Magmatic-hydrothermal Processes Research Articles

Fluid inclusion LA-ICP-MS constraint on hydrothermal evolution of proximal cassiterite-bearing quartz veins in the giant Gejiu orefield: Implications for controls on metallogenic potential of granite-related skarn system

Sn and Cu are proposed to have their mineralization potential predetermined by their contents in initial fluids of granite-related magmatic-hydrothermal systems. However, it remains ambiguous whether the giant Sn-mineralized skarn system is applicable, and whether the Sn-Cu association in some deposits is predominantly determined by their initial metal contents. The Gejiu orefield is one of the most essential Sn-polymetallic districts worldwide, with proven resources of 3.27 million tons of tin, 3.25 million tons of copper, 4.29 million tons of lead and zinc, and >20 other metals with economic significance. Sn-polymetallic mineralization at Gejiu constitutes a composite skarn ore system that includes proximal skarn and related cassiterite-sulfide, greisen, and tourmaline-vein types. The Laochang Sn-polymetallic deposit hosts several largest skarn and cassiterite-sulfide orebodies in the eastern part of Gejiu. Recent exploitation at Laochang discovered Sn-mineralized quartz veins hosted in the concealed granite, providing a valuable opportunity to characterize the proximal magmatic-hydrothermal process of the mineralizing granitic system. Here, fluid inclusion analysis is carried out on these veins to discuss the fluid evolution, cassiterite precipitation mechanism and whether metal content in early proximal magmatic fluids determines the metal association and endowment in the deposit.Based on the paragenesis of ore and gangue minerals, three hydrothermal stages are distinguished, including quartz-tourmaline stage (Stage I), cassiterite-arsenopyrite-quartz stage (Stage II) and late sulfide stage (Stage III). Fluid evolution controlling vein formation is constrained by microthermometry and LA-ICP-MS analysis of four fluid inclusions generations successively entrapped in quartz and cassiterite. The fluids involved during vein formation show an interplay between single-sourced magmatic fluids and meteoric water. The intermediate-density single phase fluid recorded at stage I quartz is derived from initial fluids directly exsolving from granitic magma. At stage II, fluid immiscibility occurred and the separated brines were entrapped in quartz and early-formed cassiterite. Along with cassiterite precipitation, brines were mixed with low-salinity and cooler meteoric water, leading to entrapment of low-salinity aqueous fluid in outer growth zones of cassiterite at stage II. The constructed fluid evolution history suggests that fluid immiscibility may have facilitated the nucleation of cassiterite crystals at the onset of deposition while mixing of magmatic fluid with meteoric water likely dominate later cassiterite mineralization.Compared with the fluid dataset of barren and mineralized granitic systems worldwide, pre-ore fluids of the studied quartz veins are enriched in Sn, confirming that high Sn content in the initial magmatic fluid can serve as indicator to distinguish mineralized system. In contrast, although Cu mineralization is economically important in the Laochang deposit, predicted Cu contents in pre-ore proximal magmatic fluids are as low as those obtained from Cu-barren system. This implies introduction of Cu into the hydrothermal system from other sources.

Genesis of the Ulaan silver-lead–zinc deposit in Northeast Mongolia: Constraints from S and Pb isotopes, together with U-Pb and Rb-Sr geochronology

The Ulaan silver-lead–zinc deposit (hereinafter referred to as the Ulaan deposit) is identified as the largest silver-lead–zinc polymetallic deposit in Mongolia, with proved reserves including 2,240 tons of silver (Ag; average grade: 49 g/t), 440,000 tons of lead (Pb; average grade: 1.13 %), and 810,000 tons of zinc (Zn; average grade: 2.07 %). However, the genesis of this deposit remains unclear. The Ag-Pb-Zn ore bodies in the deposit, occurring as cylinders in shape within the Middle-Late Jurassic rhyolites, are governed by a concealed breccia pipe. The ore minerals include galena, sphalerite, and pyrite, followed by chalcopyrite, hematite, stibnite, and siderite. The primary alterations of the surrounding rocks include silicification, chloritization, kaolinization, argillization, carbonatization, and skarnization. The Rb-Sr dating of sulfide minerals and associated vein minerals in the ores yielded isochron ages varying in a range of 146 ± 3 Ma (n = 6, MSWD=1.3), suggesting mineralization during the Late Jurassic. The δ34S values of sulfide minerals in the ores range from 1.6 ‰ to 4.3 ‰, suggesting that the sulfur originated primarily from magmas or deep sources. The isotopic compositions of coexisting sphalerite-galena minerals in the deposit revealed mineralization temperature estimates ranging between 331 °C and 449 °C, indicating a medium- to high-temperature ore-forming conditions. The sulfide minerals exhibit 208Pb/204Pb ratios ranging from 38.138 to 38.301, 207Pb/204Pb ratios from 15.543 to 15.594, and 206Pb/204Pb ratios from 18.318 to 18.354, suggesting that ore-forming metals, represented by Pb, also originated primarily from mantle source. The zircon U-Pb dating of rhyolites in the ore-hosting strata and ore-controlling breccia pipes yielded ages of 160.6 ± 1.7 Ma (n = 24, MSWD=0.68) and 161.6 ± 1.6 Ma (n = 30, MSWD=0.89), respectively, indicating volcanic eruptions during the early Late Jurassic. These ore-hosting rhyolites exhibit characteristics of A-type rhyolites, suggesting that they were formed in an intracontinental extensional environment. These rhyolites share similar rare earth element (REE) distribution patterns with fluorite formed in the main mineralization stage, suggesting a genetic link between the mineralization and magmatic processes. This study proposes that the Ulaan deposit was a hydrothermal deposit formed in an extensional environment following the closure of the Mongol-Okhotsk Ocean, with ore-forming metals and hydrothermal fluids associated with volcanic rocks or magmatic-hydrothermal processes.

Genesis studies of Li–Rb deposits in pegmatites from Bailongshan, western China: Evidence from chronology, fluid inclusions, and H–O isotope analysis

The Bailongshan Pegmatite deposit, located in the West Kunlun Orogenic Belt, Northwest China, is a newly discovered, super-large Li–Rb (Be–Ta–Nb) rare-metal deposit. Since complex magmatic-hydrothermal processes are responsible for the mineralization of such rare-element pegmatites, it is desirable to study the evolution and sources of ore-forming fluids to analyze the genesis of ore deposits. In this study, the 40Ar/39Ar plateau ages of muscovite and biotite were determined to be 171.36 ± 1.87 and 172.39 ± 1.66 Ma, respectively, indicating that the duration of hydrothermal mineralization was approximately 170 Ma. Based on the zonal nature of the mineral assemblage, the Bailongshan area was divided into four zones and stages (I–IV), namely the albite–quartz–lithium tourmaline (AQT, stage I), albite–quartz-bearing mica (AQM, stage II), albite–quartz–spodumene (AQS, stage Ⅲ), and spodumene–quartz (SQ, stage IV) zones. Among these, AQS and SQ were the main ore-bearing areas. In terms of the fluid inclusions found in quartz and spodumene, the different types include a gas-rich phase (V-type), a liquid-rich phase (L-type), a daughter mineral-bearing three-phase (S-type), and a carbon dioxide-bearing phase (C-type). In stage I, the homogeneous temperatures of the V- and S-type fluid inclusions varied from 365 to 415 °C, while their corresponding salinities were 8.5–12.9 and 44.8–47.2 wt% NaCl equiv., respectively. In stage II, the homogeneous temperature and salinity of the L-type inclusions were 315–365 °C and 9.9–13.3 wt% NaCl equiv., respectively, while in stages Ⅲ and IV, the homogeneous temperatures of the L- and S-type fluid inclusions were between 235 and 335 °C, while their salinities were 7.2–12.3 and 32.1–37.0 wt% NaCl equiv., respectively. Furthermore, for the C-type inclusions, the homogeneous temperature and salinity were 235–320 °C and 4.9–10.6 wt% NaCl equiv., respectively. The laser Raman results showed that the fluid in the metallogenic stage was an H2O–NaCl–CO2–CH4 system. Based on the homogeneous temperature and salinity results, the fluid capture pressure from stage III to stage IV was calculated to be 280–150 MPa, and the depth of the capture was >6 km. Moreover, the H–O isotope results suggested that the early ore-forming fluids are mainly magmatic hydrothermal fluids, whereas the later (stage IV) mineralizing fluids may be mixed with a small amount of meteoric water. The subsequent immiscibility of the fluid may be one of the factors responsible for the discharge and precipitation of minerals.

Geochronology and decoupling controls of Sn-(Ta-Li) and W-(Sn) mineralization in the Iberian Variscan Massif, Spain and Portugal

Sn-W mineralization in the Iberian Variscan Massif (corresponding with the western zone of the Iberian Peninsula, in Spain and Portugal) occurs closely related to metaluminous to peraluminous granitoids of Variscan age. The deposits are grouped into two main styles of mineralization; Sn-(Ta-Li) and W-(Sn) deposits. Within this work we present a first attempt to correlate timing of W-Sn mineralization and plutonic events at a regional scale. We report new 40Ar/39Ar dates of muscovite related to the quartz-muscovite alteration of eleven deposits, molybdenite Re-Os dates from six deposits and two new zircon U-Pb dates of granitoids genetically related to the mineralization. The dates obtained support the relationship between W-Sn mineralization with specific, but not uniquely just one, granite suites. The dominant S-type peraluminous Variscan granitic suites in Iberia, the S1-type dated at ca. 330–311 Ma and the S2-type at ca. 314–296 Ma, are related to both, Sn-(Ta-Li) and W-(Sn) mineralization. A subgroup of deposits of the W-(Sn) group, generally enriched only in W but not in Sn is associated with the youngest but volumetrically less abundant I-type (ca. 303–280 Ma) metaluminous magmatism. The relationship of both the Sn-rich and W-(Sn)-rich deposits with the highly peraluminous S-type granites suggest that the ultimate source of the melts is not related to the decoupling between Sn and W. Therefore, the causes of W and Sn separation may be related to late-stage magmatic and magmatic-hydrothermal processes.

In situ Cu isotopes reveal the mechanism of Sn-Cu mineralization: A case study from the Jinkeng deposit, South China

This study presents high-resolution in situ Cu isotope data for chalcopyrite from the Jinkeng Sn-Cu deposit, Guangdong Province, China, with the aim of understanding how the Sn-Cu mineralization was formed. Results show that early chalcopyrite (quartz-cassiterite stage) has the lowest δ65Cu values (–0.01 to +0.02 ‰), similar to δ65Cu values (∼0‰) in most granites. In contrast, chalcopyrite from the subsequent cassiterite-sulfide stage exhibits the highest δ65Cu values (+0.90 to +0.97 ‰), comparable to those of the volcanic country rocks (+0.87 to +1.00 ‰). δ65Cu values in late chalcopyrite gradually decrease (from +0.79 to +0.45 ‰) across the latest ore-forming stages, from quartz-sulfide to quartz-calcite-sulfide mineral assemblages. Observed variation in δ65Cu is explained by water–rock interaction. Quantitative geochemical modeling also demonstrates that the Cu isotopic compositions of chalcopyrite record variable degrees of water/rock ratios during water–rock interactions. Therefore, our results suggest that water–rock interaction plays a critical role in providing Cu for Sn-Cu ore systems. The study further indicates that in situ Cu isotope analysis provides an accurate and efficient tool for diagnosis of magmatic-hydrothermal processes.

Apatite and pyroxene as records of magmatic–hydrothermal processes and platinum-group mineral (PGM) formation in the Wengeqi mafic–ultramafic intrusion, Inner Mongolia, China: The role of oxidized, H2O-rich magmas

The Devonian Wengeqi mafic–ultramafic intrusion, situated on the northern margin of the North China Craton (NCC) — an Andean-style convergent margin during the Paleozoic — hosts many platinum-group minerals (PGMs), especially within the S-deficient, magnetite-rich clinopyroxenite zones. These PGMs occur in two distinct associations: Pt-rich PGMs (e.g., sperrylite) closely associated with primary magnetite and Pd-rich PGMs (e.g., sudburyite, kotuskite, arsenopalladinite) associated with secondary minerals (e.g., actinolite, pyrite). The mechanisms underlying the formation of PGMs in S-deficient rocks and the spatial decoupling of various PGM types remain elusive. The relationship of PGM formation and characteristics of magmas at convergent margins is also not well understood. In this contribution, we utilized apatite and clinopyroxene textures and chemistry alongside whole-rock SrNd isotopes to characterize i) the nature of the parental magma from which the Wengeqi intrusion crystallized, and ii) the magmatic–hydrothermal processes that operated to generate the Pt- and Pd-rich PGM. Based on the composition of clinopyroxene and clinopyroxene–melt partition coefficients, the parental magma of the Wengeqi intrusion is estimated to have an arc-like affinity on a primitive mantle-normalized trace-element diagram. This, together with the EMI-like SrNd isotope signature, implies that the Wengeqi magma was sourced from metasomatized SCLM beneath the NCC with an EMI-like composition. Three types of apatite (Ap1, Ap2, and Ap3) were identified within the intrusion. Ap1 and Ap2 are magmatic in origin, and appear as isolated grains, whereas Ap3 occurs as stringers or heterogeneous domains within Ap1 and Ap2, and likely resulted from hydrothermal modification of magmatic apatite. Notably, the abundant Ap2 exhibits higher VS contents and Eu/Eu* ratios than the less common Ap1, and contains S predominantly in the form of S6+, suggesting that the Wengeqi magma was relatively oxidized, with fO2 > FMQ + 1.2. Based on the chemistry of magmatic apatite, the Wengeqi magma had ∼5 wt% H2O, which, together with its high fO2, facilitated crystallization of magnetite, causing reduction of the magma by removal of Fe3+. This reduction process promoted PGM nucleation by decreasing PGE solubility in the magma, leading to the association of PGM with magnetite. Additionally, the oxidized, H2O-rich magma likely released oxidizing fluids, selectively mobilizing Pd rather than Pt, separating Pt-rich PGMs from Pd-rich PGMs. The budget of PGE in the parental magma could have been increased by i) metasomatism of the SCLM source (e.g., by carbonatitic fluids), which would have elevated the concentration of PGE in the mantle source, and ii) the high fO2 and H2O levels of the magma, which would have delayed sulfide saturation. Accordingly, mantle metasomatism and high fO2–H2O are deemed favorable for enrichment of PGE in magmas within convergent margins.

Understanding the extreme differentiation of granitic magmas through elemental geochemistry and Fe isotope signatures

The petrogenesis of extremely fractionated igneous rocks is closely linked to the evolution of the continental crust and the formation of rare metal mineralization. Extremely fractionated magmas evolve via fractional crystallization, hydrothermal evolution, and volatile-rich fluid–melt interaction, but the specific effects of these magmatic and magmatic–hydrothermal processes remain unclear. To understand the mechanisms by which extremely fractionated granitic magmas evolve, we characterized the geochemical and Fe isotope signatures of a suite of granites and pegmatites from the Baishitouquan (BST) granitic pluton in northwest China. The BST granitic system evolved from a high SiO2 and volatile-poor system to a low SiO2 and volatile-rich system as it transitioned from an evolutionary stage dominated by magmatic processes to one dominated by magmatic–hydrothermal processes. This transition is supported by changes in the degree of melt polymerization (NBO/T) and other geochemical indicators of fluid activity (e.g., TE1,3 (REE tetrad effect), Zr/Hf, Nb/Ta, and F/Cl ratios), suggesting that extremely fractionated granites form as a result of a combination of fractional crystallization and volatile-rich fluid–melt interactions. The bulk-rock samples of the BST pluton exhibit significant Fe isotope variability, with δ56Fe values ranging from 0.40 ± 0.02‰ in the least evolved leucogranite (Zone-a) to 0.65 ± 0.02‰ in the most evolved topaz albite granite (Zone-e). Notably, the increase in bulk-rock δ56Fe values during magma evolution is accompanied by a decrease in SiO2 contents, which is opposite to the general trend during granitic magma evolution. Given the correlations between δ56Fe values and indicators of magmatic differentiation (e.g., Fe2O3T, Rb, (Na + K)/(Mg + Ca), and (La/Lu)N), the variability in bulk-rock Fe isotope composition of granites is likely due to changes in magma composition, with garnet removal being the most likely mechanism fractionating Fe isotopes. Rhyolite-MELTS modeling, coupled with geochemical and petrographic characterization, indicate that the high concentrations of F and H2O in felsic magmas likely play critical roles in structurally modifying granitic melts by dramatically reducing their viscosity and enhancing fluid flow. The distinct geochemical–isotopic features of granites can, therefore, be used as tracers for identifying magmatic–hydrothermal processes and, potentially, rare metal mineralization.

Experimental evidence reveals the mobilization and mineralization processes of rare earth elements in carbonatites.

Whereas the genesis of carbonatitic rare earth element (REE) deposits has long been a focus of study, the controls on mobilization and mineralization of REEs during magmatic-hydrothermal processes still remain open to debate. Here, we present our investigation of the dissolution and crystallization of REE (fluor)carbonate minerals in alkaline carbonate brine-melts up to 850°C and 11.6 kbar. Our results show that REEs are soluble in Na2CO3 brine-melts, achieving concentrations exceeding 8 weight % at temperatures above 650°C. The addition of calcium and/or fluoride has minimal impact on REE mobilization, whereas introduction of silica suppresses REE solubilities by half, due to britholite formation above 550°C. Upon cooling, sodium and REEs combine to crystallize in burbankite or carbocernaite in sodium-enriched brine-melts, even at fluoride saturation. However, while the brine-melts contain substantial ferro- or aluminosilicate, REE mineralization in fluorcarbonates occurs after sufficient sodium precipitation in alkaline silicate minerals, hence revealing how silicate and sodium carbonate govern REE mineralization.

Tracking the porphyry-epithermal mineralization transition using U-Pb carbonate dating

Key metals important for the green energy transition concentrate during magmatic-hydrothermal processes. In porphyry deposits, epithermal mineralization can overprint earlier higher-temperature systems. It is not well understood whether mineralization occurs in a single evolving system or forms during pulsed, episodic overprinting events. The timing and duration of fluid flow therefore remain key data gaps in deposit models, but they are essential factors for understanding metal (re)mobilization and concentration processes. Carbonates are common gangue minerals that precipitate during fluid flow and can be dated using the U-Pb method, thereby directly dating hydrothermal processes. Here, 41 new U-Pb dates from a fault-controlled porphyry-epithermal system in Yukon, Canada, reveal a >50 m.y. record of carbonate precipitation between ca. 77 and 19 Ma. Results support a model of pulsed, episodic fluid flow, rather than a single evolving system, where epithermal carbonate precipitation at ca. 74−67 Ma was both coeval with and significantly postdated Cretaceous porphyry-related magmatism. Overprinting events at ca. 62−56 Ma, ca. 51−47 Ma, and younger than 40 Ma were not responsible for primary metal deposition but may have contributed to metal enrichment. Carbonate dates coincide with periods of brecciation and fault slip. Fault movement therefore enabled episodic overprinting by epithermal mineralization, mobilizing and (re)concentrating metals. This comprehensive reconstruction of a long-lived magmatic-hydrothermal system tracks the transition from porphyry to epithermal environments, demonstrating the power of carbonate U-Pb dating for critical minerals research.

Sulfur isotopic variations in the products of the 1895 CE eruption at Zao volcano (NE Japan): Implications for connecting eruption source and syn-eruptive magmatic-hydrothermal processes

Sulfur isotopic ratio in sulfate and sulfide in subvolcanic hydrothermal systems is a valuable tracer to study the magmatic-hydrothermal processes from the magma source through to volcanic eruptions. Zao volcano is among the most active volcanoes in NE Japan, with historical explosive eruptions occurring during the last thousand years and unrest episodes since 2013. This necessitates a detailed assessment of the potential risk of future volcanic hazards. We investigated the magmatic-hydrothermal processes that occurred during the 1895 CE eruption sequence at Zao volcano by conducting mineralogical and sulfur isotope analyses in the exposed well: (i) six volcanic units (Layers 1–6) of the 1895 CE eruption products (clayish ash deposits with andesitic bombs, lapilli of scoria, and minor altered lithic fragments) deposited on the rim of Okama crater lake; and (ii) clay-altered and silicified rocks from the Nigorikawa alteration zone (NGA) surrounding the Goshikidake cone. Mineralogical data show that the samples mainly consist of alunite, pyrite, and gypsum. Alunite and pyrite occur as fine crystal mixtures associated with mineral assemblages of both advanced argillic alteration (i.e., those of cristobalite and kaolinite) and silicification (i.e., those of cristobalite, tridymite and native sulfur). Gypsum typically appears as isolated euhedral crystals of several millimeters in size. Samples of the 1895 CE eruption products have a narrow range of δ34S values from +3 ‰ to +5 ‰ for gypsum, from +9 ‰ to +13 ‰ for alunite, and approximately −10 ‰ for pyrite. For the NGA samples, the δ34Sgypsum, δ34Snative sulfur, and δ34Spyrite values range from −12 ‰ to −9 ‰, whereas for alunite, these range from +8 ‰ to +18 ‰. This indicates that alunite and pyrite in the 1895 CE eruption products were derived from the advanced argillic alteration and silicification zones that developed under Okama crater, which is exposed as the NGA. Estimated alteration temperatures based on the sulfur isotopic equilibrium between alunite and pyrite pairs are 200 °C–300 °C. By contrast, δ34Sgypsum values in the 1895 CE products are significantly higher than those in the NGA (which are derived from oxidation of pyrite or H2S, or both), ranging between an estimated parental fluid of δ34Sbulk-initial = ca. +1 ‰ and the Quaternary volcanic rocks of the Japan arc. This suggests that gypsum in the 1895 CE eruption products derived from magmatic vapor condensate (anhydrite) formed in the volcanic conduit during the eruption, thus becoming replacement of anhydrite by gypsum after or during the tephra deposition on the Zao summit surface. Our results on sulfur-bearing minerals provide new clues for better understanding (and monitoring) the syn-eruptive processes of volcanic eruptions focused on subvolcanic hydrothermal systems.

W-rich zircons from the granite in the Hukeng tungsten deposit, South China: Genesis and exploration significance

South China is endowed with copious hydrothermal tungsten ore deposits, which are generally suggested to be associated with highly fractionated granites. However, the mechanism of tungsten enrichment and mineralization during magmatic-hydrothermal processes is not clear. Here, we clearly identified W-rich zircons (up to several thousand ppm) from the granite in the Hukeng tungsten deposit in South China. W-rich zircons are generally dark in cathodoluminescence images with irregular cracks, cavities and blurry oscillatory zones. They also show high contents of U, Nb, REEs, and high W/Gd ratios, which are not possible to be produced only by magma differentiation. Raman spectra of zircons indicate that these W-rich zircons have experienced different degrees of metamictization. Thus, these W-rich zircons should be crystallized from the late magma and subsequently altered by W-rich magmatic-hydrothermal fluids. W-rich zircons record the activity of W-rich ore-forming fluids which were exsolved from the granitic magma. We suggested that the W/Gd ratios of > 0.2 of zircons can be used as an indicator to estimate the W mineralization potential of a granite. This study provides a new pathway for using zircon to record tungsten mineralization processes and to guide tungsten ore prospecting.

The correlation between Rare Earth Elements and tin in granite, quartz vein, and weathered granite samples, in South Bangka, Bangka Belitung Islands, Indonesia

The presence of Rare Earth Elements (REEs) is often correlated with tin (Sn), particularly at placer deposits in the Bangka Belitung Islands. However, there is limited information on the correlation between Sn and REEs. Therefore, this study aimed to investigate the correlation between REEs and Sn using data analysis of Sn-W, REEs, Y, Th, and U in granite, quartz veins, and weathered granite samples from South Bangka. The statistical analysis carried out using the Pearson correlation coefficient and multivariate processing showed that Sn-REEs have a weakly negative correlation. The examination of genetic aspects through chemical analysis, mineralogy, and Scanning Electron Microscope (SEM) data, showed that Sn and REE originated from the same magmatic fluids but different depositional phases due to magmatic-hydrothermal processes. The results show that REEs were formed during the early magmatic crystallization as mineral and stannite (Cu-Sn) in granite, while Sn was enriched as cassiterite in the deposition of late-stage hydrothermal fluid in parental granite. Moreover, the variation in deposition stage and temperature during the formation process is depicted in statistically uncorrelated values for Sn and REEs.

Enrichment mechanisms of Nb, Zr, and REY in the Late Permian coal-bearing strata in western Guizhou, SW China

Niobium, Zr, REE, and Y are widely enriched in the Upper Permian coal-bearing strata in southwestern China and are regarded as a substantial resource. To better understand the occurrence modes and enrichment mechanisms of these rare metals, comprehensive heavy-mineral separation, Micro-Raman spectroscopy, EPMA, and LA-ICP-MS analyses of primary and secondary metal minerals were conducted in the polymetallic beds in western Guizhou. In addition, the XRD, XRF, and ICP-MS analyses of bulk rocks were carried out. Our results suggest that Nb is primarily hosted in secondary TiO2 polymorphs which converted from primary Nb-rich rutile, and occurs as minor ilmenorutile and columbite-(Fe). The Zr is sequestered in both detrital zircon and secondary microcrystalline zircon. REE and Y (REY) are mainly incorporated into secondary florencite-(Ce), rhabdophane-(Ce), churchite-(Y), and zircon, also partially adsorbed by clay minerals. The assemblage of detrital zircon, Nb-rich rutile, and discrete Nb minerals reveals that rare metals are preconcentrated during the waning-stage Emeishan alkaline magmatisms. Complex zonings in rutile crystals may result from the diffusion of Nb5+ and Fe2+, and these grains are further overprinted by magmatic-hydrothermal and enveloped by ilmenorutile and columbite-(Fe). Furthermore, magmatic rutile is commonly converted into anatase, brookite, and leucoxene under supergene conditions, and then persisted as stable phases. Authigenic REY-rich (Al)-phosphates and zircon are sourced from the leaching, even decomposition of primary REY-phosphates and zircons. Their colloidal aggregates are precipitated from the acidic and oxidizing low-temperature fluids, which are superposed onto clay matrix. The mineralogical and geochemical features suggest that the polymetallic beds are enriched by both alkaline magmatic-hydrothermal processes in source rocks and supergene fluid alterations in sediments. This study gives new insights into the enrichment processes and conditions, and further extraction of critical metals in the coeval coal-bearing strata in southwestern China.

Origin and evolution of a porphyry-skarn-stratabound system: constraints from geology, magmatic-hydrothermal zircon U–Pb and molybdenite Re–Os geochronology, and in situ S isotopes of the Dongguashan Cu(–Au) deposit, eastern China

Intrusion-related stratabound deposits within Late Carboniferous carbonate units are an abundant and highly economically significant ore type in eastern China. In such deposits, stratabound mineralization commonly coexists with porphyry and/or skarn mineralization, and the vast majority of reserves (>90 %) are derived from extensive stratabound orebodies, which are easy to exploit and of great interest to geologists. However, it is unclear whether these deposits were formed via the Late Carboniferous seafloor sedimentary exhalation formation or the Early Cretaceous magmatic-hydrothermal processes. Moreover, the fluid and sulfur isotope variations within porphyry-skarn-stratabound systems have not been adequately constrained. We investigated the Dongguashan deposit, one of the largest and most representative stratabound Cu(–Au) deposits in eastern China. Three mineralization types were recognized based on field and petrologic studies: porphyry, skarn, and stratabound. In the stratabound mineralization zone, magmatic and hydrothermal zircons from laminated ores yielded concordant U–Pb ages of 137.3 ± 1.1 and 135.7 ± 1.4 Ma, respectively, while molybdenite samples from vein-like ores yielded Re–Os model ages of 137.8–133.1 Ma (isochron age, 135.9 ± 1.4 Ma). These ages were consistent with the zircon U–Pb age of quartz monzodiorite (137.8 ± 1.7 Ma). A total of 146 in situ S isotope analyses yielded δ34S values (1.9–7.4 ‰) indicating that the sulfur was derived from a magmatic source. Therefore, the Dongguashan deposit resulted from Early Cretaceous magmatism rather than submarine exhalative sedimentary processes. The fluctuations in S isotopes of sulfides across the three mineralization types are attributable to different factors (pH, temperature, and oxygen fugacity) during the evolution of hydrothermal ore-forming fluids. This study demonstrates the importance of geochronology of mineralization and in situ sulfur isotope analysis under robust geological and petrographic frameworks, which can yield information about the ore-forming processes and ore genesis.

Cadmium isotope fractionation in a S-type granite related large magmatic–hydrothermal system

Granite-associated deposits are one of the important ore types in the Earth’s crust and can dominantly be subdivided into S-, I- and A-type granite-related deposits with different mineralization elements and isotopic signatures (e.g., sulphur and boron). The object of this study is to investigate whether Cd isotopic difference exists between I- and S-type granite-related deposits, and to provide new insights on geochemical behavior of Cd in such systems that have not been well constrained. The Dulong deposit in southwest China is a world-class skarn-type polymetallic Zn–Sn–In deposit that is thought to be genetically related to the emplacement of the highly fractionated S-type Laojunshan granite. The extremely negative δ114/110Cd values of sulfides (−0.82 ‰ to −0.42 ‰) within the Dulong deposit are all lower than those of sulfides from other Zn–Pb ore deposits globally. In comparison, representative sphalerites from I-type granite-related deposits yield heavier Cd isotopic compositions relative to the samples from the Dulong deposit. The Laojunshan granite samples are enriched in light Cd isotopes and have δ114/110Cd values that range from −0.73 ‰ to −0.40 ‰, overlapping with the δ114/110Cd values of sphalerite within the Dulong deposit and suggesting that the Cd in the deposit was derived from the Laojunshan granite. Similarly, I-type granite-related deposits elsewhere have Cd isotopic compositions that are similar to mafic–intermediate igneous rocks, suggesting little or no Cd isotopic fractionation took place during the magmatic–hydrothermal processes that formed these deposits. These results suggest that geochemical signatures of metal sources are the most likely control on Zn/Cd ratios and δ114/110Cd values of sulfides in these deposits, with different mineral deposit types having different Zn/Cd ratios and δ114/110Cd values. In summary, Cd isotopes provide a potentially effective tool for discriminating between different types of hydrothermal system and may also be useful in the investigation of granite petrogenesis.

Sulfur isotope and trace element geochemistry of sulfides from the unique Yaojialing Zn-Au-Cu deposit, Lower Yangtze River Metallogenic Belt, China: Implications for ore-forming process and exploration

The Yaojialing Zn-Au‑Cu deposit is a porphyry-skarn-epithermal vein-type compound deposit that consists of epithermal vein-type lead‑zinc‑silver orebodies, skarn Zn-Cu-Au orebodies, and porphyry CuAu orebodies from shallow level to depth. We decipher the source and metallogenic mechanism by studying the trace element and S isotopic compositions of sulfides (pyrite, sphalerite, chalcopyrite, and galena) from three types of orebodies. The collected pyrite can be divided into two types. PyI coexists with chalcopyrite, and PyII coexists with sphalerite or galena. In addition, PyI was further divided into PyIa (collected from porphyry copper bodies) and PyIb (collected from skarn copper bodies). PyII can be further divided into PyIIa (collected from skarn-type lead‑zinc ore body) and PyIIb (collected from vein lead‑zinc ore body in strata). Sphalerite and galena from skarn-type PbZn ore bodies and shallow vein-type PbZn ore bodies are named SpI and GnI, and SpII and GnII, respectively.Pyrite and sphalerite trace element thermometers revealed that the temperature of the ore-forming fluids decreased from 500 to 600 °C in the porphyry ore body to 300– 360 °C in the skarn ore body and then to 240– 280 °C in the shallow vein ore body. The decrease in the Co and Ni contents of pyrite collected from deep to shallow depths may indicate that meteoric water precipitated in the late ore-forming hydrothermal system. Rapid crystallization and variations in the physicochemical states (such as temperature, pH, fO2, and geochemical composition) of the fluids resulted in an obvious oscillating zone of euhedral PyI pyrite particles. It also affects the solubility of trace metal elements and leads to the selective entry of these elements into pyrite. PyII also shows obvious zonation characteristics rather than oscillating zonation, indicating that the growth rate of pyrite is relatively slow. Moreover, the relationships between the Au and As contents in the two types of pyrite are different. PyI is coupled, while PyII shows decoupling. We believe that this phenomenon is due to the high content of As in ore-forming fluid systems, which may inhibit the absorption of Au on the surface of pyrite rather than the decoupling of Au and As caused by rapid crystallization, based on the rapid increase in As content and non-oscillating zonation in PyII. According to the analysis of the sulfur isotopes of various sulfides, the solid evidences suggest that the ore-forming materials of each type of orebody in the Yaojialing deposit were mainly derived from magmatic-hydrothermal processes and that the fractionation of sulfur isotopes was the result of variations in physicochemical conditions caused by magma-hydrothermal evolution rather than the addition of foreign sulfur sources.

Zircon in tin granite as tracer for fluid metasomatism and Sn mineralization

Most tin deposits in the world are genetically related to tin granite and form during complex magmatic-hydrothermal processes. Zircon is a common accessory mineral in granite and related ore systems and can host a number of ore metals, such as Sn, W, Nb, Ta, U and Th, in its crystal lattice. However, whether metal enrichment/depletion can trace ore-forming processes is still unclear. Here, we report that the metal concentrations in various types of zircons from the Mopanshan tin granites in the southern Great Xing'an Range (Northern China) can be used as good indicators of fluid metasomatism and Sn mineralization. Two lithological zones are developed in the Mopanshan pluton, including porphyritic syenogranite (PG) in the center and fine-grained syenogranite (FG) at the margin. Zircons in the PG (PGZ-1, PGZ-2, and PGZ-3) are all magmatic in origin, while zircons in the FG can be categorized into magmatic zircons (FGZ-1 and FGZ-2) and metasomatic zircons (FGZ-3). The PGZ-1 and FGZ-1 grains are transparent prismatic crystals with bright oscillatory zonation, whereas the PGZ-2 grains are murky crystals with dark oscillatory zonation. PGZ-3 and FGZ-2 grains occur as overgrowths of previously formed zircon (PGZ-1, PGZ-2, and FGZ-1) or as brown individual crystals, showing dark and homogeneous cathodoluminescence (CL) textures. The metasomatic FGZ-3 grains are translucent-opaque porous crystals with vermicular CL zonation and commonly replace FGZ-2. The trace element compositions of magmatic zircons are completely melt controlled, providing a record of magmatic evolution as a constant decrease in Zr/Hf ratios and a gradual increase in Th, U, Nb, and Ta contents. Moreover, the structure of magmatic zircons transforms from a crystalline state to an amorphous state as a consequence of radioactive decay of U and Th. A coupled dissolution-reprecipitation process is proposed for the formation of metasomatic FGZ-3. The reactive fluid is the magmatic fluid that exsolved from the melt in the late magmatic stage. The magmatic fluid replaced biotite and rare earth phosphates (mainly monazite and apatite) enclosed within biotite, resulting in significant amounts of Nb, Ta, Sn, P, Al, Ca, Fe, and REEs, which subsequently reacted with the FGZ-2 zircons to leach Th, U, Y, and HREEs. Eventually, REEs, Y, Th, and U in the fluid combined with P to form monazite and xenotime, while the other elements partially precipitated with the crystallization of the FGZ-3 zircons. Although the alteration of biotite only released approximately 190 ppm of Sn into the fluid, this is still a significant Sn source for the Sn deposits surrounding the Mopanshan pluton, taking the granite size (∼50 km2) and the volume proportion of biotite (∼5%) into account. Furthermore, based on previous studies on tourmaline from the Mopanshan granite and regional geochemistry, it may be inferred that the addition of wall rock components may also play an important role in Sn mineralization.

New precise age constraints of the Hatu gold belt, west Junggar, NW China: Implications for a 300 Ma magmatic hydrothermal event in post-collisional setting

Abstract A 300 Ma magmatic hydrothermal ore-forming process is identified in the Hatu gold belt in west Junggar, northwest China, based on precise age constraint by secondary ion mass spectroscopy U-Pb dating of hydrothermal zircon and Ar-Ar dating of muscovite. The gold deposits in the Hatu belt (Hatu, Qi-V, Huilvshan, etc.) are similar in geology, with NE- and NW-trending orebodies composed of gold-bearing quartz veins and auriferous altered tuffaceous wall-rocks. Hydrothermal zircon grains separated from gold-bearing quartz veins in the Qi-V gold deposit provide a concordia age of 299.6 Ma and a nearly identical weighted mean 206Pb/238U age of 300 ± 2 Ma. Muscovite samples also from the gold-bearing quartz veins yield 40Ar/39Ar plateau ages of 299.6 ± 1.7 Ma, 299.9 ± 1.8 Ma, and 300.6 ± 1.9 Ma. By comprehensive compilation of geological and geochemical characteristics, tectonic evolution, and geochronology of the gold deposits in the Hatu gold belt, our new precise age data confirm that the gold deposits in the Hatu belt formed simultaneously at ca. 300 Ma, and likely formed during a post-collisional extensional setting by magmatic hydrothermal fluid from cooling magmatic sources.

Apatite as a Record of Magmatic–Hydrothermal Evolution and Metallogenic Processes: The Case of the Hongshan Porphyry–Skarn Cu–Mo Deposit, SW China

Apatite, as a common accessory mineral found in magmatic–hydrothermal deposits, effectively yields geochemical insights that facilitate our understanding of the mineralization process. In this research, multiple generations of magmatic and hydrothermal apatite were observed in the Hongshan porphyry–skarn Cu–Mo deposit in the Yidun Terrane in SW China. The geochemical compositions of the apatite were studied using in situ laser ablation–inductively coupled plasma mass spectrometry and an electron probe microanalysis to understand the magmatic–hydrothermal processes leading to ore formation. The apatite (Ap1a) occurs as subhedral to euhedral inclusions hosted in the phenocrysts of the granite porphyry. The Ap1b occurs later than Ap1a in a fine-grained matrix that intersects the earlier phenocrysts. Increases in F/Cl, F/OH, and F/S and decreases in ΣREE and (La/Yb)N from Ap1a to Ap1b suggest the exsolution of a volatile-rich phase from the magma. The skarn hosts three types of hydrothermal apatite (Ap2a, Ap2b, and Ap3), marking the prograde, retrograde, and quartz–sulfide stages of mineralization, respectively. The elemental behaviors of hydrothermal apatite, including the changes in Cl, Eu, As, and REE, were utilized to reflect evolutions in salinity, pH, oxygen fugacity, and fluid compositions. The composition of Ap2a, which occurs as inclusions within garnet, indicates the presence of an early acidic magmatic fluid with high salinity and oxygen fugacity at the prograde skarn stage. The composition of Ap2b, formed by the coupled dissolution-reprecipitation of Ap2a, indicates the presence of a retrograde fluid that is characterized by lower salinity, higher pH, and a significant decrease in oxygen fugacity compared to the prograde fluid. The Ap3 coexists with quartz and sulfide minerals. Based on studies of Ap3, the fluids in the quartz–sulfide stage exhibit relatively reducing conditions, thereby accelerating the precipitation of copper and iron sulfides. This research highlights the potential of apatite geochemistry for tracing magmatic–hydrothermal evolution processes and identifying mineral exploration targets.

Indium partitioning between silicate melts and magmatic fluids: implications for indium ore genesis and the tracing of magma degassing

Most of the global indium resources are from deposits associated with felsic rocks. Considering that the indium concentration in the average upper crust is extremely low, magmatic-hydrothermal processes play a critical role in the enrichment and mineralization of indium. However, the extraction efficiency of indium by magmatic fluids remains unclear. We performed experiments at 800 °C, 150 MPa and oxygen fugacity of Ni-NiO buffer to determine the partition coefficient of indium between aqueous fluids and granitic melts (DInf/m). To counteract the rapid loss of indium into the noble metal container wall, the DInf/m were obtained by the method of local equilibrium between microscopic-sized fluid bubbles and surrounding silicate melt. The results show that indium has the highest fluid-melt partition coefficients of all metals investigated so far. At a constant aluminum saturation index (ASI = 1.07–1.12), DInf/m correlates linearly with the total Cl concentration in the coexisting fluid (mCltotal), increasing from 61 ± 11 (1σ) at mCltotal = 1.0 mol/kg H2O to 895 ± 105 (1σ) at mCltotal = 16 mol/kg H2O. When the HCl concentration in the solution increases from 0.13 to 0.49 mol/kg H2O at a fixed mCltotal = 2 mol/kg H2O, DInf/m increases parabolically from 129 ± 21 to 320 ± 24. The observed partitioning data suggest that indium was dominantly present as In(OH)2Cl in the low-HCl and In(OH)Cl2 in high-HCl aqueous fluid at the experimental conditions. Numerical modeling indicates that the extraction efficiency of indium from S-type felsic magmas is very high (>85 %) and magmatic fluids may be the major source of indium for most indium deposits. Due to the high DInf/m values, fluid saturation and exsolution result in a sharp drop of indium concentration in both the residual melt and crystallized minerals, which makes the indium concentration in whole rock and minerals an indicator of fluid exsolution.