Hydrothermal Deposits Research Articles

Compositional Remote Sensing and Hyperspectral Laboratory Analyses of Sinters in Hydrothermal Fields in Chile, With Relevance to Astrobiological Targets on Mars

AbstractSiliceous hot spring deposits, or sinters, deposit from hot spring discharge at Earth's surface and are sites of exceptional preservation of biosignatures. Their macro‐ and micro‐textures are regarded as important evidence of past microbial activities in hydrothermal environments. However, biology mimics do occur, and bona fide microbial textures could be destroyed by subsequent diagenesis or other post‐depositional processes. Thus, it is paramount to narrow the search for prospective Martian silica‐rich deposits that may contain biosignatures from both orbital and rover‐based perspectives. This study investigates hydrothermal deposits in Chile, which are analogs of high‐silica deposits discovered in the Gusev crater on Mars, through remote sensing and laboratory analysis. Results indicate that compositional remote sensing based on multispectral data with a high spatial resolution of <4 m/pixel reflects various concentrations of silica, which assisted in identifying the direction of discharged hydrothermal flows from the vent to the apron. Micro‐infrared mapping of sinters from similar hydrothermal fields linked spectral features to specific textures revealed by scanning electron microscope and chemical compositions confirmed by electron microprobe analysis, indicating that sinters with no shift in their emissivity minimum in the thermal infrared range were more likely to preserve cellular structures. An instrument for collecting multispectral data with higher spatial resolution could aid in characterizing the geologic settings of potential hot springs on Mars. Locating emissivity minima in the infrared regions of silica that do not shift to a lower position would suggest the potential for well‐preserved microbial structures in Martian sinters, if life ever did exist there.

Performance enhancement of Sb2(S,Se)3 solar cells through neodymium ion flow doping

Doping the light absorber layer of antimony chalcogenides with extrinsic ions is an effective approach for improving their photovoltaic quality. These dopant ions generally reside at positions other than the crystal lattice or form an alloy (e.g., AgSb(S,Se)3) with a poor device performance. Therefore, incorporating such ions into an antimony chalcogenide lattice such that there is a positive influence on device quality would be highly useful. Herein, doping of Nd3+ for Sb2(S,Se)3 is carried out via a modified hydrothermal deposition process. Notably, these ions are incorporated into the crystal lattice and migrate to the CdS/Sb2(S,Se)3 interface after doping, which are characterized using X-ray diffraction, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. Nd3+ doping produces benign effects on the crystal orientation, film morphology, optoelectronic properties, and defect passivation of the Sb2(S,Se)3 films. Consequently, all the photoelectrical parameters of Sb2(S,Se)3 solar cells doped with Nd3+ are enhanced, delivering a remarkable efficiency of 8.24 %. Furthermore, the best device stored in air only shows a slight decrease in efficiency in the 2400-h aging test. Overall, this study provides an effective doping strategy to improve the photovoltaic quality of Sb2(S,Se)3 films.

Axially Modified Square-Pyramidal CoN4-F1 Sites Enabling High-Performance Zn-Air Batteries.

Cobalt-nitrogen-carbon (Co-N-C) catalysts with a CoN4 structure exhibit great potential for oxygen reduction reaction (ORR), but the imperfect adsorption energy toward oxygen species greatly limits their reduction efficiency and practical application potential. Here, F-coordinated Co-N-C catalysts with square-pyramidal CoN4-F1 configuration are successfully synthesized using F atoms to regulate the axial coordination of Co centers via hydrothermal and chemical vapor deposition methods. During the synthesis process, the geometry structure of the Co atom converts from six-coordinated Co-F6 to square-pyramidal CoN4-F1 in the coordinatively unsaturated state, which provides an open binding site for the O2. The introduction of axial F atoms into the CoN4 plane alters the local atomic environment around Co, significantly improving the ORR activity and Zn-air batteries performance. In situ spectroscopy proves that CoN4-F1 sites strongly combine with the OOH* intermediate and facilitate the splitting of O-O bond, making OOH* readily decompose into O* and OH* via a dissociative pathway. Theoretical calculations confirm that the axial F atom effectively reduces the electronic density of the Co centers and facilitates the desorption of the OH* intermediate, efficiently accelerating the overall ORR kinetics. This work advances a feasible synthesis mechanism of axial ligands and provides a route to construct efficient high-coordination catalysts.

Ultrapotassic plutons as a source of uranium of vein-type U-deposits (Moldanubian Zone, Bohemian Massif): insights from SIMS uraninite U–Pb dating and trace element geochemistry

The Bohemian Massif hosts significant hydrothermal U-deposits associated with shear zones in the high-grade metamorphic basement. But there is a lack of evidence of a genetic link between mineralization and U-fertile igneous rocks. This contribution provides constraints on the major U source of the vein-type U-deposits, the timing of ore formation and the metallogenetic model. The anomalous trace element signatures of the low-temperature hydrothermal deposits (high Zr, Y, Nb, Ti, ∑REE) and their close spatial relation with ultrapotassic rocks of the durbachite series point to a HFSE and REE enriched source rock. The durbachites have high U content (13.4–21.5 ppm) mainly stored in magmatic uraninite and other refractory minerals (e.g., thorite, zircon, allanite) that became metamict over a time interval sufficient to release U from their crystal structure, as suggested by the time gap between emplacement of the durbachites (EMP uraninite U–Pb age ~ 338 Ma) and hydrothermal activity (SIMS uranium ore U–Pb age ~ 270 Ma). Airborne radiometric data show highly variable Th/U ratios (1.5–6.0), likely reflecting a combination between (1) crystallization of magmatic uraninite, (2) hydrothermal alteration, and (3) leaching and mobilization of U along NW–SE-trending fault zones, manifested by elevated Th/U values in the radiometric map. The presence of rare magmatic uraninite in durbachites suggests almost complete uraninite dissolution; EMP imaging coupled with LA-ICP-MS analyses of refractory accessory phases revealed extensive mobilization of U together with HFSE and REE, providing direct evidence for metal leaching via fluid-driven alteration of radiation-damaged U-rich minerals. The large-scale HFSE and REE mobilization, demonstrated by the unusual trace element signatures of the U-deposits, was likely caused by low-temperature (270–300 °C), highly alkaline aqueous solutions containing F-, P-, and K-dominated complexing ligands. The first SIMS U–Pb age of 270.8 ± 7.5 Ma obtained so far for U-mineralization from the Bohemian Massif revealed a main Permian U mineralizing event, related to crustal extension, exhumation of the crystalline basement, and basin formation, as recorded by U–Pb apatite dates (280–290 Ma) and AFT thermal history models of the durbachites. The Permo-Carboniferous sedimentary cover probably represented a source of oxidized basinal brines infiltrating the basement-hosted durbachite plutons and triggering massive metal leaching. The interaction between basin-derived brines and durbachites resulted in significant modification of the chemical composition of the hydrothermal system (K and F release during biotite chloritization, P liberation through monazite alteration), leading to the formation of ore-bearing fluids responsible for the metallogenesis of the basement-hosted unconformity-related U-deposits in shear zones in the Bohemian Massif.

High-precision microcline 40Ar/39Ar dating by combined techniques

K-feldspar is one of the most common minerals applied for 40Ar/39Ar dating because of its high K content and ubiquitous presence. Excess 40Ar in K-feldspar resulting in unreliable ages has long been reported, however, its occurrence and trapping time are still inconclusive. Combined argon extraction techniques, including laser step heating, and step crushing, as well as succedent furnace incremental heating, have been applied to six microcline samples from two hydrothermal ore deposits in South China, to address these issues. Two microcline samples (09SZ37 & 39) measured by all the above three gas extraction techniques yield flat age spectra and concordant inverse isochron ages respectively. However, one sample (09NL10) produces a flat spectrum but with abnormally low radiogenic 40Ar, and the other three samples obtain uneven age spectra, by laser heating. All six samples measured by step crushing yield quite similar age spectra characterized with declining staircases for the first several steps, and followed with very flat plateaus of high-precision plateau ages for the subsequent later crushing steps. The declining sections with abnormally old ages indicate that excess 40Ar (and obvious atmospheric argon) was trapped in the microcracks and the secondary fluid inclusions. The data points corresponding to age plateaus well define inverse isochron ages which are in consistence with their plateau ages respectively. Furthermore, the crushed powders of all six samples by further furnace step heating also yield very flat age spectra, whose plateau ages are well concordant with those obtained by the foregoing step crushing experiments. The trapped excess 40Ar caused the total fusion ages of laser heating 0.7–17.8% older than their true ages. Mineral grains of ca. 0.10 mm may effectively remove excess 40Ar in microcracks and secondary fluid inclusions, proposed for direct 40Ar/39Ar step heating. Stepwise crushing, combined with furnace heating, is not only very useful to date fluid inclusions, but also robust to remove excess 40Ar and obtain more precise true ages for K-bearing minerals, e.g., K-feldspar, amphibole, tourmaline, and so on.

Construction of Au/ZnWO4/CdS Ternary Photocatalysts with Oxygen Vacancy Modification for Efficient Photocatalytic Hydrogen Production

AbstractRational design and optimization of the photocatalyst architecture, aimed at effectively enhancing light absorption and accelerating charge separation and transfer, can lead to the accomplishment of sustainable photocatalytic hydrogen production. In this study, a ternary system of Au/ZnWO4/CdS is prepared with oxygen vacancy modification through a combination of hydrothermal, chemical precipitation, and photochemical deposition methods. The addition of CdS and Au nanoparticles significantly enhances the light absorption range of ZnWO4 (ZWO) and creates more active sites for hydrogen production. The type‐II engineered heterojunction, in combination with Au as a cocatalyst, is a viable and efficient method for enhancing the separation and transport of electron–hole pairs, thereby facilitating the effective precipitation of hydrogen through photocatalysis. 5A10ZC exhibits a hydrogen production rate of 5483.62 µmol g−1 h−1, which is 167 times higher than that of unmodified ZWO and 29 times higher than that of pure CdS. In addition, it exhibits excellent cycle stability in the hydrogen production cycle stability test. The photoelectrochemical test results show that the construction of the system improves the separation and transfer efficiency of photogenerated carriers. This study provides a new inspiration for the construction of high‐performance photocatalytic materials.

Apatite as a Record of Magmatic–Hydrothermal Evolution and Metallogenic Processes: The Case of the Hongshan Porphyry–Skarn Cu–Mo Deposit, SW China

Apatite, as a common accessory mineral found in magmatic–hydrothermal deposits, effectively yields geochemical insights that facilitate our understanding of the mineralization process. In this research, multiple generations of magmatic and hydrothermal apatite were observed in the Hongshan porphyry–skarn Cu–Mo deposit in the Yidun Terrane in SW China. The geochemical compositions of the apatite were studied using in situ laser ablation–inductively coupled plasma mass spectrometry and an electron probe microanalysis to understand the magmatic–hydrothermal processes leading to ore formation. The apatite (Ap1a) occurs as subhedral to euhedral inclusions hosted in the phenocrysts of the granite porphyry. The Ap1b occurs later than Ap1a in a fine-grained matrix that intersects the earlier phenocrysts. Increases in F/Cl, F/OH, and F/S and decreases in ΣREE and (La/Yb)N from Ap1a to Ap1b suggest the exsolution of a volatile-rich phase from the magma. The skarn hosts three types of hydrothermal apatite (Ap2a, Ap2b, and Ap3), marking the prograde, retrograde, and quartz–sulfide stages of mineralization, respectively. The elemental behaviors of hydrothermal apatite, including the changes in Cl, Eu, As, and REE, were utilized to reflect evolutions in salinity, pH, oxygen fugacity, and fluid compositions. The composition of Ap2a, which occurs as inclusions within garnet, indicates the presence of an early acidic magmatic fluid with high salinity and oxygen fugacity at the prograde skarn stage. The composition of Ap2b, formed by the coupled dissolution-reprecipitation of Ap2a, indicates the presence of a retrograde fluid that is characterized by lower salinity, higher pH, and a significant decrease in oxygen fugacity compared to the prograde fluid. The Ap3 coexists with quartz and sulfide minerals. Based on studies of Ap3, the fluids in the quartz–sulfide stage exhibit relatively reducing conditions, thereby accelerating the precipitation of copper and iron sulfides. This research highlights the potential of apatite geochemistry for tracing magmatic–hydrothermal evolution processes and identifying mineral exploration targets.

Diversity, spatial distribution and evolution of inactive and weakly active hydrothermal deposits in the TAG hydrothermal field

Introduction: Although, there is an increasing focus on inactive or extinct seafloor massive sulfide (SMS) deposits driven by the possibility of marine mining, only few studies have been devoted to them so far. The Trans-Atlantic Geotraverse (TAG) hydrothermal field is probably one of the best-studied hydrothermal systems even if the relict SMS deposits known since the mid-1980s have not been thoroughly explored.Objectives: The main objective of this study was to describe the characteristics of these so-called inactive sites.Methods: During four different expeditions, we acquired high-resolution acoustic data and performed numerous human occupied vehicle (HOV) dive operations including extensive rock sampling and in-situ temperature measurements.Results and Discussion: We discovered thirteen new hydrothermal mounds including six large (i.e. > 5,000 m2) deposits making the TAG hydrothermal field one of the largest accumulation of hydrothermal materials (21.1 Mt) known on the seafloor. However, copper and zinc grades of the largest SMS deposits remain low (i.e. < 1.4 wt%) even compared to on-land volcanogenic massive sulfide deposits. Additionally, eight areas of diffuse hydrothermal fluid flow were identified challenging the presumed inactivity of these SMS deposits and, for the first time, emphasizing the importance of low temperature (LT) hydrothermal activity in whole the TAG field. Inactive and weakly active SMS deposits exhibit a large diversity of surface mineralization (e.g. sulfides, Fe-Mn mineralization, jasper) illustrating complexity of hydrothermal activities but also different ageing history. Several mounds no longer have visible sulfide chimneys and are covered by a widespread layer of manganese and iron oxyhydroxides attesting the longevity of diffuse fluid flow at specific locations even long after last high-temperature (HT) hydrothermal activity has ceased. This contrasts with SMS deposits that are devoid of extensive LT precipitates but characterized by standing or topped sulfide chimney indicating a relatively abrupt cessation of HT hydrothermal activity.Conclusion: Together these results allow us to propose evolution models to explain the diversity of active, weakly active and inactive SMS deposits in the TAG hydrothermal field.

Enhanced stability and catalytic activity of subnanometric platinum cluster by surface doping of zirconium in CeO2

There has been a continuous effort to improve the thermal stability of subnanometric platinum (Pt) cluster (<2 nm) catalyst because Pt cluster on CeO2 support can be mobile and aggregated into nanoparticle on heating at elevated temperatures, yet this great challenge remains. In this study, a strategy is reported to improve the thermal stability of subnanometric Pt cluster by hydrothermal deposition method. Based on this method, zirconium (Zr) was precisely doped on surface of Ce0.95Zr0.05O2 by accurate control of Pt subnanometric cluster size. The surface doping of Zr is favorable for forming the Zr–O–Ce site and activating surface lattice oxygen atoms, which results in strong electronic interactions to stabilize the Pt subnanometric cluster. After high-temperature aging treatment at 1000 °C/4 h, the single atom Pt supported on CeO2 is aggregated into larger sized (>3 nm) nanoparticle. In contrast, the single atom Pt supported on Ce0.95Zr0.05O2 displays less agglomeration into subnanometric cluster with size of (1.4 ± 0.3) nm. Moreover, the CO oxide catalytic performance of Ce0.95Zr0.05O2–Pt is 26 % and 31 % higher than that of CeO2–Pt and commercial Al2O3–Pt catalysts, respectively. The experimental and density functional theory (DFT) calculations indicate that the Zr–O–Ce site and Pt subnanometric cluster interface have more defect sites and active oxygen species than CeO2–Pt interface, which activate the Mars van Krevelen (MvK) mechanism, facilitating the catalytic performance.

Occurrence of State of Gold in Crude Oil and Its Economic Significance

Gold and petroleum are also strategic resources of great importance to national security. With the increasing demand for energy, multi-energy cooperative exploration has become an inevitable trend of resource development and utilization. Petroleum and hydrothermal gold deposits may form together, with similar evolutionary trends in their formation, migration, and enrichment. Petroleum reservoirs and gold deposits are closely coupled under certain geological conditions. The solubility of gold in crude oil and its forms of occurrence are important in determining the mechanisms of interaction between gold and petroleum and in facilitating the recovery of gold from gold-bearing petroleum. In this study, the occurrence of gold in crude oil from the Linnan Depression in the Bohai Bay Basin, China, was studied using inductively coupled plasma–mass spectrometry and X-ray photoelectron spectroscopy. Concentrations of gold in crude oil from the Linpan and Shanghe oilfields averaged 44.5 ppb, which is well above the minimum concentration required for hydrothermal gold mineralization. Gold has an affinity with carbon, oxygen, and sulfur, and its concentration in crude oil is positively correlated with total acid and sulfur contents. We speculate that gold may exist in crude oil as complexes with organic acids or thiols, with crude oil thus being a transport medium for gold.

Global Occurrence, Geology and Characteristics of Hydrothermal-Origin Kaolin Deposits

Kaolin-group minerals occur in nature as the result of high-sulfidation acid sulfate, sulfur-poor HCl-, HF- and H2CO3-rich acidic fluid-related hydrothermal alterations and in situ geochemical weathering. These minerals possess different crystallographic and chemical properties that determine their application areas, mainly in the ceramic and paper industries, and as nanocomposite materials. The physicochemical properties of hydrothermal kaolin deposits are the result of the type of parent rock, the effect of the regional tectonism-associated magmatism, and the chemical features of hydrothermal fluids that interact with the deep basement rocks. However, understanding these geothermal systems is one of the most challenging issues due to the rich mineralogical assemblages, complex geochemistry and isotopic data of hydrothermal alteration zones. This study evaluates the formation of hydrothermal-origin kaolin-group minerals by considering their characteristics of hydrothermal alteration, isotopic compositions and differences in characteristic properties of low- and high-sulfidation occurrences; this paper also addresses mineralogical and structural differences between hypogene and supergene kaolin formations, and kaolin–alunite–pyrophyllite association, and it provides examples of worldwide occurrences. The study of the mineralogical assemblages, geochemistry and isotopic data of the hydrothermal alteration zones is one of the most challenging subjects in terms of gaining a detailed understanding of the geothermal systems. Silicification processes are subsequent to late-stage alteration after the completion of kaolinization processes, erasing existing hydrothermal mineralogical and geochemical traces and making interpretation difficult. In the early stages involving magmatic–hydrothermal-origin acidic geothermal fluids, the latter comes from the disproportionation of SO2 (+H2O) and H2S oxidation to H2SO4 in hydrothermal environments. In the later stages, due to spatial and temporal changes over time in the chemistry of geothermal fluids, the system comes to have a more alkali–chloride composition, with neutral pH waters frequently saturated with amorphous silica which characteristically precipitate as siliceous sinter deposits containing large amounts of opal-A.

Gold source and deposition in the Sanakham gold deposit, SW Laos: Constrains from textures, trace element geochemistry and in-situ sulfur isotopes of pyrite

The Luang Prabang (Laos) – Loei (Thailand) metallogenetic belt is endowed with major porphyry-skarn, and epithermal gold deposits. The Sanakham gold deposit is a newly discovered hydrothermal vein-type orogenic gold deposits (10.6 t Au @ 3.05 g/t) in the belt, and consist of a series of quartz-sulfide veins that are controlled by secondary structures of the regional NNE-trending brittle-ductile shear zone. Its mineralization can be divided into four stages: (I) quartz–pyrite–arsenopyrite, (II) quartz–pyrite–pyrrhotite–chalcopyrite, (III) quartz–pyrite–base-metal sulfide, and (IV) quartz–carbonate. Three pyrite generations were identified: py1 (stage I) as disseminated euhedral to subhedral coarse grains; py2 (stage II) as subhedral to anhedral fine grains occur around the cataclastic and corrosion textures in py1; py3 (stage III) as subhedral to anhedral fine grains occurred in sulfide veins or veinlets that overprint the existing quartz-sulfides. All three generations of pyrite have low trace-element contents including very low lattice-bound gold (py1: 0.040 ppm; py2: 0.098 ppm; py3: 0.028 ppm) and arsenic (py1: 227 ppm; py2: 133 ppm; py3: 13.3 ppm) contents. Visible gold grains are sited in textures of pyrite grains that relate to brittle cataclastic deformation. Considering the relatively low contents of pyrite in the ores of Sanakham, it is impossible to derive the high-gold grade orebodies through local remobilization of originally lattice-bound gold in pyrite. The py2 might be formed during hydrothermal overprinting and dissolution of py1 led by continuous supply of ore fluids with relatively higher contents of Au, Ag, Cu, Sb, Te, Pb, and Bi. A reduction reaction related to reduced carbon species in wallrock is an assignable cause for gold deposition, even though the fluid-rock interaction and fluid immiscibility processes might be important. The Au- and As-poor pyrites have similar δ34S values (py1: –2.58 to –0.83 ‰; py2: –2.17 ‰ to + 0.25 ‰; py3: –1.24 to –0.60 ‰ ppm) that close to 0 ‰, indicating the sulfur may have been originated from magmatic or mantle sources. Therefore, we propose that the Sankham gold deposit is a member of the orogenic deposit class, but notably characterized by the low concentrations of invisible gold in the relatively As-poor pyrite lattice.

Zoneamento geoquímico vertical do depósito de Pb-Zn (Cu-Ag) Santa Maria, região de Caçapava do Sul, Rio Grande do Sul

The Pb-Zn (Cu-Ag) Santa Maria deposit, part of the Camaquã Mines, south-center of the Rio Grande do Sul state, corresponds to one of the largest base metal deposits hosted by the Neoproterozoic volcano-sedimentary successions of the Camaquã Basin. Because of their economic importance, Camaquã Mines already were the target of a serie of studies, with the consequent proposition of diverse metalogenetic models, which point to an epithermal or magmatic-hydrothermal origin. Hydrothermal deposits have a common geochemical zoning pattern of indicator elements which can be used as an effective prospective criterion. Several geochemical hydrothermal halos are identified in this paper that can potentially serve as a useful exploration guide in the Camaquã Mines region. For that, the vertical geochemical zoning of the Santa Maria deposit was investigated through petrographic and/or geochemical study of 562 samples from his 3 ore bodies. The results obtained here are preliminary (they need to be tested in soil geochemical profiles over Santa Maria ore bodies), but indicate that the multiplicative ratios (Ag × Cd)/(Pb × Zn) and (Ag × Cd)/(Cu × Zn) and the elemental ratios Ag/Zn and Ag/Cu can be useful in the search for new Pb-Zn deposits in the Camaquã Mines.

Ornamental kale-like ZnO nanostructure/CdS nanoparticle/MoS2 nanosheet ternary heterojunctions for efficient charge transfer and robust visible-light photocatalytic performance

Photocatalytic technology utilizing Z-scheme protocol offers a promising method for eliminating contaminants from water in the presence of visible light. In this work, by combining hydrothermal and chemical deposition methods, a new type of ornamental kale-like ZnO nanostructure/CdS nanoparticle/MoS2 nanosheet (ZCM) ternary photocatalyst was fabricated, which exhibits excellent visible light photocatalytic performance. A small amount of MoS2 nanosheets significantly improves the activity of the double Z-scheme ZCM photocatalyst. As compared to ZnO/CdS, the pseudo-first-order kinetic constant of the best ZCM sample for degradation of rhodamine B is 2.2 times higher. In light of free radical capture and PL results, a Z-scheme transport mechanism was revealed to increase the carrier separation rate and maintain strong redox stability. This study provides a solid basis for designing Z-scheme photocatalysts and developing a range of visible light-responsive photocatalysts.

Genetic association between carbonates and gold precipitation mechanisms in the Jinshan deposit, eastern Jiangnan orogen

Carbonates have been traditionally regarded as post-ore minerals in hydrothermal deposits, but they can also occur in pre- and syn-ore stages. However, the genetic relationships between multistage carbonates and gold precipitation mechanisms remain unclear. The Jinshan gold deposit, the largest gold deposit in the eastern Jiangnan orogen, is characterized by the occurrence of abundant hydrothermal carbonates. The nature of the carbonates, especially their association with gold precipitation, was examined in this study through petrographic and geochemical analyses as well as geochemical modeling. Field and petrographic work recognized four paragenesis stages in the Jinshan deposit: (1) quartz (Q1)-carbonate, (2) pyrite-quartz (Q2), (3) gold-polysulfide-quartz (Q3)-carbonate, and (4) chlorite-quartz (Q4)-carbonate. Carbonates associated with gold mineralization are mainly present in the first and third stages. Among them, the first-stage carbonates are pre-ore ankerites (Ank1), which are generally crosscut by syn-ore sulfides. Such carbonates mostly occur in altered host rocks that are characterized by bleaching. Mineralogical and geochemical analyses revealed that chlorite was consumed while ankerite was produced, and Fe contents of the host rocks remained generally unchanged during alteration. Consequently, ankerite (Ank1) is interpreted to have been generated by the interaction of CO2-bearing fluids and chlorite in the host rocks. Geochemical modeling revealed that both Fe-bearing chlorite and ankerite (Ank1) can lead to gold precipitation by triggering sulfidation, but ankerite has higher chemical reactivity and therefore is kinetically favorable for more efficient gold deposition. Syn-ore carbonates were mainly formed in the third stage, primarily consisting of ankerite (Ank2) with minor calcite, and they were coprecipitated with native gold, galena, sphalerite, and chalcopyrite. Two stages of carbonates shared similar δ13CVPDB values and Pb, Zn, and Cu contents but different Ca, Mg, Mn, and Sr contents, indicating they formed at different stages of the same hydrothermal event. Geochemical modeling demonstrated that pH increases, as indicated by the formation of syn-ore carbonates, together with the consumption of S due to the precipitation of pyrite and arsenopyrite in the second stage, resulted in the decrease of Au, Pb, Zn, and Cu solubility in aqueous fluids. This would have led to the coprecipitation of native gold with galena, sphalerite, and chalcopyrite, forming the general small-scale but commonly occurring native gold−polysulfide veins in the hydrothermal gold deposits. Consequently, both pre- and syn-ore carbonates in the Jinshan deposit were genetically associated with efficient Au-polymetallic deposition through distinct mechanisms. Pre-ore carbonates caused the large-scale bleaching of the host rocks, while syn-ore carbonates were closely related to native gold−polysulfides, and they can both be used as exploration indicators for the Jinshan deposit and other similar hydrothermal gold deposits worldwide.

Influence of different tectonic settings on fracture formation and fluid flow around upper-crustal magmatic intrusion: insights from numerical modelling

Large porphyry Cu and epithermal Au deposits tend to form in distinct tectonic, porphyry and high-sulfidation epithermal deposits in compressional settings, and low-sulfidation epithermal deposits in extensional settings. Given that the analysis of the shallow metallogenic dynamic processes at the upper-crust scale is insufficient, especially the ore-bearing fracture formation and fluid-focusing mechanism around the mineralizing magmatic intrusion under different tectonic backgrounds, we aimed to study how tectonic settings influence fracture formation and fluid hydrodynamics in and around a hot intrusion. We developed a finite element model coupling thermal-hydrological-mechanical processes to simulate the fracture formation, evolution of fluid velocities, and accumulation of water-rock interactions. The model results show that tectonic compression increases the degree of fracturing, hydrothermal fluid velocities, and water-rock interaction within and laterally around the intrusion; tectonic extension enhances fracturing, hydrothermal fluid velocities, and water-rock interaction at shallow depth. These results confirm that tectonic compression may promote the formation of porphyry Cu deposits, while tectonic extension may promote the formation of shallow hydrothermal deposits. Our model explains the effects of tectonic activity on fracture formation and fluid flow around hot magmatic intrusions in upper crust and deepens our understanding of the relationship between tectonic activity and deposit formation there.

Element geochemical differences in lower Cambrian black shales with hydrothermal sedimentation in the Yangtze block, South China

Abstract Hydrothermal activities occurred in the Yangtze block, South China, and affected the process of black shale sedimentation in the early Cambrian. Their specific influences, such as the sources, sedimentary environment, and mineralization, have not yet been revealed. Fortunately, the influences are explained through the geochemistry comparison of different wells FY1, XJ1, HY1, and XA1 in northwestern Hunan. The outcomes of the tectonic setting, distinguishable by element indicators, are disorganized. This is caused by the variable element composition, sedimentary recirculation of material source, and hydrothermal materials. FY1, the closest well to Zhangjiajie where Ni–Mo ores were formed by hydrothermal sedimentation, has more different features on the elemental geochemistry, but many indexes still indicate that it is normal sediments. XA1, which is far from the other wells and deposited in the deep-water basin, has significantly more differences in geochemical properties and shows more about normal marine deposition. XJ1 and HY1 are intermediate between them. Based on these wells, the hydrothermal contribution to the black shale sedimentation is not significant. However, some contents of trace and rare earth elements change widely because hydrothermal materials can diffuse and deposit over long distances. The concentration of Ag, As, Ba, Mo, Ba, U, and V generally has dozens of times higher than that of Upper Continental Crust. The early Cambrian environment was primarily anoxic/euxinic with enough sulfur, which is beneficial for enriching metal elements and organic matter. The sequence FY1, XJ1, HY1, and XA1 in turn has the same performance on the distance with Zhangjiajie, different intervals of suboxic environment and element enrichment, and hydrothermal-fluid-addition Ni abundance. Therefore, hydrothermal processes indeed provide materials for element enrichment and support the reducing environment, but the impact of hydrothermal activity decreases on the plane.

The impact of apatite on sulfuric acid baking of a monazite concentrate and the benefit of goethite addition on rare earth leaching

Sulfuric acid baking of monazite ((Ce,La,Th)PO4) bearing ores is one of the major processes used in commercial production of rare earth elements. In hydrothermal vein type rare earth deposits, apatite is often found together with monazite. Rare earth enriched fluorapatite ores may also contain significant amounts of rare earths hosted in monazite. An understanding of the effect of apatite on the sulfuric acid baking of monazite is therefore important for the development of effective sulfuric acid based treatment methods for such ores. In this work, the addition of a natural hydroxyapatite (Ca5(PO4)3(OH)) sample to a monazite acid bake followed by acid leach was investigated using a combination of chemical analyses, SEM-EDS, XRD and TG-DSC. Hydroxyapatite addition significantly decreased the dissolution of rare earth elements from monazite in the leach after baking at temperatures above 300 °C. For a bake temperature of 500 °C, the rare earth dissolution in the leach dropped from 80% for monazite alone, to 30% for a 1:1 (w/w) addition of hydroxyapatite. This decrease in rare earth leaching was attributed to the formation of an insoluble thorium and rare earth bearing polyphosphate. The rare earth elements were incorporated into this polyphosphate phase in preference to calcium. At 800 °C, monazite was re-formed, causing a further reduction in rare earth extraction, while simultaneous formation of calcium pyrophosphate (Ca2P2O7) led to an increase in calcium and phosphorus dissolution. The detrimental effect of apatite could be partially overcome by the addition of goethite. Addition of goethite to the acid bake of a monazite/apatite mixture at 500 °C improved the total rare earth dissolution from 29% to 85% in the subsequent leach. Results also demonstrated that the order of reactivity, in terms of formation of polyphosphates is Fe > REE > Ca.

Fluid Mixing, Organic Matter, and the Origin of Permian Carbonate-Hosted Pb-Zn Deposits in SW China: New Insights from the Fuli Deposit

The Fuli Pb-Zn deposit is situated at the southwestern margin of the Yangtze Block in Yunnan. The deposit, which is hosted in the Permian Yangxin Formation dolomite, is a recent discovery. Our study indicates a significant presence of fluid inclusions in sphalerite from the Fuli Pb-Zn deposit, with fewer inclusions observed in dolomite and calcite. We conducted comprehensive petrographic, microthermometric, and laser Raman analyses on the inclusions within sphalerite and dolomite. Additionally, six samples of dolomite from the mineralization period were selected for H-O isotope analysis. The results of our study reveal the characteristics of ore-forming fluids and explore the mechanisms of ore formation. The study results indicate that the Fuli Pb-Zn deposit is a low- to medium-temperature hydrothermal deposit with fluid inclusions mainly composed of two-phase gas-liquid inclusions. Salinity and homogenization temperature analyses affirmed that there are two types of fluids present, one with low salinity and the other with high salinity. Laser Raman tests demonstrated the presence of CH4, N2, and CO2 in the gas phase of the inclusions. Microthermometric analyses indicated that the sphalerite ore-forming fluids consist of a multicomponent system of Mg2+ and Ca2+ enriched fluids. The features of the ore-forming fluids in the Fuli deposit arise from a blend of high-temperature, low-salinity metamorphic fluids and low-temperature, high-salinity basin brines. The basin brines in question have the potential to emanate from the Youjiang Basin. The formation of the ore is ascribed to the TSR and the mixing of fluids. The combination of these processes provided the requisite materials (SO42−), catalysts (Mg2+), and reducing agents (organic matter, CH4, and H2S) required to initiate the thermochemical sulfate reduction (TSR). As the TSR proceeded, it caused a shift in the pH of the fluids, thus promoting the precipitation of metal sulfides.

Linear Correlations of Gibbs Free Energy of REE Phosphates (Monazite, Xenotime, and Rhabdophane) and Internally Consistent Binary Mixing Properties

Rare Earth Elements (REE) phosphates (monazite, xenotime, and rhabdophane) are critical REE-bearing minerals typically formed in hydrothermal and magmatic ore deposits. The thermodynamic properties of those REE minerals are crucial to understanding the solubility, speciation, and transport of REE complexes. However, the standard-state Gibbs free energy of formation (∆G°f) values reported for these minerals in the literature vary by up to 25 kJ mol−1. Here, we present linear free energy relationships that allow the evaluation and estimation of the ∆G°f values at 25 °C and 1 bar for the three minerals from the ionic radius (rREE3+) and the non-solvation Gibbs free energy contribution to the REE3+ aqua ion (∆G°n, REE3+): ∆G°f,monazite − 399.71 rREE3+ = 1.0059 ∆G°n,REE3+ − 2522.51; ∆G°f,xenotime − 344.08 rREE3+ = 0.9909 ∆G°n,REE3+ − 2451.53; and ∆G°f,rhabdophane − 416.17 rREE3+ = 1.0067 ∆G°n, REE3+ − 2688.86. Moreover, based on the new dataset derived for REE end-members, we re-fitted the binary Margules parameter (W) from previous theoretical calculations into linear correlations: W + 0.00204 ∆G°’n,monazite = 39.3549 ∆V + 0.0641; W + 0.00255 ∆G°’n,xenotime = 25.4885 ∆V − 0.0062. The internally consistent thermodynamic properties of these REE phosphates are incorporated into the computer program Supcrtbl, which is available online at Zhu’s research website.