Pb Isotopic Compositions Of Sulfides Research Articles

Origin of Ag-Pb-Zn mineralization at Huanaote, Inner Mongolia, NE China: Evidence from fluid inclusion, H-O-S-Pb and noble gas isotope studies

The newly-discovered Huanaote Ag-Pb-Zn deposit, containing 1173 tons Ag with a grade of 154 g/t, is situated in the western part of the Great Xing’an Range metallogenic belt. The source of metals and the fluid evolution for this large metallogenic system are still ambiguous. Mineralized Ag-Pb-Zn veins are primarily hosted in Late Carboniferous monzogranite and Devonian slate. Three paragenetic stages of mineralization were recognized at Huanaote, including (stage I) early pyrite + arsenopyrite + quartz ± K-feldspar; (stage II) the main ore stage sulfide (sphalerite, galena, chalcopyrite and pyrite) + sulfosalt (freibergite, bournonite, wittichenite and tetrahedrite) + quartz + sericite + chlorite ± epidote ± fluorite; and (stage III) late pyrite + quartz + calcite. The homogenization temperatures of fluid inclusion assemblage for stages I and II range from 254 to 337 ℃ and 143 to 270 ℃, respectively, while the fluid salinity varied from 2.3 to 14.2 and 0.9 to 11.8 wt% NaCl equiv. for stages I and II, respectively. The fluid δ18OH2O and δDH2O values range from −0.4 to +6.2‰ and −116.8 to −104.8‰, respectively, indicating that the source of the fluids was primarily derived from a magma with less contribution from meteoric waters. Sulfur isotope analyses of sulfides exhibit δ34S values from −4.3 to +8.0‰, consistent with those observed in other Ag-Pb-Zn deposits in this region, suggesting the sulfur was mainly magmatic origin with minor sedimentary sulfur addition. Similarly, the Pb isotope compositions of sulfides resemble those of local Mesozoic magmatism, implying a Mesozoic magmatic source for the metals. Additionally, the noble gas isotope compositions, specifically the 3He/4He ratios (ranging from 4.41 to 7.18 Ra, mean of 5.56 Ra) for fluid inclusions,strongly support a deep magmatic fluid responsible for the formation of Huanaote deposit. Fluid cooling, mixing with meteoric waters and dilution are suggested to be important processes for Ag-Pb-Zn deposition at Huanaote.

Geology, geochemistry, fluid inclusions, and H–O–C–S–Pb isotope constraints on the genesis of the Atash-Anbar epithermal gold deposit, Urumieh–Dokhtar magmatic arc, central-northern Iran

The newly discovered Atash-Anbar gold deposit, with ∼2 Mt of ore grading 2.13 g/t Au (locally up to 14 g/t), is located in the Buin-Zahra Range, central-northern Iran. Hosted by Middle Eocene (ca. 39.0 Ma) volcanic-subvolcanic rocks, the Au-polymetallic orebodies occur as NW− and NE − trending quartz-sulfide veins that are structurally controlled by NW-trending faults. The Middle Eocene host rocks are characterized by high-K calc-alkaline, peraluminous signatures, and moderately Eu negative anomalies (Eu/Eu* = 0.2–0.6). Four primary paragenetic stages of veining have been recognized: (I) smoky-grey quartz-chalcopyrite stage, (II) grey-white quartz-polysulfide stage, (III) white-pinkish barite-sulfide stage, and (IV) late quartz-carbonate stage. Fluid inclusion investigations coupled with laser Raman analyses indicate that the ore-forming fluids were formed in a NaCl − H2O ± CO2 system with two types of FIs: two phase, liquid-rich inclusions (type I) and two phase, vapor-rich inclusions (type II). The primary coexisting types I and II inclusions are observed in gold-bearing ore-stage II, sharing similar homogenization temperatures in the range of 233–286 °C and 243–281 °C, but contrasting salinity values of 10.7–14.8 and 14.6–15.5 wt% NaCl equivalent, respectively. Fluid inclusion examinations show that fluid phase separation occurred concurrently with gold precipitation during the ore-stage II. The δ18Ofluid values calculated from the δ18OSMOW and δDSMOW values of the inclusions in quartz veins are 4.9–11.1 ‰ and −84.6 ‰ to −68.3 ‰, respectively. δ13CPDB and δ18OSMOW values of Fe-dolomite are −6.5 ‰ to −5.0 ‰ and 3.1 ‰–4.9 ‰, respectively. H–O–C isotope data indicate magmatic origin of initial ore-forming fluids with minor addition of meteoric water through time. The δ34S values (−3.1 ‰ to −1.2 ‰, avg. = −2.0 ‰) of the ore-stage II sulfides suggest that sulfur comes from a homogeneous magmatic source. The Pb isotopic compositions of sulfides (207Pb/204Pb = 15.420–15.525, 206Pb/204Pb = 18.423–18.536, 208Pb/204Pb = 37.135–38.208) indicate that the Pb in the Atash-Anbar gold deposit is a mixture of crust and mantle components. We conclude that (1) the Atash-Anbar is an IS epithermal system that (2) resulted from Eocene subduction of the NeoTethys Ocean plate beneath the central Iran plate and thus (3) ore-forming fluid and its metal components (i.e., Ag, Pb, and Zn) were emanated through crystallization of the final phase of a granite porphyry intrusion.

Age, fluid inclusion, and H–O–S–Pb isotope geochemistry of the Baiyinchagan Sn–Ag–polymetallic deposit in the southern Great Xing'an Range, NE China

The superlarge Baiyinchagan Sn–Ag–polymetallic deposit of Inner Mongolia is located in the west slope of the southern Great Xing'an Range, NE China. The vein orebodies of the deposit occur in the NEE-trending fault zones. The mineralization process at the deposit can be divided into four stages: quartz–fluorite–cassiterite–sphalerite stage (stage I), quartz–fluorite–cassiterite–sulfide stage (stage II), quartz–calcite–sulfide stage (stage III), and quartz–stibnite stage (stage IV). Cassiterite U–Pb dating indicates that the Baiyinchagan deposit formed approximately 140 Ma ago, and zircon U–Pb dating for granite porphyry in the Baiyinchagan deposit yielded an age of 140.8 Ma. Two types of fluid inclusions (FIs), including liquid-rich and gas-rich inclusions, have been distinguished in quartz and fluorite veins. The homogenization temperature of the FIs in the stage I ranges from 318 °C to 351 °C with salinities of 1.2–3.8 wt% NaCl eqv. The homogenization temperature of the FIs in the stage II is 262–276 °C with salinities of 1.8–3.4 wt% NaCl eqv. The homogenization temperature of the FIs in the stage III ranges from 174 °C to 233 °C with salinities of 1.8–3.0 wt% NaCl eqv. The homogenization temperature of the FIs in the stage IV is in the range of 136–168 °C, and the salinity is 0.8 wt% to 2.4 wt% NaCl eqv. The ore-forming fluid of the Baiyinchagan deposit is characterized by medium–high temperature and low salinity. The δ18Owater and δD values of ore-forming fluid range from −13.5 ‰ to 9.5 ‰ and −119 ‰ to −84 ‰, respectively, indicating that the ore-forming fluid was dominantly derived from magmatic fluid mixed with meteoric water. The calculated δ34SH2S values range from −12.3 ‰ to −6.2 ‰, implying that the sulfur mainly came from granitic magma, but magmatic degassing occurred during mineralization. The 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb values of the sulfides are in the ranges of 18.180–18.339, 15.525–15.643, and 38.005–38.477, respectively. The Pb isotopic compositions of sulfides indicate that the Pb mainly derived from granitic magma that may be formed by partial melting of orogenic materials. Fluid immiscibility and mixing were the two primary mechanisms for mineral precipitation.

Mixed crustal-mantle source of porphyry Cu-Mo deposits of the Urals: Pyrite trace element geochemistry and Pb – S isotope data

Developing genetic models of porphyry Cu-, Mo-, and Cu-Mo deposits requires knowledge on the source of metals for these deposits. Even though porphyry Cu deposits worldwide were relatively well-studied and the corresponding sources of metals were considered, porphyry Cu-Mo deposits of the Urals were not previously investigated. The paper presents new data on two porphyry Cu-Mo deposits of Paleozoic age: namely Late Devonian to Early Carboniferous Verkhneuralskoe in the South Urals and Late Carboniferous to Early Permian Talitsa in the Middle Urals. Pyrite trace element data indicate minor input of Ni, Tl, and Ag from host rocks of the Talitsa deposit. Talitsa and Vekhneuralskoe deposits are heterogeneous in Pb isotope composition and, on the contrary, homogeneous in S isotope composition which is typical for porphyry deposits worldwide. The both deposits show similar age-corrected Pb isotope compositions of sulfides (18.228 to 18.521 for 206Pb/204Pb, 15.598 to 15.705 for 206Pb/204Pb, and 38.087 to 38.474 for 208Pb/204Pb) and of magmatic and hydrothermal K-feldspars (from 18.291 to 18.449 for 206Pb/204Pb, from 15.598 to 15.608 for 207Pb/204Pb, and from 38.023 to 38.127 for 208Pb/204Pb); δ34S varies from −0.4 to +3.4 ‰. The isotope data suggest that granitoid melts were the dominant source of both sulfides and ore-bearing magmatic rocks. Mantle-crustal mixing model calculated for the Urals shows 95 % of mantle Pb in porphyry Cu-Mo deposits.

Geology, geochemistry and genesis of Keyue: A newly discovered Pb-Zn-Sb-Ag polymetallic deposit associated with magmatic center in Southern Tibet, China

The Keyue Pb-Zn-Sb-Ag polymetallic deposit is located within the North Himalayan Metallogenic Belt (NHMB). This study aims to clarify whether the Keyue deposit has close association in time and space with magmatism, and discuss the significance for further exploration. Orebodies are hosted by the Lower Jurassic Ridang Formation black carbonaceous slate and controlled by the NE-trending faults. Keyue is characterized by multiple stages of hydrothermal veins, including Mn-Fe Carbonate-sulfide (I), quartz-sulfide-sulfosalt mineral (II) and quartz-calcite-stibnite veins (III).Hydrothermal minerals contain six types of fluid inclusions, including H2O-rich bi-phase aqueous (type I), pure CO2 (type II), CO2-rich H2O-CO2-NaCl tri-phase (type III), H2O-rich H2O-CO2-NaCl tri-phase (type IV), halite-bearing tri-phase (type V) and halite-bearing H2O-CO2-NaCl multiphase inclusions (type VI). All six types of inclusions were observed in stage II quartz, whereas only types I and III inclusions in stage I siderite and sphalerite and type I inclusions in stage III quartz and calcite. Type I inclusions in stage I display total homogenization temperatures (Th, total) ranging from 250.1 to 289.3 °C, with salinities of 9.6–16.3 wt% NaCleq. Types I, III, IV and V inclusions in stage II yield Th, total of 175.5–282.7 °C, 188.8–286.3 °C, 214.3–287.5 °C and 198.3–266.0 °C, with corresponding salinities of 4.0–21.5 wt% NaCleq, 0.6–2.9 wt% NaCleq, 0.0–11.0 wt% NaCleq and 30.1–33.2 wt% NaCleq, respectively. Type I inclusions in stage III have Th,total values of 172.3–240.7 °C and salinities of 3.1–12.6 wt% NaCleq. Fluid phase separation occurred in stages I and II, resulting in CO2 and H2S release, pH increase and rapid Pb-Zn-Ag precipitation, whereas mixing of magmatic fluids and meteoric water in stage III caused the cooling, dilution and stibnite precipitation.Fluid inclusion analysis and C-H-O isotopic compositions indicate that the initial hydrothermal fluids were magmatic water, with increasing input of meteoric water with time. The δ34SCDT values of sulfides from three stages are similar and range from 4.8 to 10.3 ‰ (average 7.7 ‰), showing characteristics of mixture of magmatic and sedimentary sulfur. The Pb isotopic compositions of sulfides are closely consistent with those of Cenozoic leucogranite and Precambrian metamorphic crystalline basement in the NHMB, suggesting that the ore-forming metals were sourced from the hidden causative Himalayan leucogranite formed by the decompression melting of metamorphic crystalline domains.Combining evidence from geochronology, fluid inclusions, isotopes suggest that the Keyue Pb-Zn-Sb-Ag and Cuonadong W-Sn-Be mineralization at different locations around the Cuonadong Dome constitute an integrated magmatic-hydrothermal system, with the distal end-member Pb-Zn-Sb-Ag veins centered on the Cuonadong leucogranites-related W-Sn-Be mineralization. Pegmatite-skarn-type W-Sn-Be polymetallic mineralization may occur at deeper sites beneath the Keyue area, and the distal Pb-Zn-Sb-Ag veins controlled by faults within strata also need more attention around these leucogranite domes in the NHMB.

Constraints of S–Pb–Sr Isotope Compositions and Rb–Sr Isotopic Age on the Origin of the Laoyingqing Noncarbonate-Hosted Pb–Zn Deposit in the Kunyang Group, SW China

The Laoyingqing Pb–Zn deposit is located on the southwestern margin of the Yangtze block and on the east side of the Xiaojiang deep fault in the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic triangle area (SYGT). This deposit was first discovered in the silty and carbonaceous slate of the Middle Proterozoic Kunyang Group that is structurally controlled by thrust faults and anticlines. This study is aimed at investigating whether the Laoyingqing deposit has the same ore-forming age and type as other Pb–Zn deposits related to the Pb–Zn metallogenic system and prospecting prediction of the deep and peripheral areas of the deposits in the SYGT. Based on the sphalerite Rb–Sr age dating and S–Sr–Pb isotopic composition analysis of the Laoyingqing Pb–Zn deposit, the following results were obtained. First, the Rb–Sr isochron age of sphalerite is 209.8 ± 5.2 million years (Ma), consistent with the ages of most Pb–Zn deposits in the SYGT (approximately 200Ma), thereby potentially indicating that these Pb–Zn deposits may have been formed synchronously during the late Indosinian orogeny. Second, the Pb isotopic compositions of sulfides show a linear trend on the average crustal Pb evolution curve in 207Pb/204Pb vs. 206Pb/204Pb plot. In addition, Pb isotopic ratios were consistent with the age-corrected Pb isotopic ratios of basement rocks, consequently suggesting that the source of mixed crustal Pb is mainly derived from basement rocks. Combined with the initial 87Sr/86Sr ratios of sphalerite between the (87Sr/86Sr)200Ma value of the basement rocks and that of the Upper Sinian–Permian carbonates, it can be concluded that the ore-forming metals were mainly derived from basement rocks. Third, sulfur isotopic composition of sphalerite from the Laoyingqing deposits shows δ34SCDT values that range mainly from -2.62‰ to 1.42‰, which is evidently lower than the δ34SCDT values of sulfides (8–20‰) from other Pb–Zn deposits in the SYGT. This can be interpreted as a result of mixing with reduced S that was mainly derived from the thermochemically reduced S in the overlying strata and a small amount of reduced S produced by the pyrolysis of S-containing organic matter. We conclude that the Laoyingqing deposit and most of the Pb–Zn deposits in the SYGT are Mississippi Valley-type deposits, thereby providing new ideas for investigating the deep and peripheral areas of Pb–Zn deposits.

Timing and origin of the Shesuo skarn Cu-polymetallic deposit in the northern Lhasa subterrane, central Tibet: Implications for Early Cretaceous Cu(Mo) metallogenesis in the Bangong-Nujiang metallogenic belt

The Bangong-Nujiang metallogenic belt is a newly discovered copper-polymetallic belt in the Tethyan domain. To date, the Shesuo skarn Cu-polymetallic deposit is the only productive Early Cretaceous Cu deposit in the middle segment of this belt. We conducted zircon U-Pb and molybdenite Re-Os dating of this deposit, and the results show that the Shesuo skarn Cu-polymetallic deposit formed at 117–112 Ma. Within the mining area, granodiorites and monzogranites are the main metallogenic granitic bodies. The petrogeochemical features imply that the granodiorites and monzogranites were derived from the partial melting of juvenile lower crust resulting from mantle-derived magmatic underplating, with the additional involvement of ancient crust in the magma chamber, whereas the monzogranites experienced significant fractional crystallization. The δ34S values of sulfide ores suggest that they were mainly sourced from the magma and slightly contaminated by surrounding strata. The Pb isotope compositions of sulfides and Re contents of molybdenite indicate that the metals were derived from the juvenile lower crust, with a small fraction from ancient crustal materials. Our study suggests that the generation of the Shesuo deposit was most likely triggered by slab breakoff during the southward subduction of the Bangong-Nujiang Ocean lithosphere. The Shesuo and Xiongmei deposits have low zircon Ce4+/Ce3+ and EuN/Eu* ratios and low whole-rock average V/Sc, Sr/Y and (EuN/Eu*)/YbN ratios. We propose that these values are due to the input of reduced components, leading to the generation of metallogenic magmas with relatively low magmatic oxidation states and water contents and rendering the magmas infertile for later porphyry-skarn Cu formation in the Xiongmei area.

Genesis of the Zhangquanzhuang gold deposit in the northern margin of North China Craton: Constraints from deposit geology and ore isotope geochemistry

The genesis of orogenic gold deposits in the northern margin of the North China Craton (NCC) is still ambiguous, and this is addressed in this case study on the Zhangquanzhuang gold deposit. This deposit shows features typical of orogenic gold deposits, including quartz vein-type mineralization controlled by shear zones, sericite-quartz-pyrite-carbonate alteration along shear zones, absence of connection to any magmatic intrusion, and occurrence of native gold and electrum. The Zhangquanzhuang gold deposit, which is hosted in Archean high-grade metamorphic rocks, was formed in Mesozoic and largely later than the regional metamorphism. In this deposit, the Pb isotope compositions of sulfides in ores have low 206Pb/204Pb ratios of 16.874–17.007, 207Pb/204Pb ratios of 15.368–15.410, and 208Pb/204Pb ratios of 37.023–37.215, and these are much less radiogenic than those of regional metamorphic and magmatic rocks. This finding precludes the possible derivation of ore fluid from regional magmatism and metamorphism. In pyrite-hosted fluid inclusions in the ores, the 3He/4He and 40Ar/36Ar ratios are 1.26–1.75 Ra and 1622–2816, respectively, showing prominent signature of mantle sources. These geochemical features, together with the large temporal discrepancy between regional metamorphism and mineralization, suggest that ore fluid and metal had a subcrustal source similar to the gold deposits in the Jiaodong gold province in the southeastern margin of the NCC. The calculated δ34SH2S values for the ore fluid are 2.31–4.48‰, which are heavier than the δ34S of depleted mantle. The δ18O of ore-related quartz mostly cluster around 11‰, implying high δ18O of subcrust-derived ore fluid. The stable O and S isotope data indicate that the subcrustal source has been metasomatized by subducted crustal sediments.

Genesis of the giant Caixiashan Zn-Pb deposit in Eastern Tianshan, NW China: Constraints from geology, geochronology and S-Pb isotopic geochemistry

The Caixiashan Zn-Pb deposit is the largest carbonate-hosted Zn-Pb deposit in Eastern Tianshan, NW China. The deposit comprises the No. Ⅰ, Ⅱ, III and IV ore zones with a proven reserve of 131 Mt ore at 3.95% Pb + Zn. The orebodies generally occur as irregular lenses and pods in altered carbonate rocks of the Mesoproterozoic Kawabulake Group near faults. The mineralization is characterized by massive, disseminated and vein/veinlet sulfides including pyrite, pyrrhotite, sphalerite and galena with minor arsenopyrite and chalcopyrite, as well as sulfosalt minerals of Ag, As, Sb and Pb. The mineralization is associated with tremolite, chlorite, silica and carbonate alterations. Rb-Sr isotopic dating of sphalerite and pyrrhotite yields an isochron age of 337.2 ± 5.7 Ma, which is interpreted as the mineralization age. Zircon U-Pb dating reveals that stocks of diorite, quartz diorite, K-feldspar granite and monzonitic granite that occur in the deposit area were emplaced at 348.2 ± 3.7 Ma, 351.9 ± 3.5 Ma, 333.6 ± 3.6 Ma and 330.0 ± 3.6 Ma, respectively. These age data suggest that the mineralization is coeval with Carboniferous granitic magmatism. The δ34SV-CDT values of sulfides (excluding the syn-sedimentary pyrite) range from −2.42‰ to 19.1‰, suggesting that the reduced sulfur was mainly derived from thermal sulfate reduction (TSR) of seawater-derived sulfates in the marine sedimentary basement rocks and minor contribution by replacement of syn-sedimentary pyrite, as well as a possible input of magmatic sulfur. The Pb isotopic compositions of sulfides, with 206Pb/204Pb ranging from 17.074 to 17.361, 207Pb/204Pb from 15.422 to 15.614, and 208Pb/204Pb from 36.685 to 37.303, partly overlap with those of basement rocks of the Mesoproterozoic Kawabulake Group and the Carboniferous intrusions, suggesting that the ore metals were derived from both the basement and Carboniferous magmatism. On the basis of the spatio-temporal relations between hydrothermal alterations/mineralization and Carboniferous magmatism, we conclude that the Caixiashan Zn-Pb deposit is a high-temperature carbonate replacement deposit related to concealed granitic intrusions, which were formed in an arc environment related to the subduction of the South Tianshan Ocean plate beneath the Central Tianshan massif during the Carboniferous time. The results of this study indicate that there is a great potential of finding more large-scale Zn-Pb deposits similar to Caixiashan in Eastern Tianshan.

Epithermal gold mineralization in Cretaceous volcanic belt, SE China: Insight from the Shangshangang deposit

Low sulfidation (LS) epithermal gold deposits within the Southeastern China Fold Belt (SCFB) are generally associated with Early Cretaceous volcanism (91–110 Ma). The Shangshangang (SSG) gold deposit (3 t Au @ 2.7 g/t) is proposed to be a LS ore system hosted by Early Cretaceous volcanic-subvolcanic rocks in the Dongkeng Basin (DVB), northern SCFB. Early Cretaceous felsic volcanic-subvolcanic rocks within the DVB possess high-K calc-alkaline and metaluminous to weakly peraluminous signatures. They show rare trace element (REE) and trace element patterns resembling those of Early Cretaceous A-type granites and rhyolites in the SCFB with significantly Eu negative anomalies (Eu/Eu* = 0.1–0.3). These volcanic-subvolcanic rocks are potentially formed by mixing of melts from crust and Early Cretaceous enriched mantle under an extensional tectonic setting. This is indicated by their negative εHf(t) values (−8.8 to −5.2), young two-stage Hf model ages (TDM2 = 1.32–1.48 Ga), and variable Sr-Nd isotopic compositions.The epithermal event at SSG is represented by three mineralization stages characterized by four distinct quartz vein types. These are: (1) greyish green crustiform comb quartz veins (type A) and smoky grey fine-grained (<0.5 mm) quartz veins (type B) in the early stage, (2) ivory medium- to coarse-grained (>1 mm) quartz veins (type C) in the middle stage, and (3) late white calcite-rich quartz veins (type D). Quartz veins are typically accompanied by hydrothermal alteration with zoning (kaolinite-illite-chlorite zone, adularia-chlorite-quartz zone, and adularia-sericite-quartz zone). Gold mineralization is identified in the early stage and free gold exists as micrometer-sized inclusions of native gold within pyrite. Pb–Zn mineralization dominates the middle stage. Hydrothermal fluids within the ore system are of low salinity (<7 wt% NaCl) and gas-poor. The fluid temperatures decreases from 224 − 316 °C for Au mineralization to 190–261 °C for Pb-Zn mineralization. No indication for fluid boiling is found. The H–O isotopes indicate mixing of magmatic and meteoric fluids and a larger portion of meteoric water at a later stage. The δ34S values of pyrite related to Au mineralization are 1.1–2.0‰ and of sphalerite and galena related to Pb-Zn mineralization range from −1.8 to 2.5‰. The Pb isotopic compositions of sulfides from the early and middle stages are relatively homogeneous and similar with those of subvolcanic rocks within the DVB. Deposit geology, microthermometric result, and isotopic data support a LS epithermal origin for the SSG gold deposit, and therefore suggest a co-existing relationship between low and intermediate sulfidation epithermal gold mineralization within the DVB.

The continental crust contributes to magmatic hydrothermal gold deposit in Ciemas, West Java, Indonesia: Constraints from Hf isotopes of zircons and in situ Pb isotopes of sulfides

Multiple periods of arc magmatism induced by the subduction of the Indian-Australian Plate northward developed on Java Island, and multistage porphyry-epithermal metallogenic systems occurred within the Late Eocene-Early Miocene and the Late Miocene-Early Pleistocene magmatic belts. These porphyry-epithermal metallogenic systems have obvious spatial variations. In West Java, there are large populations of low-sulfidation type epithermal deposits, while East Java and its east are characterized by the occurrences of porphyry deposits. However, the newly discovered Ciemas deposit in West Java, a Middle Miocene (~17 Ma) porphyry-epithermal Au deposit, provides an opportunity for further understanding the porphyry-epithermal mineralization in Java. To elucidate the controlling factors of porphyry-epithermal mineralization in West Java, we analyzed the Hf isotopies of zircons from the igneous rocks and in situ Pb isotopes of sulfides (galena, pyrite, arsenopyrite) in the Ciemas deposit. The results show that the zircons εHf (t) of igneous rocks are uniform with an average value of −11.5 ± 0.39, and the peak value of TDM2 is 1500–1650 Ma, suggesting the Middle Miocene arc magmatism in Ciemas suffered intense crustal contamination. The Pb isotopic compositions of sulfides are very uniform and have high amounts of radiogenic lead. The mean ratios of 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb are 39.343 ± 0.059, 15.73 ± 0.015 and 18.854 ± 0.025, respectively, indicating that the mineralization materials of the Ciemas gold deposit mainly originated from ancient continental crust. The multistage arc magmatism induced by the subduction of the Indian-Australian Plate northward beneath Java Island control the porphyry and epithermal mineralization in Java. The Middle Miocene arc magmatism in Ciemas contaminated intensely by the Sundaland, and the ancient continental crust provides the main metal source for the Ciemas deposit in West Java.

Genesis of the Wulong gold deposit, Liaoning Province, NE China: Constrains from noble gases, radiogenic and stable isotope studies

The Wulong lode deposit contains over 80 tonnes of gold with an average grade of 5.35 g/t. It is one of the largest deposits in Dandong City, Liaoning Province in northeast China. Previous studies on the deposit focused on its geological characteristics, geochemistry, fluid inclusions, and the timing of gold mineralization. However, controversy remains regarding the origin of the ore-forming fluids and metals, and the genesis of the gold deposit. This paper presents zircon U–Pb and pyrite Rb–Sr ages and S, Pb, He, and Ar isotopic results along with quartz H and O isotopic data for all litho-units associated with the deposit. Laser ablation inductively coupled mass spectrometry measurements yielded zircon U–Pb dates for samples of pre-mineralization rocks like granite porphyry dike, the Sanguliu granodiorite, fine-grained diorite, and syn-mineralization diorite, as well as post-mineralization dolerite, and lamprophyre; their emplacement ages are 126 ± 1 Ma, 124 ± 1 Ma, 123 ± 1 Ma, 120 ± 1 Ma, 119 ± 2 Ma, and 115 ± 2 Ma, respectively. The pyrite Rb–Sr isochron age is 119 ± 1 Ma, indicating that both magmatism and mineralization occurred during the Early Cretaceous. The δ18OH2O values of ore-forming hydrothermal fluids from the quartz–polymetallic sulfide vein stage vary from 4.8‰ to 6.5‰, and the δDV-SMOW values are between −67.7‰ and −75.9‰, indicating that the ore-forming fluids were primarily magmatic. The noble gas isotope compositions of fluid inclusions hosted in pyrite suggest that the ore-forming fluids were dominantly derived from crustal sources with minor mantle input. Sulfur isotopic values of pyrite vary between 0.2‰ and 3.5‰, suggesting that S was derived from a homogeneous magmatic source or possibly from fluids derived from the crust. The Pb isotopic compositions of sulfides (207Pb/204Pb = 15.51–15.71, 206Pb/204Pb = 17.35–18.75, 208Pb/204Pb = 38.27–40.03) indicate that the Pb of the Wulong gold deposit is a mixture of crust and mantle components. Geochronological and geochemical data, together with the regional geological history, indicate that Early Cretaceous magmatism and mineralization of the Wulong gold deposit occurred during the rollback of the subducting Paleo-Pacific Plate, which resulted in lithospheric thinning and the destruction of the North China Craton (NCC), which indicates that the deposit is of magmatic–hydrothermal origin.

Ore Genesis of the Chuduoqu Pb-Zn-Cu Deposit in the Tuotuohe Area, Central Tibet: Evidence from Fluid Inclusions and C–H–O–S–Pb Isotopes Systematics

The Chuduoqu Pb-Zn-Cu deposit is located in the Tuotuohe area in the northern part of the Sanjiang Metallogenic Belt, central Tibet. The Pb-Zn-Cu ore bodies in this deposit are hosted mainly by Middle Jurassic Xiali Formation limestone and sandstone, and are structurally controlled by a series of NWW trending faults. In this paper, we present the results of fluid inclusions and isotope (C, H, O, S, and Pb) investigations of the Chuduoqu deposit. Four stages of hydrothermal ore mineralization are identified: quartz–specularite (stage I), quartz–barite–chalcopyrite (stage II), quartz–polymetallic sulfide (stage III), and quartz–carbonate (stage IV). Two types of fluid inclusions are identified in the Chuduoqu Pb-Zn-Cu deposit: liquid-rich and vapor-rich. The homogenization temperatures of fluid inclusions for stages I–IV are 318–370 °C, 250–308 °C, 230–294 °C, and 144–233 °C, respectively. Fluid salinities range from 2.07 wt. % to 11.81 wt. % NaCl equivalent. The microthermometric data indicate that the fluid mixing and cooling are two important mechanisms for ore precipitation. The H and O isotopic compositions of quartz indicate a primarily magmatic origin for the ore-forming fluids, with the proportion of meteoric water increasing over time. The C and O isotopic compositions of carbonate samples indicate that a large amount of magmatic water was still involved in the final stage of mineralization. The S and Pb isotopic compositions of sulfides, demonstrate that the ore minerals have a magmatic source. On a regional basis, the most likely source of the metallogenic material was regional potassium-enriched magmatic hydrothermal fluid. Specifically for the Chuduoqu Pb-Zn-Cu deposit, the magmatic activity of a syenite porphyry was the likely heat source, and this porphyry also provided the main metallogenic material for the deposit. Mineralization took place between 40 and 24 Ma. The Chuduoqu deposit is a mesothermal hydrothermal vein deposit and was formed in an extensional environment related to the late stage of intracontinental orogenesis resulting from India–Asia collision. The determination of the deposit type and genesis of Chuduoqu is important because it will inform and guide further exploration for hydrothermal-type Pb and Zn deposits in the Tuotuohe area and in the wider Sanjiang Metallogenic Belt.

Genesis of the Wulong gold deposit, northeastern North China Craton: Constraints from fluid inclusions, H-O-S-Pb isotopes, and pyrite trace element concentrations

The Wulong vein-type gold deposit, located along the northeastern margin of the North China Craton (NCC), contains > 80 tonnes of gold at an average grade of 5.35 g/t. A total of 380 auriferous quartz veins are hosted in Late Jurassic gneissic two-mica granite and Early Cretaceous granodiorite. A paragenetic sequence, representing three hydrothermal stages, has been identified: (1) quartz ± pyrite; (2) quartz-polymetallic sulfide; and (3) quartz-calcite ± pyrite. Petrography, fluid inclusion microthermometry, and laser Raman spectroscopy revealed three types of fluid inclusions: CO2 ± CH4 (type I), H2O-CO2 ± CH4 (type II), and H2O-NaCl (type III). Fluid inclusion data indicate that during mineralization, fluid temperatures evolved from 283 to 395 °C to 219–328 °C to 144–255 °C, and salinities varied from 0.70 to 8.95 wt% to 0.18–7.86 wt% to 0.18–4.96 wt% NaCl equivalent. Quartz yielded δ18OH2O-SMOW and δDSMOW values of 0.9–7.3‰ and −65‰ to −48‰, respectively, indicating that the ore-forming fluids were derived from magmatic water and mixed with meteoric water during the later stages of mineralization. Sulfides have δ34SCDT sulfur isotopic compositions ranging from 0.9‰ to 3.9‰, suggesting that the S was derived from a magmatic source. Pb isotopic compositions of sulfides (206Pb/204Pb = 17.488–17.718, 207Pb/204Pb = 15.565–15.631, and 208Pb/204Pb = 38.190–38.766) indicate that the Pb was derived primarily from the upper crust, with minor input from the mantle. In situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) trace element analyses of three generations of pyrite (Py1, Py2, and Py3) reveal that gold concentrations in Py2 are higher than those in Py1 and Py3, which indicates that gold mineralization occurred primarily during the middle stage. High Co/Ni ratios of pyrite are consistent with a hydrothermal origin. We suggest that the Wulong gold deposit formed during lithospheric thinning associated with destruction of the NCC, this process was triggered by subduction of the Paleo-Pacific plate during the Early Cretaceous.

Lead isotope constraints on the genetic relationships among different ore types in the Dongshengmiao deposit, northern China

The giant Dongshengmiao Cu-Zn-Pb-S deposit is the most representative Proterozoic sedimentary exhalative (SEDEX) deposit in China. A detailed investigation of Pb isotope compositions of sulfides from various types of ores and associated host rocks has been carried out to determine the genetic relationships among different ore types and to provide important insights on whether younger fluids have contributed mineralizing materials in the formation of the Dongshengmiao Cu-Zn-Pb ores. The substantial similarity of the Pb isotope composition between the studied stratiform Cu-Zn-Pb and S orebodies suggests that the bulk of the Dongshengmiao Cu-Zn-Pb ores belong to the same polymetallic metallogenic system with the syngenetic S ores of the Proterozoic age. Comparatively, vein-type ores show relative scattered Pb isotope signatures that fall along a well-correlated linear trend, whereas their less radiogenic end member projects towards the Pb isotope compositions of the overlying stratiform main orebody. In addition, the overall Pb isotope compositions of these vein-type ores have shown an apparent overlap and similar trend with the radiogenic disseminated pyrites in the mica schists, indicating their radiogenic Pb most likely originated from host rocks as well. The scatter of Pb isotope compositions of the Dongshengmiao Cu-Zn-Pb ores shows that lead was not homogenized regionally during subsequent metamorphism, ruling out the possibility of a deposit-scale remobilization. Furthermore, the significant difference and lack of intermediate Pb isotope values between the previously studied Hercynian feldspars and the bulk of the Dongshengmiao sulfide ores suggest that a significant introduction of metals from, or overprinting by, fluids derived from Hercynian magmatism is unlikely to have played an important role in the metal endowment. Taken together, all sulfide orebodies associated with various ore types in the Dongshengmiao deposit belong to an integrated and progressive hydrothermal ore-forming system of the Proterozoic age, and a portion of the vein-type ores and associated disseminated pyrites experienced a minor addition of evolved rock lead during subsequent greenschist face metamorphisms.

Fluid evolution and mineralization mechanism of the East Kounrad porphyry Mo-W deposit in the Balkhash metallogenic belt, Central Kazakhstan

The East Kounrad Mo-W deposit is located in the eastern part of the Balkhash metallogenic belt, Central Kazakhstan. The intrusion in the East Kounrad deposit is a Permain complex that includes medium- and fine-grained granites. Both the primary magma and hydrothermal fluids of the East Kounrad deposit are characterized by high fluorine and high oxygen fugacity, which would be important for the formation of high-grade large Mo deposit. Four mineralization stages are identified in this study. Stage I quartz–wolframite ± molybdenite ± fluorite veins, which were associated with intensively greisen alteration, were formed from fluids with high temperature (340–460 °C), high pressure (250–400 bars), high/low salinity (54.5 wt% and 3.4–10.2 wt%, respectively), and high oxygen fugacity with a fluid system of H2O-NaCl-CO2. Stage II quartz–molybdenite ± pyrite veins, which were accompanied by K-feldspars–muscovite–fluorite alteration, were formed from fluids with medium-high temperature (260–400 °C), medium pressure (100–250 bars), high/low salinity (39.1–58.4 wt% and 2.4–11.7 wt%, respectively), and relatively low oxygen fugacity. After the main stage of W and Mo mineralization, stage III quartz–pyrite ± molybdenite veins, associated with quartz–sericite alteration, were formed from fluids with medium-low temperature (160–340 °C), low pressure (less than 100 bars), various salinity (4.5–46.2 wt%) and high oxygen fugacity. Stage IV quartz–polymetallic sulfide veins, related to argillic alteration, were formed under temperature of 120–220 °C and salinity of 1.7–8.1 wt%. Remarkably, fluid boiling is the most important precipitation mechanism of molybdenite and wolframite. In addition, the decreasing oxygen fugacity and temperature also play a vital role in triggering deposition of molybdenite. The Pb isotopic composition of sulfides shows that the ore-forming materials at East Kounrad are dominantly derived from the lower crust.

Simultaneous measurement of sulfur and lead isotopes in sulfides using nanosecond laser ablation coupled with two multi-collector inductively coupled plasma mass spectrometers

We herein report the coupling of a nanosecond laser ablation system with a large-scale multi-collector inductively coupled plasma mass spectrometer (Nu1700 MC-ICPMS, NP-1700) and a conventional Nu Plasma II MC-ICPMS (NP-II) for the simultaneous laser ablation and determination of in situ S and Pb isotopic compositions of sulfide minerals. We found that the required aerosol distribution between the two spectrometers depended on the Pb content of the sample. For example, for a sulfide containing 100–3000 ppm Pb, the aerosol was distributed between the NP-1700 and the NP-II spectrometers in a 1:1 ratio, while for lead contents >3000 and <100 ppm, these ratios were 5:1 and 1:3, respectively. In addition, S isotopic analysis showed a pronounced matrix effect, so a matrix-matched external standard was used for standard-sample bracketing correction. The NIST NBS 977 (NBS, National Bureau of Standards; NIST, National Institute of Standards & Technology) Tl (thallium) dry aerosol internal standard and the NIST SRM 610 (SRM, standard reference material) external standard were employed to obtain accurate results for the analysis of Pb isotopes. In tandem experiments where airflow conditions were similar to those employed during stand-alone analyses, small changes in the aerosol carrier gas flow did not significantly influence the accurate determination of S and Pb isotope ratios. In addition, careful optimization of the flow ratio of the aerosol carrier (He) and makeup (Ar) gases to match stand-alone analytical conditions allowed comparable S and Pb isotope ratios to be obtained within an error of 2 s analytical uncertainties. Furthermore, the results of tandem analyses obtained using our method were consistent with those of previously reported stand-alone techniques for the S and Pb isotopes of chalcopyrite, pyrite, galena, and sphalerite, thus indicating that this method is suitable for the simultaneous analysis of S and Pb isotopes of natural sulfide minerals, and provides an effective tool to determine S and Pb isotope compositions of sulfides formed through multi-stage deposition routes.

Isotope geochemistry and genesis of the Liyuan gold deposit, Shanxi, North China

The Liyuan lode gold deposit is located in the Shanxi province, central North China Craton. Gold orebodies are mainly hosted in Archean metamorphic rocks and structurally controlled by the NNE-trending faults. Gold occurs in disseminated and auriferous quartz-sulfide veins and veinlets within hydrothermally altered rocks. Mineralization can be divided into three intervals: (1) quartz-pyrite stage, (2) quartz-polymetallic sulfides stage, and (3) quartz-carbonate stage. Gold formed mainly in the middle stage. Sericite sample associated with the middle stage pyrite from phyllic alteration zones yields an well-defined 40Ar/39Ar plateau age of 133.3 ± 1.2 Ma, which is remarkably consistent with zircon U-Pb age (133.4 ± 1.1 Ma) of the quartz porphyry dikes in the Liyuan mine, indicating a close relationship between gold mineralization and granitic magmatism in the area. The sulfur isotopic compositions of pyrite (Py1-2) from the early stage have a narrow range from −0.3 to 4.1‰, indicating a deep-seated magmatic source. However, the sulfides (Py3-5, sphalerite, galena) from the middle stage have lower δ34SV-CDT values of −7.2 to 3.0‰, which is thought to be a result of fluid oxidation during gold mineralization. The Pb isotopic compositions of sulfides from Liyuan ores have 206Pb/204Pb, 207Pb/204Pb, and 208Pb/204Pb ratios of 16.671–16.860, 15.236–15.255, and 41.452–44.159, respectively, indicting a high-thorium lower continental crust source of ore-forming materials. The δ13CVPDB and δ18OVSMOW values of late stage calcite ranging from −7.1 to −5.8‰ and 12.2 to 13.7‰, respectively, illustrating a deep-seated magmatic source of carbon-bearing portion. Given the absence of granite bodies at the present mining levels, we speculate that the ore-forming fluids may have been exsolved from a concealed granite pluton at greater depth. Based on the regional tectono-magmatic events, ore geology, geochronologic and isotopic data obtained in this study together with the previous published fluid inclusion data, we suggest that the Liyuan deposit is an orogenic gold deposit that is probably related to the early Cretaceous granite magmatism in the interior of the North China Craton.

Fluid Inclusion, H-O, S, Pb and noble gas isotope studies of the Aerhada Pb-Zn-Ag deposit, Inner Mongolia, NE China

The Aerhada Pb-Zn-Ag deposit is located in the western segment of the Great Hinggan Range Ag-Pb-Zn-Cu-Mo-Au-Fe metallogenic belt in NE China. Orebodies occur mainly as vein type and are hosted by sandstone and siliceous slate. Three stages of primary mineralization, including an early arsenopyrite-pyrite-quartz, a middle polymetallic and silver sulfides-quartz and a late sphalerite-pyrite-calcite-fluorite are recognized. Four types of fluid inclusions have been identified in the ore-bearing quartz and fluorite veins, i.e., liquid-rich, gas-rich, three-phase CO2 aqueous inclusions, and pure gas or liquid aqueous inclusions. Microthermometric studies on fluid inclusions reveal that homogenization temperatures from early to late stages range from 253° to 430°C, 195° to 394°C and 133° to 207°C, respectively. Fluid salinities range from 2.9 to 14.0wt.% NaCl equiv. The vapor composition of the ore fluid is dominated by H2O, CO2 and CH4, with minor proportions of N2. The fluid δ18OH2O and δDH2O values vary from +1.6 to +9.3‰ and −122 to −56‰, respectively, and reflect a magmatic fluid and a meteoric fluid dominant hydrothermal system for the early and late stages of mineralization, respectively. The calculated δ34SH2S values of hydrothermal fluids in equilibrium with sulfides range from +5.2 to +7.1‰, suggesting a mixed source for sulfur, i.e., the local magmatic and sedimentary rocks. The Pb isotope compositions of sulfides are similar to those of the local magmatic and sedimentary rocks, implying that lead and possibly silver relate to these sources. The noble gas isotope compositions of fluid inclusions hosted in ore minerals suggest that the ore-forming fluids were dominantly derived from a deep mantle source. Fluid mixing and dilution are inferred as the dominant mechanisms for ore deposition. The Aerhada Pb-Zn-Ag deposit can be classified as a medium to low temperature hydrothermal vein type deposit.

Sulfur and lead isotopic compositions of massive sulfides from deep-sea hydrothermal systems: Implications for ore genesis and fluid circulation

Studies of sulfur and lead isotopic compositions in hydrothermal deposits are an important tool to determine the source and processes of both sulfur and lead, and to understand the origin of hydrothermal ore deposits. Here, the sulfur and lead isotopic compositions of sulfide minerals have been studied for different hydrothermal fields in the East Pacific Rise (EPR), Mid-Atlantic Ridge (MAR), Central Indian Ridge (CIR), Southwest Indian Ridge (SWIR), and North Fiji Basin (NFB). The sulfur isotopic compositions of the studied sulfide samples are variable (δ34S 0.0 to 9.6‰, avg. δ34S 4.7‰; n=60), being close to the associated igneous rocks (~0‰ for, e.g., basalt, serpentinized peridotite), which may reflect the S in the sulfide samples is derived mainly from the associated igneous rocks, and a relatively small proportion (<36%) of seawater sulfur incorporated into these sulfides during mixing between seawater (δ34S 21‰) and hydrothermal fluid. In contrast for a mixed origin for the source of S, the majority of the lead isotopic compositions (206Pb/204Pb 17.541±0.004 to 19.268±0.001, 207Pb/204Pb 15.451±0.001 to 15.684±0.001, 208Pb/204Pb 37.557±0.008 to 38.988±0.002, n=21) of the sulfides possess a basaltic Pb isotopic composition, suggesting that the lead in the massive sulfide is mainly leached from local basaltic rocks that host the sub-seafloor hydrothermal systems in sediment-free mid-ocean ridges and mature back-arc basins. Furthermore, sulfide minerals in the super-fast and fast spreading mid-ocean ridges (MORs) exhibit less spread in their the δ34S values compared to sulfides from super-slow, and slow spreading MORs, which is most easily explained as a lesser degree of fluid-rock interaction and hydrothermal fluid-seawater mixing during hydrothermal ore-forming process. Additionally, the S and Pb isotope compositions of sulfides are controlled by the fluid processes for forming seafloor massive sulfide deposits. We demonstrate that the variable sulfur and lead isotopic compositions exhibit a relationship with the sulfur and lead sources, fluid–rock interaction, and fluid–seawater mixing.