Hydrothermal Fluids Research Articles

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

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

Hydrothermal activity near the Permian–Triassic transition in the south‐western Ordos Basin, China: Evidence from carbonate cementation in Upper Permian sandstones

ABSTRACTCarbonate cementation in the Upper Permian sandstones informs the timing and temperature of hydrothermal activity in the south‐western Ordos Basin. This study presents a detailed examination of these hydrothermally influenced carbonate cements, constraining their age, carbonate diagenesis and relationship with regional geodynamic evolution. Sedimentological analyses demonstrate the development of deltaic plain and front sand bodies in the study area, which resulted in interbeds of volcanic matrix‐rich sandstones with matrix‐free sandstones. Petrography and electron microprobe analysis reveal four carbonate mineral growth phases of matrix‐free sandstones in the following sequence; scarce pure siderite, scarce Mg‐rich siderite, abundant blocky calcite and moderately abundant grain‐replacing calcite. The fluid inclusion data show anomalies of homogenization temperature of blocky carbonate cements during early diagenesis, over a wide range of ca 148 to 228°C. In addition, blocky carbonate cements show low δ13C (−5.9 to −13.1‰ Vienna PeeDee Belemnite) and δ18O (clustered tightly from −12.4 to −14.6‰ Vienna PeeDee Belemnite) values, interpreted to result from elevated temperatures during cementation, associated with activation of basement faults and concomitant hydrothermal fluid intrusion triggered by oceanic crust subduction in the south‐west margin of the Ordos Basin. Using in situ calcite U–Pb geochronology, the timing of hydrothermal activity was constrained to ca 247.0 ± 11 to 248.2 ± 4.7 Ma. This work provides a case study for applying intergranular calcite U–Pb dating to determine the absolute timing of fluid flow in sedimentary basins, offering tremendous potential to capture snapshots of various diagenetic evolution stages in sediments. The proposed diagenetic model can also provide new insights and understanding regarding hydrothermally influenced sediments. More importantly, hydrothermal activity may have commenced earlier than previously thought. The North Qinling Orogen uplift and associated Mianlue oceanic crust subduction may have begun at the Permian–Triassic transition with a protracted hydrothermal event in the south‐western Ordos Basin.

Combined effect of magmatic fluid–seawater mixing and host rock alteration on the formation of gold-enriched massive sulfides in the Forecast vent field, southern Mariana Trough

Massive sulfides and sulfide-bearing breccia were collected from the Forecast vent field in the southern Mariana Trough. These samples exhibit varying degrees of hydrothermal alteration and/or mineralization, with the former type having significant enrichments in Au (up to 101 ppm). In this study, detailed analyses of mineralogy, geochemistry, S isotope, and fluid inclusion were conducted to understand the unusual Au-rich mineralization. Mineralogical investigations and geochemical analyses (LA–ICP–MS and EPMA) of dominant sulfide minerals indicate that electrums, the main phase of Au mineralization, are characterized by two different generations based on mineralogical relationships and fineness. Early-stage high fineness electrums (930–981 ‰) are associated with sphalerite under relatively high-temperature fluid conditions, whereas galena is main host mineral related to late-stage low fineness electrums (773–868 ‰). Sphalerite geothermometry (231–264 °C), the occurrence of colloform textured sulfides, and microthermometric characteristics of fluid inclusions (Th = 220–304 °C; Salinity = 1.4–6.6 wt% NaCl equivalent; a general trend of decreasing salinity with decreasing Th) indicate that significant decreases in H2S activity, attributed to seawater dilution and rapid precipitation of sulfide minerals, facilitated the efficient destabilization and deposition of Au transported as sulfide complexes from hydrothermal fluids. In particular, the lower 34S values (+0.2 ‰ to + 1.3 ‰) of sulfides compared to those of arc/back-arc lavas (δ34S = +5‰ to + 11 ‰), along with the prevalence of CO2 in the vapor phase of fluid inclusions, reflect that the significant contribution of magmatic volatile influx supplied most of the sulfur and metals (including Au) to the Forecast hydrothermal fluids. Additionally, the abundance of montmorillonite and varying proportions of sulfide and gangue minerals observed in hydrothermal samples suggest that the chemical buffering of fluids by associated substrates and/or sediments could be another significant factor in promoting Au-rich mineralization. Therefore we conclude that the combination of magmatic fluid–seawater mixing and host rock alteration plays an important role in the formation of Au-enriched massive sulfides in the Forecast vent field.

Structural controls on hydrothermal fluid flow in a carbonate geothermal reservoir: Insights from giant carbonate veins in western Germany

This study examines the impact of polyphase tectonics on the development of structurally controlled hydrothermal fluid pathways in carbonate geothermal reservoirs. Our case study focuses on hydrothermal carbonate veins and vein-filled faults in Devonian carbonates from the North Rhine-Westphalia region in western Germany, currently being explored as a potential low-enthalpy geothermal reservoir at depths of 4–5 km. These veins, which can be up to 20 m thick, are subvertical and strike NNW, N, or ESE. They exhibit pinch-and-swell undulating geometries, faulted vein-wall contacts, and occasional fillings of hydrothermal breccias. Vein-filled normal faults show hybrid shear-dilatant openings, with fault tips characterized by horsetail vein terminations. The textures, orientations, and age of the veins suggest their formation at low confining pressures and at depths < 2 km during the Post-Variscan East-West extension. Orthogonal North- and East-striking strike slip faults, inherited from the Variscan orogeny, were likely reactivated during post-Variscan extension, with a significant dilatant component that formed the observed veins. In the Ruhr Basin, the dilation tendency analysis indicates that NNW-striking veins or joints are optimally oriented for re-opening under the current strike-slip stress regime, characterized by NNW-trending maximum horizontal stress. The intersections of fractures may currently create moderately SSE-plunging linear zones of enhanced fluid flow. The main uncertainty regards the presence of similar structures at geothermal reservoir depths of ∼4–5 km in the Middle Devonian carbonates underneath the Ruhr Basin. As the study veins are likely to have formed at depths <2 km, the existence of analogous dilatant conduits at greater depths remains speculative. Eventually, we propose that zones characterized by open discontinuities and channelized fluid flow in carbonate geothermal reservoir in strike-slip tectonic settings can be: (a) dilational jogs between overlapping strike-slip faults, (b) bends along faults, and (c) strike-slip fault terminations with horsetail extensional structures. These zones can also be prone to enhanced karstification.

Deep subseafloor sediments in Guaymas Basin harbor cosmopolitan microbiota and traces of hydrothermal populations

Environmental factors shape subsurface microbial ecosystems, and well-characterized sites are ideal for determining how environmental parameters shape sediment communities. Sediments from eight geologically and thermally distinct sites were drilled during International Ocean Discovery Program Expedition 385 in Guaymas Basin, an expedition focused on the hydrothermal deep biosphere. Using high-throughput 16S ribosomal nucleic acid sequencing, cell counts, phylogenetics, metatranscriptomics, and mineralogical/elemental X-ray spectroscopy, we examine linkages and feedbacks between mineral composition, temperature, geochemistry, and microbial populations. We show subsurface life is dominated by heterotrophic, cosmopolitan prokaryotes that thrive within a range of sediments and temperature conditions across Guaymas Basin. Hydrothermally-affiliated lineages are detected in low numbers at sites with steepest temperature gradients, within communities of mesophilic taxa that occur throughout Guaymas Basin and in other marine subsurface habitats. Thus, hydrothermal lineages do not replace the cosmopolitan, mesophilic subsurface community, but remain specific to sites where volcanic intrusions drive hydrothermal circulation.

Oxygen and silicon isotopic compositions of Archean silicified lava and cherts of the Onverwacht Group: Implication for seafloor hydrothermalism and the nature of recycled components in the source of granitoids

Cherts are commonly used as proxies for Archean environmental conditions such as oceanic temperature. However, because cherts encompass a wide variety of silica-rich rocks, including post-depositional silicified of clastic sediments or chemical precipitates from seawater, reconstructions of the Archean environment based on their O and Si isotopic compositions remain controversial. In this study, we present triple O isotope analyses associated with SIMS O and Si isotope measurements of Palaeoarchean pervasively silicified lavas and clastic sediments, which have been less studied than the associated cherts within the Onverwacht Group (Barberton Greenstone Belt, South Africa). We also provide triple O isotopic compositions of seawater-precipitated cherts. The O and Si isotope composition of silicified clastic sediments and lavas is not considerably variable through the Onverwacht succession. These lithologies display relatively low δ18O (11.3–14.9 ‰) and high Δ’17O values (−0.05 to - 0.07 ‰) attributed to precipitation of silica from hydrothermal fluids at lower temperatures than 200 °C. Using these results, we reconstruct the approximate O isotope composition of the hydrothermal fluids. Water-rock interaction models suggest that this fluid composition is consistent with the existence of low δ18O oceans, but the exact δ18O value of the Palaeoarchean ocean remains elusive. Seawater-precipitated cherts show a mixture of hydrothermal and seawater-like triple O isotope signatures, confirming that cherts are not a straightforward proxy for constraining Archean seawater composition or temperature. The average δ30Si value of the pervasively silicified lavas and clastic sediments is positive (> +0.19 ‰) and compositionally similar to published values of the seawater-precipitated cherts. This suggests comparable δ30Si values between Archean hydrothermal fluids and seawater. A gradual increase of δ18O values of silicified lavas and cherts from 10 to 13 ‰ to 15–20 ‰ observed along the Onverwacht succession is ascribed to local lithospheric cooling occurring between 3.47 Ga and 3.3 Ga, while Si isotope compositions remained mostly unchanged in the silica-rich rocks. As silicified lavas are likely part of materials that melted to generate Palaeoarchean granitoids, the evolutional difference between O and Si isotopes may have characterised the silicified rocks that were recycled in different generations of granitoid sources. This may explain the variation in O isotopic compositions measured in different granitoid generations in the Barberton area.

Tidal triggering of seismic swarm associated with hydrothermal circulation at Blanco ridge transform fault zone, Northeast Pacific

Seismicity associated with hydrothermal systems (e.g., submarine volcanoes, mid-oceanic ridges, oceanic transform faults, etc.) share a complex relationship with the tidal forcing and induced fluid flow process under different tectonic settings. The hydrothermal circulation drives the deformation at the brittle-ductile transition zone within a permeable brittle crust. Although the tidal loading amplitudes are too small to generate a brittle deformation, the incremental pressure exerted by the tidal loading can modulate the flow of hydrothermal fluid circulation and trigger the critically stressed faults or fracture zones. We present a compelling case of tidal modulation in seismicity along the Blanco Ridge Transform Fault Zone (BRTFZ), in the northeast Pacific. The strong diurnal and fortnightly periodicity has been observed in the deeper seismic swarm (7–15 km), whereas the shallow seismic swarm (0–7 km) does not exhibit any such tidal periodicity. The dominance of diurnal and fortnightly periodicity in the deeper seismic swarm is explained by the high amplitude tidal cycles providing additional stress on the fluid circulation at the crust-mantle boundary. Moreover, our robust statistical correlation of seismicity with tidal stress and resonance destabilization model under rate-and-state friction formalism suggests that the fault segments are conditionally unstable and more sensitive to periodic tidal stress perturbation.

Effect of CO2 and H2SO4 on the dissolution of a carbonate basement and alteration of silicates in a volcano-sedimentary system in central Mexico

This study explores the hydrogeochemical and isotopic characteristics of groundwater in the Irapuato Valley and Celaya Valley Aquifers in central Mexico, specifically focusing on the role of CO2 in mineral alteration during water-rock interaction. The study is grounded in the principles of hydrogeochemistry and stable isotope geochemistry, analyzing the impact of CO2 and H2SO4 on the weathering of carbonates and silicates. Hydrogeochemical analysis, including Piper diagrams, and isotopic measurements (δ13C, δ18O, δ2H), were conducted on water samples from wells in four municipalities (Irapuato, Salamanca, Villagrán, and Juventino Rosas). The data was statistically evaluated using Shapiro-Wilk tests to assess normality, skewness, and kurtosis, ensuring the reliability of the findings. The results indicate that HCO3− dominates the groundwater composition, with CO2 and H2SO4 significantly influencing mineral alteration processes. The isotopic data suggest that CO2 is primarily released from carbonate rock degassing, with slight isotopic enrichment in δ13C due to water-carbonate interaction. Hydrothermal fluids contribute to the geochemical evolution of the aquifer, leading to the formation of minerals such as tridymite, alunite, and kaolinite. Additionally, some groundwater samples exhibit evidence of thermalism and water-rock interactions, influencing their isotopic signatures and temperatures. These findings underscore the importance of CO2 in groundwater chemistry and highlight the need for further studies to understand regional flow dynamics and the potential impact of geothermal systems on water quality.

Carbonatites and related mineralization: an overview

Despite of their scarcity, carbonatites are documented from diverse geological settings, including cratons, continental rifts, orogenic belts and large igneous provinces, which range in age from the Archean to Recent. This study provides a concise overview of the evolution of igneous carbonatites, compiling data on their diverse characteristics and classifying them into mantle- and crustal-derived subtypes. Mantle-derived carbonatites, typically associated with alkaline rocks, are enriched in rare earth elements (REEs) and display geochemical affinities to the mantle. By contrast, crustal-derived carbonatites usually show much lower REE contents and crustal-affinity geochemical features similar to sedimentary carbonaceous rocks. Our study documents the significant economic potential of carbonatites that can host world-class deposits of REE, rare metals, alkaline earth metals and non-metallic resources. Typically, the key processes controlling REE mineralization include the low-degree melting of refertilized mantle, liquid immiscibility, fractional crystallization and hydrothermal fluids. Thus, carbonatites are of significant economic value due to the rapidly increasing global demand for REEs, mainly driven by the ‘green energy transition’.

Diagenetic and hydrothermal events revealed by an Ediacaran dolomite breccia from the Araras-Alto Paraguai basin, southern Amazon Craton

The establishment of extensive carbonate platforms characterized the Ediacaran period during CaCO3 oversaturation events and the exceptional creation of accommodation space associated with the aftermath of the Marinoan glaciation (∼635 Ma). Carbonate deposits in the Araras Group record the early Ediacaran period, stage 1, in the Amazon Craton. The Serra do Quilombo Formation is an intermediate unit characterized by heavily fractured and faulted dolomites, as well as the presence of dolomite-cemented breccias (CB) overlying thick limestone packages associated with diagenetic and hydrothermal modifications. These features are commonly attributed to structurally controlled hydrothermal dolomitization (HTD) and are of significant economic importance as hydrocarbon reservoirs and Mississippi Valley-type (MVT) lead-zinc mineralization hosts. This study aims to unravel the origin of cemented breccias and the diagenetic/burial processes within the unit, focusing on dolomitization processes. Dolomite samples were analyzed using petrographic, scanning electron microscopy, microprobe, micro-Raman, cathodoluminescence, and isotopic analyses (δ13C, δ18O, 87Sr/86Sr) to unravel their burial history. CBs are sub-vertical to sub-horizontal bodies with complex geometries, generally cutting bedding at high angles, indicating hydrofracturing processes related to vertical flows of hydrothermal fluids (hydraulic breccia) and present the typical cockade texture of expansion breccias in dilatational faults. The substitutive matrix RD1 is the main constituent of the Serra Quilombo Formation, its low correlation between δ13C and δ18O (R2 = 0.009), the well-preserved fabric, and the similarity with the isotopic values (C and Sr) documented for Ediacaran carbonates, suggest that the syndepositional dolomitization. The first generation of dolomite cement (DC1) and the last phase of dolomitic cementation (saddle dolomite - SD) occur, filling pores, CBs, and fractures. The cockade texture of the breccias evidences a low precipitation rate or a pause in precipitation between DC1 and SD. Concurrently, DC1 has isotopic signals of δ18O = −4.34 ± 1.32‰ (n = 18) and 87Sr/86Sr = 0.708831 (n = 2), while SD has values of δ18O = −9.57 ± 2.51‰ (n = 15) and 87Sr/86Sr = 0.711464 (n = 3). The large isotopic fractionation between DC1 and SD suggests different dolomitizing fluids. This relationship shows an increase in 87Sr in the fluid as the temperature increases; moreover, the enrichment in 87Sr of the fluid is explained by the interaction of this fluid with rocks from the crystalline basement. Thus, the main conduit for the ascent of this radiogenic fluid would be faults with deep roots spatially close to tectonically active zones. Lastly, the presence of tectonic stylolites cutting cemented breccias and rotated zebra-like strata-bound structures suggests that brecciation occurred before the installation of fragile post-Ordovician transtensional structures, preceding the establishment of Paleozoic Basins on the South American Platform.

Assessment of REY resource potential in deep-sea sediments with Fe–Mn (oxyhydr)oxides in the Pacific Ocean

Deep-sea sediments with an abundance bioapatites and Fe–Mn (oxyhydr)oxides in the Pacific Ocean have been considered potential reservoirs of rare earth elements and yttrium (REY). However, comprehensive assessment of the resource potential of REY in deep-sea sediments with Fe–Mn (oxyhydr)oxides throughout the Pacific Ocean is limited due to difficulties in accurately predicting the distribution of extensive Fe–Mn (oxyhydr)oxides and the associated REY. In this study, we predicted the prospective area and resource potential of REY-rich sediments with Fe–Mn (oxyhydr)oxides by considering multiple factors that control REY enrichment based on data from International Ocean Discovery Program (IODP) samples and previous research. According to the distribution map inferred by comprehensively evaluating lithology (clay sediment), hydrothermal fluid influence (δ3He), and water depth (bathymetry), deep-sea sediments with Fe–Mn (oxyhydr)oxides, which have higher than 1000 ppm REY concentration, are distributed in the vicinity of the East Pacific Ridge within a water depth range of 4000–4600 m, and their distribution area is estimated to be approximately 1.1 million km2. If the sedimentation rate (<1.5 m/Myr) is considered, which is a crucial factor influencing REY enrichment, we can achieve a more precise assessment of their distribution area. Assuming a recovery depth of only 1 m, the REY resource amount was estimated to be approximately >450 million tons of REY oxide. Even without accounting for REY resource amount associated with bioapatite, the minimum REY resource amount estimated in this study exceed the world's current land reserves. Furthermore, these sediments contain a significant abundance of industrially important heavy REY, accounting for 53 % of REY resources. This implies that the deep-sea sediments with Fe–Mn (oxyhydr)oxides in the Pacific Ocean are a promising resource of REY. Our findings will serve as essential information for the technological progress required in the exploration and development of REY resources in deep-sea sediments in the future.

Deformation and fluid flow history of a fractured basement hydrocarbon reservoir below the Sab'atayn Basin, Habban Field, Yemen

Fractured crystalline basement reservoirs are of increasing economic interest for oil and gas exploration and subsurface fluid storage. The successful characterization of these reservoirs is commonly challenged by their structural heterogeneity, complexity in fracture distribution and flow properties at multiple scales, and the difficulty of imaging fractures in exploration seismic. We analyzed the fracture geometry and fracture diagenetic attributes in two oriented cores from the Habban Field in the Late Jurassic Sab'atayn Basin (Yemen) to evaluate the multi-phase deformation history and fracture flow pathway evolution for (hydrothermal) fluids and hydrocarbons. Analyses included petrographic and fluid inclusion analysis of fracture-filling cements, and stable sulfur isotope analyses of fracture-filling pyrite.The Paleoproterozoic basement consists of amphibolite-facies metamorphic ortho- and paragneiss cut by several phases of Neoproterozoic granitoid intrusions. The investigated lithologies in the drill cores comprise (1) epidote quartzite, (2) amphibolite, (3) monzogranite, (4) meta-arkose, and (5) quartz-feldspar porphyry. These lithologies show an inhomogeneous fracture network that is partially cemented. Ediacaran brittle-ductile deformation (D1) recognized only within a Pan-African monzogranite lead to cataclasis and porosity generating alteration. Late Jurassic – Early Cretaceous extension (D2) related to the break-up of Gondwanaland and the formation of the Sab'atayn Basin is found in all lithologies and likely resulted in pervasive quartz cementation. Late Jurassic fractures parallel to the NW-SE trending long axis of the Sab'atayn Basin are best recognized in a strongly foliated amphibolites. Cenozoic extensional fracturing (D3) reactivated older structures, which probably formed during activity of the Neoproterozoic Najd Fault System and caused multi-phased (pyrite-(saddle) dolomite-calcite) fracture cementations. The sulfur isotope compositions of pyrite with δ34S values ranging between −17.4 and + 26.4‰ vs. V-CDT reflects the variability of the fluid source during sulphide mineral formation from hydrocarbon-rich hydrothermal solutions. Fluid inclusions indicate that cementation reactions occurred in a relatively narrow temperature field between 120 °C and 140 °C, ideal for hydrocarbon maturation. Our results demonstrate the potentially complex charge history of basement reservoirs, involving multiple phases of fracture formation and cementation, and fluid charge episodes.

Fluid flow in the Katanga Supergroup: From Lufilian brittle tectonic stages to the post-Lufilian period (Democratic Republic of Congo)

The metasedimentary rock succession of the Neoproterozoic-Cambrian Katanga Supergroup in the Central Africa Copperbelt shows evidence of several complex tectonic events. The deformation of this supergroup started from the tectonic inversion at about 570 Ma and lasted up to today, but reached paroxysm at ∼550 Ma. This long period was characterized by folding and faulting throughout multiple compressive and extensional events, which controlled the regional fluid flow on the one hand, and played an important role during formation of the stratiform to stratabound Cu-Co (Ni, U) deposits and the polymetallic Cu-Zn-Pb (Ag, Ge, Mo, Cd) vein type deposits on the other hand. Based on the structural analysis and paleostress reconstruction, coupled with fluid inclusion characterization from mineralized structures in rocks from the Nguba, Kundelungu and Biano Groups, this study demonstrates that the composition of hydrothermal fluids changed during brittle tectonic deformation during the Lufilian orogeny and subsequent uplift and post-Lufilian faulting.During early brittle tectonic deformation along strike slip faults with sinistral and dextral movement related to a NE-SW transpression, the Cu-mineralizing fluid was hypersaline (27.9–31.1 eq. wt% NaCl) with moderate temperatures (Th = 128–216 °C). The subsequent Cu or Cu (Zn, Pb) mineralization formed within an E-W extensional stress regime, related to the late Lufilian orogenic collapse. The fluid inclusions present in the gangue minerals associated with this latter mineralization show a large range in Th (50–264 °C) and salinity (26.7–36.0 eq. wt% NaCl). The decrease in temperature is interpreted to be due to migration of the fluids at shallower depth in the subsurface after uplift and erosion of the orogen. The increased salinity of the fluid is related to the dissolution of evaporites, mainly NaCl. A second H2O-NaCl-CaCl2 fluid with a homogenization temperature below 55 °C has also been found associated with this brittle stage and mineralization phase, but only in rocks belonging to the Kundelungu Group. A third mineralization phase, also characterized by Cu or Cu (Zn, Pb), formed during the post-Lufilian period within a NW-SE transpressional inversion regime. The fluid inclusion in the gangue minerals of this mineralization phase have a smaller range in homogenization temperature (Th = 37–172 °C) and the largest range in salinity (0.71–30 eq. wt% NaCl), compared to the earlier fluid inclusions generations. This large range in salinity may be explained by the mixing of a high salinity fluid, already present during the earlier tectonic stages in the sedimentary basin, with meteoric water. During the more recent rift-related extension, a fluid with again a large and higher range in homogenization temperatures (Th = 47–257 °C) and with a typical low salinity (<10 eq. wt% NaCl) has been recognized in minerals filling NNE-SSW to NE-SW oriented faults and fractures. The upward migration of a relatively low-salinity fluid from deeper parts in the subsurface explains the variation in the temperatures observed with this tectonic event.

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

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

Y-Ho fractionation during basalt alteration in hydrothermal system: An implication for superchondritic Y/Ho signature recorded in Precambrian banded iron formations

The concentration of rare earth elements (REE) in Precambrian sedimentary rocks is widely used to estimate their depositional environment. Specifically, superchondritic Y/Ho value is a powerful indicator for determining whether a sedimentary rock was deposited in a marine environment. Currently, superchondritic Y/Ho value in seawater is believed to result from the preferential adsorption of Y onto Fe-Mn oxides. In modern oceans, Fe-Mn oxides are considered the sink for subchondritic Y/Ho value. On the contrary, Precambrian banded iron formations (BIFs) display superchondritic Y/Ho value, suggesting that Precambrian seawater also possessed a superchondritic Y/Ho value. However, Precambrian BIFs cannot account for the sink of subchondritic Y/Ho value. Thus, other processes must have been responsible for maintaining the superchondritic Y/Ho value of Precambrian seawater. A hydrothermal experiment involving mid-ocean ridge basalt (MORB) and a Cl-rich fluid was conducted at 300 °C and 500 bars to assess the role of basalt-hosted hydrothermal systems on the Y/Ho value of seawater. Over time, the fluid's Ca concentration increased while Na decreased, suggesting plagioclase albitization occurred. The REE pattern of the reacted fluids exhibited superchondritic Y/Ho values up to 63.2. Based on the presence of positive Eu anomaly and the degree of light REE depletion, the REE in the hydrothermal fluids was mainly sourced from plagioclase during albitization. The superchondritic Y/Ho values in the fluids can be explained by the preferential leaching of these elements due to differences in chloride complexing strength between REE. Subchondritic Y/Ho values observed in Precambrian hydrothermally altered basalts may be interpreted as remnants generating superchondritic Y/Ho values in coexisting Precambrian hydrothermal fluids. Therefore, we believe that the superchondritic Y/Ho value of Precambrian seawater was maintained by basalt-hosted hydrothermal system.

Metals, Volatiles, and Lithostratigraphy of Brothers Submarine Volcano

AbstractRelatively fresh volcanic rocks have been sampled by a remotely operated vehicle in situ from the NE caldera wall of Brothers submarine volcano, associated with Seafloor Massive Sulfide‐SMS deposits. Here, we present the first complete stratigraphic column of the NE caldera wall, comprising at least 12 massive dacitic lava flows, up to 80 m‐thick intercalated with multiple volcaniclastic layers associated with tuffaceous sediment layers. Detailed petrographic and geochemical analyses from hand specimen to crystal to silicate melt scale show chemical variability with depth, correlating partly with an increase in pervasive alteration due to volatile degassing. Moreover, while sulfide saturation occurred prior to volatile exsolution—which sequestrated most chalcophile elements as confirmed by the low metal contents of melt inclusions (e.g., Cu ≤ 1.3 μg/g and Au ≤ 7.0 μg/g)—silicate glass records a Cu enrichment and Au loss with differentiation, with interstitial glass accounting for Cu = 4.2 μg/g and Au = 6.6 μg/g and matrix glass for Cu = 6.0 μg/g and Au = 2.8 μg/g, respectively. Our findings suggest multiple sources for metals compensating for the low initial metal contents: (a) from hydrothermal fluids and volatile percolation ensuing interaction with the host rock and thus also replacement and/or dissolution of pre‐existing magmatic sulfides, (b) directly from the magma, consistent with metal release during magma degassing of metal‐ and Cl‐, and S‐ rich volatiles, and (c) from fluid circulation within unusually metal‐rich andesitic volcaniclastic layers (Cu = 40 μg/g, Au = 1.5 ng/g, and Pt = 0.99 ng/g). Our results elucidate the capacity of such hybrid mineralizing submarine volcanic systems to effectively scavenge, transport, and concentrate metals.

Episodic fluid charging and mixing triggers calcite-bearing agates in the Permian Emeishan Basalt, SW China

ABSTRACT Agate, a distinctive form of banded chalcedony, derives its characteristic appearance from the deposition of silica and the presence of impurities. A significant variety of agate-bearing calcite was identified in the Permian Emeishan Basalt located in the southwestern Sichuan Basin. This calcite-bearing agate provides valuable insights into the complex interplay and evolution of fluids and minerals. This study aims to provide a detailed description and analysis of the microscopic textural and geochemical characteristics of the agate, while elucidating the sequence of mineral deposition, fluid properties, and the genetic mechanism underlying its formation. The findings reveal that the agate primarily consists of lamellar calcite and banded chalcedony, exhibiting a variety of textures, thicknesses, and colours. Through the analysis of the transformation and precipitation of epidote and allanite, and the identification of four types of calcites and five micro-silica textures, it has been confirmed that the early stage of fluid in geodes involved the mixing of meteoric water with post-magmatic hydrothermal fluid. The middle and late stages involve the mixing of magmatic-hydrothermal fluid with organic-acid fluid. The charging of silica-rich hydrothermal fluids and the generation of hydrocarbons from organic matter cause fluctuations in SiO2 concentration, pH, and crystallization rates, contributing to the diversity of silica minerals, such as chalcedony and quartz. The interlayered growth observed between chalcedony and calcite is attributed to secondary metasomatism, which occurs after the dehydration and transformation of chalcedony due to increasing temperatures. Notably, the internal texture of the agate is somewhat influenced by pressure variations caused by the episodic charging of the fluid.

Transition metals in alkaline Lost City vent fluids are sufficient for early-life metabolisms

Despite the importance of alkaline seafloor hydrothermal vents in broadening our understanding of deep-sea hydrothermal ecosystems, little is known about the mobility and concentrations of micronutrient transition metals in these environments. Here, we present new analyses of micronutrient transition metal concentrations in vent fluids from the iconic Lost City Hydrothermal Field (LCHF) and report concentrations of Fe = 2.9–18.3 µmol/kg, Zn = 1.30–5.86 µmol/kg, Cu = 0.43–5.06 µmol/kg, Ni = 86.4–556 nmol/kg, Mn = 8.3–274 nmol/kg, V = 25.9–127 nmol/kg, Mo = 24–94 nmol/kg, Co = 8.0–135 nmol/kg, W = 4.8–16 nmol/kg, and Cd = 1.7–4.5 nmol/kg. We additionally present results of a hydrothermal lherzolite alteration experiment conducted at 300 °C, 500 bar. Transition metal concentrations and major chemical parameters of experimental reaction fluids are broadly similar to LCHF vent fluids, indicating that transition metal concentrations in LCHF vent fluids, and alkaline hydrothermal fluids more generally, reflect metal solubility controlled by underlying rock-buffered hydrothermal reactions.Concentrations of Ni and Mo are especially noteworthy because of their recognized importance for biological methanogenesis (Ni) and nitrogen fixation (Mo). When compared with known biological thresholds, our findings indicate that Ni concentrations in LCHF vent fluids are sufficient to support the robust methane-metabolizing microbial communities observed in the immediate vicinity of LCHF vents and suggest that Ni availability influences the spatial distribution of LCHF methanogens. Furthermore, our laboratory hydrothermal experiments demonstrate that Mo concentrations of similar magnitude to those observed in LCHF vent fluids (and also modern seawater) can be obtained by hydrothermal alteration of ultramafic rocks with Mo-free (Na, Ca) Cl aqueous solution. Thus, we conclude that alkaline hydrothermal fluids were likely similarly enriched in Mo prior to oxidation of the Earth’s atmosphere and ocean, providing localized Mo-rich geochemical environments capable of supporting Mo-dependent nitrogen fixation at currently recognized threshold concentrations.

Settings Trace elements and garnet formation in a distal skarn zone: a case study of the Rudnik deposit, Central Serbia

The Rudnik Pb-Zn deposit is hosted in skarns and hornfels formed in the late Oligocene by contact metamorphism of limestones, sandstones and shales. Garnets, together with epidote, represent the main non-metallic minerals in the Rudnik skarn. In the distal skarn zone, the garnets are rare and their occurrence is related to the flow path of hydrothermal fluids. To constrain the hydrothermal and physicochemical conditions, in situ elemental SEM-WDS and LA-ICP-MS analyses, and fluid inclusion microthermometric measurements, were made. The Rudnik garnets from the distal skarn zone are predominantly of andradite-grossular composition (Adr39.3–88.9Grs2.9–53.9Alm0.5–10.0), with a small amount of spessartine. Generally, the Fe-rich garnets show a positive Eu anomaly with LREE enrichment and a HREE flat pattern, with homogenization temperatures and salinities of fluid inclusions ranging from 373 to 392°C and from 14.25 to 15.27% NaCl equivalent, respectively. The trace elements and microthermometric properties indicate that the garnets formed at moderately high temperatures, mildly acidic pH levels and increased oxygen fugacity

Non-Stationary ETAS Model: How It Works for External Forcing

Abstract The stationary epidemic-type aftershock sequence (ETAS) model is based on the important empirical laws in aftershock statistics with a self-similar feature, and is therefore useful for the statistical analysis of many common earthquake occurrence series. However, because earthquake catalogs become richer, the non-stationarity arising from geophysical heterogeneity becomes more pronounced. This article discusses the utility of a model that assumes time dependence of the first two ETAS parameters, which are sensitive to the short-term prediction. The inversion analyses of the non-stationary ETAS model in this article show heuristic results for swarm earthquakes and complex mainshock–aftershock-type seismicity. The case studies demonstrate how these parameters change quantitatively in swarm seismicity associated with slow slips, increases in pore-fluid pressure such as magma and hydrothermal fluids, stress changes associated with an earthquake motion, and interseismic-induced effects due to geological properties.