Hydrothermal Fluids Research Articles

A hydrothermal plume on the Southwest Indian Ridge revealed by a multi-proxy approach: Impact on iron and manganese distributions (GEOTRACES GS02)

Iron (Fe) and manganese (Mn) are crucial micronutrients that limit oceanic primary productivity in the Southern Ocean. It has been recently suggested that hydrothermal activity may be an important source of oceanic dissolved iron, yet, this contribution is still not fully understood and only one active hydrothermal site has been reported on the Southwest Indian Ridge (SWIR), south of 40°S.Using a multi-proxy approach, this study demonstrates the occurrence of hydrothermal venting on the SWIR in the near vicinity of the location 44°51.690 S, 36°10.460 E, which is likely to be a low or moderately high temperature fluid. Indeed, we report high values of dissolved methane to manganese ratios (up to 11.1 ± 1.2 mol mol−1), low particulate iron (pFe) and manganese (pMn) concentrations (with maximum values of 0.7 nmol L−1 and 0.06 nmol L−1, respectively) associated with the presence of few oxyhydroxides, as well as high 223Radium (Ra) and 224Ra activities near the seafloor. The Fe and Mn data revealed a significant enrichment at depths influenced by hydrothermal circulation on the seafloor, within the Upper Circumpolar Deep Water. Dissolved Fe (dFe) and dissolved Mn (dMn) concentrations were enriched by 3- and 7-fold, respectively, and pFe and pMn by 2- and 1.5-fold, respectively, compared to a reference station located outside the SWIR. They were however lower than concentrations reported so far near high temperature vents, suggesting a weaker influence of this hydrothermal system on deep Fe and Mn reservoirs. We show that a large fraction of the dFe could be stabilized by organic complexation with humic substances (eHS, estimated 27–60% of dFe). High prokaryotic abundance related to the proximity of the hydrothermal vent suggests that other Fe-complexing ligands of biological origin might also stabilize Fe in its dissolved form. Collectively, these measurements integrated within the concept of a “multi-proxy approach”, helped painting a more detailed picture of the complex interactions and processes in this region of the SWIR. Although the system is a source of both dFe and dMn to the deep ocean, the low current velocities and the bathymetry likely limit the fertilization of surface water by dFe and dMn along this section of the SWIR.

Genesis of W mineralization in the Yangla Cu-polymetallic deposit (NW Yunnan, China): Constraints from scheelite microstructure, trace element, U-Pb dating and Sr isotope geochemistry

The Yangla Cu-polymetallic deposit is the largest skarn Cu deposit in the Jinshajiang suture zone. Recently, an new W orebody was identified in the depths of the Cu orebodies. However, the genetic relationship between W and Cu orebodies, along with the tungsten ore-forming processes, remains unclear. This study delves into the careful investigation of three types of scheelites focusing on microstructure, trace element compositions and Sr isotope geochemistry. The aim is to elucidate the source and evolution of ore-forming fluids and ore genesis in the multi-episodic metallogenic systems. Primary scheelite (Sch-I) generally displays oscillatory zoning in CL images with the lowest REE (3.8–142 ppm) and highest Sr (604–1480 ppm) contents. Secondary scheelite (Sch-III), commonly precipitated as overprinting rims on primary crystal, has the highest REE (145–1071 ppm) and lowest Sr (376–793 ppm) contents. In contrast, Sch-II represents a transitional stage from primary to secondary, with REE and Sr contents at intermediate levels. Sch-I is characterized by LREE enrichment and a positive Eu anomaly in the chondrite-normalized REE patterns, whereas Sch-III shows MREE-rich patterns with a weak positive Eu anomaly. Scheelite U-Pb dating (30.3 ± 1.5 Ma) indicates that the W mineralization is not genetically related to Triassic granitoids in the Yangla district. Instead, it is likely associated with magmatic activities and tectono-thermal events in the Jinshajiang fault zone during the Cenozoic. The high initial 87Sr/86Sr ratios (0.71771–0.72229) in the scheelite, significantly higher than those of Triassic granites and ore-hosting marble, suggest that the geochemical features of Sch-I are inherited from the parental ore-forming fluids. These fluids are likely derived from the mixed hydrothermal fluids involved by the Neoproterozoic strata and/or concealed magmatism.

Tellurium Transport and Enrichment in Volcanogenic Massive Sulfide Deposits: Numerical Simulations of Vent Fluids and Comparison to Modern Sea-Floor Sulfides

Abstract Volcanogenic massive sulfide deposits may represent a significant future source of Te, which is a critical element important for the green energy transition. Tellurium is enriched in these settings by up to 10,000 times over its crustal abundance, indicating that fluids in sea-floor hydrothermal systems may transport and precipitate Te. The major element composition of these hydrothermal fluids is controlled by fluid-rock interaction and is well documented based on experimental, modeling, and natural studies; however, controls on Te mobility are still unknown. To better understand Te enrichment in this deposit type, numerical simulations of the mafic-hosted Vienna Woods and the felsic-hosted Fenway sea-floor vents in the Manus basin were performed to predict Te mobility in modern sea-floor hydrothermal vent fluids and Te deposition during sulfide formation. These simulations demonstrate that the mobility of Te in sea-floor hydrothermal systems is primarily controlled by fluid redox and temperature. Tellurium mobility is low in reduced hydrothermal fluids, whereas mobility of this metal is high at oxidized conditions at temperatures above 250°C. Numerical simulations of the reduced vent fluids of the mafic-hosted Vienna Woods site at the back-arc spreading center in the Manus basin yielded Te concentrations as low as 0.2 ppt. In contrast, the more oxidized model fluids of the felsic-hosted Fenway site located on Pual Ridge in the eastern Manus basin contain 50 ppt Te. The models suggest that Te enrichment in these systems reflects rock-buffer control on oxygen fugacity, rather than an enriched source of Te. In fact, the mafic volcanic rocks probably contain more Te than felsic volcanic rocks. The association of elevated Te contents in the felsic-hosted Fenway system likely reflects magmatic volatile input resulting in lower pH and higher Eh of the fluids. More generally, analysis of sulfide samples collected from modern sea-floor vent sites confirms that redox buffering by the host rocks is a first-order control on Te mobility in hydrothermal fluids. The Te content of sulfides from sea-floor hydrothermal vents hosted by basalt-dominated host rocks is generally lower than those of sulfides from vents located in felsic volcanic successions. Literature review suggests that this relationship also holds true for volcanogenic massive sulfides hosted in ancient volcanic successions. Results from reactive transport simulations further suggest that Te deposition during sulfide formation is primarily temperature controlled. Modeling shows that tellurium minerals are coprecipitated with other sulfides at high temperatures (275°–350°C), whereas Te deposition is distinctly lower at intermediate (150°–275°C) and low temperatures (100°–150°C). These predictions agree with geochemical analyses of sea-floor sulfides as Te broadly correlates positively with Cu and Au enrichment in felsic-hosted systems. The findings of this study provide an important baseline for future studies on the behavior of Te in hydrothermal systems and the processes controlling enrichment of this critical mineral in polymetallic sulfide ores.

Complexation of REE in Hydrothermal Fluids and Its Significance on REE Mineralization

Rare earth elements (REEs) have recently been classified as critical and strategic metals due to their importance in modern society. Research on the geochemical behaviors and mineralization of REEs not only provides essential guidance for mineral exploration but also holds great significance in enhancing our understanding of Earth’s origin and evolution. This paper reviews recent research on the occurrence characteristics, deposit types, and hydrothermal behaviors of REEs, with a particular focus on comparing the complexation and transport of REEs by F, Cl, S, C, P, OH, and organic ligands in fluids. Due to the very weak hydrolysis of REE ions, they predominantly exist as either hydrated ions or free ions in low-temperature and acidic to weakly basic fluids. As the ligand activity increases, the general order of transporting REEs is Cl− ≈ SO42− > F− ≈ PO43− > CO32− > OH− under acidic conditions or OH− > SO42− ≈ Cl− > F− under alkaline conditions. In acidic to neutral hydrothermal systems, the transport of REEs is primarily dominated by SO42− and Cl− ions while the deposition of REEs could be influenced by F−, CO32−, and PO43− ions. In neutral to alkaline hydrothermal systems, REEs mainly exist in fluids as hydroxyl complexes or other ligand-bearing hydroxyl complexes. Additionally suggested are further comprehensive investigations that will fill significant gaps in our understanding of mechanisms governing the transport and enrichment of REEs in hydrothermal fluids.

Epithermal Ag–Au mineralization at Galim-Legalgorou, Cameroon Volcanic Line: insights from alteration mineralogy and mineral chemistry of electrum and sphalerite

The Galim-Legalgorou area, located along the north-western branch of the Cameroon Volcanic Line (CVL), is known for artisanal gold mining and primary gold exploration, but the style and origin of the mineralization has not been fully described in the scientific literature. The close spatial association of the mineralization with Tertiary volcanic rocks raises the question of whether or not this is an epithermal system in a region where all previously studied gold occurrences have been classified as orogenic. In this contribution, we use ore mineral and alteration assemblage and mineral microchemistry to constrain the origin and evolution of the mineralization. Gold is alloyed mainly with Ag (max. 53.1 wt%) and show fineness values that vary 379 and 721 with an average of 455. A cumulative percentile plot of Ag concentrations in the cores of all electrum particles, and the observed step-change from Au-rich cores to more Ag-rich mantles in zoned electrum particles, suggest that the mineralization was deposited by two distinct hydrothermal fluid influxes. The observed ore mineral association-electrum, Se/Tl-acanthite, pyrite, Fe-rich sphalerite, ± galena; the measured FeS contents of sphalerite (average 23.1 mol%), and the presence of colloform banded chalcedony and hydrothermal breccia are all consistent with features of low sulfidation epithermal deposits. This study, therefore, demonstrates for the first time, the presence of significant low sulfidation epithermal Ag–Au mineralization on the CVL, an intracontinental rift region only previously known for orogenic gold mineralization.Graphical

Numerical Simulation of Chemical Reactions’ Influence on Convective Heat Transfer in Hydrothermal Circulation Reaction Zones

Chemical reactions, mineral diffusion, and deposition are pivotal in understanding the mechanisms of mineral deposition and the formation of seafloor sulfides in the hydrothermal circulation process. To understand the formation process of anhydrite in submarine hydrothermal systems, a computational model that combined component transport and chemical reactions was established and simulated using the mass transport model. The deposition rate of calcium sulfate was defined, and the effects of factors such as porosity, ion concentration, and inflow velocity on the temperature field in the reaction zone were thoroughly investigated. The distribution of temperature, porosity, and velocity during the reaction process was obtained, allowing for the identification of the chemical reaction patterns of certain ions in the early stages of hydrothermal activity. The simulation revealed the occurrence of biochemical reactions between two types of ions, leading to their deposition on the solid framework of a porous medium. With the increase in inflow velocity and solute concentration, the average porosities of the porous medium decreased by 0.495% and 0.468%, respectively, which consequently altered the structure of the rock. Such findings contribute to the inference of formation and extinction mechanisms of seafloor crusts and hydrothermal chimneys.

Trace element concentrations and chemical zoning of spodumene from magmatic and hydrothermal origins

Spodumene is a major lithium ore mineral mined from granitic pegmatites and can crystallize (1) from magma, (2) from hydrothermal fluid in miarolitic cavities or fracture-filling units, or (3) as a product of petalite breakdown. Although spodumene’s purity influences the economic value of lithium ore, its trace-element geochemistry is not entirely understood. This study investigated 24 unaltered spodumene samples from 21 localities formed through each of these three modes of origin. The chemical zoning of each spodumene sample was characterized using cathodoluminescence (CL), micro-X-Ray fluorescence mapping (µXRF), and/or qualitative laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) line scans, whereas the concentrations of trace elements were quantified using LA-ICP-MS point analyses. Intra-crystalline chemical zoning was present in all three spodumene types as either oscillatory growth bands and/or sector zoning. For the four most abundant transition and post-transition metals analyzed (Fe, Mn, Ga, Sn), the concentrations ranged from below detection to 10510 ppm (Fe), 1850 ppm (Mn), 300 ppm (Ga), 320 ppm (Sn), whereas Rb and Cs were below detection. Magmatic spodumene had the highest mean concentrations of Fe (2345 ppm) and Sn (94 ppm), hydrothermal spodumene had the highest mean concentrations of Mn (641 ppm) and Ga (94 ppm), and spodumene formed from the breakdown of petalite consistently had the lowest mean concentrations, though there was significant overlap in the datasets. In addition, texturally similar spodumene-quartz intergrowths of primary and secondary origins were distinguished via trace-element geochemistry. Principle component analysis of Fe, Mn, Ga, Sn, Ti, and Zn values from all 325 LA-ICP-MS measurements showed discrimination by CL color, as well as color in handsample for gem-varieties of hydrothermal spodumene.

High Sulphidation Mineralization and Advanced Argillic Alteration within Concealed Gajah Tidur Porphyry, Grasberg District, Papua

High sulphidation (HS) mineralization and associated advanced argillic alteration have been intersected by three drill holes below the Grasberg porphyry Cu-Au deposit, known as the Gajah Tidur prospect. The prospect is located between 1,500 ̶ 2,750 m level, in Grasberg District, Papua, Indonesia. The holes are of KL98-10-21, KL98-10-22, and GRD39-08 which intersected 3.4 Ma Gajah Tidur monzonite, Grasberg Igneous Complex, the wall rocks of Kembelangan, and New Guinea Limestone Group. This research aims to determine the characteristics of high sulphidation mineralization associated with advanced argillic alteration at Gajah Tidur. Petrographic, XRD, SEM, fluid inclusion, and XRF (geochemical) analyses were applied to identify the mineralogy, geochemistry, and ore fluid properties. The major element plots show a differentiated intrusion. The alteration consists of potassic materials composed of biotite and K-feldspar, overprinted by phyllic and advanced argillic ones typified by alunite, pyrophyllite, and kaolinite. The high sulphidation mineralization characterized by pyrite-covellite, chalcopyrite-chalcocite, enargite, and digenite is also present. Fluid inclusion homogenization temperature of mineralized quartz vein ranges from 393 to 542°C, indicating a magmatic fluid origin predominantly. Two distinct porphyry systems, consisting of the Gajah Tidur Cu-Mo and the Main Grasberg Cu-Au porphyry systems are emplaced at the Gajah Tidur level. Advanced argillic is less intense compared to a pervasive phyllic alteration, overprinting the stockwork and surrounding rocks, emplaced at the upper part of quartz stockwork. It is possibly associated with a late stage of Gajah Tidur porphyry hydrothermal fluids which became cooler and highly acidic. Similar to other porphyry systems such as Oyu Tolgoi in Mongolia, the Gajah Tidur porphyry did not have its hydrothermal fluid ascent to the surface to form lithocap. Instead, the ascending fluids cooled at shallower depths resulting in the formation of advanced argillic alteration.

Recycled materials and secondary processes controlled the chemical and isotopic compositions of bubbling gases discharged from two adjacent geothermal springs in the Northern Luzon Arc

Gas emissions from hydrothermal systems can serve as indicators of subsurface activity. In addition to gas sources, hydrothermal gas geochemistry is strongly influenced by secondary processes that occur during/after hydrothermal circulation. Here, we observed statistically significant differences in the geochemical characteristics (except for helium isotopes) of bubbling gases discharged from two adjacent vents in the Northern Luzon Arc. Helium (3He/4He = 4.25–7.09 Ra) in both vents was controlled by mixing between mantle and crustal components, where about 74% of helium was contributed by the mantle. Differences in N2/Ar ratios (∼ 300–330) of the two neighboring springs are attributed to subducted materials and seawater mixing (contributing ∼2.5% N2 and Ar), rather than phase separation in the reaction zone. Specifically, Ar was mainly supplied by atmospheric components that dissolved in the percolated seawater with only 8%–9% contributed by the excess radiogenic 40Ar. Excess N2 relative to Ar was mainly supplied by the decomposition of subducted materials (83%–92%) of the South China Sea plate beneath the Philippine Sea Plate. The Lutao gases showed low CO2 concentrations (0.07–22.2 mmol/mol), despite the high 3He/4He ratios indicating a significant contribution of magmatic components. Magmatic CO2 may have been largely consumed by the high Ca Lutao vent fluids via carbonate precipitation in the reaction zone. Alternatively, stable carbon isotope compositions (δ13C) indicate that Lutao CO2 may be supplied by microbial oxidation of alkanes (e.g., CH4 with concentrations of 14.6–173 mmol/mol in the samples), with fractionation factor ΔCO2–CH4 ranging from −15‰ to −25‰ and conversion rates of <10%. Up to 65% of the CO2 in the 2016 samples experienced secondary calcite precipitation in the discharge zone. Our results indicate that recycled subducted materials could potentially affect the geochemical characteristics of gases discharged from arc-volcanic systems. In addition, the influence of secondary processes needs to be considered before tracing the sources of hydrothermal fluids and/or gases, especially in shallow-water hydrothermal systems.

Genesis of Rare Metal Granites in the Nubian Shield: Tectonic Control and Magmatic and Metasomatic Processes

The Igla Ahmr region in the Central Eastern Desert (CED) of Egypt comprises mainly syenogranites and alkali feldspar granites, with a few tonalite xenoliths. The mineral potential maps were presented in order to convert the concentrations of total rare earth elements (REEs) and associated elements such as Zr, Nb, Ga, Y, Sc, Ta, Mo, U, and Th into mappable exploration criteria based on the line density, five alteration indices, random forest (RF) machine learning, and the weighted sum model (WSM). According to petrography and geochemical analysis, random forest (RF) gives the best result and represents new locations for rare metal mineralization compared with the WSM. The studied tonalites resemble I-type granites and were crystallized from mantle-derived magmas that were contaminated by crustal materials via assimilation, while the alkali feldspar granites and syenogranites are peraluminous A-type granites. The tonalites are the old phase and are considered a transitional stage from I-type to A-type, whereas the A-type granites have evolved from the I-type ones. Their calculated zircon saturation temperature TZr ranges from 717 °C to 820 °C at pressure &lt; 4 kbar and depth &lt; 14 km in relatively oxidized conditions. The A-type granites have high SiO2 (71.46–77.22 wt.%), high total alkali (up to 9 wt.%), Zr (up to 482 ppm), FeOt/(FeOt + MgO) ratios &gt; 0.86, A/CNK ratios &gt; 1, Al2O3 + CaO &lt; 15 wt.%, and high ΣREEs (230 ppm), but low CaO and MgO and negative Eu anomalies (Eu/Eu* = 0.24–0.43). These chemical features resemble those of post-collisional rare metal A-type granites in the Arabian-Nubian Shield (ANS). The parent magma of these A-type granites was possibly derived from the partial melting of the I-type tonalitic protolith during lithospheric delamination, followed by severe fractional crystallization in the upper crust in the post-collisional setting. Their rare metal-bearing minerals, including zircon, apatite, titanite, and rutile, are of magmatic origin, while allanite, xenotime, parisite, and betafite are hydrothermal in origin. The rare metal mineralization in the Igla Ahmr granites is possibly attributed to: (1) essential components of both parental peraluminous melts and magmatic-emanated fluids that have caused metasomatism, leading to rare metal enrichment in the Igla Ahmr granites during the interaction between rocks and fluids, and (2) structural control of rare metals by the major NW–SE structures (Najd trend) and conjugate N–S and NE–SW faults, which all are channels for hydrothermal fluids that in turn have led to hydrothermal alteration. This explains why rare metal mineralization in granites is affected by hydrothermal alteration, including silicification, phyllic alteration, sericitization, kaolinitization, and chloritization.

Application of geological and short wavelength infrared (SWIR) spectroscopy mapping in the Mailong gold deposit, East Kunlun: Implications for exploration targeting

Widespread regolith cover makes it difficult to identify the anomalous size of their mineralogical or geochemical footprint at the surface in gold exploration. Short wavelength infrared (SWIR) spectroscopy with effective identification of clays and other hydrous minerals shows potential application in gold exploration. The detailed geological and short wavelength infrared (SWIR) spectroscopy mapping was conducted in the newly-discovered orogenic-type Mailong gold deposit (13.06 t @ 6.29 g/t Au), East Kunlun, to determine alteration stage and mineral assemblages and discuss the potential values of SWIR spectral in gold exploration.In the Mailong area, magmatic rocks consist of granodiorite, biotite granodiorite, plagiogranite and mafic dikes, and the gold mineralization shows a close spatial and temporal relationship with mafic dikes. The earliest chloritization (chlorite-quartz) is widely distributed in granodiorite, biotite granodiorite and plagiogranite. The following potassic alteration (hydrothermal K-feldspar and quartz) is developed along high-angle fault/fracture, which cut through granodiorite, biotite granodiorite and plagiogranite. The subsequent sulfide alteration (chlorite-muscovite-sulfide-carbonate) overprints the former potassic and chloritization alteration, and shows spatial association with mafic dikes. Native gold occurs in fracture arsenopyrite or associated with minerals such as pyrite, and chalcopyrite during the early sulfide stage. Supergene alteration is characterized by limonite and malachite. At Mailong, the SWIR data indicate that the most abundant alteration minerals (chlorite, white micas and ankerite) mainly occurred in the northern area. White mica Al-OH absorption occurs at longer wavelengths (Pos2200 = 2202.5 ∼ 2203 nm) and higher Illite crystallinity (IC = 1.2 ∼ 3.1) probably reflecting a higher temperature and pH conduit at the bottom of ZK0001 and ZK0801. The sharp shift of IC values near the bottom reflects the control of fault. This area is also situated at the V-shaped intersections of the three granitic intrusions and structural transection, indicating more of a possible hydrothermal fluid channel than a mineralization center. Low-grade Au mineralization (Au = 0.1 ∼ 0.5 g/t) is mainly distributed within hydrothermal channels with higher Pos2200 (mainly 2022.5 ∼ 2203 nm) and IC values (mainly 1.2 ∼ 3.1), while high-grade Au endowment associated with mafic dikes has low Pos2200 (mainly 2201 ∼ 2202.5 nm) and IC values (mainly 0.43 ∼ 1.2). Meanwhile, an equation of distance = -15*IC + 31 (R2 = 0.47) can be summarized for low-grade orebodies vectoring. Integrating geological mapping and spectral data, target areas for high-grade ore bodies can be outlined using the criteria of white mica, shorter wavelength of Al-OH absorption position (Pos2200 = 2201 ∼ 2202.5 nm), lower IC values (IC = 0.43 ∼ 1.2), and chlorite Fe-OH absorption position Pos2250 (>2247 nm) along with occurrences of mafic dikes. This study demonstrates that utilizing the detailed SWIR identification in conjunction with accurate geological mapping has great potential for greenfield exploration of orogenic gold deposits.

A comprehensive study of apatite grains in Ryugu rock fragments

AbstractApatite is present as an accessory phase in many meteorites and is often formed as a secondary product of aqueous alteration. Its propensity to incorporate rare earth elements (REE) results in apatite usually being the main REE‐bearing phase in hydrously altered meteorites. Asteroid Ryugu is thought to have experienced pervasive aqueous alteration and material collected from the surface of Ryugu is expected to provide insight into asteroidal aqueous alteration processes without influence by terrestrial weathering. Morphologies and mineral associations of apatite grains from five rock fragments collected from the asteroid Ryugu by the Hayabusa2 spacecraft were examined and their REE concentrations were measured by synchrotron X‐ray fluorescence (SXRF) spectroscopy. The main minerals associated with apatite are dolomite, magnetite, and pyrrhotite. Grain boundary corrosion of the interfaces between apatite assemblages and the surrounding matrix suggest that paragenetic formation on the asteroid was followed by a later episode of hydrous alteration. Light REE (LREE) concentration levels recorded at 20–150 times those of bulk CI levels together with a steady increase from LREE toward enrichment of medium REE (MREE, up to Er) at 50–400 times bulk CI levels may suggest postgenetic removal of LREE from Ryugu apatite grains by late‐stage circulation of a hydrothermal fluid.

Quantitative in situ Raman spectroscopy investigation on HSO4− dissociation at high pressures (up to 420 MPa) and its geological implication

Sulfate-bearing hydrothermal fluids are widespread in crustal environments, and recent papers highlight a possible important role of sulfate as an agent for mass and electron transfers in subduction zone. The geochemical characters of sulfate-bearing fluids (e.g., ability of complexing with ore-forming elements) depend largely on the dissociation behavior of HSO4−. However, the dissociation of HSO4− was only investigated at vapor saturation pressures and the pressure dependence of the dissociation behavior is thus unclear. In this study, we modified the fused silica capillary capsule (FSCC) method to explore the dissociation behavior of HSO4− quantitatively via in situ Raman spectroscopy experiments. We designed a new heating stage that can accommodate a 7 cm-long FSCC, and we show that thick-walled FSCCs with high degrees of filling can withstand pressures up to 645 MPa at temperatures to 450 °C. The sulfate concentrations in Cs2SO4–H2SO4 solutions were measured using Raman spectroscopy with increasing pressures and temperatures (P–T). The sulfate concentrations were calibrated using Cs2SO4 solutions with known concentrations, and the concentrations of HSO4− were determined by mass balance. According to our experimental results, increasing pressure increases the dissociation of HSO4− into SO42− and H+ while increasing temperature promotes ion association, which means that HSO4− dissociation is favored in high-density fluids. Comparisons between our experimental results with those of thermodynamic predictions using currently available thermodynamic properties indicate that the dissociation of HSO4− is stronger than previously thought in high-density fluids, especially at high pressures. We then optimized the thermodynamic properties of HSO4− based on our experimental results, and used them to simulate the S(VI) speciation in slab-derived fluids. Similar with our experimental results, the simulations also predict that the HSO4− will largely dissociate into SO42− and H+ in fluids with high P–T conditions, causing the SO42− as the predominant S(VI) speciation in subduction zone.

2730–2670 Ma rifting triggers sagduction prior to the onset of orogenesis at ca 2650 Ma: implications for gold mineralisation, Eastern Goldfields, Western Australia

The dominant structural fabric in the Eastern Goldfields is the steep north- to north-northwest-trending S2 foliation that is axial planar to upright F2 folds, developed during intense horizontal east–west shortening (D2–4 event). These structures consistently overprint D1 structures, which comprise layer-parallel S1 foliation, extensional shears, thrusts and recumbent F1 folds. The D1 event represents a separate and distinct episode of deformation with a markedly different stress regime (dominant vertical σ1), compared with the stress regime during the D2–4 events (horizontal east–west oriented σ1). There is little evidence for pre-2670 Ma ductile deformation in the Eastern Goldfields, as: (1) the ca 2730–2670 Ma greenstone sequences are deposited conformably on the older ca 2800 Ma greenstone sequences, with the first significant angular unconformities observed at the base of the post greenstone late basins; (2) a lack of schist or gneiss clasts in the late basins suggests that the surrounding uplifted sequence was largely undeformed; (3) the layer-parallel S1 foliation is observed throughout the 2720–2670 Ma greenstone sequence; and (4) the dominant low north- and south-plunges of F2 folds suggest that the sequence was predominantly flat-lying prior to strong east–west shortening (D2–4 events). The ca 2670–2655 Ma D1 event represents a period of sagduction that occurred immediately after cessation of rifting as a result of gravitational instability from deposition of dense, cold, greenstone sequences onto thinned, light, hot felsic crust. Late basins represent depocentres on the sinking greenstones during sagduction. Marked contrasts in the structural style of gold deposits, metallogeny and fluid sources, typically attributed to progressive deformation during orogenesis, could instead reflect temporally distinct mineralising events during changing tectonic regimes. In the East Yilgarn, an early plumbing system dominated by north-northwest-trending basin-controlling structures was likely established during rifting and focused fluids during multiple hydrothermal circulation events.

Reactive transport numerical modeling of intermediate sulfidation epithermal deposit: A case study of Haopinggou Ag-Au-Pb-Zn deposit, Henan province, China

The Haopinggou Ag-Au-Pb-Zn deposit is the only deposit that simultaneously contains Au and Ag-Pb-Zn vein-type ores at the Xianyu ore field in Xiong'ershan District, Henan Province, China. The early-stage gold-bearing pyrite-quartz veins are cut or surrounded by late-stage silver-bearing Pb-Zn-sulfide veins. However, there is controversy whether these two-stage veins were formed from distinct fluid systems associated with discrete mineralization events or via hydrothermal evolution processes of individual mineralization events. To study the metallogenic dynamics of how the Au and Ag-Zn-Pb veins were formed at the same depth in the Haopinggou deposit under these two distinct metallogenic models, we established a series of reactive transport numerical models. We studied the influence of the temperature of the hydrothermal fluid, fault permeability, and HS−, Au+, and Ag+ concentrations on the mineralization of Au, Ag, Pb, and Zn. Based on the model results, two distinct mechanisms causing Au and Ag to precipitate at the same depth has been established: (1) Under the assumption of the single hydrothermal fluid metallogenic model, the deep part of the early Au precipitation will be overlapped by the shallow part of the late Ag precipitation due to temperature and permeability decreases, causing Au and Ag to precipitate at the same deep depth; (2) Under the assumption of the distinct hydrothermal fluids metallogenic model, the shallow part of the early Au precipitation will be overlapped by the late Ag precipitation due to high concentration of HS−, causing Au and Ag to precipitate at the same shallow depth. The metallogenic mechanisms behind these two controversial understandings indicate that the deeper parts of the Haopinggou deposit have a high metallogenic potential for gold or silver.

Enrichment mechanism of selenium in Lujiaping formation in central South Qinling: Controls from mixed sources, sedimentary environment, primary productivity and paleo-climate during Ediacaran to early Cambrian period

The Ediacaran to lower Cambrian Lujiaping Formation in South Qinling exhibited extremely high level of Se enrichment, which has provoked extensive concerns since the critical role of Se in paleo-biological evolution and diversification as well as its bidirectional effects on current ecological environment and human health. Because of complex geological setting within South Qinling during the Ediacaran–early Cambrian interval, distribution pattern and mechanism of Se enrichment in Lujiaping Formation have not been fully understood. In this study, therefore, stratigraphic variations of Se concentration and enrichment level together with enrichment mechanism in Lujiaping Formation in the central part of South Qinling were systematically explored. The result showed that, in the whole Lujiaping Formation, Se concentrations varied from 0.19 to 129 μg/g, with an average of 13.28 μg/g. According to the enrichment factor, most of samples can be classified as strong enrichment and anomaly levels (EF = 10–1000) which mainly occurred in organic matter-enriched siliciclatic rocks including mudstone, shale and stone coal seams. Meanwhile, Se enrichment was accompanied with enrichment of Ag, Mo, As, Cd and V in Lujiaping Formation. Various geochemical proxies were collectively employed to identify potential mechanism of Se enrichment. The results indicated that Se was derived from both terrestrial detrital materials and deep hydrothermal fluids. Strong Se anomaly was intimately linked to authigenic enrichment of U and Mo, manifesting advantageous role of euxinic benthic condition to Se accumulation. Besides, weak watermass restriction, intermittent upwelling, high primary productivity and warm and humid climate were also beneficial to ultimate Se enrichment in Lujiaping Formation. This study complemented fundamental data of Se concentration and enrichment degree in strata of the Ediacaran–early Cambrian period in central South Qinling. Meanwhile, preliminary insight of correlation among Se enrichment, sedimentary environment, paleo-climate and biological blooming during the Ediacaran to early Cambrian interval was obtained, which laid the foundation for further researches.

Using Hg isotopes and trace elements to constrain the origin of the Ordovician Xiangquan Tl deposit, South China

Sediment-hosted stratiform sulfide (SHSS) deposits commonly contain large amounts of strategic metals, such as Tl, Hg, Cd, Ge and Ga, however, sources of these metals remain debate. Here we present new elemental and Hg isotopic data to constrain the metal sources for the Xiangquan Tl deposit (South China), a unique SHSS deposit with 250 t Tl at an average grade of 928 ppm. Stratiform pyrite orebodies are hosted in the Ordovician marine sedimentary succession of mostly limestone with minor mudstone. Pyrite, the dominant ore mineral, is rich in Hg (up to 1360 ppm). Bulk ores and pyrite separates from this deposit have significant variations of δ202Hg (−5.48 to −0.65 ‰) and Δ199Hg (−0.01 to 0.36 ‰). The Δ199Hg values are mostly positive, similar to those of seawater and marine sediments. Ore petrography, trace element enrichment coefficients, rare earth element patterns, Re-Os ages (478 ± 33 Ma) and S isotope compositions of pyrite indicate that Hg and other metals were derived from hydrothermal fluids venting at the seafloor. We suggest that the ore-forming fluids of the Xiangquan deposit were predominantly originated from large-scale circulation of evolved seawater, which leached Hg and Tl from the marine country rocks. These metal-rich fluids migrated upward, vented to the seafloor, and mixed with anoxic H2S-rich seawater to precipitate Hg- and Tl-rich pyrite. Our study highlights that the combined application of Hg isotopes and trace elements could be used to trace the sources of metals in hydrothermal ore deposits such as SHSS deposits.

Paragenetic and geological setting of the Starra iron oxide copper–gold deposits, Mount Isa Inlier, Queensland, Australia: constraints on IOCG deposit models

The five Starra iron oxide copper–gold (IOCG) deposits, which are located in the Cloncurry district of the Mount Isa Inlier, NW Queensland, are hosted in a N-trending zone of deformed iron-rich metasedimentary rocks that are underlain by two mineralogically distinct mafic–intermediate meta-igneous rocks. Copper–Au mineralisation is subdivided into two stages—an early main stage that transitioned from a magnetite-dominated Cu substage comprising chalcopyrite, pyrite, biotite and chlorite, to a hematite–muscovite-bearing Cu–Au substage with chalcopyrite, bornite and rare chalcocite, as well as Au–Ag-tellurides and native Au. This second stage was followed by a subordinate but nonetheless important carbonate–quartz–barite vein stage with minor but locally high-grade Cu–Au mineralisation characterised by abundant chalcocite and bornite, minor native bismuth and wittichenite (Cu3BiS3), together with minor Au–Ag telluride minerals. Bornite in these carbonate–quartz–barite veins contains considerable amounts of Au (>10 ppm), which appears to be deported either as lattice substitution in the bornite crystal structure or as homogeneously distributed Au0 nanoparticles. An earlier, coarse-grained mafic intrusion was affected by early Na–Ca alteration, whereas a second mafic intrusion lacks evidence of Na–Ca alteration but was exposed to K–Fe alteration and subsequent mineralisation at Starra 222. Mushketovite (magnetite after specular hematite) is only observed in ironstone lodes proximal to the mafic–intermediate rocks. The close spatial and mineralogical associations of the mafic–intermediate bodies and the ironstone lodes point to a stronger link between magmatic activity and IOCG mineralisation than has previously been recognised at Starra. Remobilisation of gold by late-stage hydrothermal fluids aided by the relatively low fluid temperatures during the main pulse of Cu–Au mineralisation refined gold grades at Starra, making it a relatively gold-rich IOCG deposit. We show that the Cu–Au deposits of the Starra trend feature mineralogical and geochemical elements common to both Cloncurry IOCG deposits (e.g. abundant magnetite) and IOCG deposits of the Tennant Creek district (e.g. Au–Cu–Bi mineralisation; hematite–bornite–chalcocite assemblages), making them a unique and important member of this complex family of deposits.

A Late Jurassic Epithermal Pb-Zn Deposit: Insights from Rb-Sr Dating of Quartz-Hosted Fluid Inclusions and Sphalerite Chemical Composition

The Kangjiawan Pb-Zn deposit, situated within the Shuikoushan polymetallic ore field in Changning, Hunan Province, China, is a large-scale Pb-Zn deposit unearthed in 1976. Based on detailed geological field investigations, this study presents the results of the Rb-Sr isotopic dating, electron probe microanalyses (EPMAs), and LA-ICP-MS analyses of the Kangjiawan Pb-Zn deposit in order to determine the ore-forming age and the occurrence of trace elements in sphalerite and thereby constrain the genesis of the deposit. The Rb-Sr dating of quartz-hosted fluid inclusions yielded an Rb-Sr isochron age of 150 ± 4 Ma, with an initial 87Sr/86Sr ratio of 0.71101 ± 0.00008 (MSWD = 1.1), suggesting that the Pb-Zn mineralization of the Kangjiawan deposit took place during the Late Jurassic, coeval with the magmatic activities within the ore field. EPMA and LA-ICP-MS analyses showed that Fe, Mn, and Cd were primarily incorporated into the sphalerite lattice through isomorphous substitution. Specifically, Fe and Mn substituted for Zn, whereas Cd replaced both Fe and Zn. Other elements such as Cu, Sb, and Sn occurred within the sphalerite lattice through mineral micro-inclusions or isomorphic substitution. EPMAs and LA-ICP-MS results showed that the FeS contents in sphalerite were less than 14.33%, with corresponding ore-forming temperatures below 259 °C. The LA-ICP-MS results showed that sphalerites from the Kangjiawan Pb-Zn deposit had relatively high Ga/In ratios ranging from 0.01 to 144, providing further support for medium-to-low-temperature mineralization. The trace element compositions of sphalerites from the Kangjiawan Pb-Zn deposit exhibit skarn-type characteristics, suggesting a potential association with contemporary magmatic activities within the Shuikoushan ore field. During the Late Jurassic, extensive granitic magmatic activities occurred in the study area. At the late stage of magma crystallization, hydrothermal fluid containing Pb and Zn precipitated at medium-to-low temperatures and generated the Kangjiawan Pb-Zn deposit.

Coupled Detachment Faulting and Hydrothermal Circulation at 49.7°E Southwest Indian Ridge Revealed by Seafloor Magnetism

AbstractDetachment faults at slow‐ and ultraslow‐spreading mid‐ocean ridges are essential for lithosphere‐hydrosphere interactions. However, their coupling with subseafloor hydrothermal circulation is poorly understood. Here, we investigated shallow hydrothermal fluid circulations in the active Dragon Horn detachment fault system of the Southwest Indian Ridge using combined near‐bottom magnetic anomaly data and rock magnetic analyses. We observed enhanced magnetic anomalies related to the high magnetization of basaltic country rocks and highly serpentinized (&gt;80%) peridotite, whereas the hydrothermally altered basalts and sulfide deposits had weak magnetization and reduced magnetic anomalies. Therefore, the low‐magnetization zone was interpreted as a proxy for the hydrothermal fluid channel. The spatial distribution of the low‐magnetization zone revealed that the inactive Suye field expanded more than 500 m in diameter horizontally and ∼100 m vertically, and the active Longqi hydrothermal field had a &gt;1 km fluid channel, both centered around the detachment fault fracture zone. Our results establish a robust link between detachment faulting and shallow hydrothermal circulation in which the detachment fault system provides critical fluid paths. Therefore, detachment tectonics are important elements for evolving seafloor hydrothermal fields along the Southwest Indian Ridge and possibly other slow‐ and ultraslow‐spreading mid‐ocean ridges globally.