly derived from basement rocks. Hydrothermal calcite yields a Sm–Nd isotopic age of 196 ± 13 Ma, possibly reflecting the timing of Pb–Zn mineralization in the SYG province, younger than the Permian Emeishan mantle plume (∼260 Ma). All data combined suggests that hydrothermal fluids circulated through basement rocks where they picked up metals and migrated to surface, mixed with reduced sulfur-bearing fluids and precipitated metals. Ore genesis of the Maozu deposit is different from known magmatic–hydrothermal, Sedimentary Exhalative or Mississippi Valley-types, which maybe represent a unique ore deposit type, named as the SYG-type.     

Geologic and geochemical insights into the formation of the Taiyangshan porphyry copper–molybdenum deposit,Western Qinling Orogenic Belt,China

Taiyangshan is a poorly studied copper–molybdenum deposit located in the Triassic Western Qinling collisional belt of northwest China. The intrusions exposed in the vicinity of the Taiyangshan deposit record episodic magmatism over 20–30 million years. Pre-mineralization quartz diorite porphyries, which host some of the deposit, were emplaced at 226.6 ± 6.2 Ma. Syn-collisional monzonite and quartz monzonite porphyries, which also host mineralization, were emplaced at 218.0 ± 6.1 Ma and 215.0 ± 5.8 Ma, respectively. Mineralization occurred during the transition from a syn-collisional to a post-collisional setting at ca. 208 Ma. A barren post-mineralization granite porphyry marked the end of post-collisional magmatism at 200.7 ± 5.1 Ma. The ore-bearing monzonite and quartz monzonite porphyries have a ε_Hf(t) range from − 2.0 to + 12.5, which is much more variable than that of the slightly older quartz diorite porphyries, with T_DM2 of 1.15–1.23 Ga corresponding to the positive ε_Hf(t) values and T_DM1 of 0.62–0.90 Ga corresponding to the negative ε_Hf(t) values. Molybdenite in the Taiyangshan deposit with 27.70 to 38.43 ppm Re suggests metal sourced from a mantle–crust mixture or from mafic and ultramafic rocks in the lower crust. The δ³⁴S values obtained for pyrite, chalcopyrite, and molybdenite from the deposit range from + 1.3‰ to + 4.0‰, + 0.2‰ to + 1.1‰, and + 5.3‰ to + 5.9‰, respectively, suggesting a magmatic source for the sulfur. Calculated δ¹⁸O_fluid values for magmatic K-feldspar from porphyries (+ 13.3‰), hydrothermal K-feldspar from stockwork veins related to potassic alteration (+ 11.6‰), and hydrothermal sericite from quartz–pyrite veins (+ 8.6 to + 10.6‰) indicate the Taiyangshan deposit formed dominantly from magmatic water. Hydrogen isotope values for hydrothermal sericite ranging from − 85 to − 50‰ may indicate that magma degassing progressively depleted residual liquid in deuterium during the life of the magmatic–hydrothermal system. Alternatively, δD variability may have been caused by a minor amount of mixing with meteoric waters. We propose that the ore-related magma was derived from partial melting of the ancient Mesoproterozoic to Neoproterozoic middle to lower continental crust. This crust was likely metasomatized during earlier subduction, and the crustal magmas may have been contaminated with lithospheric mantle derived magma triggered by MASH (e.g., melting, assimilation, storage, and homogenization) processes during collisional orogeny. In addition, a significant proportion of the metals and sulfur supplied from mafic magma were simultaneously incorporated into the resultant hybrid magmas.     

Using dual isotopic data to track the sources and behaviors of dissolved sulfate in the western North China Plain

This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ³⁴S_SO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ¹⁸O_SO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ³⁴S_SO4 and δ¹⁸O_SO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II₁) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II₂) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II₃) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ³⁴S_SO4 = 10–35‰ and δ¹⁸O_SO4 = 7–20‰), soil sulfate (δ³⁴S_SO4 = 5.9‰ and δ¹⁸O_SO4 = 5.8‰) and sewage water (δ³⁴S_SO4 = 10.0‰ and δ¹⁸O_SO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II₃), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ³⁴S_SO4 and δ¹⁸O_SO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers.     

Structural,textural, geochemical and isotopic signatures of synglaciogenic Neoproterozoic banded iron formations (BIFs) at Bafq mining district (BMD), Central Iran: The possible Ediacaran missing link of BIFs in Tethyan metallogeny

The Neoproterozoic magnetite–apatite–hematite–pyrolusite–jaspilite deposits in the Bafq mining district (BMD) contain more than 1.7 Gt ores with an average grade of 50 wt.% Fe and 0.01 to 7.78 wt.% P and were probably formed between 635 and 547 Ma in a riftogenic felsic submarine exhalative sequence of the Esfordi Formation. The ore zones occur in proximal zone of magnetite-rich albitized rhyolite (keratophyres), interdistal zone of rhyolitic tuff–tuffaceous sediments and distal zone of pyrolusite–jaspilite. These sequences are covered by the diamictites and cap carbonates. The BIFs are linked to the altered rhyolites–rhyodacites, jaspilites and diamictites and contain magnetite, hematite and apatite. The presence of Spriggina, Dickinsonia, Medusites and Persimedusites chahgazensis (Sennewald and Krüger, 1979; Hahn and, Pflug; McCall, 2006) in the Kushk shale member of the Esfordi Formation conforms to the Australian fauna of the Ediacaran period (635–540). This relative age is supported by some reliable Pb isotopic data (635–547 Ma) on galena, monazite and apatite (Huckriede et al., 1962; Torab, 2008; Stosch et al., 2011). The most frequent structures–textures in the ore zones include felsic autobrecciation, massive, colloidal, banded, detrital and glaciogenic. The BIFs are highlighted by high values of LREE fractionation and no significant Eu and Ce anomalies. The ores show high values of Fe₂O₃ (14–60%), and SiO₂ (4–34%), and low contents of Al (3.32%), Cr (21.48 ppm), Co (42.82 ppm), Ni (125 ppm), V (868 ppm), and Ti (0.13%) similar to those of the Ediacaran–Rapitan BIFs. The cap carbonates show depletion in δ¹³C, with a range from − 0.43 to − 6.6 per mil and then return to near excursion of about + 2.97‰ in the Lower Cambrian carbonates. These are followed by δ¹⁸O values, which range from − 6.64 to − 11.86‰. The presence of jaspilites, diamictites, C and O isotopic signatures, REE patterns, and immobile element relationships highlights a glaciogenic BIF. Importantly, the glaciogenic structures–textures and jaspilites do not support the misconception of the previously proposed magmatic–carbonatitic and metasomatic–hydrothermal IOCG–Kiruna ore deposits.     

SHRIMP zircon U–Pb geochronology,geochemistry and H–O–Si–S–Pb isotope systematics of the Kanggur gold deposit in Eastern Tianshan,NW China: Implication for ore genesis

The Kanggur gold deposit is located in the southern margin of the Central Asia Orogenic Belt and in the western segment of the Kanggur–Huangshan ductile shear belt in Eastern Tianshan, northwestern China. The orebodies of this deposit are hosted in the Lower Carboniferous volcanic rocks of the Aqishan Formation and mainly consist of andesite, dacite and pyroclastic rocks. The SHRIMP zircon U–Pb age data of the andesite indicate that the volcanism in the Kanggur area might have occurred at ca. 339 Ma in the Early Carboniferous, and that the mineralization age of the Kanggur gold deposit was later than the age of volcanic rocks in the area. Geochemically, the andesite rocks of the Aqishan Formation belong to low-tholeiite and calc-alkaline series and display relative depletions in high field strength elements (HFSEs; i.e. Nb, Ta and Ti). The δ¹⁸O_w and δD_w values vary from − 9.1‰ to + 3.8‰ and − 66.0‰ to − 33.9‰, respectively, indicating that the ore-forming fluids were mixtures of metamorphic and meteoric waters. The δ³⁰Si values of 13 quartz samples range from − 0.3‰ to + 0.1‰ with an average of − 0.15‰, and the δ³⁴S values of 18 sulphide samples range from − 0.9‰ to + 2.2‰ with an average of + 0.54‰. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values of 10 sulphide samples range from 18.166 to 18.880, 15.553 to 15.635 and 38.050 to 38.813, respectively, showing similarities to orogenic Pb; these values are consistent with those of the andesite from the Kanggur area, suggesting a common lead source. All of the silicon, sulphur and lead isotopic systems indicate that the ore-forming fluids and materials were mainly derived from the Aqishan Formation, and that the host volcanic rocks of the Aqishan Formation probably played a significant role in the Kanggur gold mineralization. Integrating the data obtained from studies on geology, geochronology, petro-geochemistry and H–O–Si–S–Pb isotope systematics, we suggest that the Kanggur gold deposit is an orogenic-type deposit formed in Eastern Tianshan orogenic belt during the Permian post-collisional tectonism.     

Boron,sulphur and copper isotope systematics in the orogenic gold deposits of the Archaean Hattu schist belt,eastern Finland

The Hattu schist belt is located in the western part of the Archaean Karelian domain of the Fennoscandian Shield. The orogenic gold deposits with Au–Bi–Te geochemical signatures are hosted by NE–SW, N–S and NW–SE oriented shear zones that deform 2.76–2.73 Ga volcanic and sedimentary sequences, as well as 2.75–2.72 Ga tonalite–granodiorite intrusions and diverse felsic porphyry dykes. Mo–W mineralization is also present in some tonalite intrusions, both separate from, and associated with Au mineralization. Somewhat younger, unmineralized leucogranite intrusions (2.70 Ga) also intrude the belt. Lower amphibolite facies peak metamorphism at 3–5 kbar pressures and at 500–600 °C temperatures affected the belt at around 2.70 Ga and post-date hydrothermal alteration and ore formation. In this study, we investigated the potential influence of magmatic-hydrothermal processes on the formation of orogenic gold deposits on the basis of multiple stable isotope (B, S, Cu) studies of tourmaline and sulphide minerals by application of in situ SIMS and LA ICP MS analytical techniques.Crystal chemistry of tourmaline from a Mo–W mineralization hosted by a tonalite intrusion in the Hattu schist belt is characterized by Fe^3 +–Al^3 +-substitution indicating relatively oxidizing conditions of hydrothermal processes. The range of δ¹¹B data for this kind of tourmaline is from − 17.2‰ to − 12.2‰. The hydrothermal tourmaline from felsic porphyry dyke swith gold mineralization has similar crystal chemistry (e.g. dravite–povondraite compositional trend with Fe^3 +–Al^3 + substitution) and δ¹¹B values between − 19.0‰ and − 9.6‰. The uvite–foitite compositional trend and δ¹¹B ‰ values between − 24.1% and − 13.6% characterize metasomatic–hydrothermal tourmaline from the metasediment-hosted gold deposits. Composition of hydrothermal vein-filling and disseminated tourmaline from the gold-bearing shear zones in metavolcanic rocks is transitional between the felsic intrusion and metasedimentary rock hosted hydrothermal tourmaline but the range of average boron isotope data is essentially identical with that of the metasediment-hosted tourmaline. Rock-forming (magmatic) tourmaline from leucogranite has δ¹¹B values between − 14.5‰ and − 10.8‰ and the major element composition is similar to that of the metasediment-hosted tourmaline.The range of δ³⁴S_VCDT values measured in pyrite, chalcopyrite and pyrrhotite is from − 9.1 to + 8.5‰, which falls within the typical range of sulphur isotope data for Archaean orogenic gold deposits. In the Hattu schist belt, positive δ³⁴S_VCDT values characterize metasediment-hosted gold ores with sulphide parageneses dominated by pyrrhotite and arsenopyrite. The δ³⁴S_VCDT values are both positive and negative in ore mineral parageneses within felsic intrusive rocks in which variable amounts of pyrrhotite are associated with pyrite. Purely negative values were only recorded from the pyrite-dominated gold mineralization within metavolcanic units. Therefore the shift of δ³⁴S_VCDT values to the negative values reflects precipitation of sulphide minerals from relatively oxidizing fluids. The range of measured δ⁶⁵Cu_NBS978 values from chalcopyrite is from − 1.11 to 1.19‰. Positive values are common for mineralization in felsic intrusive rocks and negative values are more typical for deposits confined to metasedimentary rocks. Positive and negative δ⁶⁵Cu_NBS978 values occur in the ores hosted by metavolcanic rocks. There is no correlation between sulphur and copper isotope data obtained in the same chalcopyrite grains.Evaluation of sulphur and boron isotope data together and comparisons with other Archaean orogenic gold provinces supports the hypothesis that the metasedimentary rocks were the major sources of sulphur and boron in the orogenic gold deposits in the Hattu schist belt. Variations in major element and boron isotope compositions in tourmaline, as well as in the δ³⁴S_VCDT values in sulphide minerals are attributed to localized involvement of magmatic fluids in the hydrothermal processes. The results of copper isotope studies indicate that local sources of copper in orogenic gold deposits may potentially be recognized if the original, distinct signatures of the sources have not been homogenized by widespread interaction of fluids with a large variety of rocks and provided that local chemical variations have been too small to trigger changes in the oxidation state of copper during hydrothermal processes.     

Ore-forming process of the Huijiabao gold district,southwestern Guizhou Province,China: Evidence from fluid inclusions and stable isotopes

The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO₂ inclusions, CO₂–H₂O inclusions, hydrocarbon inclusions, and hydrocarbon–H₂O inclusions. The ore-forming fluids are characterized by a H₂O + CO₂ + CH₄ ± N₂ system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H₂O + NaCl → H₂O + NaCl + CO₂ + CH₄ ± N₂ → H₂O + NaCl ± CH₄ ± CO₂ with a slight decrease in homogenization temperature and salinity. The δ¹⁸O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δD_H2O and calculated δ¹⁸O_H2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H₂O–NaCl–CO₂ fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.