Search Results (104)

The Mianhuakeng deposit, located within the Zhuguangshan batholith in the Nanling area, is currently recognized as the largest granite-related uranium deposit in China. A portion of the uranium ore bodies is spatially associated with NE-trending mafic veins within the granite. In this study, the field investigation, zircon U-Pb dating, S and Pb isotope analysis, and whole-rock geochemical analysis were conducted on these mafic veins to explore their crystallization age, petrogenesis, tectonic setting, and relationships with uranium mineralization. The weighted mean result of zircon U-Pb is 189 ± 3 Ma, suggesting that the mafic dyke was crystallized during the Early Jurassic. The whole-rock geochemistry and isotopes exhibit characteristics of intraplate basalts, suggesting that the mafic dykes originate from an enriched mantle source consisting of garnet–spinel lherzolite, with an estimated partial melting of 1%–5%. Mafic magmas underwent low-degree contamination from the lower crust during upwelling, induced by the extension of the lithosphere during the Early Jurassic. The analyses of pyrite sulfur isotopes in mafic samples vary between −2.9‰ and 1.8‰, significantly different from that of pyrite (−14.4‰ to −7.8‰) formed during the uranium mineralization. Furthermore, the ages of the pitchblende of 127–54 Ma are much younger than the crystallization ages of mafic dykes, indicating that the mafic magmas did not contribute to the uranium mineralization of Mianhuakeng deposit during magmatism. However, the abundant reducing minerals (e.g., pyrite, hornblende, and Fe²⁺-bearing minerals) in the mafic dykes can act as a redox barrier, reducing mobile U⁶⁺ to immobile U⁴⁺ during fluid–rock interaction, thereby facilitating uranium precipitation from the hydrothermal ore-forming fluids. The secondary fractures created by the intrusion of mafic magma probably provided favorable pathways for the movement of hydrothermal fluids. Full article

As rapidly developing consumer products, cosmetics confront challenges regarding safety, especially hazardous ingredients, like sex hormones. Prolonged exposure to trace sex hormones in cosmetics can inflict immeasurable damage to human health. To accurately detect the trace amounts of sex hormones in cosmetics, a reliable method was developed and validated using ultra-high performance liquid chromatography–mass spectrometry (UHPLC-MS/MS) with magnetic solid-phase extraction (MSPE) and isotope-labeled internal standards (IL-ISs). The conditions of sample pretreatment, chromatography, and mass parameters were systemically investigated. In the MSPE procedure, the commercial Fe₃O₄@HLB magnetic material was employed for sample pretreatment, which was beneficial for operation, as well as sample purification and analyte enrichment. The utilization of IL-ISs compensated for potential matrix effects and losses during sample preparation, thereby improving precision and accuracy. Based on the proposed MSPE technology, UHPLC-MS/MS can address the qualitative and quantitative analysis needs for target analytes in complex cosmetic matrices. At three fortification levels, recoveries were in the range of 71.7–116.2%, with a relative standard deviation (RSD) ranging from 1.6% to 8.3%. Furthermore, based on the method proposed here, a total of 116 batches of cosmetics were analyzed, and trace progestins and estrogens were discovered in 10 samples. The MSPE method, coupled with UHPLC-MS/MS using IL-ISs, was convenient, efficient, and feasible for detecting trace amounts of sex hormones in cosmetics. The method scored 0.66 (out of 1) on the AGREE metric, confirming its green profile. Based on the detected concentrations, a preliminary safety evaluation was performed to assess the potential health risks of residual progesterone in hair loss prevention cosmetics by calculating the margin of safety (MoS). Full article

Jiaodong Gold Province is a globally rare giant gold cluster, with ongoing debates regarding its metallogenic material sources and mineralization mechanisms. This study focuses on the Linglong quartz-vein-type gold deposit within the Zhaoping Fault Zone, conducting in situ trace element and S-Pb isotope analyses of pyrite from different mineralization stages. The trace element characteristics were investigated to explore the sources of metallogenic materials, the evolution of ore-forming fluids, and the mechanisms of gold precipitation. The main findings are as follows: (1) In the Linglong gold deposit, gold primarily enters the pyrite lattice as a solid solution (Au⁺) through Au-As coupling. From the Py1 to Py3 stages, Co and Ni contents significantly decrease, while Cu, As, Au, and polymetallic element contents continuously increase. Additionally, Cu mainly replaces Fe²⁺ in the form of Cu²⁺, whereas Pb predominantly exists as micro inclusions of galena. (2) The S isotope (Py1: δ³⁴S = +7.60‰–+8.25‰, Py2: δ³⁴S = +6.15‰–+8.15‰, Py3: δ³⁴S = +6.90‰–+9.10‰) and Pb isotope (²⁰⁶Pb/²⁰⁴Pb = 16.95–17.715, ²⁰⁷Pb/²⁰⁴Pb = 15.472–15.557, ²⁰⁸Pb/²⁰⁴Pb = 37.858–38.394) systems collectively constrain the ore-forming materials such that they are dominated by metasomatized enriched lithospheric mantle, with simultaneous mixing of crustal materials. (3) The ore-forming fluid underwent a continuous evolution process characterized by persistently decreasing temperatures and a transition from mantle-dominated to crust–mantle mixed sources. The Py1 stage was predominantly composed of mantle-derived magmatic fluids uncontaminated by crustal materials, representing a high-temperature, closed environment. In the Py2 stage, the fluid system transitioned to an open system with the incorporation of crustal materials. Through coupled substitution of “As³⁺ + Au⁺ → Fe²⁺” and dissolution–reprecipitation processes, gold was initially activated and enriched. During the Py3 stage, pyrite underwent dissolution–reprecipitation under tectonic stress and fluid activity, promoting extraordinary element enrichment and serving as the primary mechanism for gold precipitation. Concurrently, bismuth–tellurium melt interactions further facilitated the precipitation of gold minerals. Full article

The Dongping manganese (Mn) deposit, located within the Lower Triassic Shipao Formation of the Youjiang Basin, is one of South China’s most significant sedimentary Mn carbonate ore deposits. To resolve longstanding debates over its metallogenic pathway, we conducted integrated sedimentological, mineralogical, and geochemical analyses on three drill cores (ZK5101, ZK0301, and ZK1205) spanning the Mn ore body. X-ray diffraction and backscatter electron imaging reveal that the ores are dominated by kutnohorite, with subordinate quartz, calcite, dolomite, and minor sulfides. The low enrichment of U/Al, V/Al, and Mo/Al, as well as positive Ce anomalies, consistently suggest that Mn, in the form of oxides, was deposited in an oxic water column. Carbon isotope compositions of Mn carbonate ores (δ¹³C_VPDB: −2.3 to −6.1‰) and their negative correlation with MnO suggest that Mn carbonate, predominantly kutnohorite, show a diagenetic reduction in pre-existing Mn oxides via organic-matter oxidation in anoxic sediments pore waters. Elemental discrimination diagramms (Mn-Fe-(Co+Ni+Cu) × 10 and Co/Zn vs. Co+Cu+Ni) uniformly point to a hydrothermal Mn source. We therefore propose that hydrothermal fluids supplied dissolved Mn²⁺ to an oxic slope-basin setting, precipitating initially as Mn oxides, which were subsequently transformed to Mn carbonates during early diagenesis. This model reconciles both the hydrothermal and sedimentary-diagenetic processes of the Dongping Mn deposit. Full article

The Junggar Basin contains a large amount of coal resources and is an important coal production base in China. The coal seam in Zhundong coalfield has a large single-layer thickness and high content of inertinite, but large particle Fe-sulphide minerals are associated with coal seams in some mining areas. A series of economic and environmental problems caused by the combustion of large-grained Fe-sulphide minerals in coal have seriously affected the economic, clean and efficient utilization of coal. In this paper, the ultra-thick coal seam of the Xishanyao formation in the Yihua open-pit mine of the Zhundong coalfield is taken as the research object. Through the analysis of coal quality, X-ray fluorescence spectrometer test of major elements in coal, inductively coupled plasma mass spectrometry test of trace elements, SEM-Raman identification of Fe-sulphide minerals in coal and LA-MC-ICP-MS test of sulfur isotope of marcasite, the coal quality characteristics, main and trace element characteristics, macro and micro occurrence characteristics of Fe-sulphide minerals and sulfur isotope characteristics of marcasite in the ultra-thick coal seam of the Xishanyao formation are tested. On this basis, the occurrence state and genesis of large particle Fe-sulphide minerals in the ultra-thick coal seam of the Xishanyao formation are clarified. The main results and understandings are as follows: (1) the occurrence state of Fe-sulphide minerals in extremely thick coal seams is clarified. The Fe-sulphide minerals in the extremely thick coal seam are mainly marcasite, and concentrated in the YH-2, YH-3, YH-8, YH-9, YH-14, YH-15 and YH-16 horizons. Macroscopically, Fe-sulphide minerals mainly occur in three forms: thin film Fe-sulphide minerals, nodular Fe-sulphide minerals, and disseminated Fe-sulphide minerals. Microscopically, they mainly occur in four forms: flake, block, spearhead, and crack filling. (2) The difference in sulfur isotope of marcasite was discussed, and the formation period of marcasite was preliminarily divided. The overall variation range of the δ³⁴S value of marcasite is wide, and the extreme values are quite different. The polyflake marcasite was formed in the early stage of diagenesis and the δ³⁴S value was negative, while the fissure filling marcasite was formed in the late stage of diagenesis and the δ³⁴S value was positive. (3) The coal quality characteristics of the thick coal seam were analyzed. The organic components in the thick coal seam are mainly inertinite, and the inorganic components are mainly clay minerals and marcasite. (4) The difference between the element content in the thick coal seam of the Zhundong coalfield and the average element content of Chinese coal was compared. The major element oxides in the thick coal seam are mainly CaO and MgO, followed by SiO₂, Al₂O₃, Fe₂O₃ and Na₂O. Li, Ga, Ba, U and Th are enriched in trace elements. (5) The coal-accumulating environment characteristics of the extremely thick coal seam are revealed. The whole thick coal seam is formed in an acidic oxidation environment, and the horizon with Fe-sulphide minerals is in an acidic reduction environment. The acidic reduction environment is conducive to the formation of marcasite and is not conducive to the formation of pyrite. (6) There are many matrix vitrinite, inertinite content, clay content, and terrigenous debris in the extremely thick coal seam. The good supply of peat swamp, suitable reduction environment and pH value, as well as groundwater leaching and infiltration, together cause the occurrence of large-grained Fe-sulphide minerals in the extremely thick coal seam of the Xishanyao formation in the Zhundong coalfield. Full article

This study explores the provenance of white marble architectural elements from Roman Philippopolis, with a particular focus on the Eastern Gate complex. By determining the origin of the marble, we aim to elucidate economic, social, and urban dynamics related to material selection and trade networks. The investigation examines the symbolic significance of prestigious marble in elite representation and highlights the role of quarry exploitation in the region’s economic and technological development. The Eastern Gate, a monumental ensemble integrated into the city’s urban fabric, was primarily constructed with local Rhodope marble, alongside imported materials such as Prokonnesian marble. Analytical methods included petrographic examination, chemical analysis of trace elements (Mn, Mg, Fe, Sr, Y, V, Cd, La, Ce, Yb, and U), and stable isotope analysis (δ¹⁸O, δ¹³C). Statistical evaluations were performed for each sample (37 in total) and compared with a comprehensive database of ancient quarry sources. The results underscore the dominance of local materials while also indicating selective use of imports, potentially linked to symbolic or functional criteria. The findings support the hypothesis of local workshop activity in the Asenovgrad/Philippopolis area and shed light on regional and long-distance marble trade during the Roman Imperial period, reflecting broader economic and cultural interconnections. Full article

The authentication of high-value spices such as paprika and cinnamon is critical due to increasing food fraud. This study explored the potential of a multi-analytical approach, combined with chemometric tools, to differentiate 45 paprika and 46 cinnamon samples from the Slovenian market based on their geographic origin, production methods, and possible adulteration. The applied techniques included stable isotope ratio analysis (δ¹³C, δ¹⁵N, δ³⁴S), multi-elemental profiling, FTIR, and antioxidant compound analysis. Distinct isotopic and elemental markers (e.g., δ¹³C, δ³⁴S, Rb, Cs, V, Fe, Al) contributed to classification by geographic origin, with preliminary classification accuracies of 90% for paprika (Hungary, Serbia, Spain) and 89% for cinnamon (Sri Lanka, Madagascar, Indonesia). Organic paprika samples showed higher values of δ¹⁵N, δ³⁴S, and Zn, whereas conventional ones had more Na, Al, V, and Cr. For cinnamon, a 95% discrimination accuracy was achieved between production practice using δ³⁴S and Ba, as well as As, Rb, Na, δ¹³C, S, Mg, Fe, V, Al, and Cu. FTIR differentiated Ceylon from cassia cinnamon and suggested possible paprika adulteration, as indicated by spectral features consistent with oleoresin removal or azo dye addition, although further verification is required. Antioxidant profiling supported quality assessment, although the high antioxidant activity in cassia cinnamon may reflect non-phenolic contributors. Overall, the results demonstrate the promising potential of the applied analytical techniques to support spice authentication. However, further studies on larger, more balanced datasets are essential to validate and generalize these findings. Full article

Arsenic (As) contamination in groundwater represents a major global public health threat, particularly in alluvial aquifer systems where redox-sensitive geochemical processes facilitate the mobilization of naturally occurring trace elements. This study investigates groundwater quality, particularly focusing on the origin of arsenic contamination in shallow and deep alluvial aquifers of the Lower Sakarya River Basin, which are crucial for drinking, domestic, and agricultural uses. Groundwater samples were collected from 34 wells—7 tapping the shallow aquifer (<60 m) and 27 tapping the deep aquifer (>60 m)—during wet and dry seasons for the hydrogeochemical characterization of groundwater. Environmental isotope analysis (δ¹⁸O, δ²H, ³H) was conducted to characterize origin and groundwater residence times, and the possible hydraulic connection between shallow and deep alluvial aquifers. Mineralogical and geochemical characterization of the sediment core samples were carried out using X-ray diffraction and acid digestion analyses to identify mineralogical sources of As and other metals. Pearson correlation coefficient analyses were also applied to the results of the chemical analyses to determine the origin of metal enrichments observed in the groundwater, as well as related geochemical processes. The results reveal that 33–41% of deep groundwater samples contain arsenic concentrations exceeding the WHO and Turkish drinking water standard of 10 µg/L, with maximum values reaching 373 µg/L. Manganese concentrations exceeded the 50 µg/L limit in up to 44% of deep aquifer samples, reaching 1230 µg/L. On the other hand, iron concentrations were consistently low, remaining below the detection limit in nearly all samples. The co-occurrence of As and Mn above their maximum contaminant levels was observed in 30–33% of the wells, exhibiting extremely low sulfate concentrations (0.2–2 mg/L), notably low dissolved oxygen concentration (1.45–3.3 mg/L) alongside high bicarbonate concentrations (450–1429 mg/L), indicating localized varying reducing conditions in the deep alluvial aquifer. The correlations between molybdenum and As (rdry = 0.46, rwet = 0.64) also indicate reducing conditions, where Mo typically mobilizes with As. Arsenic concentrations also showed significant correlations with bicarbonate (HCO₃⁻) (rdry = 0.66, rwet = 0.80), indicating that alkaline or reducing conditions are promoting arsenic mobilization from aquifer materials. All these correlations between elements indicate that coexistence of As with Mn above their MCLs in deep alluvial aquifer groundwater result from reductive dissolution of Mn/Fe(?) oxides, which are primary arsenic hosts, thereby releasing arsenic into groundwater under reducing conditions. In contrast, the shallow aquifer system—although affected by elevated nitrate, sulfate, and chloride levels from agricultural and domestic sources—exhibited consistently low arsenic concentrations below the maximum contaminant level. Seasonal redox fluctuations in the shallow zone influence manganese concentrations, but the aquifer’s more dynamic recharge regime and oxic conditions suppress widespread As mobilization. Mineralogical analysis identified that serpentinite, schist, and other ophiolitic/metamorphic detritus transported by river processes into basin sediments were identified as the main natural sources of arsenic and manganese in groundwater of deep alluvium aquifer. Full article

The Bayan Obo deposit, located on the northern margin of the North China Plate (NCP), is the world’s largest comprehensive Fe-REE-Nb deposit. After its formation, this deposit was affected by multiple tectonic thermal events, but the ages of these geological events are controversial. To determine the evolutionary history of the Bayan Obo deposit, we conducted a detailed study of the macroscopic and microscopic deformation characteristics of the ore district and selected representative minerals, such as riebeckite and biotite, which are widely present in the banded rocks of the deposit, for an ⁴⁰Ar-³⁹Ar isotopic analysis. The results show that a large number of deformation structures have developed in the carbonatite and surrounding rocks, including mineral bands, boudins, tight folds, and rotated porphyroclasts, suggesting that the region has undergone intense compression and shearing and that the deformation temperature can reach ~550 °C. ⁴⁰Ar-³⁹Ar plateau ages of 414.9 ± 1.4 Ma and 264.5 ± 2.5 Ma were obtained for the riebeckite and biotite, respectively. Using these results in conjunction with regional geological data and considering the closure temperature of the mineral isotope system, it was inferred that these two ages corresponded to two distinct reworking events experienced by the deposit during the Early Paleozoic and Late Paleozoic following its initial formation. These events corresponded to the collision between the Bainaomiao Arc and the NCP and the magmatic activity induced by a continental–continental collision during the closure of the Paleo-Asian Ocean (PAO), respectively. Full article

This study critically examines the early Cretaceous carbonate-hosted Zn-Pb (±Ba±Cu) deposits of the Malayer-Esfahan (MEMB) and Yazd-Anarak (YAMB) metallogenic belts in Iran, which have been inaccurately classified as Mississippi Valley type (MVT) deposits by Nejadhadad et al. (2025). Our findings reveal significant differences in mineralogy, fluid inclusion characteristics, and geochemical signatures compared to typical MVT deposits. These deposits are more akin to Irish-type Zn-Pb mineralization and formed in extensional and passive margin environments around the Nain–Baft back-arc basin. The normal faults in this back-arc rift can transform significantly during inversion and compressional tectonics, reactivating to behave as reverse faults and leading to new geological structures and landscapes. Our study highlights barite replacement as a crucial factor in forming sediment-hosted Zn-Pb (±Ba±Cu) and barite-sulfide deposits. Based on textural evidence, fluid inclusion data, and sulfur isotope analyses, we propose that barite plays a fundamental role in controlling subsequent Zn-Pb (±Ba±Cu) mineralization by serving as both a favorable host and a significant sulfur source. Furthermore, diagenetic barite may act as a precursor to diverse types of sediment-hosted Zn-Pb (±Ba±Cu) mineralization, refining genetic models for these deposits. Sulfur isotope analyses of Irish-type deposits show a broad δ³⁴S range (−28‰ to +5‰), indicative of bacterial sulfate reduction (BSR). Nevertheless, more positive δ³⁴S values (+1‰ to +36‰) and textural evidence in shale-hosted massive sulfide (SHMS) deposits suggest a greater role for thermochemical sulfate reduction (TSR) in sulfide mineralization. Full article

A diverse range of granitoids in the North Qilian Orogenic Belt (NQOB) offers valuable insights into the region’s tectonomagmatic evolution. In this study, we undertook a geochronological, mineralogical, geochemical, and zircon Hf isotopic analysis of granodiorites from the Yaogou area of the NQOB. Zircon U-Pb dating reveals that the Yaogou granodiorites formed during the Early–Middle Ordovician (473–460 Ma). The Yaogou granodiorites have high SiO₂ (63.3–71.1 wt.%), high Al₂O₃ (13.9–15.8 wt.%) contents, and low Zr (96–244 ppm), Nb (2.9–18 ppm), as well as low Ga/Al ratios (10,000 × Ga/Al ratios of 1.7–2.9) and FeO^T/MgO ratios (1.9–3.2), and are characterized by elevated concentrations of light rare earth elements and large-ion lithophile elements such as Rb, Th, and U, coupled with significant depletion in heavy rare earth elements and high-field-strength elements including Nb, Ta, and Ti. Additionally, the presence of negative europium anomalies further reflects geochemical signatures typical of I-type granitic rocks. The zircon grains from these rocks display negative ε_Hf(t) values (−14.6 to −10.7), with two-stage Hf model ages (T_DM2) from 2129 to 1907 Ma. These characteristics suggest that the magmatic source of the Yaogou granodiorites likely originated from the partial melting of Paleoproterozoic basement-derived crustal materials within a tectonic environment associated with subduction in the North Qilian Ocean. Integrating regional geological data, we suggest that during the Early Paleozoic, the North Qilian Oceanic slab underwent double subduction: initially southward, followed by a northward shift. Due to the deep northward subduction of the Qaidam continental crust and oceanic crust along the southern margin of the Qilian Orogenic Belt, the southward subduction of the North Qilian ocean was obstructed, triggering a reversal in subduction polarity. This reversal likely decelerated the southward subduction and initiated northward subduction, ultimately leading to the formation of the Yaogou granodiorites. These findings enhance our understanding of the complex tectonic processes that shaped the North Qilian Orogenic Belt during the Early Paleozoic, emphasizing the role of subduction dynamics and continental interactions in the region’s geological evolution. Full article

Superdeep diamonds and their syngenetic inclusions are crucial for understanding Earth’s deep carbon cycle and slab–mantle redox dynamics. The origins of these diamonds, especially their links to iron (Fe) carbides and ferropericlase with varying Mg# [=Mg/(Mg+Fe)_at], however, remain elusive. In this study, we performed high pressure–temperature (P-T) experiments (10–16 GPa and 1200–1700 K) across cold-to-warm subduction zones using a multi-anvil press. The results reveal a stepwise Fe-mediated carbonate reduction process for the formation of superdeep diamonds: MgCO₃ → Fe-carbides (Fe₃C/Fe₇C₃) → graphite/diamond. This mechanism explains two phenomena regarding superdeep diamonds: (1) anomalous ¹³C depletion results from kinetic isotope fractionation during ¹²C enrichment into the intermediate Fe-carbides; (2) nitrogen scarcity is due to Fe-carbides acting as nitrogen sinks. Ferropericlase [(Mg,Fe)O] formed during the reactions in our experiments shows Mg# variations (0.2–0.9), similar to those found in natural samples. High Mg# (>0.7) variants from lower temperature experiments indicate diamond crystallization from carbonatitic melts in the shallow lower mantle, while the broad Mg# range (0.2–0.9) from experiments at higher temperatures suggests multi-depth formation processes as found in Brazilian diamonds. These findings suggest that slab–mantle interactions produce superdeep diamonds with distinctive Fe-carbides and ferropericlase assemblages as inclusions, coupled with their ¹³C- and nitrogen-depleted signatures, which underscore thermochemical carbon cycling as a key factor in deep carbon storage and mantle mineralogy. Full article

The Emeishan Large Igneous Province (ELIP) is one of the largest igneous provinces, containing some of the world’s richest mineral resources. It mainly comprises magmatic Fe-Ti-V deposits and Cu-Ni sulfide deposits, with minor subvolcanic-type Fe deposits related to mafic–ultramafic rocks. The evaporite layer is involved in the metallogenic system, yet its contribution has not been examined in detail. In this study, an integrated geological study, single-mineral S and O isotopic analysis, and in situ S isotope analysis were carried out on pyrite and magnetite from the Kuangshanliangzi (KSLZ) subvolcanic-type Fe deposit to examine the role of evaporite layers in Fe mineralization. The O isotopic values of magnetite and the S isotopic values of pyrite were abnormally high in the KSLZ deposit. This indicates that the ore-forming system of the KSLZ deposit is contaminated by ¹⁸O- and ³⁴S-enriched evaporite layers, inferred from the Dengying Formation, which significantly increase the oxygen fugacity, sulfur fugacity, and water content of the metallogenic system via the basic–ultrabasic magma-upwelling process, thus promoting the formation of Fe ores. When the SO₄²⁻ (from evaporite layers) oxidizes Fe²⁺ to Fe³⁺, the SO₄²⁻ is reduced to S²⁻, and the ore-forming system can be changed from unsaturated sulfide to supersaturated sulfide, which also benefits the Cu-Ni sulfide deposit formation. Full article

The dispersed elements Ga, Ge, and In are crucial strategic mineral resources often enriched in Pb-Zn deposits. The Chipu Pb-Zn deposit, located on the western edge of the Yangtze Block, lies to the north of the Sichuan-Yunnan-Guizhou (SYG) Pb-Zn metallogenic province with large amounts of Emeishan basalt. Based on trace element and in situ sulfur isotope analyses by (LA)-ICP-MS, sphalerite is the main carrier mineral for Ga (17~420 ppm), Ge (3.87~444 ppm), and In (31~720 ppm). Ga or Ge correlate significantly with Cu, while In substitutes for Zn in sphalerite alongside Fe. Key substitution reactions include Ga³⁺ + Cu⁺ ↔ 2Zn²⁺, Ge⁴⁺ + 2Cu⁺ ↔ 3Zn²⁺, and 2In³⁺ + Fe²⁺ ↔ 4Zn²⁺. Sphalerite crystallized at medium to low temperatures (114–195 °C). Sulfide δ³⁴S values (+3.48 to +24.74‰) suggest sulfur mainly originated from Dengying Formation marine sulfates via thermochemical sulfate reduction (TSR). Metal-bearing fluid release at 30 Ma post-Emeishan mantle plume activity (261–257 Ma) coincides with the Chipu deposit’s mineralization period (230–200 Ma), suggesting the Chipu deposit is associated with Emeishan plume activity. The magmatic activity drove basinal brine circulation, extracting In from intermediate-felsic igneous rocks and metamorphic basement. Elevated temperatures promoted the coupling of Fe and In into sphalerite, causing anomalous In enrichment. Full article

Siderite and baryte are common non-sulphide phases in sedimentary exhalative (SEDEX) deposits, but their formation remains poorly understood. Siderite is important as an exploration vector in some deposits, whereas baryte is important as a S source in some deposits. The past-producing Walton deposit (Nova Scotia, Canada) consists of two ore types: (1) a sulphide body primarily hosted by sideritised Viséan Macumber Formation limestone (0.41 Mt; head grade of 350 g/t Ag, 4.28% Pb, 1.29% Zn, and 0.52% Cu), and (2) an overlying massive baryte body of predominantly microcrystalline baryte (4.5 Mt of >90% baryte). This study used optical microscopy, SEM-EDS, cathodoluminescence (CL), LA-ICP-MS, and SIMS sulphur isotope analysis of siderite and baryte to elucidate their origin and role in deposit formation. Siderite replaces limestone and contains ≤9 wt. % Mn, is LREE-depleted (PAAS-normalised REEY diagrams), and has low (<20) Y/Ho ratios. Sideritisation occurred due to dissimilatory iron reduction (DIR) that led to the breakdown of Fe-Mn-oxyhydroxides and organic matter, as indicated by light δ¹³C_VPBD values and negative Y anomalies. The baryte body is dominated by a microcrystalline variety that locally develops a radial texture and coarsens to a tabular variety; it also occurs intergrown with, and as veins in, massive sulphides. Based on fluid inclusion data from previous studies, the coarser baryte types grew from a hot (>200 °C) saline (25 wt. % NaCl) fluid containing CO₂-CH₄ and liquid petroleum. Marine sulphate δ³⁴S_VCDT values typical of the Viséan (~15‰) characterise the baryte body and some tabular baryte types, whereas heavier (~20‰) and lighter (~10‰) values typify the remaining tabular types. The variations in tabular baryte relate to distinct zones identified by CL imaging and are attributed to the sulphate-driven anaerobic oxidation of methane (SDAOM) and oxidation of excess H₂S after sulphide precipitation. These results highlight the importance of hydrocarbons (methane and organic matter) in the formation of both the siderite and the baryte at Walton and that DIR and the SDAOM can be important contributing processes in the formation of SEDEX deposits. Full article