S,Pb, and Sr isotope geochemistry and genesis of Pb–Zn mineralization in the Huangshaping polymetallic ore deposit of southern Hunan Province,China

The Huangshaping Pb–Zn–W–Mo polymetallic deposit, located in southern Hunan Province, China, is one of the largest deposits in the region and is unique for its metals combination of Pb–Zn–W–Mo and the occurrence of significant reserves of all these metals. The deposit contains disseminated scheelite and molybdenite within a skarn zone located between Jurassic granitoids and Carboniferous sedimentary carbonate, and sulfide ores located within distal carbonate-hosted stratiform orebodies. The metals and fluids that formed the W–Mo mineralization were derived from granitoids, as indicated by their close spatial and temporal relationships. However, the source of the Pb–Zn mineralization in this deposit remains controversial.Here, we present new sulfur, lead, and strontium isotope data of sulfide minerals (pyrrhotite, sphalerite, galena, and pyrite) from the Pb–Zn mineralization within the deposit, and these data are compared with those of granitoids and sedimentary carbonate in the Huangshaping deposit, thereby providing insights into the genesis of the Pb–Zn mineralization. These data indicate that the sulfide ores from deep levels in the Huangshaping deposit have lower and more consistent δ³⁴S values (− 96 m level: + 4.4‰ to + 6.6‰, n = 13) than sulfides within the shallow part of the deposit (20 m level: + 8.3‰ to + 16.3‰, n = 19). The δ³⁴S values of deep sulfides are compositionally similar to those of magmatic sulfur within southern Hunan Province, whereas the shallower sulfides most likely contain reduced sulfur derived from evaporite sediments. The sulfide ores in the Huangshaping deposit have initial ⁸⁷Sr/⁸⁶Sr ratios (0.707662–0.709846) that lie between the values of granitoids (0.709654–0.718271) and sedimentary carbonate (0.707484–0.708034) in the Huangshaping deposit, but the ratios decreased with time, indicating that the ore-forming fluids were a combination of magmatic and formation-derived fluids, with the influence of the latter increasing over time. The lead isotopic compositions of sulfide ores do not correlate with sulfide type and define a linear trend in a ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagram that is distinct from the composition of the disseminated pyrite within sedimentary carbonates and granitoids in the Huangshaping deposit, but is similar to the lead isotopic composition of sulfides within coeval skarn Pb–Zn deposits in southern Hunan Province. In addition, the sulfide ores have old signatures with relative high ²⁰⁷Pb/²⁰⁶Pb ratios, suggesting that the underlying Paleoproterozoic basement within southern Hunan Province may be the source of metals within the Huangshaping deposit.The isotope geochemistry of sulfide ores in the Huangshaping deposit shows a remarkable mixed source of sulfur and ore-forming fluids, and the metals were derived from the basement. These features are not found in representative skarn-type Pb–Zn mineralization located elsewhere. The ore-forming elements (S, Pb, and Zn) from the granitoids made an insignificant contribution to sulfide precipitation in this deposit. However, the emplacement of granitoids did provide large amounts of heat and fluids to the hydrothermal system in this area and extracted metals from the basement rocks, indicating that the Jurassic magmatism associated with the Huangshaping deposit was crucial to the Pb–Zn mineralization.     

Genesis of the Nanyangtian scheelite deposit in southeastern Yunnan Province,China: evidence from mineral chemistry,fluid inclusions,and C–O isotopes

The Nanyangtian skarn-type scheelite deposit is an important part of the Laojunshan W–Sn polymetallic metallogenic region in southeastern Yunnan Province, China. The deposit comprises multiple scheelite ore bodies; multilayer skarn-type scheelite ore bodies are dominant, with a small amount of quartz vein-type ore bodies. Skarn minerals include diopside, hedenbergite, grossular, and epidote. Three mineralization stages exist: skarn, quartz–scheelite, and calcite. The homogenization temperatures of fluid inclusions in hydrothermal minerals that formed in different paragenetic phases were measured as follows: 221–423 °C (early skarn stage), 177–260 °C (quartz–scheelite stage), and 173–227 °C (late calcite stage). The measured salinity of fluid inclusions ranged from 0.18% to 16.34% NaCleqv (skarn stage), 0.35%–7.17% NaCleqv (quartz–scheelite stage), and 0.35%–2.24% NaCleqv (late calcite vein stage). Laser Raman spectroscopic studies on fluid inclusions in the three stages showed H₂O as the main component, with N₂ present in minor amounts. Minor amounts of CH₄ were found in the quartz–scheelite stage. It was observed that the homogenization temperature gradually reduced from the early to the late mineralization stages; moreover, δ¹³C_PDB values for ore-bearing skarn in the mineralization period ranged from ? 5.7‰ to ? 6.9‰ and the corresponding δ¹⁸O_SMOW values ranged from 5.8‰ to 9.1‰, implying that the ore-forming fluid was mainly sourced from magmatic water with a minor amount of meteoric water. Collectively, the evidence indicates that the formation of the Nanyangtian deposit is related to Laojunshan granitic magmatism.     

In-situ LA-ICPMS trace elements and U–Pb analysis of titanite from the Mesozoic Ruanjiawan W–Cu–Mo skarn deposit,Daye district,China

In this paper, we present U–Pb ages and trace element compositions of titanite from the Ruanjiawan W–Cu–Mo skarn deposit in the Daye district, eastern China to constrain the magmatic and hydrothermal history in this deposit and provide a better understanding of the U–Pb geochronology and trace element geochemistry of titanite that have been subjected to post-crystallization hydrothermal alteration. Titanite from the mineralized skarn, the ore-related quartz diorite stock, and a diabase dike intruding this stock were analyzed using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). Titanite grains from the quartz diorite and diabase dike typically coexist with hydrothermal minerals such as epidote, sericite, chlorite, pyrite, and calcite, and display irregular or patchy zoning. These grains have low LREE/HREE and high Th/U and Lu/Hf ratios, coupled with negative Eu and positive Ce anomalies. The textural and compositional data indicate that titanite from the quartz diorite has been overprinted by hydrothermal fluids after being crystallized from magmas. Titanite grains from the mineralized skarn are texturally equilibrated with retrograde skarn minerals including actinolite, quartz, calcite, and epidote, demonstrating that these grains were formed directly from hydrothermal fluids responsible for the mineralization. Compared to the varieties from the quartz diorite stock and diabase dike, titanite grains from the mineralized skarn have much lower REE contents and LREE/HREE, Th/U, and Lu/Hf ratios. They have a weighted mean ²⁰⁶Pb/²³⁸U age of 142 ± 2 Ma (MSWD = 0.7, 2σ), in agreement with a zircon U–Pb age of 144 ± 1 Ma (MSWD = 0.3, 2σ) of the quartz diorite and thus interpreted as formation age of the Ruanjiawan W–Cu–Mo deposit. Titanite grains from the ore-related quartz diorite have a concordant U–Pb age of 132 ± 2 Ma (MSWD = 0.5, 2σ), which is 10–12 Ma younger than the zircon U–Pb age of the same sample and thus interpreted as the time of a hydrothermal overprint after their crystallization. This hydrothermal overprint was most likely related to the emplacement of the diabase dike that has a zircon U–Pb age of 133 ± 1 Ma and a titanite U–Pb age of 131 ± 2 Ma. The geochronological results thus reveal two hydrothermal events in the Ruanjiawan deposit: an early one forming the Wu–Cu–Mo ores related to the emplacement of the quartz diorite stock and a later one causing alteration of the quartz diorite and its titanite due to emplacement of diabase dike. It is suggested that titanite is much more susceptible to hydrothermal alteration than zircon. Results from this study also highlight the utilization of trace element compositions in discriminating titanite of magmatic and hydrothermal origins, facilitating a more reasonable interpretation of the titanite U–Pb ages.     

Metallogeny of the Shilu Fe–Co–Cu deposit,Hainan Island,South China: Constraints from fluid inclusions and stable isotopes

The Shilu deposit is a world-class Fe–Co–Cu orebody located in the Changjiang area of the western part of Hainan Island, South China. The distribution of Fe, Co, and Cu orebodies is controlled by strata of the No. 6 Formation in the Shilu Group and the Beiyi synclinorium. Based on a petrological study of the host rocks and their alteration assemblages, and textural and structural features of the ores, four mineralization stages have been identified: (1) the sedimentary ore-forming period; (2) the metamorphic ore-forming period; (3) the hydrothermal mineralization comprising the skarn and quartz–sulfide stage; and (4) the supergene period. The fluid inclusions in sedimentary quartz and/or chert indicate low temperatures (ca. 160 °C) and low salinities from 0.7 to 3.1 wt.% NaCl_eq, which corresponds to densities of 0.77 to 0.93 g/cm³. CO₂-bearing or carbonic inclusions have been interpreted to result from regional metamorphism. Homogenization temperatures of fluid inclusions for the skarn stage have a wide range from 148 °C to 497 °C and the salinities of the fluid inclusions range from 1.2 to 22.3 wt.% NaCl_eq, which corresponds to densities from 0.56 to 0.94 g/cm³. Fluid inclusions of the quartz–sulfide stage yield homogenization temperatures of 151–356 °C and salinities from 0.9 to 8.1 wt.% NaCl_eq, which equates to fluid densities from 0.63 to 0.96 g/cm³.Sulfur isotopic compositions indicate that sulfur of the sedimentary anhydrite and Co-bearing pyrite, and the quartz–sulfide stage, was derived from seawater sulfate and thermochemical sulfate reduction of dissolved anhydrite at temperatures of 200 °C and 300 °C, respectively. H and O isotopic compositions of the skarn and quartz–sulfide stage demonstrate that the ore-forming fluids were largely derived from magmatic water, with minor inputs from metamorphic or meteoric water. The Shilu iron ore deposit has an exhalative sedimentary origin, but has been overprinted by regional deformation and metamorphism. The Shilu Co–Cu deposit has a hydrothermal origin and is temporally and genetically associated with Indosinian granitoid rocks.     

Mineralization and fluid evolution of the Jiyuan polymetallic Cu–Ag–Pb–Zn–Au deposit,eastern Tianshan,NW China

The newly discovered Jiyuan Cu–Ag–(Pb–Zn–Au) deposit is located in the southern section of the eastern Tianshan orogenic belt, Xinjiang, northwestern China. It is the first documented deposit in the large Aqikekuduke Ag–Cu–Au belt in the eastern Tianshan orogen. Detailed field observations, parageneses, and fluid inclusion studies suggest an epithermal ore genesis for the main Cu–Ag mineralization, accompanied by a complicated hydrothermal alteration history most likely associated with the multi-stage tectonic evolution of the eastern Tianshan. The Jiyuan Cu–Ag ore bodies are located along the EW-striking, south-dipping Aqikekuduke fault and are hosted by Precambrian marble and intercalated siliceous rocks. Early-stage skarn alteration occurred along the contact zone between the marble layers and Early Carboniferous diorite–granodiorite and monzogranite intrusions; the skarns are characterized by diopside–tremolite–andradite–pyrite–(magnetite) assemblages. Local REE-enriched synchysite–rutile–arsenopyrite–(clinochlorite–microcline–albite) assemblages are related to K–Na alteration associated with the monzogranite intrusions and formed under conditions of high temperature (310°C) and high salinity (19.9 wt.% NaCl). Subsequent hydrothermal alteration produced a series of quartz and calcite veins that precipitated from medium- to low-temperature saline fluids. These include early ‘smoky’ quartz veins (190°C; 3.0 wt.% NaCl) that are commonly barren, coarse-grained Cu–Ag mineralized quartz veins (210°C; 2.4 wt.% NaCl), and late-stage unmineralized calcite veins (140°C; 1.1 wt.% NaCl). Tremolite and Ca-rich scapolite veins formed at an interval between early and mineralized quartz veins, indicating a high-temperature, high-salinity (>500°C; 9.5 wt.% NaCl) Ca alteration stage. Fluid mixing may have played an important role during Cu–Ag mineralization and an external low-temperature Ca-rich fluid is inferred to have evolved in the ore-forming system. The Jiyuan auriferous quartz veins possess fluid characteristics distinct from those of the Cu–Ag mineralized quartz veins. CO₂-rich fluid inclusions, fluid boiling, and mixing all demonstrate that these auriferous quartz veins acted as hosts for the orogenic-type gold mineralization, a common feature in the Tianshan orogenic belt.     

Genesis of the Fuxing porphyry Cu deposit in Eastern Tianshan,China: Evidence from fluid inclusions and C–H–O–S–Pb isotope systematics

The Fuxing porphyry Cu deposit is a recently discovered deposit in Eastern Tianshan, Xinjiang, northwestern China. The Cu mineralization is associated with the Fuxing plagiogranite porphyry and monzogranite, mainly presenting as various types of hydrothermal veins or veinlets in alerted wall rocks, with potassic, chlorite, phyllic, and propylitic alteration developed. The ore-forming process can be divided into four stages: stage I barren quartz veins, stage II quartz–chalcopyrite–pyrite veins, stage III quartz–polymetallic sulfide veins and stage IV quartz–calcite veins. Four types of fluid inclusions (FIs) can be distinguished in the Fuxing deposit, including hypersline (H-type), vapor-rich two-phase (V-type), liquid-rich two-phase (L-type), and trace amounts of pure vapor inclusions (P-type), but only the stage I quartz contains all types of FIs. The stages II and III quartz have two types of FIs, with exception of H- and P-types. In stage IV quartz minerals, only the L-type inclusions can be observed. The FIs in quartz of stages I, II, III and IV are mainly homogenized at temperatures of 357–518 °C, 255–393 °C, 234–322 °C and 145–240 °C, with salinities of 1.9–11.6 wt.% NaCl equiv., 1.6–9.6 wt.% NaCl equiv., 1.4–7.7 wt.% NaCl equiv. and 0.9–3.7 wt.% NaCl equiv., respectively. The ore-forming fluids of the Fuxing deposit are characterized by high temperature, moderate salinity and relatively oxidized condition. Carbon, hydrogen and oxygen isotopic compositions of quartz indicate that the ore-forming fluids were gradually evolved from magmatic to meteoric in origin. Sulfur and lead isotopes suggest that the ore-forming materials were derived from a deep-seated magma source. The Cu mineralization in the Fuxing deposit occurred at a depth of ~ 1 km, and the changes of oxygen fugacity, decompression boiling, and local mixing with meteoric water were most likely critical for the formation of the Fuxing Cu deposit.     

Geology,fluid inclusions,and geochemistry of the Zhazixi Sb–W deposit,Hunan, South China

The Zhazixi Sb–W deposit in the Xuefeng uplift, South China, exhibits a unique metal association of W and Sb, where the W orebodies are hosted by interlayer fractures and the Sb orebodies are contained within NW-trending faults. This study proposes that the W and Sb mineralization took place in two separate periods. The mineral paragenesis of the W mineralization reveals a mass of quartz, scheelite and minor calcite. The mineral assemblage of the Sb mineralization developed after W mineralization and consists of predominantly quartz and stibnite, and small amounts of native Sb, berthierite, chalcostibnite, pyrite, and chalcopyrite. Fluid inclusions in quartz and coexisting scheelite are dominated by two-phase, liquid-rich, aqueous inclusions at room temperature. Microthermometric studies suggest that ore-forming fluids for W mineralization are characterized by moderate temperatures (170–270 °C), low salinity (3–7 wt% NaCl equiv.), low density (0.75–0.95 g/cm³), and moderate to high pressure (57.2–99.7 MPa) and these fluids experienced a cooling and dilution evolution during W mineralization. Ore-forming fluids for Sb mineralization are epithermal types with low temperatures (150–230 °C), low salinity (4–6 wt% NaCl equiv.), moderate density (0.82–0.94 g/cm³), and high pressure (42.2–122.5 MPa) and these fluids display an evident decline in homogenization temperature during Sb mineralization. Laser Raman analyses of the vapor phase indicate that the ore-forming fluids for both W and Sb mineralization contain a small amount of CO₂.The ore-forming fluids for Sb mineralization are identified as predominantly originating from the continental crust, as suggested by the low ³He values (0.009 × 10⁻¹² cc.STP/g) and ³He/⁴He ratios (0.002–0.056 Ra) as well as high ³⁶Ar values (1.93 × 10⁻⁹ cc.STP/g) and ⁴⁰Ar/³⁶Ar ratios (909.5–2279.7). The source of S is identified to be the Neoproterozoic Wuqiangxi Formation, as traced by the δ³⁴S_V-CDT values of stibnite (3.1–9.4‰). The ²⁰⁸Pb/²⁰⁴Pb (37.643–40.222), ²⁰⁷Pb/²⁰⁴Pb (15.456–15.681), and ²⁰⁶Pb/²⁰⁴Pb (17.093–20.042) ratios suggest a mixture of lower crustal and supracrustal Pb sources.It is thus concluded that the ore genesis of the Zhazixi Sb–W deposit is related to the intracontinental orogeny during the early Mesozoic. Fluid mixing is considered to be the critical mechanism involved in W mineralization, whereas a fluid cooling process is responsible for Sb mineralization. Furthermore, the absence of Au is attributed to the low Σa_s content in Sb-mineralizing fluids.     

Some new data on the genesis of the Linghou Cu–Pb–Zn polymetallic deposit—Based on the study of fluid inclusions and C–H–O–S–Pb isotopes

The Linghou deposit, located near Hangzhou City of Zhejiang Province, eastern China, is a medium-sized polymetallic sulfide deposit associated with granitic intrusion. This deposit is structurally and lithologically controlled and commonly characterized by ore veins or irregular ore lenses. In this deposit, two mineralization events were identified, of which the former produced the Cu–Au–Ag orebodies, while the latter formed Pb–Zn–Cu orebodies. Silicification and calc-silicate (skarn type), phyllic, and carbonate alternation are four principal types of hydrothermal alteration. The early Cu–Au–Ag and late Pb–Zn–Cu mineralizations are characterized by quartz ± sericite + pyrite + chalcopyrite + bornite ± Au–Ag minerals ± magnetite ± molybdenite and calcite + dolomite + sphalerite + pyrite + chalcopyrite + galena, respectively. Calcite clusters and calcite ± quartz vein are formed during the late hydrothermal stage.The NaCl–H₂O–CO₂ system fluid, coexisting with NaCl–H₂O system fluid and showing the similar homogenization temperatures (385 °C and 356 °C, respectively) and different salinities (16.89–21.68 wt.% NaCl eqv. and 7.70–15.53 wt.% NaCl eqv.), suggests that fluid immiscibility occurred during the Cu–Au–Ag mineralization stage and might have given rise to the ore-metal precipitation. The ore-forming fluid of the Pb–Zn–Cu mineralization mainly belongs to the NaCl–H₂O–CO₂ system of high temperature (~ 401 °C) and mid-high salinity (10.79 wt.% NaCl eqv.).Fluids trapped in the quartz-chalcopyrite vein, Cu–Au–Ag ores, Pb–Zn–Cu ores and calcite clusters yielded δ¹⁸O_H2O and δD values varying from 5.54‰ to 13.11‰ and from − 71.8‰ to − 105.1‰, respectively, indicating that magmatic fluids may have played an important role in two mineralization events. The δ¹³C_PDB values of the calcite change from − 2.78‰ to − 4.63‰, indicating that the CO₃^2 − or CO₂ in the ore-forming fluid of the Pb–Zn–Cu mineralization was mainly sourced from the magmatic system, although dissolution of minor marine carbonate may have also occurred during the ore-forming processes. The sulfide minerals have homogeneous lead isotopic compositions with ²⁰⁶Pb/²⁰⁴Pb ranging from 17.958 to 18.587, ²⁰⁷Pb/²⁰⁴Pb ranging from 15.549 to 15.701, and ²⁰⁸Pb/²⁰⁴Pb ranging from 37.976 to 39.052, indicating that metallic elements of the Linghou deposit came from a mixed source involving mantle and crustal components.Based on geological evidence, fluid inclusions, and H–O–C–S–Pb isotopic data, the Linghou polymetallic deposit is interpreted as a high-temperature, skarn-carbonate replacement type. Two types of mineralization are both related to the magmatic–hydrothermal system, with the Cu–Au–Ag mineralization having a close relationship with granodiorite.     

In-situ LA–ICP–MS U–Pb geochronology and trace elements analysis of polygenetic titanite from the giant Beiya gold–polymetallic deposit in Yunnan Province,Southwest China

The Beiya gold–polymetallic deposit, located in the middle of the Jinshajiang–Ailaoshan alkaline porphyry metallogenic belt, is one of the largest gold deposits in China. The mineralization mainly occurs in skarn along the intrusive contacts between the alkaline porphyries and Middle Triassic limestone. In this paper, we present U–Pb age as well as major and trace element geochemistry of titanite from the Beiya deposit, and distinguish the titanite into a magmatic- and a hydrothermal suite. Our study indicates that the titanite from the ore-related porphyry and from the mineralized skarn is texturally and geochemically very different. The euhedral, envelope-shaped titanite from the ore-related porphyry has lower FeO, F, HFSEs, Nb/Ta and Lu/Hf, together with higher TiO₂ and Th/U than the subhedral titanite from the mineralized skarn. The titanite from the porphyry also displays higher LREE/HREE and more subtle negative Eu anomaly than its mineralized skarn counterpart. This suggests a magmatic- and a hydrothermal origin for, respectively, the titanite from the ore-related porphyry and from the mineralized skarn. In-situ magmatic titanite U–Pb dating has yielded an Eocene age of 36.0 ± 5.9 Ma, consistent with the porphyry zircon U–Pb age (36.07 ± 0.43 Ma) obtained in previous studies. Hydrothermal titanite has yielded a weighted average ²⁰⁶Pb/²³⁸U age of 33.1 ± 1.0 Ma (MSWD = 2.0), which represents the age of the retrograde skarn alteration and the maximum age for the gold mineralization. Together with the previous molybdenite Re–Os age, we have further constrained the Beiya gold–polymetallic metallogeny to 33.1–34.1 Ma. The mineralization age is slightly younger than the porphyry emplacement, indicating that the Beiya metallogeny was likely to be a post-magmatic hydrothermal product of the Himalayan orogenic event. The REE characteristics of hydrothermal titanite also reveal that the ore forming fluids may have been derived from a highly oxidized magma.     

The geological significance of Pb–Bi- and Pb–Sb-sulphosalts in the Damajianshan tungsten polymetallic deposit,Yunnan Province,China

The Sanjiang Tethyan domain in SE Asia is one of the most important mineral belts in China. Cu, Pb–Zn, Ag, Au and Sn are the most important resources in this domain, while the tungsten mineralization is poorly reported. In this study, we report on mineralogy in recent discovered Damajianshan (DMJS) tungsten (–Cu–As–Mo–Bi) polymetallic deposit in the southern part of Sanjiang Tethyan domain related to Triassic quartz porphyry. Studies have shown that besides common ore minerals, such as native bismuth, bismuthinite, ikunolite, some specific minerals of Pb–Bi- and Pb–Sb-sulphosalts (e.g. izoklakeite, bournonite, cosalite, and boulangerite) have also been found. Based on paragenetic mineral assemblages, fluid inclusions, and thermodynamic studies, the physicochemical conditions were evaluated for the entire metallogenic process. The sulfur fugacity (logf_S2) ranges from − 9.7 to − 37 with ore-forming temperatures between 190 °C and 330 °C, and the oxygen fugacity (logf_O2) ranges from − 37.5 to − 38.5 when the temperature is 250 °C. The sulfur fugacity and oxygen fugacity show strong fluctuations with broadly negative correlation, indicating that these variations in physicochemical conditions should be responsible for mineral assemblages, and are one of the most significant factors leading to the formation of the DMJS deposit. Our mineralogical studies provide new information for tungsten mineralization and further exploration of tungsten resources in the Sanjiang Tethyan mineralization domain.     

Hydrothermal evolution of the Sar-Cheshmeh porphyry Cu–Mo deposit,Iran: Evidence from fluid inclusions

The Sar-Cheshmeh porphyry Cu–Mo deposit is located in Southwestern Iran (∼65 km southwest of Kerman City) and is associated with a composite Miocene stock, ranging in composition from diorite through granodiorite to quartz-monzonite. Field observations and petrographic studies demonstrate that the emplacement of the Sar-Cheshmeh stock took place in several pulses, each with associated hydrothermal activity. Molybdenum was concentrated at a very early stage in the evolution of the hydrothermal system and copper was concentrated later. Four main vein Groups have been identified: (I) quartz+molybdenite+anhydrite±K-feldspar with minor pyrite, chalcopyrite and bornite; (II) quartz+chalcopyrite+pyrite±molybdenite±calcite; (III) quartz+pyrite+calcite±chalcopyrite±anhydrite (gypsum)±molybdenite; (IV) quartz±calcite±gypsum±pyrite±dolomite. Early hydrothermal alteration produced a potassic assemblage (orthoclase-biotite) in the central part of the stock, propylitic alteration occurred in the peripheral parts of the stock, contemporaneously with potassic alteration, and phyllic alteration occurred later, overprinting earlier alteration. The early hydrothermal fluids are represented by high temperature (350–520 °C), high salinity (up to 61 wt% NaCl equivalent) liquid-rich fluid inclusions, and high temperature (340–570 °C), low-salinity, vapor-rich inclusions. These fluids are interpreted to represent an orthomagmatic fluid, which cooled episodically; the brines are interpreted to have caused potassic alteration and deposition of Group I and II quartz veins containing molybdenite and chalcopyrite. Propylitic alteration is attributed to a liquid-rich, lower temperature (220–310 °C), Ca-rich, evolved meteoric fluid. Influx of meteoric water into the central part of the system and mixing with magmatic fluid produced albitization at depth and shallow phyllic alteration. This influx also caused the dissolution of early-formed copper sulphides and the remobilization of Cu into the sericitic zone, the main zone of the copper deposition in Sar-Cheshmeh, where it was redeposited in response to a decrease in temperature.     

Research on the growth orientation of pyrite grains in the colloform textures in Baiyunpu Pb–Zn polymetallic deposit,Hunan, China

Mineralogy and Petrology - A large number of colloform-textured pyrites were found in Baiyunpu Pb–Zn ore bodies in Xinshao County, Hunan, China. This study investigates the growth orientation...     

Insights into ore genesis of the Jinding Zn–Pb deposit,Yunnan Province,China: Evidence from Zn and in-situ S isotopes

The Jinding Zn–Pb deposit located in the Mesozoic-Cenozoic Lanping Basin of southwest China has ore reserves of ∼ 220 Mt with an average grade of 6.1% Zn and 1.3% Pb. The mineralization is hosted by sandstone in the Early Cretaceous Jingxing Formation and limestone breccia in the Paleocene Yunlong Formation. Mineralization in both types of host rocks is characterized by a paragenetic sequence beginning with marcasite–sphalerite (Stage 1) followed by pyrite–marcasite–sphalerite–galena (Stage 2), and then galena–sphalerite–pyrite–sulfate–carbonate (Stage 3). Pyrite from these stages have different δ³³S compositions with pyrite from Stage 1 averaging − 9.6‰, Stage 2 averaging − 8.9‰, and Stage 3 averaging + 0.3‰. Sphalerite hosted by the sandstone has similar δ⁶⁶Zn values ranging from 0.10 to 0.30‰ in all stages of the mineralization, but sphalerite samples from the limestone breccia-hosted ore show variable δ⁶⁶Zn values between − 0.03 and 0.20‰. Our data on sphalerite precipitated during the earlier stages of mineralization has a constant δ⁶⁶Zn value and cogenetic pyrite displays a very light sulfur isotope signature, which we believe to reflect a sulfur source that formed during bacterial sulfate reduction (BSR). The Stage 3 sphalerite and pyrite precipitated from a late influx of metal-rich basinal brine, which had a relatively constant variable δ⁶⁶Zn isotopic composition due to open system isotope fractionation, and a near zero δ³³S composition due to the influence of abiotic thermochemical sulfate reduction from observed sulfates in the host rock.     

K–Ar ages of plutonism and mineralization at the Shizhuyuan W–Sn–Bi–Mo deposit,Hunan Province,China

The Qianlishan granite complex, situated 16 km southeast of Chenzhou City, Hunan Province, China, hosts the Shizhuyuan W–Sn–Bi–Mo deposit. This complex, which intruded the Protozoic metasedimentary rocks and the Devonian clastic sedimentary and carbonate rocks, consists of mainly medium- to coarse-grained biotite granites and minor amounts of fine-grained biotite granite in addition to granite and quartz porphyry. K–Ar ages suggest three episodes of plutonism: the medium- to coarse-grained biotite granite (before 152 Ma), the fine-grained biotite granite (137 Ma), and the granite porphyry (129–131 Ma). Muscovite ages of the greisen are 145–148 Ma, suggesting that the W–Sn–Bi–Mo mineralization was related to the main, medium- to coarse-grained biotite granites. The K–Ar age of the hydrothermal vein mineralization is 92 Ma and is probably related to the porphyries.     

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

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

Ore-forming material sources of the Jurassic Cu–Pb–Zn mineralization in the Qin–Hang ore belt,South China: Constraints from S–Pb isotopes

The Qin–Hang ore belt in South China, which serves as the boundary between the Yangtze and Cathaysia blocks, is marked by extensive Jurassic porphyry-skarn-metasomatic Cu–Pb–Zn polymetallic mineralization. In this contribution, S and Pb isotopic compositions of the Baoshan Cu–Pb–Zn deposit in the western portion of the Qin–Hang ore belt were analyzed to determine the ore-forming material sources in the area. This is coupled by the first systematic collection, compilation and interpretation of previously published S and Pb isotopic data of multiple sulfide minerals to reveal the metal origin and accumulation mechanism of the Cu–Pb–Zn mineralization from the significant deposits in the region (i.e., Dexing, Qibaoshan, Shuikoushan, Baoshan, Huangshaping, Tongshanling and Dabaoshan). The results show that Cu mineralization is characterized by low and narrow δ³⁴S (‰) range of values (–5 to 6) and Pb isotopic ratios (²⁰⁸Pb/²⁰⁴Pb = 38.0–39.0, ²⁰⁷Pb/²⁰⁴Pb = 15.4–15.8, and ²⁰⁶Pb/²⁰⁴Pb = 17.7–18.7), which are consistent with those of local porphyries. In contrast, the Pb–Zn mineralization reveals higher and more variable δ³⁴S (‰) values (–4 to 18) and Pb isotopic ratios (²⁰⁸Pb/²⁰⁴Pb = 38.0–39.5, ²⁰⁷Pb/²⁰⁴Pb = 15.3–16.0, and ²⁰⁶Pb/²⁰⁴Pb = 18.0–19.0) that correspond to wall-rock and basement rock compositions in the region. This indicates that the sulfur and lead that formed the Cu mineralization in the Qin–Hang ore belt was mainly sourced from regional magmatism with mantle contributions, whereas the sulfur and lead for the Pb–Zn mineralization was likely derived from the host sedimentary rocks and Proterozoic metamorphic basement rocks, respectively. The S and Pb isotopic data, combined with the geochemical signatures of mineralization-related porphyries, suggest that the Cu was sourced from the deeper levels along with mantle-derived magmas. In contrast, the Pb–Zn probably originated from the crust, with partial melting of the crystalline basement in the Cathaysia Block. Consequently, a three-stage genetic model is proposed to explain the ore-forming processes of the Qin–Hang Cu-polymetallic belt in South China.     

Genesis of the Angeer Yinwula Pb–Zn deposit,Inner Mongolia,China: constraints from fluid inclusions,C–H–O–S–Pb isotope systematics,and zircon U–Pb geochronology

Arabian Journal of Geosciences - Soil toxic metal pollution is one of the most prominent environmental problems in the rapid industrialization of societies because of the considerable harm caused...     

Geochemistry of major and trace elements and Pb–Sr isotopes of a weathering profile developed on the Lower Cambrian black shales in central Hunan,China

This paper reports a geochemical study on the major and trace elements and Pb–Sr isotopes of a weathering profile developed in the Lower Cambrian black shales in central Hunan (China). Six weathering horizons were identified and sampled vertically throughout the profile. The chemical composition of the profile consists of variable concentrations of the major elements Fe₂O₃, FeO, MnO, MgO, CaO, Na₂O, and P₂O₅ and of less variable concentrations of SiO₂, TiO₂, Al₂O₃, and K₂O. The chemical change caused by weathering is estimated by mass-balance calculations, and the results show that the element mobility is characterised by substantial loss of SiO₂, FeO, CaO, K₂O, Na₂O, LOI, Cr, V, Ba, Cs, Rb, Sr, U, and Th, and moderate loss of Al₂O₃, MgO, Fe₂O₃, Ni, Cu, Pb, Tl, Sn, Sc, Ge and REE (Y). The high field strength elements TiO₂, Sn, Sc, U, Ga, Ge, Zr, Hf, Nb, and Ta were immobile during weathering. The chemical changes and the Pb–Sr isotopic data suggest that four types of chemical reactions occurred: the oxidation of sulphide minerals (e.g., pyrite) and organic carbon (OS), the dissolution of less resistant clinochlore-Ia, calcite, and P-bearing minerals (DL), the dissolution of detrital albite and microcline (DA), and the transformation of clay (TC) minerals (e.g., muscovite and illite–smectite). These chemical reactions then led to two stages of geochemical processes, an early stage of chemical differentiation and a later stage of chemical homogenisation. The chemical differentiation dominated by the OS, DL, and DA reactions, led to the leaching of mobile elements (e.g., MgO, Na₂O, K₂O, P₂O₅, Sr, and REE) and the redistribution of some less mobile elements (e.g., SiO₂ and Al₂O₃). In contrast, the chemical homogenisation, which was caused by TC reactions, led to the leaching of both mobile and less mobile elements from the system and ultimately transformed the weathered black shales into soil. Soils derived from black shales in South China might result from the above two geochemical processes.