Composition Of Hydrothermal Fluids Research Articles

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.

Thermotogota diversity and distribution patterns revealed in Auka and JaichMaa 'ja 'ag hydrothermal vent fields in the Pescadero Basin, Gulf of California.

Discovering new deep hydrothermal vent systems is one of the biggest challenges in ocean exploration. They are a unique window to elucidate the physical, geochemical, and biological processes that occur on the seafloor and are involved in the evolution of life on Earth. In this study, we present a molecular analysis of the microbial composition within the newly discovered hydrothermal vent field, JaichMaa 'ja 'ag, situated in the Southern Pescadero Basin within the Gulf of California. During the cruise expedition FK181031 in 2018, 33 sediment cores were collected from various sites within the Pescadero vent fields and processed for 16S rRNA amplicon sequence variants (ASVs) and geochemical analysis. Correlative analysis of the chemical composition of hydrothermal pore fluids and microbial abundances identified several sediment-associated phyla, including Thermotogota, that appear to be enriched in sediment horizons impacted by hydrothermal fluid flow. Comparative analysis of Thermotogota with the previously explored Auka hydrothermal vent field situated 2 km away displayed broad similarity between the two locations, although at finer scales (e.g., ASV level), there were notable differences that point to core-to-core and site-level factors revealing distinct patterns of distribution and abundance within these two sediment-hosted hydrothermal vent fields. These patterns are intricately linked to the specific physical and geochemical conditions defining each vent, illuminating the complexity of this unique deep ocean chemosynthetic ecosystem.

A geochemical model for the transformation of gabbro into vesuvianite-bearing rodingite

Rodingite is a Ca-rich and Si-poor metasomatic rock commonly occurring in association with serpentinites. This rock is characterized by specific mineral assemblages consisting of hydrated garnet, diopside, vesuvianite, epidote-zoisite, chlorite, or prehnite. However, natural rodingites are significantly heterogeneous in mineral composition and vesuvianite occurs only in some extensively rodingitized rocks. Major factors controlling the mineral diversity as well as details on fluid-rock interactions leading to the evolution of mineral and chemical composition during rodingitization have not yet been fully constrained. In this work, we use PHREEQC software to present a geochemical model for the transformation of a mafic rock into vesuvianite-bearing rodingite at a temperature of 300 °C. Through these simulations, we investigate the effect of fluid composition and progress of the metasomatic process on rodingite formation. Our results show that rodingitization requires an open system with a high input of hydrothermal fluid. Additionally, a decrease in the Si/Ca ratio in the metasomatized rock is correlated to an increase in the volume of incoming fluid. Whole rock chemical and mineral composition in natural rodingites are well reproduced by the model. Furthermore, the diversity of mineral parageneses results mainly from different degrees of transformation and only to a lesser extent to the chemical composition of hydrothermal fluid or protolith. The hydrothermal fluid doesn't need to be especially rich in calcium to transform a mafic rock into rodingite, but it must be low in magnesium, silicon, and have a high pH, which is naturally controlled by serpentinization of surrounding ultramafic rocks.

Fluid Flow, Mineralization and Deformation in an Oceanic Detachment Fault: Microtextural, Geochemical and Isotopic Evidence From Pyrite at 13°30′N on the Mid‐Atlantic Ridge

AbstractHydrothermal fluids in ultramafic‐hosted hydrothermal systems associated with oceanic detachment faults can be more oxidizing compared to mafic‐hosted vent sites. These fluids form a mineral assemblage of pyrite, magnetite and hematite. At 13°30′N on the Mid‐Atlantic Ridge, chlorite‐quartz breccias recovered from an exposed fault scarp contain pyrite, with abundant magnetite and hematite, indicating that the redox of the fluids was variable. In primary micron‐scale zonations in pyrite, Ni, Co, and Se have a decoupled relationship, recording fluctuations in the chemical composition and temperature of hydrothermal fluid as the grains grew. Secondary zonations that erase and overprint primary zonations are limited to the grain margin and permeable regions within the grain core. Secondary zonations formed via two processes: (a) grain dissolution followed by overgrowth, and (b) remobilization of metals during oxidizing fluid flow events. In both instances, Ni and Co have been mobilized and concentrated, and are not lost to the hydrothermal fluid. Superimposed on these features is evidence of grain scale deformation related to periods of fault movement along the detachment surface. Sulfur isotope ratios (δ34S) in pyrite systematically decrease from the grain margin to the grain core, indicating that increased amounts of sulfur were derived from thermochemical sulfate reduction of seawater. Thus, pyrite records the evolution of fluid flow and deformation events during exhumation along the detachment surface from ∼1 to 2 km below the seafloor at the base of the lava pile, with temporal fluctuations in fluid redox identified as an important process in controlling Ni and Co enrichment in pyrite.

Geochemistry and geochronology of Beiya giant Au polymetallic deposit: Implications for multistage ore-fluid pulses in a skarn system

Garnet is one of the most typical minerals in skarn deposits, and its texture and composition is a proxy for the changing physicochemical conditions. Thus, mineralogical and geochemical characterization of different garnet types can provide important information on the nature and evolution of ore-forming fluids. The Beiya gold-polymetallic deposit is China’s largest skarn-type Au deposit with Au reserves of >380 t. Although several studies have addressed the skarn formation mechanism and nature of fluid evolution, a systematic study on the changes in the composition and texture of garnet from wall rocks to ore-related intrusion has not yet been attempted. In this work, we carry out a systematic investigation along a horizonal profile in the open pit of the Beiya deposit. Our results show that the garnet in the profile belongs to grossular-andradite solid solution series with all grains showing well-developed fine oscillatory zoning. The garnets are of two types: the first type (Grt I) formed within the endoskarn, is reddish to red with euhedral-subhedral megacryst structure (>10 mm) and has altered surfaces. The second type (Grt II) occur in the proximal exoskarn, is red to brown–red, euhedral-subhedral, with medium- to fine- grained structure (0.3–4 mm) and displaying oscillatory zoning. Unlike Grt I, hydrous minerals occur in the pores among Grt II garnets, such as calcite, quartz, epidote and chlorite. Also, calcite-chlorite vein, quartz vein and quartz-chalcopyrite-pyrite vein cuts the Grt II garnets. Grt I is dominantly grossular (Adr14.88-43.58Grs55.25-82.87), depleted in the large ion lithophile elements (LILE), relatively enriched in high field strength elements (HFSEs) and enriched in heavy rare earth elements (HREEs) with negative Eu anomalies. Grt II is mostly andradite (Adr62.18-98.91Grs0-36.22), depleted in the LILE and HFSE, enriched in light rare earth elements (LREEs) with slightly positive Eu anomalies. Here we selected Grt II for in-situ LA-ICP-MS U-Pb dating, since Grt I contains negligible uranium. The results yielded a lower intercept 206Pb/238U age of 35.3 ± 1.8 Ma (MSWD = 0.68, n = 23). The calculated oxygen isotopic compositions of hydrothermal fluids in equilibrium with two types of garnets range from 6.46 ‰ to 8.56 ‰ (average 7.89 ‰), which are within the range of values for magmatic fluids. We infer that the physicochemical conditions of the hydrothermal fluid changed from relatively reduced, nearly neutral, and low water/rock ratios to slightly oxidized, slightly acidic, and high water/rock ratios. The chlorine content in the fluid increased during garnet growth. The fluctuating compositions of garnets in the skarn suggest multistage ore-fluid activities and the fluid evolution provide insights into the ore-forming process.

Genesis and Evolution of the Yolindi Cu-Fe Skarn Deposit in the Biga Peninsula (NW Turkey): Insights from Genetic Relationships with Calc-Alkaline Magmatic Activity

The current work investigates the impact of magmatic fluids and metasomatic processes on the Yolindi Cu-Fe skarn deposit in the Biga Peninsula, Turkey. It traces the stages of skarn evolution, from prograde to retrograde alterations, and investigates findings within a broader geological, mineralogical, and geochemical framework. Additionally, it assesses the evolutionary history of the Yolindi deposit in relation to calc-alkaline magmatic activity in an island-arc environment and compares its mineral compositions and genesis with other global and regional Cu-Fe skarn deposits. The Yolindi Cu-Fe skarn deposit in the Biga Peninsula was formed by the intrusion of Şaroluk quartz monzonite pluton into Upper Paleozoic Torasan Formation rocks such as phyllite, schists, hornfels, marble, and serpentinites. During skarnification, reactions between the magmatic fluids from the Şaroluk quartz monzonite pluton and the Torasan Formation produced skarn minerals associated with metals such as Fe and Cu. Initially, these reactions formed prograde skarn minerals such as augite-rich pyroxenes and andradite garnets with magnetite and pyrite. As the system cooled, these initial minerals underwent retrograde alteration, leading to the formation of minerals such as epidote, actinolite, and chlorite, as well as other copper and iron minerals including chalcopyrite, bornite, secondary magnetite, and specular hematite. Therefore, four main stages influenced the formation of the Yolindi Cu-Fe deposit: metamorphic bimetasomatic, prograde metasomatic, and retrograde metasomatic stages. Later, oxidation and weathering resulted in supergene minerals such as cerussite, malachite, and goethite, which serve as examples of the post-metamorphic stage. The mineralogical shifts, such as the andradite–grossular transition, reflect changing hydrothermal fluid compositions and characteristics due to the addition of meteoric fluids. Importantly, the formation of magnetite after garnet and clinopyroxene during the retrograde stage is evidenced by magnetite crystals within garnet. The mineral associations of the Yolindi Cu-Fe skarn deposit align with the global skarn deposits and specific Turkish skarns (e.g., Ayazmant Fe-Cu and Evciler Cu-Au skarn deposits). The Yolindi Cu-Fe skarn deposit, in association with ore-bearing solutions having magmatic origins, developed in an island-arc setting.

Using pyrite composition to track the multi-stage fluids superimposed on a porphyry Cu system

Abstract The Yulekenhalasu porphyry Cu-Mo deposit (0.2 Mt Cu at 1.04 wt% and 0.012 Mt Mo at 0.06 wt%) is located in the Devonian Halasu copper belt, East Junggar block, northwest China. At Yulekenhalasu, Cu and Mo mineralization commonly occurs as disseminated sulfides or veinlets in porphyry-related alteration zones. Five alteration stages have been identified, including porphyry-type alteration, i.e., sodic-calcic (stage I), potassic (stage IIa), propylitic (stage IIb), and phyllic (stage III) alteration, and widespread late Cu sulfide-bearing veins (stage IV) cross-cutting porphyry-type alteration, plus a post-ore fault-controlled argillic alteration (stage V). Stages IV and V have overprinted porphyry-type alteration (stages I–III). Anomalous concentrations of trace elements in stage IIb pyrite (e.g., Ti, Zr, Gd, and Hf) are due to the presence of micro-inclusions (e.g., zircon and rutile) in the low-temperature (~200 °C) propylitic zone. Cu, Ag, Co, and Mn, occurring as stoichiometric substitutions or as tetrahedrite inclusions in overprinting stage IV pyrite, were sourced directly from the primary hydrothermal fluid. The enrichment of distal pathfinder elements (e.g., Cr, Au, and Tl) in overprinting stage V pyrite was caused by a low-temperature (~160 °C) hydrothermal event related to regional orogenic Au mineralization. The spatial variation of Se/S in pyrite among various paragenetic stages were influenced by changes in the hydrothermal fluid composition and temperature, with the latter having the effect of decreasing pyrite Se/S. Lower Se concentrations in pyrite of stages IIb and III close to the orebody are explained by relatively higher temperatures in the locus of mineralization. This may provide a potential vectoring tool to mineralization using pyrite geochemistry in porphyry deposits. Systematic thermodynamic calibrations were applied to pyrite compositions to fingerprint the corresponding Se/S and Co/Ni ratios of fluids and further to develop a complete metallogenic model for Yulekenhalasu. The Devonian diorite porphyry generated fluids that produced the early porphyry-type alteration. High Co/Fe (average ~1 × 10–4) and Ni/Fe (average ~3 × 10–6) ratios of fluid for late Cu sulfide-bearing veins, combined with higher Se/S (average ~6 × 10–7) than orogenic Au deposits (average ~3 × 10–8), indicate that the fluids possibly derived from a Late Devonian-Carboniferous mafic intrusion. Argillic alteration assemblages forming at ca. 280 Ma host pyrite relatively enriched in Au (average 0.1 ppm, with native gold inclusions). Therefore it is likely related to a regional orogenic gold mineralizing event in the Early Permian that overprinted Devonian mineralization. Although spatially contiguous, hydrothermal alteration and hypogene mineralizing stages identified herein represent discrete episodes of hydrothermal activities at Yulekenhalasu. The multi-stage alteration features observed at Yulekenhalasu may provide insights into the complete evolutionary history of Paleozoic porphyry Cu deposit systems in the Central Asian orogenic belt. This study contributes to a better understanding of the metallogenic and exploration models of porphyry Cu deposits overprinted by multi-stage hydrothermal events, which is economically important in Phanerozoic orogenic belts.

A conceptual model for the Tufiño-Chiles-Cerro Negro (TCCN) geothermal system (Ecuador-Colombia): New insights into geothermal exploration from chemical and isotopic composition of hydrothermal fluids

The Tufiño-Chiles-Cerro Negro (TCCN), located on the border between Colombia and Ecuador, is one of the most promising geothermal systems in the Andean Northern Volcanic Zone, presenting an estimated geothermal potential of 130–138 MWe associated with two reservoirs located at 500–1000 m, and > 1500 m of depth, respectively. In this work, we present a geochemical conceptual model for TCCN to explore the physicochemical conditions acting on the reservoir, based on a comprehensive dataset of water, gas geochemistry, and stable isotopes of the hydrothermal manifestations of the geothermal system, integrated with previously published data. Four new water samples and two bubbling gas samples were collected from the TCCN area during fieldwork in January 2015. Waters from TCCN, which show temperatures up to 54.7 °C, are near-neutral to slightly acidic and have variable TDS values (687 to 3095 mg/L) that generally increase at increasing temperature. All the samples fall far from the chloride-mature waters field, being characterised by SO42− or HCO3−dominated composition, suggesting steam-heated and peripheral water characteristics. The 3He/4He ratios (R/Ra) of gas samples range between 2.4 and 4.6, indicating an important mantle He contribution diluted by the addition of radiogenic and atmospheric 4He. Based on their CO2/3He and δ13C–CO2 ratios, gas samples show a carbon origin prevailing from subducted limestone, likely connected to the presence of the subducting Carnegie ridge. A mixing between a thermogenic and biogenic origin for methane is suggested, consistent with the dominant inputs from microbial methanogenesis and thermal maturation of sedimentary organic matter in the TCCN system. The high δ34S-H2S values of gas (+6.7 ‰ and 10.7 ‰ vs. V-CDT) and δ34S-SO4 of water (+19.2 ‰ and + 19.3 ‰ vs. V-CDT) samples coupled with the high values of S/3He indicate that the sulphur signature could be mostly controlled by the incorporation of subducted sulphate. Gas geothermometric estimations in the CO2-H2 system indicate a temperature between 245 and 250 °C for the geothermal reservoir. The gas samples appear to be in disequilibrium concerning the redox conditions related to the FeO/FeO1.5 buffer typical for hydrothermal systems, implying that these samples represent immature vapours. This could be explained by the input of magmatic fluids into the roots of the TCCN geothermal systems, possibly related to the seismic crisis linked to the unrest of the volcanic complex at the end of 2014.

Evolution of the composition of hydrothermal mineral-forming fluid of ore deposits in early Precambrian of the Ukrainian Shield

The aim of the study, the results of which are presented in this article, is to study changes in the composition of hydrothermal fluid ore systems of the early Precambrian on the example of gold and uranium ore deposits of the Ukrainian shield in connection with the evolution of exo- and endogenous processes in the outer shells of the Earth. The method used is a complex isotope-geochemical study of the composition of gas-liquid inclusions of hydrothermal fluid of ore systems. Based on experimental isotope-geochemical studies of the fluid of gas-liquid inclusions in the minerals of Precambrian deposits of uranium and gold of the Serednoprydniprovsky and Ingul megablocks of the Ukrainian Shield, a consistent change in the quantitative and isotopic composition of hydrothermal fluids of mineral formation from Mesoarchean to Paleoproterozoic was established. The content of H2O and CO2 was investigated and the isotopic composition of carbon CO2 fluids in quartz, pyrite, and feldspar were studied. The age range of the studied deposits is 3200—1750 million years. A decrease in the carbon dioxide content in the hydrothermal mineral-forming fluid of the Precambrian occurred in the Neoarchean, that is, before the Great Oxygen Event (Great Oxidation Event) — an increase in the oxygen content in the atmosphere in the Paleoproterozoic and is probably associated with the processes of exogenous and endogenous hydration of ultramafic rocks during the formation of the protocontinental crust. Molar fraction of CO2 in the mineral-forming fluid, in the Precambrian correlates to some extent with atmospheric pressure. The increase in the content of the carbon-12 isotope in the Paleoproterozoic in the mineral-forming fluid occurred due to the oxidation of organic matter with an increase in the oxygen content in the atmosphere.

S, Pb, and Fe isotope compositions of sulfides in middle and southern Okinawa Trough: Implying the complicated hydrothermal systems in back-arc spreading centers

Sulfur, lead, and iron isotopic systematics of sulfides from the Iheya North hydrothermal field in middle Okinawa Trough and the Yonaguni Knoll IV hydrothermal field in southern Okinawa Trough were investigated to understand the origin of ore-forming material and isotope fractionation during sulfide precipitation in back-arc spreading centers. The δ34S values (from 8.60‰ to 9.68‰) of sulfide minerals in Iheya North field suggest sulfur was derived from the leaching of basement rocks and the reduction of seawater sulfate. But an additional light sulfur source from the dissolution of biogenic sulfides in sediments is indispensable for the observed low δ34S values (between 4.78‰ and 4.97‰) of Yonaguni Knoll IV sulfides. Lead isotope compositions of all sulfides vary in a relatively wide range (206Pb/204Pb = 18.432 to 18.563, 207Pb/204Pb = 15.579 to 15.671, and 208Pb/204Pb = 38.539 to 38.979, respectively) which involves the mixing of mantle-derived and sediment-derived lead in varying proportions. Unusually high radiogenic lead isotope ratios of Yonaguni Knoll IV sulfides (207Pb/204Pb = 15.628 to 15.671, and 208Pb/204Pb = 38.854 to 38.979) imply the presence of old crustal fragments beneath southern OT. The hydrothermal fluids in OT are characterized by extremely low calculated δ56Fe values (−1.00‰ to −1.32‰) which is attributed to reducing sediments. The paired Fe-isotope compositions of pyrite and chalcopyrite revealed significantly different iron isotope compositions of hydrothermal fluids in study areas and extremely complicated ore-forming processes. Rapid precipitation of pyrite from FeS precursors accompanying iron isotopic disequilibrium moves from FeS-fluid equilibrium to pyrite-fluid equilibrium during pyrite recrystallization. The combination of sulfur, lead, and iron isotopic data suggests that hydrothermal systems in back-arc spreading centers related to plate subduction are generally affected by mantle, overlying sediments as well as potential old continental crust fragments, which results in various hydrothermal fluids and complicated mineralization processes.

The composition of gas emissions at Petite Terre (Mayotte, Comoros): inference on magmatic fingerprints

The Comoros archipelago is an active geodynamic region located in the Mozambique Channel between East continental Africa and Madagascar. The archipelago results from intra-plate volcanism, the most recent eruptions having occurred on the youngest island of Grande Comore and on the oldest one of Mayotte. Since 2018, the eastern submarine flank of Mayotte has been the site of one of the largest recent eruptive events on Earth in terms of erupted lava volume. On land, the most recent volcanic activity occurred in Holocene on the eastern side of Mayotte, corresponding to the small Petite Terre Island, where two main and persistent gas seep areas are present (Airport Beach, namely BAS, and Dziani Dzaha intracrateric lake). The large submarine eruption at the feet of Mayotte (50 km offshore; 3.5 km b.s.l.) is associated with deep (mantle level) seismic activity closer to the coast (5–15 km offshore) possibly corresponding to a single and large magmatic plumbing system. Our study aims at characterizing the chemical and isotopic composition of gas seeps on land and assesses their potential link with the magmatic plumbing system feeding the Mayotte volcanic ridge and the recent submarine activity. Data from bubbling gases collected between 2018 and 2021 are discussed and compared with older datasets acquired between 2005 and 2016 from different research teams. The relation between 3 He/ 4 He and δ 13 C-CO 2 shows a clear magmatic origin for Mayotte bubbling gases, while the variable proportions and isotopic signature of CH 4 is related to the occurrence of both biogenic and abiogenic sources of methane. Our new dataset points to a time-decreasing influence of the recent seismo-volcanic activity at Mayotte on the composition of hydrothermal fluids on land, whose equilibrium temperature steadily decreases since 2018. The increased knowledge on the gas-geochemistry at Mayotte makes the results of this work of potential support for volcanic and environmental monitoring programs.

The nature and composition of hydrothermal fluids related to gold mineralization in parts of Akobo greenstone belt, southwestern Ethiopia

Gold mineralization in the Akobo greenstone belt of Southwestern Ethiopia is confined to metamorphosed volcano-sedimentary rocks of greenschist-amphibolite facies and is closely associated with shear/fault zones. Gold is found in quartz veins of the Gindibab-Wolleta area, while altered mafic-ultramafic rocks are the hosts for Chamo-Segele prospects. Microstructures found in vein quartz indicate intra-crystalline ductile deformation followed by fracturing during later brittle deformation episode. The assemblage of fluid inclusions in mineralized quartz veins in Gindibab-Wolleta area has been grouped into three types and inferred to be compositionally and texturally modified during the formation-deformation of quartz veins. Aqueous biphase inclusions are the only fluid inclusions found in the vein quartz of the Chamo-Segele area and retain the primary nature of fluid entrapment. Microthermometric analyses of inclusions indicate a striking difference in the composition of hydrothermal fluids responsible for the quartz vein formation in Gindibab-Wolleta and Chamo-Segele areas. The ore-forming fluids related to vein formation and gold mineralization in the Gindibab-Wolleta area were low saline aqueous carbonic. In contrast, in the case of the Chamo-Segele area, the quartz veins were formed by low to moderate saline aqueous fluid. The results of the fluid inclusion in the Akobo Greenstone Belt indicate an orogenic type of lode gold mineralization in the Gindibab-Wolleta area of the Gambella region, Ethiopia.

The retrograde evolution of F-rich skarns: Clues from major and trace element chemistry of garnet, scheelite, and vesuvianite from the Belka Pahar wollastonite deposit, India

Skarn settings host many ore deposits and are ideal for studying the mobility of elements in hydrothermal fluids. Belka Pahar, in the Sirohi district of Rajasthan (NW India), is the largest wollastonite deposit in India (estimated wollastonite reserve of 56 million tonnes). No detailed textural and geochemical study has been conducted on these skarn rocks. In this study, we use petrographic studies, and major-trace element chemistry of skarn minerals from Belka Pahar to deduce the sequence of mineral transformations and to characterize the changes in the composition of the fluid with the progress of fluid-rock interaction during skarn formation. Two major rock types from the exoskarn have been considered for detailed study: prograde skarn rocks comprising pyroxene, garnet, wollastonite, quartz, and calcite, and retrograde skarn rocks containing garnet, scheelite, vesuvianite, fluorite, and sphalerite. Two types of garnet are recognized in the rocks-texturally earlier prograde garnet (Grt 1 ) and texturally late retrograde oscillatory-zoned Grt 2 , which is further sub-divided into three generations Grt 2a , Grt 2b and Grt 2c . The Grt 1 (And 27–47 ) and Grt 2a (And 50–60 ) have high Y-concentrations, and high HREE/LREE ratio, which is in stark contrast to the late Grt 2b (And 40–50 ) and Grt 2c (And 27–40 ), which is characterized by high F, low Y-concentrations, and HREE-depleted REE patterns. The chemistry of different generations of garnet suggests a shift from diffusive to more advective metasomatic conditions and increasing water/rock ratio, accompanied by a shift in pH of the fluid from neutral to acidic to weakly acidic. The crystallization of F-rich garnet, vesuvianite, and fluorite indicates an increase in F-concentration in the later-stage fluid. An increase of W concentration in Grt 2b and co-precipitation of scheelite and fluorite also suggests its possible link with scheelite crystallization. The high grossular component of Grt 2b and Grt 2c suggests transport of Al in the hydrothermal fluid as F-complexes. The hydrothermal fluid composition extrapolated from scheelite chemistry agrees with the LREE enriched patterns exhibited by all skarn minerals. Principal Component Analysis done on a compiled dataset of skarn garnet shows that its trace element composition can be a useful proxy of fluid composition and can be used as an indicator of associated ore type. • Garnet composition is a useful proxy of fluid chemistry in the skarn system. • High F concentration in fluid enhanced Al mobilization, forming grossular-rich garnet. • Scheelite precipitation is linked to interaction of F-rich fluid with calc-silicate rocks. • PCA shows control of fluid composition on garnet chemistry. • Garnet trace element chemistry is a robust proxy of ore-genetic association.

Systematic variations in trace element composition of pyrites from the 26°S hydrothermal field, Mid-Atlantic Ridge

Variations in trace element composition of pyrites in inactive chimneys from the SMAR 26°S hydrothermal field provide important insights into the genesis and evolution of volcanic-hosted hydrothermal mineralization. Petrographic observations of zoned chimney samples integrated with in-situ LA-ICP-MS analysis of morphologically different pyrites allowed the assessment of fluid evolution during the chimney growth. Pyrite varieties precipitated with increasing temperatures from the outermost chimney wall (zone A) through the intermediate zone (zone B) to the inner zone (zone C). At the late mature stage, pyrite precipitates as interstice pore fillings. The distribution of trace elements in pyrites across the chimney indicates a strong dependence on time, temperature, and associated sulfide minerals. Variations in the trace elements composition of the different pyrite varieties indicate that the hydrothermal system evolved from low-temperature low-chloride liquid-dominated fluids (enriched in Zn, Cd, Tl, Ag, Pb, Mn, Mo, and V) to higher temperature, vapor-dominated fluids (Cu, Au, Te, and Bi), and then to high-temperature fluids (Co and Se). In the waning stage of the hydrothermal system, circulating hot fluids in auxiliary conduits were depleted in most trace elements. The systematic variations in trace element compositions of hydrothermal fluids induced by changes in physicochemical conditions are properly governed by the law of normal distribution of trace elements. The LA-ICP-MS time-depth analysis indicate that Cu, Zn, Cd, Tl, Ag, Te, and Bi are related to micro-/nano-inclusions, whereas Co, Se, and Mo may occur as substitutions in pyrite lattice. The As, Pb, Au, and Sb show both modes of occurrences as substitutions and as inclusions. Adsorbed films on pyrites control the distribution of V and Mo. The incorporation processes of trace elements in pyrites change with fluid evolution during the chimney growth: trapping of micro-/nano-inclusions and surface adsorption is seen more frequently at the low-temperature stage, and lattice substitution mainly at the elevated temperature stages.

Aliphatic Aldehydes in the Earth's Crust-Remains of Prebiotic Chemistry?

The origin of life is a mystery that has not yet been solved in the natural sciences. Some promising interpretative approaches are related to hydrothermal activities. Hydrothermal environments contain all necessary elements for the development of precursor molecules. There are surfaces with possible catalytic activity, and wide ranges of pressure and temperature conditions. The chemical composition of hydrothermal fluids together with periodically fluctuating physical conditions should open up multiple pathways towards prebiotic molecules. In 2017, we detected potentially prebiotic organic substances, including a homologous series of aldehydes in Archean quartz crystals from Western Australia, more than 3 billion years old. In order to approach the question of whether the transformation of inorganic into organic substances is an ongoing process, we investigated a drill core from the geologically young Wehr caldera in Germany at a depth of 1000 m. Here, we show the existence of a similar homologous series of aldehydes (C8 to C16) in the fluid inclusions of the drill core calcites, a finding that supports the thesis that hydrothermal environments could possibly be the material source for the origin of life.

Geochemistry of Hydrothermal Fluids From the E2-Segment of the East Scotia Ridge: Magmatic Input, Reaction Zone Processes, Fluid Mixing Regimes and Bioenergetic Landscapes

The compositions of hydrothermal fluids in back-arc basins (BABs) can be affected by the influx of magmatic fluids into systems that are dominated by reactions between basement rocks and seawater-derived fluids. The East Scotia Ridge (ESR) in the Scotia Sea hosts such hydrothermal systems where the role of magmatic fluid influx has not yet been addressed. During expedition PS119 in 2019, three chimneys were sampled from the E2 segment. These samples were analysed for their chemical and isotopic composition along with fluid inclusions in corresponding precipitates. Our data provide evidence for the temporal evolution of hydrothermal fluids in this remote back-arc system. Salinity variations in anhydrite-hosted fluid inclusions indicate that phase separation takes place in the subseafloor. Moderate-temperature (&amp;lt;53°C) fluids from the newly discovered E2-West hydrothermal vent field and high-temperature (&amp;gt;320°C) fluids from the E2-South area were sampled. Depletions in fluid-mobile elements, ΣREE and low δ18OH2O show that the basement in this root zone has been leached since the previous sampling in 2010. The results indicate that high-temperature fluid-rock interactions are key in setting the composition of the fluids with cation-to-chloride ratios suggesting a common root zone for both vent sites. The concentrations of dissolved gases provide new insights in the connection between magmatic degassing and its influence on endmember vent fluid composition. Specifically, stable isotope (O, H) data and elevated CO2 concentrations point to a minor influx of magmatic vapour. Stable sulphur isotopes provide no evidence for SO2 disproportionation suggesting a H2O-CO2 dominated nature of these vapours. The concentrations of conservative elements in the E2-W fluid reflects subseafloor mixing between E2-S endmember fluid and seawater. In contrast, non-conservative behaviour, and depletion of Fe, H2, and H2S point to a combination of sub-surface abiotic and biotic reactions affecting these fluids. Similarly, E2-W fluids show evidence for H2S and CH4 being metabolized in the subseafloor. Thermodynamic computations confirm that the E2 system is dominated by sulphide oxidation as a major catabolic pathway. Our results indicate that the conditions at E2 are favourable to hosting a robust subseafloor biosphere.

Petrogenesis and rare earth element mineralization of the Elk Creek carbonatite, Nebraska, USA

Although carbonatites are the primary source of the world’s rare earth elements (REEs), the processes responsible for ore-grade REE enrichment in carbonatites are still poorly understood. In this study, we present a petrologic, geochemical, and isotopic evaluation of the Elk Creek carbonatite in southeast Nebraska to constrain the origin of REE mineralization. The Elk Creek carbonatite is a multilithologic carbonatite comprised of an early apatite-dolomite carbonatite, a middle/heavy REE-enriched magnetite-dolomite carbonatite, and a late-stage light REE-enriched, barite-dolomite carbonatite, as well as a suite of breccias. Neodymium, strontium, and carbon isotopic data from the early apatite-dolomite carbonatite, εNd(T) = 2.3 to 3.4, 87Sr/86Sr(i) = 0.702704 to 0.702857, and δ13C = −3.3 to −3.4, indicate that the parental magma and REEs were derived from the mantle, and textural and chemical data suggest that hydrothermal processes played an important role in reaching ore-grade enrichment. Higher initial 87Sr/86Sr values (∼0.7041) of REE-mineralized lithologies are evidence that these fluids were derived, in part, from meteoric water that interacted with the country rock. Modeling of the C-O isotopic data reveals that some of the isotopic variation results from closed-system Rayleigh fractionation of an evolving carbonatitic magma between 300 and 500 °C, but an excursion to heavier δ18O is likely the result of interaction with H2O-CO2-fluids at temperatures from 400 to 100 °C. Hydrothermal dolomite has higher 87Sr/86Sr values than early-formed magmatic dolomite, consistent with metasomatism by fluids derived, in part, from a more radiogenic source such as the Precambrian-age wall rock. Rare earth element mineralization occurs primarily in fine-grained, cavity filling minerals including monazite, bastnäsite, parisite, and synchysite along with barite, dolomite, quartz, and iron oxides. We interpret the LREE enrichment at Elk Creek to be the product of hydrothermal fluids derived from the evolving carbonatite magma and fluids from the wall rock. The REEs likely became enriched in late-stage fluids from the evolving magma as well as being remobilization by the dissolution of earlier formed minerals. Middle/heavy REE-enrichment in the magnetite-dolomite carbonatite is hosted in hydrothermal dolomite and is attributed to variations in the composition of hydrothermal fluids.

Sources of Hydrothermal Fluids Inferred from Oxygen and Carbon Isotope Composition of Calcite, Keweenaw Peninsula Native Copper District, Michigan, USA

The Mesoproterozoic North American Midcontinent Rift hosts the world’s largest accumulation of native copper in Michigan’s Keweenaw Peninsula. During a regional metamorphogenic-hydrothermal event, native copper was deposited along with spatially zoned main-stage minerals in a thermal high. This was followed by deposition of late-stage minerals including minor copper sulfide. Inferences from the oxygen and carbon isotopic composition of main-stage hydrothermal fluids, as calculated from 296 new and compiled isotopic measurements on calcite, are consistent with existing models that low-sulfur saline native copper ore-forming fluids were dominantly derived by burial metamorphic processes from the very low sulfur basalt-dominated rift fill at depth below the native copper deposits. Co-variation of oxygen and carbon isotopic compositions are consistent with mixing of metamorphic-derived fluids with two additional isotopically different fluids. One of these is proposed to be evolved seawater that provided an outside source of salinity. This fluid mixed at depth and participated in the formation of a well-mixed hybrid metamorphic-dominated ore-forming fluid. Secondary Ion Mass Spectrometry in-situ isotopic analyses of calcite demonstrate a high degree of variability within samples that is attributed to variable degrees of shallow mixing of the hybrid ore-forming fluid with sulfur-poor, reduced evolved meteoric water in the zone of precipitation. The oxygen and carbon isotopic compositions of 100 new and compiled measurements on late-stage calcite are mostly isotopically different than the main-stage hydrothermal fluids. The late-stage hydrothermal fluids are interpreted as various proportions of mixing of evolved meteoric water, main-stage hybrid ore-forming fluid, and shallow, evolved seawater in the relatively shallow zone of precipitation.

Zircon reveals multistage, magmatic and hydrothermal Rare Earth Element mineralization at Debert Lake, Nova Scotia, Canada

Rare Earth Element (REE) mineralization at Debert Lake (Nova Scotia, Canada) is hosted by the anorogenic Hart Lake-Byers Lake granites which are associated with the Late Devonian to Early Carboniferous Wentworth plutonic complex in the Cobequid Highlands. Mineralized zones contain up to 1.2 wt% REE2O3, 3.4 wt% ZrO2, and 0.4 wt% Nb2O5 produced by multiple, separate mineralizing events. We use a multi-faceted approach combining whole-rock and mineral geochemistry, together with U-Pb radiometric dates to uncover complex formative processes and resolve the timing for REE mineralization.Episodic mineralization yielded distinct REE assemblages including Nb-oxide (pyrochlore and fergusonite) phases, chevkinite, zircon, thorite, monazite, and titanite, formed during multiple magmatic-to-hydrothermal stages in the rare-metal bearing granites. Zircon, as a persistent phase of the REE assemblages, occurs with variable texture, morphology, and composition in all granites. Zircon grains, displaying intergranular to interstitial textures in REE rich granite, have spongy cores in which Y, Th, and Zr were redistributed by magmatic fluids. U-Pb dating of these zircons yields an age of 355 to 360 Ma, approximately coeval with igneous monazite crystallization, dated at 366 ± 5 Ma. These findings document a late-magmatic REE mineralization event. A subsequent pulse of post-magmatic hydrothermal mineralization associated with Zr-F-rich fluid complexes produced two other zircon populations, dated at ca. 309 and 318 Ma, with unusual habits and REE patterns that are interpreted to be of hydrothermal origin. Principal Component Analysis (PCA) separates zircon populations based on element concentrations and element associations. The LREE-rich hydrothermal zircon types with their distinct geochemical patterns revealed by PCA are characterized by the relative enrichment of either Na or Ca, reflecting differences in the composition of hydrothermal fluids driving sodic and calcic alteration processes, respectively

Study of fluid circulation through the chicxulub crater using Rock-Eval pyrolysis and fluid inclusions

The aim of the study is to evaluate fluids circulation through the Chicxulub crater, and to determine the composition of hydrothermal fluids after the impact. Rock-Eval pyrolysis and fluid inclusion micro-thermometry analyses were performed. The technique has been routinely used for about fifteen years and has become a standard tool for hydrocarbon exploration. Rock-Eval pyrolysis reveals the distribution of organic and mineral carbon affected by the impact and later affected by hydrothermal activity. All measured inclusions are primary and were found in basement samples only. Both the fluid inclusions data and Rock-Eval pyrolysis show that composition and temperature of the fluids changed as the fluids migrated though crater rocks. An evolution of temperatures occurs (vertical, horizontal, or both), from the surface and from the center of the crater; this spatial evolution is consistent with model of Abramov and Kring, showing a thermal evolution of temperature with depth in the crater as well as its influence on the hydrothermal system. Post-impact fluid circulation modifies the temperature distribution.