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Lead and zinc mineralization have been documented in low-temperature Mississippi Valley type (MVT), Volcanogenic Massive Sulfide (VMS), and high-temperature porphyry and skarn ore deposits. These deposits are characterized by the precipitation of galena (PbS) and sphalerite (ZnS) from a saline hydrothermal fluid. The direct relationship between metal concentration and the total chloride of the fluid has been documented previously; however, the role of acidity has not been studied extensively. Experiments were conducted in René 41 cold-seal pressure vessels at temperatures of 200, 300, and 500 °C and a pressure of 100 MPa to provide better constraints on the formation of galena and sphalerite in hydrothermal systems spanning a range of fluid acidities (pH). The concentrations of Pb and Zn in the synthetic hydrothermal fluids were determined at galena and sphalerite saturation as a function of HCl and at a total chloride of 15 wt.% NaCl_eq.. Zn concentrations ranged from 1.7 (±0.3) × 10² µg/g at 200 °C and an HCl concentration of 2.28 × 10³ µg/g to 2.55 (±0.5) × 10³ µg/g at 500 °C and an HCl concentration of 3.40 × 10⁴ µg/g. Pb concentrations were 1.8 (±0.4) µg/g at 200 °C and a HCl of 2.28 × 10³ µg/g and increased to 7.93 (±1.5) × 10³ µg/g at 500 °C and a HCl concentration of 3.40 × 10⁴ µg/g. Zn/Pb mass ratios in the fluids at sphalerite and galena saturation decreased with increasing temperature. The experimental data demonstrate that the concentration of Pb and Zn in the fluid increase with both temperature and HCl concentration and, consequently, decrease with increasing pH. These results demonstrate that acidic fluids can transport substantially greater concentrations of Pb and Zn than neutral or basic fluids. Experimentally determined slopes of Pb and Zn concentrations as a function of HCl in the fluid provide empirical measurements of the apparent dependence of metal solubility on HCl at a constant total salinity. These results are consistent with Pb and Zn being transported predominantly as chloride-complexes under acidic, although the experiments do not directly determine aqueous metal speciation. Consequently, the experimentally determined HCl dependencies should be interpreted as empirical measures of apparent metal solubility rather than direct measurements of speciation or ligand coordination. The observed dependence of dissolved metal concentrations on HCl likely reflects the combined effects of chloride complexation, increasing HCl association with increasing temperature, non-ideal solution behavior, and changes in the distribution of dissolved chloride- and possibly sulfur-based complexes. Therefore, the neutralization of an acidic Pb- and Zn-bearing, chloride-rich hydrothermal fluid could produce substantial galena and sphalerite mineralization if sufficient reduced sulfur is available. In hydrothermal fluids depleted in reduced sulfur, H₂S must be supplied through sulfate reduction or by mixing with an H₂S-rich fluid to promote galena and sphalerite precipitation. Full article

Gallium (Ga) enrichment in sphalerite has been widely recognized; however, its enrichment mechanisms remain insufficiently understood. The South Hunan district, located at the intersection of the Nanling Region and the Qin-Hang Metallogenic Belt in South China, is characterized by abundant Jurassic magmatic-hydrothermal Pb–Zn deposits, which typically host Ga-depleted sphalerite. Recently, Ga-enriched sphalerite (up to 385 ppm by LA-ICP-MS) has been identified in newly drilled cores at Zhaojinci, adding complexity to the regional Pb–Zn metallogenic framework. EPMA elemental mapping and LA-ICP-MS time-resolved spectra indicate that Ga is homogeneously distributed within sphalerite, excluding the presence of micron-scale Ga-bearing mineral inclusions. A strong positive correlation between Ga and Cu concentrations suggests that Ga incorporation is facilitated by the coupled substitution of Zn²⁺ by Cu⁺. Sphalerite geothermometry yields formation temperatures of 118–138 °C (average 126 °C for GGIMF is and ~129 °C for SPRFT), accompanied by intermediate sulfur fugacity conditions (lg fS₂ = −22.9 to −21.2), which appear to favor Ga enrichment in sphalerite. The trace element geochemistry of the Zhaojinci sphalerite (Ga-Ge-Cd-enriched and Mn-In-Sn-Co-depleted), combined with its formation under low-temperature (120–180 °C) and intermediate fS₂ conditions (within the pyrite stability field), is consistent with MVT-like mineralization. This interpretation is supported by multiple lines of geological evidence, including the strict confinement of stratabound Pb–Zn mineralization to the Devonian Xikuangshan Formation limestone, structural control by syn-sedimentary normal faults, pervasive dolomitization of the host rocks, and the absence of genetic relationship to magmatic activity. Moreover, the sphalerite geochemical signature, corroborated by an XGBoost-based machine learning classifier, reinforce the MVT-like affinity for the Zhaojinci mineralization. This study not only emphasizes the importance of low-temperature and intermediate-fS₂ conditions in Ga enrichment within sphalerite, but also highlights the significance of discovering MVT-like sphalerite for Pb–Zn resource exploration in the South Hunan district, providing valuable new insights and directions for mineral prospecting in this geologically important region of South China. Full article

Hydrothermal fluids altered Mississippian (Osagian) carbonates in the Rebecca K. Bounds (RKB) core in western Kansas, U.S.A. Carbonate mineralization is similar to that associated with Mississippian valley type (MVT) mineralization. The RKB core displays fractures, vugs, channels, and breccias filled with saddle dolomite and blocky calcite cements. Homogenization temperature indicates that dolomite (65 to 126 °C, 18.4 to 23 wt. % NaCl) and calcite (67 to 101 °C, 13.2 to 22.4 wt. % NaCl) cements were precipitated by hot, saline fluids. These data are consistent with previous studies on the southern midcontinent. Carbon and oxygen isotope values for dolomite (δ¹³C 0.15 to 2.08‰, δ¹⁸O −6.44 to −4.66‰) and calcite (δ¹³C −1.01 to 1.79‰, δ¹⁸O −9.44 to −8.69‰) indicate multiple pulses of fluids likely sourced from basins to the south and west. Strontium isotopes data (0.7088812 to 0.7094432 in dolomite and 0.7089503 to 0.7111501 in calcite) indicate fluid interaction with granitic basement or basement-derived siliciclastics. These results are consistent with mixing of upwelling Ordovician-sourced fluids and Permian evaporitic brines, transported by advective and/or vertical migration. Although sulfide minerals were not observed in this study, earlier reports in western Kansas document sphalerite linked to hydrothermal brines in underlying strata. This study highlights the potential for MVT mineralization in the Mississippian of western Kansas. Full article

The metal-rich Vazante-Paracatu Mineral Belt, in central Brazil, hosts the Zn-Pb sulfide Morro Agudo District in the Mesoproterozoic (1.3–1.1 Ga) upper carbonate sequence of the Vazante Group. The Morro Agudo district is comprised of the Morro Agudo deposit and the Bento Carmelo, Sucuri, and Morro do Capão occurrences. This carbonate sequence also hosts the Fagundes, Ambrósia and Bonsucesso Zn-Pb sulfide deposits (northern part) and the zinc silicate Vazante and North Extension deposits (southern part). The structurally controlled, stratabound and stratiform styles of mineralization in the Morro Agudo orebodies have been variably classified as sedimentary exhalative, Irish-type and Mississippi Valley-type. In this study, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) spot analyses of sphalerite and galena from the Morro Agudo district revealed that red sphalerite (interpreted as the last stage) has higher Fe and Mn and lower Bi, Co, Cu, Ge, Hg, Tl compared to the other types of sphalerite, whereas the first generation of galena (Gn-I) is enriched in Ag, Cd, and Se and depleted in Cu and Mn relative to later galena (Gn-II). Mineral paragenesis and principal component analysis (PCA) of ore mineral composition suggest that the Morro Agudo, Sucuri and Morro do Capão mineralized zones formed by similar processes involving Zn-Pb mineralizing fluids with various compositions, comprising two main elemental associations: (1) Fe, As, In, Mn, Sb, Ag; and (2) Cd, Bi, Co, Ga, and Se. Bento Carmelo is distinguished in PCA by its unique dolomite-hosted sphalerite composition with elevated concentrations of Cu, Ge, Hg and likely formed from distinct fluids or processes. Temperatures of the mineralizing fluids for the Morro Agudo district range from 82 to 320 °C, calculated based on the trace element composition of sphalerite. The styles of mineralization and ore compositions are consistent with MVT deposits; however, fluid temperatures are hotter than typical MVT mineralizing fluids and may reflect a higher geothermal gradient or active advective fluid flow during the Brasiliano orogeny. Full article

Since the 12th century in the Silesian-Cracovian area, lead, litharge, and silver have been produced by the pyrometallurgical processing of Pb-Ag-Zn ore. Slags and soils contaminated with heavy metals (Zn, Pb, Cd, Fe, Mn, As) were the subject of this research. Samples were collected during archaeological works in the area of early medieval metallurgical settlement. The main goals of the analyses (Scanning Electron Miscroscopy-Energy Dispersive Spectroscopy (SEM-EDS), Electron Probe Microanalyzer (EPMA), X-ray diffraction (XRD), Atomic Absorption Spectroscopy (AAS)) were the determination of the mineralogical composition of furnace batches and smelting temperatures and conditions. In soils, the anthropogenic phases enriched in Pb, Zn, Fe, Mn, P, and primary minerals like goethite, ferrihydrite, sphalerite, galena, smithsonite, minrecordite, cerussite, gypsum, anglesite, jarosite, and hemimorphite were identified. The soil from former metallurgical settlements contained up to 1106 mg·kg⁻¹ Pb, 782 mg·kg⁻¹ Zn, 4.7 mg·kg⁻¹ Cd in the fine fraction. Much higher heavy metal concentrations were observed in the waste products of ore rinsing, up to 49,282 mg·kg⁻¹ Pb, 64,408 mg·kg⁻¹ Zn, and 287 mg·kg⁻¹ Cd. The medieval smelting industry and Pb-Ag-Zn ore processing are marked by highly anomalous geochemical pollution (Pb, Zn, Cd, Fe, Mn, Ba) in the topsoil. The methods of mineralogical investigation, such as SEM-EDS or EMPA, can be used to identify mineralogical phases formed during metallurgical processes or ore processing. Based on these methods, the characteristic primary assemblage and synthetic phases were identified in the area polluted by medieval metallurgy and mining of Pb-Ag-Zn ores, including MVT (Mississippi Valley Type) deposits. The minerals distinguished in slags and the structural features of metal-bearing aggregates allow us to conclude that batches have included mostly oxidised minerals (PbCO₃, ZnCO₃, CaZn(CO₃)₂, FeOOH), sulfides (PbS and ZnS) and quartz (SiO₂). The laboratory experiment of high-temperature heating of the examined slags showed that smelting temperatures used in the second half of 13th century were very high and could have reached up to 1550 °C. The results indicate, that geochemical and mineralogical methods can be used to obtain important information from archaeological sites, even after archaeological work has long ceased. Full article