Hydrothermal Deposits Research Articles

Differences in Sm/Nd ratios between early magmatic and late sulfides: The role of fluids and Nd mobility

This paper presents the results of a SmNd study of sulfide minerals and whole-rock samples from Cu-Ni-PGE layered complexes of the Fennoscandian Shield. Syngenetic (early) and epigenetic (late) sulfides were analyzed in each complex using the SmNd method. Late sulfide minerals with low Sm/Nd values (the 147Sm/144Nd ratio is often in the range of 0.02–0.07) are associated with an increased mobility of Nd relative to Sm, resulting in a relative excess of Nd compared to Sm in these sulfides. Simultaneously, early sulfides, which are deposited during the magmatic stage of ore formation, typically exhibit higher Sm/Nd values (the 147Sm/144Nd ratio is frequently above 0.07). Additionally, SmNd isotope data for sulfide minerals were used to date ore-forming processes in two Cu-Ni-PGE complexes—Nyud-II (Monchegorsk area, Russia) and Ahmavaara (Finland). The SmNd ages of syngenetic and metamorphic ore from these complexes were determined. Syngenetic ores formed at 2496 ± 36 Ma (Nyud-II) and 2441 ± 93 Ma (Ahmavaara), while metamorphic ores formed at 1940 ± 32 Ma (Nyud-II) and 1904 ± 24 Ma (Ahmavaara). Thus, SmNd isochrons yield the timing of sulfide mineralization and its relationship with the ages of the rocks containing it, while Sm/Nd ratios in sulfides help understand the processes of ore formation. A comprehensive analysis of the full isotopic dataset (this study and other published data) showed the potential of using SmNd isotope data to trace the sequence of sulfide mineralization, which has been confirmed for some hydrothermal deposits. However, this sequence has not been confirmed for magmatic sulfides; this opens up the possibility for further research.

Ore sulfur of Golovnin Volcano, Kunashir Island

Research subject. Hydrothermal deposits of Golovnin Caldera. Aim. To study the epithermal volcanogenic ore formation. Key points. Until now, there has been a consensus on the exogenous sedimentary (colloidal) genesis of sulfur in volcanic lakes. Our observations and microstructure studies indicate the presence of sulfur melt at the bottom of Kipyaschee Lake. Drops of this melt are carried to the surface of the lake as part of a light gray foam. The significant differences of sulfur spherules in the concentration of sulfide mineralization, in its composition, as well as in the presence or absence of numerous opal inclusions are most simply explained by the capture of droplets in various parts of the sulfur melt and their subsequent movement by a gas stream passing through the melt. Elemental sulfur condensate is formed in bottom sediments as a result of forced cooling of endogenous gas flows by lake water. The main condensation of sulfur occurs here (96% or more of the total potential of fluid sulfur). Residual condensation of sulfur occurs in the aquatic environment. Finely dispersed sulfur condensate in a mixture with water is unstable and breaks down over time with the release of hydrogen sulfide and the formation of sulfurous and sulfuric acids. The activity of bottom hydrotherms and coastal unrest prevents the formation of colloidal sulfur sediment at the bottom of lakes. In the crater depressions at the bottom of the lakes of the Golovnin Caldera, sulfidization of its melt occurs simultaneously with the condensation of sulfur itself. Gravitational deposition of sulfides in the sulfur melt leads to their enrichment of the root parts of crater depressions, where pyrite ore bodies are formed in real time. Terrestrial sulfur deposits, together with the modified rocks overlying them, demonstrate the full profile of endogenous apical oxidation under gas-hydrothermal action: sulfur and sulfur-opal rocks up the section are replaced by gypsum-jarosite rocks and, further, by an “iron hat” of limonite-cemented breccias of the dome mantle. Conclusions. Observations, microstructure studies and molecular chemical modeling indicate the endogenous condensate origin of ore sulfur in the Golovnin Caldera and exclude its exogenous sedimentary genesis.

Genesis of the Bailugou Vein-Type Zinc-Lead-Silver Deposit, Eastern Qinling Orogen, China: Constraints from Ore Geology and Fluid Inclusions

The Bailugou vein-type zinc-lead-silver deposit is located in the Eastern Qinling Orogen, China. There has been a long-standing debate about whether its formation is related to magmatism or metamorphism. To determine the origin of ore-forming materials and fluids, we conducted a geological and fluid inclusion investigation of the Bailugou. Field surveys show that the vein-type orebodies are controlled by faults in the dolomitic marbles of the Mesoproterozoic Guandaokou Group, and they are distal to the regional Yanshanian intrusions. Four ore stages, i.e., quartz–pyrite ± sphalerite (Stage 1), quartz–polymetallic sulfides (Stage 2), dolomite–polymetallic sulfides (Stage 3), and calcite (Stage 4), are identified through microscopic observation. The homogenization temperatures of measured fluid inclusions vary in the range of 100 °C to 400 °C, with the dominating concentration at 350 °C to 400 °C, displaying a descending trend from early to late stages. The estimated formation depth of the Bailugou deposit varies from 2 km to 12 km, which is deeper than the metallogenic limit of the epithermal hydrothermal deposit but conforms to the typical characteristics of a fault-controlled deposit. The ore-forming fluid in Stage 1 originates from a fluid mixture and experiences a phase separation (or fluid immiscibility) between the metamorphic-sourced fluid and the fluids associated with ore-bearing carbonate-shale-chert association (CSC) strata. This process results in the transition to metamorphic hydrothermal fluid due to water–rock interactions in Stage 2, culminating in gradual weakening and potential fluid boiling during the mineralization of Stage 3. Collectively, the Bailugou lead-zinc-silver mineralization resembles an orogenic-type deposit formed by metamorphic fluids in the Qinling Yanshanian intracontinental orogeny.

Role of As in the formation of giant Au deposits: Insights from sulfur isotope and geochemistry of pyrite from the Shuangwang Au deposit, West Qinling, central China

The Shuangwang Au deposit (SWGD), located in the Feng-Tai ore district, is one of the largest Au deposits in the West Qinling orogen, central China. Au orebodies in this deposit are mainly hosted in the Upper Devonian Xinghongpu Formation. The source of the fluids and metals ore-forming processes and the enrichment mechanism of Au in this ore deposit remain equivocal. Here we present results from geochemical studies of pyrite from the SWGD to address these issues through the application of Scanning electron microscopy (SEM), electron probe microanalysis (EPMA), in-situ laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and LA-MC-ICP-MS analyses. Based on detailed petrographic studies of the mineralization and host rocks, we identify seven generations of pyrite. Among these, the pre-ore syn-sedimentary pyrite (Py0) is characterized by relatively elevated concentrations of As, Co, Ni and Au compared to the Py1 in the albite-ankerite veins and Py2 in the quartz-ankerite-pyrite veins, and has positive δ34S values of + 6.00 to + 10.48 ‰, whereas Py3 forms as veinlets or aggregates in the pyrite-tourmaline veins and is enriched in As, Co, Cu, Se and Au. Py4 occur as coarse-grained subhedral to euhedral crystals or aggregates in the ankerite-pyrite veins and exhibit oscillatory zones. Py5 comprises fined-grained subhedral to anhedral grains in the fluorite-ankerite-pyrite cements, and is relatively depleted in trace elements when compared to the other pyrite types. The δ34S values of the different types of pyrite from the SWGD have significant differences, indicating a multiple and mixed source for sulfur and, by inference, for the ore-forming fluid(s). Two periods of Au mineralization are identified in the SWGD: the early NW-trending mineralization sourced from the metamorphism of the metasedimentary sequences in a compressional environment and the late NE-trending mineralization probably exsolved from an unexposed and coeval granitoid pluton at depths in a post-collisional extensional setting. The coupled geochemical behavior of Au and As can be explained by mixing-induced cooling. Our results also indicate that arsenic might have played an important role in the enrichment of Au and the formation of this hydrothermal Au deposit.

Neogene Hydrothermal Fe‐ and Mn‐Oxide Mineralization of Paleozoic Continental Rocks, Amerasia Basin, Arctic Ocean

AbstractRocks dredged from water depths of 1,605, 2,500, 3,300, and 3,400 m in the Arctic Ocean included Paleozoic continental rocks pervasively mineralized during the Neogene by hydrothermal Fe and Mn oxides. Samples were recovered in three dredge hauls from the Chukchi Borderland and one from Mendeleev Ridge north of Alaska and eastern Siberia, respectively. Many of the rocks were so pervasively altered that the protolith could not be identified, while others had volcanic, plutonic, and metamorphic protoliths. The mineralized rocks were cemented and partly to wholly replaced by the hydrothermal oxides. The Amerasia Basin, where the Chukchi Borderland and Mendeleev Ridge occur, supports a series of faults and fractures that serve as major zones of crustal weakness. We propose that the stratabound hydrothermal deposits formed through the flux of hydrothermal fluids along Paleozoic and Mesozoic faults related to block faulting along a rifted margin during minor episodes of Neogene tectonism and were later exposed at the seafloor through slumping or other gravity processes. Tectonically driven hydrothermal circulation most likely facilitated the pervasive mineralization along fault surfaces via frictional heating, hydrofracturing brecciation, and low‐ to moderate temperature Fe‐ and Mn‐rich hydrothermal fluids, which mineralized the crushed, altered, and brecciated rocks.

Heterogeneous Nucleation Regulation Amends Unfavorable Crystallization Orientation and Defect Features of Antimony Selenosulfide Film for High‐Efficient Planar Solar Cells

AbstractAntimony selenosulfide (Sb2(S,Se)3) has obtained widespread concern for photovoltaic applications as a light absorber due to superior photoelectric features. Accordingly, various deposition technologies have been developed in recent years, especially hydrothermal deposition method, which has achieved a great success. However, device performances are limited with severe carrier recombination, relating to the quality of absorber and interfaces. Herein, bulk and interface defects are simultaneously suppressed by regulating heterogeneous nucleation kinetics with barium dibromide (BaBr2) introduction. In details, the Br adsorbs and dopes on the polar planes of cadmium sulfide (CdS) buffer layer, promoting the exposure of nonpolar planes of CdS, which facilitates the favorable growth of [hk1]‐Sb2(S,Se)3 films possessing superior crystallinity and small interface defects. Additionally, the Se/S ratio is increased due to the replacement of Se by Br, causing a downshift of the Fermi levels with a benign band alignment and a shallow‐level defect. Moreover, Ba2+ is located at grain boundaries by coordination with S and Se ions, passivating grain boundary defects. Consequently, the efficiency is increased from 7.70 % to 10.12 %. This work opens an avenue towards regulating the heterogeneous nucleation kinetics of Sb2(S,Se)3 film deposited via hydrothermal deposition approach to optimize its crystalline orientation and defect features.

Heterogeneous Nucleation Regulation Amends Unfavorable Crystallization Orientation and Defect Features of Antimony Selenosulfide Film for High-Efficient Planar Solar Cells.

Antimony selenosulfide (Sb2(S,Se)3) has obtained widespread concern for photovoltaic applications as a light absorber due to superior photoelectric features. Accordingly, various deposition technologies have been developed in recent years, especially hydrothermal deposition method, which has achieved a great success. However, device performances are limited with severe carrier recombination, relating to the quality of absorber and interfaces. Herein, bulk and interface defects are simultaneously suppressed by regulating heterogeneous nucleation kinetics with barium dibromide (BaBr2) introduction. In details, the Br adsorbs and dopes on the polar planes of cadmium sulfide (CdS) buffer layer, promoting the exposure of nonpolar planes of CdS, which facilitates the favorable growth of [hk1]-Sb2(S,Se)3 films possessing superior crystallinity and small interface defects. Additionally, the Se/S ratio is increased due to the replacement of Se by Br, causing a downshift of the Fermi levels with a benign band alignment and a shallow-level defect. Moreover, Ba2+ is located at grain boundaries by coordination with S and Se ions, passivating grain boundary defects. Consequently, the efficiency is increased from 7.70 % to 10.12 %. This work opens an avenue towards regulating the heterogeneous nucleation kinetics of Sb2(S,Se)3 film deposited via hydrothermal deposition approach to optimize its crystalline orientation and defect features.

A Catalyst Tube-Equipped Dual-Stage Tube Furnace System for Accurate Hg Isotopic Determination of Ore Samples Using Neptune Plus Multicollector Inductively Coupled Plasma Mass Spectrometry.

Mercury (Hg) isotopes, which display mass-dependent fractionation and mass-independent fractionation, provide a multidimensional tracer to decipher the source of metals in mineral deposits. However, mineral ore samples usually contain abundant interfering elements (e.g., Te) that can cause inaccurate Hg isotopic analysis. Available acid digestion and combustion methods failed to remove these interfering elements, hindering the application of Hg isotopes for metallogenetic tracing. Here, we developed a new dual-stage tube furnace system employing a Mn-containing catalyst tube to pretreat mineral ore samples. This method yielded good Hg recoveries (100.5 ± 3.8%, 1SD, n = 15) and low levels of interfering elements in sample solutions, allowing for accurate analysis of a series of ore standard reference materials (GBW-11108v: coal; GSO-3: Cu-Ag sulfide ore; GBW 07859: Au-Te sulfide ore). The new method was also successfully applied to measure the Hg isotopic composition of magmatic and hydrothermal ore deposits, which yielded a large range in Δ199Hg value (-0.19 to 0.22‰) for ore deposits formed in different geological settings, highlighting the future applications of this method for metallogenic tracing, especially tracing the source of metals in mineral ore deposits.

A Comprehensive Geophysical Exploration of Sedimentary Exhalative Deposits: An Example from the Huaniushan Lead–Zinc–Silver Polymetallic Deposit in Gansu, China

The Huaniushan lead–zinc–silver deposit is a hydrothermal sedimentary exhalative deposit (SEDEX), and the mining area has complex geological conditions, with the main tectonic structure being the Huaheitan–Shuangfengshan Fault (F3), which controls the distribution of strata and magmatic rocks. Since the discovery of the Huaniushan lead–zinc–silver deposit, diverse interpretations of its genesis and metallogeny have been proposed, making it challenging to establish a definitive geological explanation. Moreover, using a single geophysical exploration method relies on limited rock physical parameters, making it difficult to effectively characterize underground structures. The combined use of multiple geophysical methods can effectively integrate the geophysical characteristics of different rock physical parameters, reducing the multiplicity and uncertainty of the inverse interpretation of geophysical data. The comprehensive interpretation of three-dimensional inversion based on various geophysical data, the construction of geological–geophysical models on geological grounds, the establishment of hidden ore exploration and positioning, and the rapid evaluation of geophysical technological systems are the current research trends in mineral exploration. In light of this, in this study, we conducted research on the three-dimensional inversion interpretation of gravity and magnetoelectric exploration data of the Huaniushan sedimentary exhalative lead–zinc–silver polymetallic deposit and constructed a three-dimensional geological–geophysical model of the study area based on the obtained three-dimensional physical structure of the underground density, magnetization intensity, resistivity, and polarizability of the study area, in combination with related geological and drilling hole data. Finally, we comprehensively interpreted the favorable mineralization sites in the study area.

Development of hydrophilic carbon fiber textiles using seed-assisted hydrothermal deposition of ZnO nanostructures for enhanced interfacial interaction in CFRP composites

Two-step hydrothermal deposition of zinc-oxide (ZnO) nanorods was used to functionalize carbon fiber textiles in order to produce increased hydrophilicity on fiber surface. On carbon fiber textiles, tightly packed ZnO nanorods developed after five seed cycles and 5 h of growth treatment in a 30 mM precursor salt based on the hydrothermal synthesis. Extensive characterizations have been performed on field emission scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, Energy-dispersive X-ray spectroscopy, High resolution transmission electron microscopy, Photoluminescence spectroscopy, and Raman spectroscopy to assess the different aspects such as structural, morphological, elemental, and wettability of the plain and ZnO-modified carbon fiber textiles. ZnO nanomaterial having hexagonal nanorods shape and wurtzite crystalline structure were uniformly deposited on the fabrics. Owing to the wettability study, ZnO prisms improved the hydrophilicity of virgin carbon fiber textiles to enable strong bonds with polymer matrix. The findings highlight the significant improvement in the static water contact angle as a result of the samples' ZnO coating's ability to reduce surface free energy. The improved hydrophilicity in carbon fiber may enhance the bonding between carbon fibers and matrix materials in composite materials. Hydrophilic carbon fibers are more easily wetted by the matrix materials, allowing for better penetration of the matrix into the fiber structure.

Geochronology, in-situ elements and sulfur isotopes of sulfides from the Songjiashan cobalt-iron deposit in the Zhongtiao mountains of North China Craton: Implications for cobalt occurrence and ore genesis

The Songjiashan Co-Fe deposit in the central part of the “Tongshan skylight” on the southeastern edge of the Zhongtiao Mountains is hosted by the volcanic-sedimentary rock series of the Paleoproterozoic Songjiashan Group. The spatial distribution of the orebodies is controlled by south-north trending rock units. Based on microscopic observations, the dominant ore minerals included magnetite, pyrite, chalcopyrite, carrollite, and linnaeite, while gangue minerals comprised quartz, calcite, sericite, and chlorite. Cobalt-iron ores had massive, banded, disseminated, and veinlet texture, and alteration of the host rocks included silicification, sericitization, pyritization, carbonation, and chloritization. Mineralization processes of the Songjiashan deposit were grouped into three periods: sedimentation, metamorphism, and hydrothermal. The Co concentrations in hydrothermal pyrite (Py-III) varied from 1.05 % to 3.75 %, with an average of 2.45 %. Cobalt in pyrite was homogeneously distributed and inversely correlated to Fe, indicating that Co isomorphically replaced Fe in pyrite. The characteristic Co/Ni ratio of pyrite varied greatly, ranging from 0.1 to 1000, reflecting various genetic types of sedimentation, metamorphism, and hydrothermal mineralization, with the main mineralization period primarily related to hydrothermal activities. Zircon U-Pb geochronology of the host rock and Re-Os isochron of Co-bearing pyrites indicate that Co mineralization mainly occurred at ∼2100 Ma. In-situ S isotopic analysis of sulfides reveals two peak δ34S values of 5–9 ‰ and 12–16 ‰. We interpret that the former value reflects the mixing of volcanic and marine sulfate sources, while the latter value is mainly artributted to marine sulfate sources. All δ34S values were lower than those of Proterozoic marine sulfates (15–20 ‰). Accordingly, we infer that thermochemical sulfate reduction plays a key role in marine sulfate reduction, and that the formation of Co-rich ore bodies in the Songjiashan deposit have undergone processes of initial sedimentation, metamorphism-deformation, and subsequent hydrothermal overprinting. Genetically, we suggest that the Songjiashan deposit belongs to a sedimentary-metamorphic hydrothermal superposition type Co-Fe deposit.

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.

Contribution of bismuth melts to gold endowment in the Baolun gold deposit, Hainan Island, South China

Bismuth (Bi) melts and related polymetallic alloys can efficiently scavenge gold (Au) from Au-unsaturated aqueous solutions, contributing to the Au endowment in many hydrothermal deposits. However, original evidence for Au–Bi melts is often poorly preserved due to post-precipitation alteration. This complicates investigation of the liquid bismuth collector model in hydrothermal Au deposits. Here we present primary evidence for the occurrence of Au–Bi melt in hydrothermal systems through an examination of the Au–Bi phases and textures in the Baolun Au deposit (Hainan Island). This study found that maldonite, native bismuth, Au–Bi symplectite and Au–Bi melt blebs appeared successively following the precipitation of native gold. Notably, large Au–Bi melt blebs were well preserved in natural systems due to the rapid cooling of fluids. The mineral assemblages and their corresponding fluid physiochemical conditions suggest that the evolution of the ore fluids at Baolun was characterized by a continuous reduction in Au and Bi concentrations and Au/Bi ratios alongside decreasing fluid temperatures and sulfur fugacity (fS2). These observations offer direct evidence for Au scavenging by Bi melts in a mesothermal (275–450 °C), low-fS2 and reduced hydrothermal system, aligning well with the Au–Bi binary phase evolution established in metallurgy. As the fluid cooled further, the Au–Bi phases were subsequently overprinted by later Te–S-rich fluids, as evidenced by the formation of bismuthinite, jonassonite, and joséite-A around the Au–Bi phases. Importantly, our study reveals that the Baolun Au deposit ischaracterizedby a Au–Bi–Te hydrothermal system and that the metamorphic country rocks at Baolun are the major source of Au, Bi, and Te.

ZnO/AgSbO3 as an improved nanophotocatalyst in the synthesis of some naphthopyranopyrimidines

The design of heterogeneous photocatalyst ZnO/AgSbO3 by incorporating zinc oxide (ZnO) and silver antimonate (AgSbO3) afforded a new efficient photocatalyst. The physicochemical and optical properties of the synthesized material were also studied by various common techniques such as FE-SEM, FT-IR, XRD, EDS, DRS, and UV–Vis. The hydrothermal deposition method was used for the synthesis of this nanocomposite and led us to control structural integrity of the nanomaterial with improved charge separation efficiency. In this study, ZnO/AgSbO3 photocatalyst effectively facilitated synthesis of different naphthopyramidines by increasing charge separation, generating reactive species, and promoting the desired chemical transformation under a green-light irradiation. This approach not only improved efficiency, but also contributed to a more environmental benign approach for the synthesis of the target heterocycles. The results showed that the reaction efficiency is around 97 % based on the isolated yield under optimal conditions. The best reaction condition involved condensation of benzaldehyde (1 mmol), 2-naphthol (1 mmol), and N,N-dimethylbarbituric acid (1 mmol) in a mixture of ethanol (3 ml) and deionized water (1 ml) in the presence of ZnO/AgSbO3 (0.006 g) at room temperature under irradiation of a green light emitting diode. Reusability experiments revealed that FT-IR, XRD, and FE-SEM of the new and reused photocatalysts are comparable, confirming stability of the nanomaterial during the condensation reaction.

Quantifying element mass transfer in the Jiling Na-metasomatic hydrothermal uranium deposit, Northwest China

The Na-metasomatic hydrothermal uranium deposits are relatively widespread, low in grade (less than 1 % U3O8) but high in tonnage. Although it has been considered that this type of deposit was formed due to hydrothermal alteration unrelated to magmatic activity, the detailed evolution of fluids and ore-forming process are still not well understood. Through element-mass-balance calculation and geochemical mapping of regional rocks, we investigated the Jiling uranium deposit in northwestern China and evaluated the composition and source of fluids and element-transfer behavior through Na-metasomatism and uranium mineralization. The findings show that, in the early Na-metasomatism stage, the Na-, HFSE- and REE-rich late-magmatic hydrothermal fluids caused Na-metasomatism of wall rocks, enriching Na2O (>53 %) while removing K2O (<-78 %), depleting SiO2 (30 % in granite and 3 % in diorite), and massively mass-transferring Fe, Ti, P and some incompatible elements. With increased rock permeability and the formation of partial Fe2+-bearing minerals, the Na-metasomatic alteration produced reducing agents and migration channels for ore-forming fluids, as well as the creation of ∼ 15 vol% porosity in the altered granite for metallogenic space. In the late uranium mineralization stage, CO2-rich fluids extracted uranium and HREEs, converted Fe2+ to Fe3+, and subsequently precipitated uranium to form pitchblende with apatite, calcite and chlorite. Thus, the Na-metasomatic alteration caused by late-magmatic hydrothermal fluids is critical for the production of large Na-metasomatic hydrothermal uranium deposits. Our new geochemical mapping reveals that the mass-concentration changes of Na, K and Si are more credible to defining Na-metasomatic alteration, while Fe, Ti, P, ∑(Zr-Hf-Nb-Ta) and ∑LREE/∑HREE vary strikingly during the uranium mineralization process.

In Situ Photoelectrodeposited Polyaniline on Ti‐Doping Hematite For Highly Selective Photoelectrochemical Oxygen Demand Determination

AbstractChemical Oxygen Demand (COD), as a detection indicator of water pollution, is of particular importance in assessing organic pollution in water. Furthermore, accurate and simple measuring COD methods are essential for water quality assessment and pollution control. However, the photoelectrochemical oxygen demand (PECOD) measurement, as one of the measuring COD methods, is affected by the reaction of water splitting, which is one of the hindrances to the commercialization of the analytical method of the PeCOD measurement. Hence, to overcome this challenge, a new PANI/Ti:Fe2O3 photoanode is constructed by hydrothermal and photoelectrochemical (PEC) deposition methods and investigated their optical properties and photoactivity. Under optimization conditions, it is discovered that the oxidation of organic compounds produces a net steady‐state current (inet) is directly proportional to COD concentration, with a detection limit of 1 mM glucose solution and a wide linear detection range of 1–78.125 mM, which is suitable for high concentration of glucose detection. As has been noted, PANI/Ti:Fe2O3 photoanode overcomes the obstacles to the practical application and eventual commercialization of the PECOD technology.

The orientation of intra-arc crustal fault systems influences the copper budget of magmatic-hydrothermal fluids

Some of the largest magmatic-hydrothermal copper ore deposits and deposit clusters are associated with arc-oblique fault systems. Whether this structural context impacts the geochemistry of hydrothermal fluids, including their copper contents, remains unknown. Here, we investigate the copper concentration and helium isotope signature of geothermal fluids as modern analogs of hydrothermal ore deposits in the Andes of central-southern Chile. We show that fault systems broadly parallel to the regional stress field facilitate the early release of fluids from deep primitive magmas. By contrast, fault systems oblique to the regional stress field prevent the early escape of fluids and promote magmatic enrichment in copper, volatiles, and ligands, enhancing the potential to form copper deposits. We conclude that the orientation of fault systems actively influences the copper budget of ascending hydrothermal fluids, explaining the contrasting distribution of metals along distinct structures often observed in porphyry-epithermal systems and other types of magmatic-hydrothermal deposits.

Control of magmatic halogen composition and redox state on the zonation of metal mineralization across active continental margins: Perspectives from the world-class South China metallogenic province

Active continental margins are the major sites of continental magmatism and associated hydrothermal ore deposits with a broad metal spectrum. Mineralization across active continental margins typically displays spatial zonation, with porphyry copper-(molybdenum‑gold) deposits in volcanic arcs and tin- and tungsten-dominated mineralization occurring further inland in a back-arc setting. Particularly, tin and tungsten commonly form separate deposits in back-arc regions, even though both metals exhibit similar lithophile behavior. The key factors governing this metallogenic zonation remain unclear. The world-class South China metallogenic province hosts over 50 % of the global tungsten resources, along with a significant amount of tin and copper resources distributed in different mineralization belts, making it an ideal location in which to study regional metal zonation. Here, we comprehensively integrate a very large dataset of the halogen volatile composition (F, Cl) and oxygen fugacity of granites related to tin, tungsten, and copper mineralization in the South China continental margin. Our compilation, derived from a substantial collection of zircon, apatite, mica, and whole-rock geochemistry data, suggests that lateral variations in granite magmatism (away from the trench), transitioning from chlorine-rich and oxic to fluorine-rich and reduced conditions, exert the primary control on copper versus tin‑tungsten mineralization in the arc and back-arc regions, respectively. Differences in oxygen fugacity have a minor impact on the decoupling of tin and tungsten mineralization despite tin granites being universally reduced (ΔFMQ = −1.8 to −0.1, where FMQ is the fayalite-magnetite-quartz redox buffer) and tungsten granites having a broader redox range (ΔFMQ = −1.5 to +1.2). Instead, the disparity in fluorine content plays a more crucial role in controlling the spatial separation of tin and tungsten mineralization observed in the back-arc setting. Nd-Hf and He-Ar isotopic modeling calculations suggest that magmas linked to tin mineralization have a more pronounced involvement of F-rich mantle components compared to those associated with tungsten. Elevated fluorine (ca. 650–8000 ppm) in tin-associated magmas allowed an extreme degree of magmatic differentiation and delayed fluid exsolution due to high H2O solubility in F-rich silicate melts, ensuring Sn enrichment in highly evolved melts. In contrast, early fluid exsolution under less F-rich conditions (ca. 100–700 ppm) led to early tin loss from the melts, ultimately resulting in tungsten-dominant mineralization. This work emphasizes the combined influence of halogen composition and redox state on the regional mineralization zonation in world-class metallogenic provinces, providing vectors for global metal exploration in both past and currently active continental margins.

Adsorbents Produced from Olive Mill Waste and Modified to Perform Phenolic Compound Removal

Olive mill waste (olive pomace, OP, and olive stone, OS) was used in this work to produce adsorbents for the removal of five phenolic acids typically found in olive mill wastewater. OP and OS were subjected to different treatments (combined or not) that were chemically modified (NaOH) or physically modified by two different methods, incipient wetness impregnation (IWI) and hydrothermal deposition (HD), and even biochar production obtaining a total of 16 materials. The materials were characterized by different analytical techniques such as N2 absorption, scanning electron microscopy, infrared spectroscopy, and pH zero-potential charge. The mixture of five phenolic acids was used to evaluate in batch conditions the adsorption capacity of the prepared materials. OS chemically modified with IWI (OSM-IWI) and OS biochar with HD (BOS-HD) presented better adsorption capacity at 157.1 and 163.6 mg/g of phenolic acids, respectively, from a total of 200 mg/g. For some materials, the surface area cannot be correlated with adsorption capacity, unlike pHzpc, where high values fit better adsorption rates. The infrared spectroscopy profile indicates the presence of O-H and N-H functional groups and, the last one, red-shifted in the IWI preparation compared to the HD one. In addition to this, the prepared material from olive mill waste can be suitably used for the mixture of phenolic compounds.

Deterministic modelling for driving factors of mineralization in Shanggong gold deposit (China)

1. Three-dimensional (3D) deterministic modeling is crucial for analyzing the controlling factors of mineralization. The Shanggong gold deposit, situated in the southern margin of North China Craton, represents a magmatic hydrothermal deposit. To construct the 3D deterministic model, boreholes, cross-sections, and geochemistry assays are integrated based on the geological characteristics of the Shanggong gold deposit. This paper summarizes its contents as follows: 1) GoCAD software can be utilized to build a 3D geology model encompassing faults and ore bodies; 2) Geostatistics and discrete smooth interpolation (DSI) can be employed to create a 3D attribute model involving grade and Au/Pb ratio. The findings reveal that: 1) High-value zones are associated with NE and NNE trending cross faults; 2) Deterministic modeling, such as grade model and Au/Pb ratio model, effectively elucidates the metallogenic process mechanism.