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Sulfate is traditionally considered to have retrograde solubility in aqueous solutions. However, our recent hydrothermal diamond-anvil cell (HDAC) experiments have shown that the solubility of Na2SO4 changes from retrograde to prograde in the presence of silica, leading to the formation of sulfate-rich solutions at high temperatures, in line with observations on natural geofluids. In this study, we use synthetic inclusions of fused silica capillary capsules containing saturated Na2SO4 solutions and Na2SO4 crystals to quantitatively investigate the solubility of Na2SO4 at different temperatures in the Na2SO4-SiO2-H2O system. Sulfate concentrations were measured using Raman spectroscopy and calibrated using Cs2SO4 solutions with known concentrations. The solubility of crystalline Na2SO4 dropped slightly when heated from 50 to 225 °C and dramatically from 225 to 313 °C. At 313 °C, the Na2SO4 crystals began to melt, forming immiscible sulfate melt coexisting with the aqueous solution, with or without solid Na2SO4. With the formation of sulfate melt, the solubility of Na2SO4 was reversed to prograde (i.e., solubility increased considerably with increasing temperatures). The solubility of Na2SO4 in the measured solution was significantly higher than that predicted in the absence of SiO2 over the entire temperature range (except for temperatures around 313 °C). This indicates that the presence of SiO2 greatly changes the dissolution behavior of Na2SO4, which may be caused by the formation of a sulfate–silicate intermediates such as Si(OH)4SO42−. Considering that most crustal fluids are silica-saturated, the solubility curve of Na2SO4 obtained in this study can better reflect the characteristics of geofluids when compared to that of Na2SO4-H2O binary system. At temperatures of 313–425 °C, the solubility of Na2SO4 increases with temperature following the function Csulfate = –3173.7/T + 5.9301, where Csulfate and T represent the solubility of Na2SO4 in mol/kg H2O and temperature in Kelvin, respectively. As an application, this temperature-solubility relationship can be used to evaluate the sulfate contents in fluid inclusions that contain sulfate daughter minerals, based on the temperature of sulfate disappearance obtained from microthermometric analysis. The sulfate concentrations of the ore-forming fluids of the giant Maoniuping carbonatite-related rare earth element (REE) deposit (southwest China) were calculated to be 4.67–4.81 m (mol/kg H2O). These sulfate concentrations were then used as internal standards to calibrate the previously reported semi-quantitative results of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis of REE-forming stage fluid inclusions at this deposit. The calculated Ce concentrations in the REE-mineralizing fluid range from 0.42 to 0.49 wt%. The high fluid REE contents suggest that the sulfate-rich fluids are ideal solvents for REE transport. A mass-balance calculation was carried out to evaluate the minimal volume of carbonatite melt that was required for the formation of the giant Maoniuping REE deposit. The result indicates that the carbonatite dikes in the mining area are enough to provide the required fluids and metals, and thus a deep-seated magma chamber is not necessary for ore formation.

China dominates the world REE (rare earth elements) resources, 98% of which are from carbonatite-related REE deposits. Extensive studies of this type of REE deposits are available, but it is still poorly understood how carbonatite magmas were generated and how REEs were transported and precipitated in such magmas. On the basis of previous studies, this paper synthesizes the spatio-temporal distribution of this type of REEs deposits in China and their major features, including characteristics of ore-forming fluids, and discusses existing genetic models regarding the origin of causative magma, and mechanics of REE enrichment, transportation and precipitation. In China, carbonatite-related REE deposits occur in the craton margin environments with four major REE metallogenic belts: the Mesoproterozoic Bayan Obo-Langshan belt (e.g., the Bayan Obo deposit), the early Mesozoic eastern Qinling-Dabie belt (e.g., the Miaoya deposit), the late Mesozoic Zibo-Laiwu-Weishan belt (e.g., the Chishan deposit), and the Cenozoic Mianning-Dechang belt (e.g., the Maoniuping deposit). In these belts, REE-hosting carbonatites were emplaced in continental rift zones or along large-scale strike-slip faults at the Precambrian craton margins. The causative magmas were originated from partial melting of enriched lithospheric mantle sources, which may have undergone metasomatism by subducted slab-related fluids/melts, and may have also asthenospheric material involvement. These magmas may have formed through melt immiscibility and fractional crystallization from primary carbonated silicate melt. The melt immiscibility may include unmixing between alkaline silicate and carbonate melts, or multi-phase melt immiscibility of carbonate melt, mafic or ultramafic melt, phosphomagnesite melt, and alkaline silicate melt. The immiscibility and/or crystal fractionation of mafic mineral can lead to the formation of carbonate melts rich in REEs. The newly discovered lithofacies zonation at Bayan Obo, with a biotitite outer zone, implies a magmatic evolution of a silica-rich parent magma. The low REE concentrations and LREE/HREE ratios of biotitite indicate possible LREE enrichment in the evolved carbonatite magma by biotite fractional crystallization. The crystallization of carbonate minerals during the upwelling and emplacement of carbonatite magmas, may further enrich late-stage carbonatite melts and carbonatite fluids in LREE. This process can better explain the REE mineralization dominantly in the late-stage of carbonatite magmatism or post-magmatic fluid stage. The melt, melt-fluid and fluid inclusion results for Bayan Obo, Maoniuping and Chishan indicate SO42− and CO2-rich carbonatite fluids. The microthermometry and SEM/EDS results for primary melt-fluid inclusions hosted in fluorite from Maoniuping indicate that carbonatite fluids were extremely rich in SO42−, and underwent an unmixing process between sulfate melt and aqueous fluid. Both inclusion and experimental results indicate that the sulfate has a very high solubility in SiO2-bearing aqueous fluids, inconsistent with the SiO2-free system. The geochemical thermodynamic results also confirm the SO42− -dominated agent for REE transportation. The unmixing process between sulfate melts and aqueous fluids would lead to extensive decrease of SO42− in the fluid, and bulk REE precipitation. The rapid evolution of carbonatite fluids prevents long distance migration of carbonatite fluids, resulting in all REE mineralization within, or proximal to the carbonatite bodies. The strong mineralization would occur in the central zone or the shallow level and then would become weaker outwards and downwards of carbonatite bodies.

In situ Raman spectra of aqueous K2WO4-HCl, K2WO4-HCl-NaCl, and K2WO4-CO2-NaCl solutions were collected at elevated temperature (T, 100–400°C) and constant pressure (P) of 30 MPa. The stretching vibration band of the W=O bond (v1) was analyzed to reveal the species of tungsten (W) responsible for the hydrothermal transport of W during mineralization. Results showed that monomeric tungstates with v1(W=O) bands at ~930 and 950 cm-1 are the dominant W species in weakly alkaline (room temperature, pH=7.7) to near-neutral (room temperature, pH=7.2) solutions under the investigated T‐P conditions. Overall, the stability of polymeric tungstate species with v1(W=O) bands at ~965–995 cm-1 decreases with rising temperature and was not detected at ≥300°C in moderately acidic solution (room temperature, pH=4.9). However, increased fluid acidity and salinity obviously enlarged the temperature stability field of polymeric tungstate species. In highly acidic solution (room temperature, pH=1.4), polymeric tungstates are the only stable W species even at 400°C. In the presence of 1.9 mol/kg NaCl, polymeric tungstate(s) can persist to at least 350°C in moderately acidic solution. Considering that 300–350°C is the major W-mineralizing T range and W-mineralizing fluid is generally characterized by a moderately acidic nature, we propose that, in addition to monomeric tungstates, polymeric tungstates can also be important W species in some natural geological fluids that are responsible for the mineralization of W. Future studies of the W mineralization mechanism should take this issue into account.

The presence of sulfate-rich fluids in natural magmatic hydrothermal systems and some carbonatite-related rare earth element (REE) deposits is paradoxical, because sulfate salts are known for their retrograde solubility, implying that they should be insoluble in high-temperature geofluids. Here, we show that the presence of quartz can significantly change the dissolution behavior of Na2SO4, leading to the formation of extremely sulfate-rich fluids (at least 42.8 wt% Na2SO4) at temperatures >∼330 °C. The elevated Na2SO4 solubility results from prograde dissolution of immiscible sulfate melt, the water-saturated solidus of which decreases from ≥∼450 °C in the binary Na2SO4-H2O system to ∼270 °C in the presence of silica. This implies that sulfate-rich fluids should be common in quartz-saturated crustal environments. Furthermore, we found that the sulfate-rich fluid is a highly effective medium for Nd mobilization. Thermodynamic modeling predicts that sulfate ions are more effective in complexing REE(III) than chloride ions. This reinforces the idea that REEs can be transported as sulfate complexes in sulfate-rich fluids, providing an alternative to the current REE transport paradigm, wherein chloride complexing accounts for REE solubility in ore fluids.

A subduction zone plays a critical role in forging continental crust via formation of arc magmas, which are characteristically enriched in large ion lithophile elements (LILEs) and depleted in high field strength elements (HFSEs). This trace element pattern results from the different mobilities of LILEs and HFSEs during slab-to-wedge mass transfer, but the mechanisms of trace element transfer from subducting crusts are not fully understood. In this study, thermodynamic simulations are carried out to evaluate the mobilities of K and Zr, as representative cases of LILE and HFSE, respectively, in slab fluids. The fluids buffered by basaltic eclogite can dissolve &gt, 0.1 molal of K at sub-arc depths (~3 to 5.5 GPa). However, only minor amounts of K can be liberated by direct devolatilization of altered oceanic basalt, because sub-arc dehydration mainly takes place at temperatures &lt, 600 °C (talc-out), wherein the fluid solubility of K is very limited (&lt, 0.01 molal). Therefore, serpentinite-derived fluids are required to flush K from the eclogite. The solubility of K can be enhanced by the addition of NaCl to the fluid, because fluid Na+ can unlock phengite-bonded K via a complex ion exchange. Finally, it is further confirmed that Zr and other HFSEs are immobile in slab fluids.

Mantle-derived carbonatites provide a unique window in the understanding of mantle characteristics and dynamics, as well as insight into the assembly and breakup of supercontinents. As a petrological indicator of extensional tectonic regimes, Archean/Proterozoic carbonatites provide important constraints on the timing of the breakup of ancient supercontinents. The majority of the carbonatites reported worldwide are Phanerozoic, in part because of the difficulty in recognizing Archean/Proterozoic carbonatites, which are characterized by strong foliation and recrystallization, and share broad petrologic similarities with metamorphosed sedimentary lithologies. Here, we report the recognition of a ~1.85 Ga carbonatite in Chaihulanzi area of Chifeng in north China based on systematic geological, petrological, geochemical, and baddeleyite U-Pb geochronological results. The carbonatite occurs as dikes or sills emplaced in Archean metasedimentary rocks and underwent intense deformation. Petrological and SEM/EDS results show that calcite and dolomite are the dominant carbonate minerals along with minor and varied amounts of Mg-rich mafic minerals, including forsterite (with Fo > 98), phlogopite, diopside, and an accessory amount of apatite, baddeleyite, spinel, monazite, and ilmenite. The relatively high silica content together with the non-arc and OIB-like trace element signatures of the carbonatite indicates a hot mantle plume as the likely magma source. The depleted Nd isotopic signatures suggest that plume upwelling might be triggered by the accumulation of recycled crust in the deep mantle. As a part of the global-scale Columbia supercontinent, the Proterozoic tectonic evolution of the North China Craton (NCC) provides important insights into the geodynamics governing amalgamation and fragmentation of the supercontinent. The Paleo-Mesoproterozoic boundary is the key point of tectonic transition from compressional to extensional settings in the NCC. The newly identified ~1.85 Ga carbonatite provides a direct link between the long-lasting supercontinental breakup and plume activity, which might be sourced from the “slab graveyard,” continental crustal slabs subducted into asthenosphere, beneath the supercontinent. The carbonatite provides a precise constraint of the initiation of the continental breakup at ~1.85 Ga.

The HighPGibbs program is designed to calculate thermodynamic equilibrium of fluid-rock minerals and solid solutions up to depths of lithospheric mantle. It uses the Gibbs free energy minimization ...

Sulfate-bearing geofluids are widespread in many geological environments and play important roles in ore-forming processes. Recent experiments provide evidences that in silica-rich fluids, Na2SO4 solubility exhibits a complex temperature dependence, first decreasing from 25 to 313 °C and then increasing from 313 to 425 °C. The fluid-borne silica have critical implications for sulfate-bearing hydrothermal systems and formations of rare earth element deposits. However, whether other sulfate salts share the same characteristics remains unknown. In this study, fused silica capillary capsules (FSCCs) containing K2SO4-saturated solutions and K2SO4 crystals are used to quantitatively investigate the solubility of K2SO4 at different temperatures in the K2SO4-SiO2-H2O system. In the K2SO4-SiO2-H2O system, K2SO4 shows prograde solubility from 50 to 400 °C, and does not melt through the whole investigated temperature range. The relationship between temperature and the solubility of K2SO4 can be described by a simple linear function with R2 = 0.991: Csulfate = 4.1307 × 10−3 × T + 0.5532, where Csulfate and T represent the solubility of K2SO4 in m (mol/kg H2O) and temperature in °C, respectively. These results show that the solubility of K2SO4 can be enhanced by 3 to 5 times at 300–400 °C by the presence of silica, compared with that in silica-absent system, even without the formation of sulfate melt. Considering that quartz is ubiquitous in the Earth's crust, the solubility of sulfate in natural geofluids may reach a much higher level than previously expected. The temperature dependences of the solubilities of K2SO4 and Na2SO4 in silica-saturated fluids were used to constrain the compositions of the mineralizing fluids of the synmetamorphic hematite-quartz veins at Ouro Fino (SE Brazil) and the Maoniuping REE deposit (SW China), based on the previously reported microthermometric results of fluid inclusions that contain sulfate daughter minerals. For the hematite-quartz vein at Ouro Fino, the sulfate concentration was calculated to be 8.9–19.2 wt%, which is in line with previous laser ablation measurements (~15.3 wt%). For the Maoniuping REE deposit, the total sulfate concentration was determined to be 16.3–27.4 wt%, and the REE concentration of the ore-fluid was further estimated to be 0.30–0.44 wt%.

The magmatic complex in Uradzhongqi, Inner Mongolia, is located in the western segment of the northern margin of the North China Craton (NCC). The dominant components in the complex include syenogranite, monzogranite, granodiorite, diorite and gabbro. Mafic microgranular enclaves (MMEs) are common in syenogranite and granodiorite. Zircon U–Pb dating shows that the ages of these rocks range from 283 to 270 Ma, suggesting an early Permian emplacement. The syenogranite and monzogranite are peraluminous I-type granites, exhibiting conspicuous negative Eu anomaly, enrichment in large-ion lithophile elements (LILE) and light rare earth elements (LREE), depletion in high field strength elements (HFSE). The granodiorites, diorites and MMEs are metaluminous in composition, show high Al2O3, MgO and Fe2O3T contents and weak negative Eu anomaly, as well as LREE and LILE enrichment and HFSE depletion. The gabbros show weak positive Eu anomaly and slight REE differentiation. The Sr–Nd isotope compositions show that the source of mafic magma was depleted mantle (DM) with possible involvement of enriched mantle II (EM II), whereas the felsic magma was derived from the Archean lower crust. Petrographic observation and analytical results of mineralogy, geochronology, geochemistry and Sr–Nd isotopes indicate that the main petrogenesis of these magmatic rocks is the mixing of underplating mafic magma and felsic magma. Tectonically, the complex pluton was formed within a post-collisional regime, and the underplating in this area provides another piece of evidence for the vertical growth of the western segment of the northern margin of the NCC.

In hydrothermal ores, gold is commonly hosted by sulfide minerals due to its affinity for reduced sulfur. In contrast, the occurrence of gold in oxide minerals remains poorly documented and incompletely understood. In this contribution, we demonstrate that magnetite can be a significant host mineral for gold. Skarn ores from the giant Beiya Au deposit (323 t Au at 2.47 g/t), southwest China, contain abundant nanometer- to micronsized gold hosted by magnetite. A range of bismuth minerals (e.g., native bismuth, maldonite, and bismuthinite) occur within the same assemblage. Textural and mineralogical studies as well as thermodynamic modeling indicate that Bi melts scavenged Au from hydrothermal fluids during magnetite growth. Fluctuating f O 2 ( g ) at the surfaces of crystallizing magnetite led to the precipitation of Bi-Au melt, ongoing gold refinement, and entrapment of gold and bismuth minerals within magnetite. Sulfidation of Bi, triggered by increased sulfur content and/or decreased temperature, further promoted gold precipitation. Bismuth melts are interpreted to have played a crucial role in Au enrichment from gold-undersaturated fluids at Beiya. The results imply that magnetite-rich systems are also potential targets for Au exploration and extraction, particularly in cases where coexisting Bi minerals are observed in abundance.

Classification algorithms were constructed based on pyrite trace elements using two machine learning methods, support vector machine (SVM) and artificial neural network (ANN), to discriminate the genesis of pyrites sampled from sedimentary rock, orogenic and volcanic hosted massive sulfide (VHMS) deposits. The classifiers were trained with a dataset including published trace element compositions of 2104 pyrite samples from 92 mineral deposits or stratigraphic units. Cross validations were conducted to evaluate the performances of the classifiers on unknown samples, using a variant of the k-fold method. Each time, all pyrite samples from one of the 92 deposits/strata were set aside as the testing set, and the classifiers were trained with samples of the remaining 91. Then, the performances of the classifiers were evaluated based on whether it can correctly determine the genesis of testing deposit/stratum. The circulation was repeated 92 times for each one of the deposits/strata in the dataset, and 91 of them were correctly classified by the SVM-based classifiers, and 90 by the ANN-based. The trained classifiers were then applied to reveal the genesis of the Jiashengpan Zn-Pb deposit, which is characterized by two stages of pyrite formation: early-stage fine-grained massive and late-stage coarse-grained hydrothermal pyrite. The trained algorithms show that the early-stage is compositionally similar to sedimentary pyrite, while the late-stage has affinity to those from orogenic deposits, consistent with geological and geochemical features revealed by previous studies. This study sheds light on the power of machine learning in decoding the geochemical data of pyrite, which can well record the history of ore formation.

The Qiaoxiahala deposit is a significant Paleozoic Fe-Cu-Au deposit in the northern margin of East Junggar, NW China, which has been confirmed to form in a basin inversion setting (dying back-arc basin). The composition of noble gases (Ar, Kr, and Xe) and halogens (Cl, Br, and I) extracted from fluid inclusions, hosted in quartz, calcite, and epidote from various mineralization stages of Qiaoxiahala, are investigated to trace the sources of ore fluids and discuss the ore genesis. Significant multistage mineralization at Qiaoxiahala is identified as magnetite mineralization (stage III), magnetite-pyrite mineralization (stage IV), and chalcopyrite mineralization (stage V). Syn-ore fluid inclusions show salinities varying from 13.2 to 15.3 wt% (NaCl eq.) associated with elevated I/Cl ratios (214 × 10−6 to 3950 × 10−6), uniformly low Br/Cl ratios (0.78 × 10−3 to 1.30 × 10−3), and low 40Ar/36Ar ratios (

The geochemistry of basaltic rocks is widely used to investigate the tectonic setting of magmatism. The limitation of traditional two-dimensional tectonic discrimination diagrams is mainly risen from the fact that they can only simultaneously use the information of two (x-y plots) or three (ternary diagrams) elements (or element ratios) for discrimination. This obstacle can be overcome with the assistance of machine learning method, which shows great performances in classification of multidimensional datasets. In this study, we present a neural network-based model that uses whole rock major and trace elements to discriminate basaltic rocks (SiO2 45–55 wt%) from a wide range of tectonic settings, including continental arc basalt (CAB), island arc basalt (IAB), intra-oceanic arc basalt (IOAB), mid-ocean ridge basalt (MORB), oceanic plateau basalt (OPB), oceanic island basalt (OIB), continental flood basalt (CFB) and continental rift basalt (CRB). Using a modified method of cross validation, it is estimated that the model can discriminate the tectonic setting with an average accuracy of ~86%, and ~98% in discriminating the major tectonic regimes (arc, spreading center, or within-plate magmatism). This discrimination model was programed as a stand-alone Microsoft Excel spreadsheet that can be directly used by pasting the whole rock data into it. The discriminator was then applied to investigate the geodynamic background of the Paleoproterozoic (~1.75 Ga) Xiong'er volcanism in the southern margin of the North China Craton (NCC). It has long been debated whether this magmatism took place in a continental arc or within-plate rift environment. The discrimination result shows that both the Xiong'er Group volcanic rocks and coeval intrusive rocks have CFB affinities, indicating that they were products of mantle plume activity and defines a large igneous province (LIP) in a within-plate setting. This, along with previous studies, constrains the breakup of NCC, a part of the Columbia supercontinent, not later than ~1.79 Ga, and supports the idea that the fragmentation of the Columbia was triggered by mantle plume impingement.

The contiguous region between Guangxi, Guizhou, and Yunnan, commonly referred to as the Golden Triangle region in SW China, hosts many Carlin-type gold deposits. Previously, the ages of the gold mineralization in this region have not been well constrained due to the lack of suitable minerals for radiometric dating. This paper reports the first SIMS U–Pb age of hydrothermal rutile crystals for the Zhesang Carlin-type gold deposit in the region. The hydrothermal U-bearing rutile associated with gold-bearing sulfides in the deposit yields an U-Pb age of 213.6 ± 5.4 Ma, which is within the range of the previously reported arsenopyrite Re–Os isochron ages (204 ± 19 to 235 ± 33 Ma) for three other Carlin-type gold deposits in the region. Our new and more precise rutile U-Pb age confirms that the gold mineralization was contemporaneous with the Triassic W–Sn mineralization and associated granitic magmatism in the surrounding regions. Based on the temporal correlation, we postulate that coeval granitic plutons may be present at greater depths in the Golden Triangle region and that the formation of the Carlin-type gold deposits is probably linked to the coeval granitic magmatism in the region. This study clearly demonstrates that in situ rutile U–Pb dating is a robust tool for the geochronogical study of hydrothermal deposits that contain hydrothermal rutile.

The Raman shift of the ν3(SiO4) mode of zircon at ~1008 cm−1 has been observed to vary with the pressure (P) and temperature (T) of the environment. The relationship between the ν3(SiO4) peak position and P-T was calibrated in previous work and used to develop a pressure sensor for high P-T experiments, up to 1000 °C and 10 GPa, to an accuracy within ±50 MPa. This pressure measurement method is valid for zircon grains for which the ν3(SiO4) Raman shift occurs specifically at or close to 1008.17 cm−1 at room temperature (25 °C). However, the peak position of ν3(SiO4) for some zircon grains may shift to a lower or higher wavenumber under ambient conditions, mainly due to the chemical composition of the grains. This may cause substantial deviation in the measured pressures. In the present study, we recalibrated the pressure sensor by determining the position of the ν3(SiO4) peak for zircon grains with different chemical compositions at given P-T conditions and developed a model applicable to both natural and synthetic zircon samples. All the zircon samples considered were found to have a universal ν-T relationship when the ν3(SiO4) wavenumbers under ambient conditions were calibrated to the same position. Based on this relationship, the temperature-induced wavenumber shift of ν3(SiO4) can be expressed as ΔνT (cm−1) = 8.00 × 10–9 × (T3 – T03) – 2.00 × 10–5 × (T2 – T02) – 2.78 × 10–2 × (T – T0), where T and T0 are the target and room temperatures, respectively. In addition, the pressure-induced wavenumber shift of ν3(SiO4) can be calculated using ΔνP (cm−1) = Δν – ΔνT, where Δν is the total frequency shift between the target and ambient P-T conditions. By the linear regression of the experimental results, the global slope (∂ν/∂P)T was determined to be 5.91 × 10–3 cm−1/MPa. In addition, high P-T experiments performed in isochoric systems using a hydrothermal diamond anvil cell (HDAC) showed that the cross-derivative term (∂2ν/∂P∂T) was equal to zero, which is the same as the previous study. The revised method was used to determine the pressures inside a fused silica capillary capsule (FSCC) containing a NaCl solution. The pressures determined from the zircon Raman spectra (PZr) were compared with those calculated using the equation of state (PEoS) of a NaCl-H2O system. The determined PZr and PEoS values agreed well for temperatures lower than ~500 °C. However, PZr was significantly lower than PEoS at higher temperatures due to the thermal expansion of the FSCC, i.e., the expansion of the sample chamber under the high internal pressures when the silica glass softened at high temperatures. The revised method was programmed in a Microsoft EXCEL spreadsheet and is presented in the Appendix B.

Measuring homogenization temperature (Th) is a basic work in fluid inclusion studies. However, the Th of some fluid inclusion is hard to obtain using the traditional microthermometric method, in particular those that is easy to decrepitate upon heating. Such inclusions are common when the host minerals have well-developed cleavages (e.g., calcite and fluorite) and the fluids are enriched in volatile components such as CO2 or CH4. In theory, upon heating of H2O-NaCl and H2O-CO2-NaCl inclusions that tends to homogenize to the liquid phase, their bubble volumes (Vg) will decrease with increasing temperatures (T) following cubic and quartic polynomial Vg-T functions, respectively. A method that can predict inclusion Th without heating it to homogenization is proposed in this study. The core idea is to retrieve the Vg-T function of a given inclusion based on a series of (Vg, T) data points that were measured before total homo genization (or decrepitation of the inclusion), and then calculate the Th based on the function (the temperature at which Vg equals to zero). To test the performance of this method, a total of 14 synthetic and natural fluid inclusions were heated to homogenization (at Th, real) and their changes in Vg were recorded with increasing temperature. It is assumed that the inclusions get decrepitated before homogenization, and their homogenization temperatures were predicted (Th, predicted) using the method proposed by this study. If the inclusions were “decrepitated” at temperatures 40 °C below the Th, real, the differences between the predicted and real homogenization are mostly smaller than 3 °C. This approach provides a quantitative estimation of the Th for inclusions that are easy to decrepitation, and is much more accurate than directly using the temperature of decrepitation as an approximation of Th. This method was programed in two Microsoft EXCEL worksheets that are available in Supplementary Materials for Th calculations of H2O-NaCl and H2O-CO2-NaCl inclusions, respectively.

Knowledge on hydrothermal tungsten (W) species is vital towards a better understanding of tungsten transport and mineralization mechanisms. In this study, in situ Raman spectra of a 0.005 – 0.1 mol/kg (m) K2WO4 solution containing CO2, HCl, and NaHCO3 were collected at 50–400 °C and 20–60 MPa. The spectra for the symmetric stretching vibration mode of the W O bond, v1(W O), were analyzed to investigate the hydrothermal tungstate species. Results showed that carbonate/bicarbonate do not associate with tungstate to form carbonic tungstate species. Nevertheless, the presence of CO2 can increase the fluid acidity, which favors the formation of polymeric tungstate species at O) modes of these species are centered at ∼930 cm-1 and 950 cm-1. Based on the above observations, we simulated the mineralization process in the context of fluid-rock interactions using tungstate and alkali tungstate ion pairs as the only aqueous W species. The thermodynamic simulations showed that (a) the timing of mineralization mainly depends on the W concentration in the initial mineralizing fluid and the availability of Ca2+, Fe2+ and Mn2+, with higher W concentrations generally favoring higher temperature mineralization; (b) highly W-enriched fluid is not essential for W mineralization, while extremely low contents of Fe, Mn and Ca in the magma are useful to maintain the mobility of aqueous W until favorable host rocks are encountered; and (c) a “hydrogen reservoir” effect was identified for dissolved CO2. The presence of CO2 can promote the extraction of Fe(II) from the pelitic host rocks, thereby facilitating a high-grade vein-type W mineralization. At O) modes are centered at ∼965 – 995 cm-1, are important hydrothermal W species along with monomeric tungstates. Therefore, polymeric tungstate species should be considered in future thermodynamic modeling of W transport and mineralization at

The genesis of the giant Dongshengmiao in the northern margin of the North China Block has been debated since its discovery in the 1950s, because it shows geological and geochemical characteristics with both syngenetic and epigenetic signatures. It has geological settings and sulfur and lead isotopic compositions that are similar with typical SEDEX (sedimentary exhalative) deposit, while the Zn-Pb-Cu mineralization was controlled by shear deformation and metamorphism, showing similarities with orogenic-type deposits. In this contribution, both the syngenetic and epigenetic features of the Dongshengmiao are envisaged, and accounted for in the context of a genetic model with two metallogenic periods. Massive pyrite at the Dongshengmiao was mostly recrystallized during metamorphism, but fine-grained texture was locally preserved, indicating its syngenetic origin. On the contrary, all the Zn-Pb-Cu ores observed in this study show characteristics of epigenetic hydrothermal mineralization that controlled by metamorphism and accompanying shear deformation. The sulfur and lead isotopic compositions of sphalerite and galena indicate that they were in situ remobilized from a syngenetic stratabound source, and the oxygen and hydrogen isotopic ratios of ore-fluid indicate that the large-scale remobilization was assisted by metamorphic fluid. The thermodynamic modeling indicates that the ore-fluid during remobilization has a great potential of transporting Cu. This may account for the abnormally enriched Cu in the remobilized SEDEX deposit. The metamorphic fluid might strip Cu from the fluid source during devolatilization, and overprint it on the Zn-Pb orebodies during remobilization. A secondary flow-through modeling reveals that Zn- and Cu-sulfides would be preferentially redistributed in Fe-rich carbonates during remobilization, as a result of fluid-rock interaction. Conclusively, a multistage genetic model is proposed. During the development of the Proterozoic rift, stratabound Zn-Pb mineralization took place in a SEDEX ore-forming system. The syngenetic sulfides subsequently underwent a large-scale fluid-assisted remobilization during the early Cretaceous metamorphism and thrusting, forming the shear zone-controlled epigenetic orebodies. During the remobilization process, Cu was scavenged from the source of metamorphic fluid, and deposited accompanying remobilized Zn-Pb sulfides. Shear structures and Fe-rich carbonates are ideal sites for redistribution and re-deposition of remobilized sulfide.