High-temperature Hydrothermal Fluids Research Articles

Geochemistry of BIF in the Quadrilátero ferrífero, Brazil, as a proxy to neoarchean paleoenvironmental and depositional conditions

Precambrian Algoma-type banded iron formations (BIFs) are biochemical metasedimentary rocks formed in the deep water environment relatively close to centers of volcanic expansion and can be characterized on the basis of their paleodepositional environment and the associated rock types. These rocks may contain geochemical signatures indicative of changes in the redox conditions of the Archean ocean. Such variations in the Meso- and Neoarchean are crucial in understanding the processes that led to the gradual increase of oxygen in the early atmosphere, culminating in the Great Oxidation Event (2.4–2.3 Ga). Oxide- and carbonate-facies BIFs were intercepted by drill cores in the Pilar gold deposit in the NE sector of the Quadrilátero Ferrífero (QF), Brazil, located in the Neoarchean Rio das Velhas greenstone belt. These rocks are interbedded with mafic and ultramafic metavolcanic rocks and carbonaceous phyllites. In light of the potential to reconstruct paleodepositional evidence indicative of the Earth's atmospheric redox history based on this stratigraphy, we have considered specific proxies from geological and geochemical observations. Pilar BIFs geochemistry exhibits positive anomalies of La, Eu, and Y, indicating characteristics inherited from seawater and high-temperature hydrothermal fluids. In addition, a superchondritic Y/Ho ratio further supports the influence of seawater. The signatures of the major elements Al2O3 and other immobile elements typical of detrital sediments corroborate the interpretation that these rocks were deposited in a deep marine environment with low clastic influence. Furthermore, negative Ce/Ce*SN anomalies in some sections of the Pilar BIF indicate limited oxygen availability which, together with Mo, U, V, and Zn trace-element enrichment factors, indicate deposition under suboxic/euxinic conditions. This research, together with other similar BIF data from the NW QF provide new insights into the paleoenvironmental conditions prevailing during the formation of the Archean volcano sedimentary basins that compose the southern São Francisco craton (SFC).

Isotopic and kinetic constraints on methane origins in Icelandic hydrothermal fluids

The origin of methane in hydrothermal fluids has long been a subject of debate – whether it is abiotic or biotic. In this study, we aim to unravel and quantify the sources of CH4 in active hydrothermal systems by adopting a holistic approach analyzing well characterized high-temperature hydrothermal fluids (∼230–310 °C) in Iceland. We employ a broad variety of geochemical and isotope indicators, encompassing chemical and isotope compositions of the targeted fluids. These signatures are then compared with results from chemical and isotope kinetic models and data from sedimentary-hosted hydrothermal systems. Carbon species in these fluids include CO2 (2.60–184 mmol/kg), CH4 (2.39·10−4–0.325 mmol/kg), dissolved organic carbon (4.78·10−3–0.112 mmol/kg), and CO (1.89·10−6–4.16·10−4 mmol/kg). Carbon and helium isotopes suggest a relatively uniform mantle-derived source of CO2 (δ13C-CO2: −4.80 to −1.50 ‰, CO2/3He: 1.49·109–4.14·1010 14C-CO2: 0.11–2.42 pMC). Methane, in contrast, has multiple sources. Overall, chemical equilibria among carbon species (CO2, CH4, CO) is not attained, suggesting kinetic controls. Tritium content (<0.8–1.42 TU) and hydrologic constraints indicate relatively short hydrothermal fluid residence times (∼5–200 years), with occasional inputs from older water components. Within this short timeframe, CH4 concentrations vary from lower, to significantly higher than those calculated using CO2 reduction kinetics. The isotope composition (δD-CH4: −172 to −138 ‰, δ13C-CH4: −32.0 to −24.6 ‰; 14C-CH4: 0.36–11.54 pMC) and geochemical and isotope modeling suggest that the majority (>80–90 %) of CH4 originates from a radiocarbon inactive source, i.e. mantle CH4, reduction of mantle CO2 and/or old organic matter, with relatively small contributions from both marine (<20 %) and terrestrial (<10 %) dissolved organic carbon. Measured isotopic compositions of CH4 do not match those expected for mantle-derived CH4 as well as values generated from reduction of mantle-derived CO2. Instead, differences in δD-CH4 and δ13C-CH4 values exist between systems fed by meteoric water and those fed by seawater, challenging the assumption of a uniform CO2 source and invariable reaction mechanisms. Differences between systems are best explained by variable extent of thermal decomposition and primary variations in the isotope composition of marine and terrestrial organic matter. Also, δD-CH4 and δ13C-CH4 values in meteoric water-fed systems closely resemble those in the Öxarfjördur sedimentary-hosted systems. In summary, our data supports a predominant thermogenic origin of CH4 in both seawater and terrestrial hydrothermal fluids in Iceland. The source of organic matter appears to be a combination of modern dissolved organic carbon and older sedimentary deposits. In addition, some of the hydrothermal systems studied (Krafla, Reykjanes, Theistareykir) which are characterized by low CH4 concentrations, may contain a significant portion of CH4 that may originate from CO2 reduction.

Geochemistry and U-Pb zircon geochronology of the Nkout banded iron formations and associated metasiliciclastic rocks, NW Congo craton, southern Cameroon

ABSTRACT The Nkout banded iron formations (BIFs)-hosted iron deposit is located in the Ntem Complex at the northwestern part of the Congo craton, southern Cameroon. We report geochronological and geochemical data of magnetite BIFs and interlayered mica schists from the Nkout iron ore deposit. The BIFs show typical features of chemical precipitates characterized by seawater-like shale-normalized rare earth elements plus yttrium spectra. Weak positive Eu anomalies indicate the contribution of high-temperature hydrothermal fluids to the BIFs, with low detrital input. The absence of true Ce anomalies indicates that the BIFs were likely to be deposited in anoxic seawater. LA-ICP-MS U-Pb detrital zircon data for the BIFs and associated metasiliciclasltic rocks constrained the maximum depositional age at ca. 2.8 Ga, suggesting that the Nkout BIFs are likely the oldest iron formations in the Ntem Complex. Our zircon U-Pb isotope data indicate that the Nkout succession experienced lower-amphibolite facies metamorphism at ca. 2.0 Ga, which correlates with the regional tectono-thermal event linked to the convergence and assembly of terranes between the Congo and São Francisco cratons during the Eburnean-Transamazonian orogeny.

Geology, geochemistry, mineralization and fluid inclusion characteristics of the SW of Hormuz Island banded iron formations, southern Iran

The Hormuz Island banded iron formations (HIBIFs) are situated at the Zagros Folded Zone in southern Iran. The BIFs occur intercalated with the Neoproterozoic Hormuz series, an evaporite and siliciclastic succession with pyroclastic rocks, and were deposited on the continental rift margin of the Arabian plate. The HIBIFs are banded rocks consisting of the alternation of dark Fe-rich and reddish-brown Si-rich layers, and belong to oxide facies iron formations. The post-Archean Australian shale normalized rare earth elements and yttrium patterns of HIBIFs have the characteristics of both hydrothermal solutions and seawater. The sharp positive Eu anomaly (2.10–6.90) may be inherited from high-temperature hydrothermal solutions, while slightly negative Ce anomalies (0.57–0.82) are inherited from seawater. The homogenization temperature and salinity of primary fluid inclusions range from 180.7 to 474.3°C and from 2.24 to 12.85 wt% NaCl, respectively, which suggests that intermediate- to high-temperature hydrothermal fluids and seawater contributed to the formation of the HIBIFs. The Eu/Sm and Sm/Yb ratios in BIFs are between the values of hydrothermal fluids and seawater. In summary, all geological and geochemical data suggest that the HIBIFs are a post-great oxidation event iron formation pulse at the end of the Ediacaran period. However, this is actually not similar to Neoproterozoic syn-glacial iron formations. Instead, this is a new occurrence of iron formation in an overlooked/understudied time period when either global or local conditions were conducive to iron deposition. The iron deposition on Hormuz Island does not appear to be triggered by fluctuating atmospheric oxygen or sea-level variations, but instead may be related to syn-basinal volcanism in the active continental rift margin environment in anoxic submarine condition. Thematic collection: This article is part of the Geochemical processes related to mined, milled, or natural metal deposits collection available at: https://www.lyellcollection.org/topic/collections/geochemical-processes-related-to-mined-milled-or-natural-metal-deposits

Neoproterozoic-Early Cambrian Northern Chah-Farsakh Cu-Zn VMS-type deposit, Iran: Constraints from geology, geochemistry, fluid inclusions and geodynamic

Northern Chah-Farsakh is the first seafloor VMS described in the Torud-Chahshirin metallogenic belt of Iran. The deposit is hosted by Neoproterozoic-Early Cambrian mafic (basaltic andesitic)-siliciclastic rocks in volcano-sedimentary basin. The evolution of the ore-bearing basin is governed by the Proto-Tethys Oceanic crust subduction beneath the Central Iranian microcontinent. Three ore facies can be distinguished based on the ore textures studies: stringer zone ore facies, massive-replacement ore facies, bedded ore and distal facies. Pyrite, chalcopyrite, magnetite and sphalerite are the main minerals, together with minor amounts of pyrrhotite, bornite, tetrahedrite and tennantite. Textures include laminated, banded, replacement, massive, and vein-veinlet texture. There is a distinct metal zonation in the massive sulfide orebody; Gold, Ag, and Zn contents increase vertically from the stringer to the bedded ore facies; Cu and Co increase in the massive ore facies, and Pb is highest in the stringer zone. Ore mineralization in the Northern Chah-Farsakh deposit has emplaced in two stages. The fine-grained ore bands (stage 1) which are intricately interlayered with host rock beds, exhibit sedimentary structure such as laminae and bedding are consistent with a syn-sedimentary origin. Coarser-grained stage 2 ores have massive and vein-veinlet textures that are considered to form by replacement during sub-seafloor fluid flow. Based on SEM-EDS analysis, significant compositional variations were observed in the Py-1b grains. Py-1b is enriched in Pb compared to Py-1a. The elemental distribution map shows that the chalcopyrite (Cpy-2) minerals in Northern Chah-Farsakh deposit do not have variable composition and are homogeneous. Fluid inclusions in quartz minerals rom the footwall stringer zone have trapping temperatures between 203 and 500 °C with salinities (3.39–16 wt% NaCl equiv.) higher than modern seawater. Fluid inclusion studies suggest that the ore-forming fluids were derived from seawater. High level of Se in the massive ore facies of the Northern Chah-Farsakh supports the formation of mineralization from a high-temperature hydrothermal fluid. The Northern Chah-Farsakh Cu-Zn VMS deposit typify the mafic-siliciclastic type (Besshi-type), where the majority of the host stratigraphy is composed of a mafic flow-volcaniclastics and sedimentary rocks.

Hydrothermal activity fuels microbial sulfate reduction in deep and distal marine settings along the Arctic Mid Ocean Ridges

Microbial sulfate reduction is generally limited in the deep sea compared to shallower marine environments, but cold seeps and hydrothermal systems are considered an exception. Here, we report sulfate reduction rates and geochemical data from marine sediments and hydrothermal vent fields along the Arctic Mid Ocean Ridges (AMOR), to assess the significance of basalt-hosted hydrothermal activity on sulfate reduction in a distal deep marine setting. We find that cored marine sediments do not display evidence for sulfate reduction, apart from low rates in sediments from the Knipovich Ridge. This likely reflects the overall limited availability of reactive organic matter and low sedimentation rates along the AMOR, except for areas in the vicinity of Svalbard and Bear Island. In contrast, hydrothermal samples from the Seven Sisters, Jan Mayen and Loki’s Castle vent fields all demonstrate active microbial sulfate reduction. Rates increase from a few 10s to 100s of pmol SO42- cm-3 d-1 in active high-temperature hydrothermal chimneys, to 10s of nmol SO42- cm-3 d-1 in low-temperature barite chimneys and up to 110 nmol cm-3 d-1 in diffuse venting hydrothermal sediments in the Barite field at Loki’s Castle. Pore fluid and sediment geochemical data suggest that these high rates are sustained by organic compounds from microbial mats and vent fauna as well as methane supplied by high-temperature hydrothermal fluids. However, significant variation was observed between replicate hydrothermal samples and observation of high rates in seemingly inactive barite chimneys suggests that other electron donors may be important as well. Sediment sulfur isotope signatures concur with measured rates in the Barite field and indicate that microbial sulfate reduction has occurred in the hydrothermal sediments since the recent geological past. Our findings indicate that basalt-hosted vent fields provide sufficient electron donors to support microbial sulfate reduction in high- and low-temperature hydrothermal areas in settings that otherwise show very low sulfate reduction rates.

Textural and chemical variations of sphalerite in the Giant Shuangjianzishan Ag-Pb-Zn deposit, South Great Xing’an Range, China: Implications for ore-forming processes

The Shuangjianzishan vein-type Ag-Pb-Zn deposit (145 Mt of ore grading 128.5 g/t Ag, 1.8 wt% Pb and 0.5 wt% Zn) in the South Great Xing’an Range (NE China) is hosted in NW- and NE-trending veins crosscutting the Lower Permian Dashizhai Formation, which is intruded by a granite porphyry. Although Ag-Pb-Zn sulfide mineralization has been extensively studied, the detailed ore-forming processes remain unclear. We have identified four stages of sulfide assemblages containing three generations of sphalerite: (1) Quartz arsenopyrite sphalerite (Sp1) stage; (2) Galena Ag-minerals sphalerite (Sp2) stage; (3) Ag-minerals pyrrhotite sphalerite (Sp3) stage; and (4) Pyrite calcite stage. Stages 2 and 3 are economically important. The textures of Sp1, Sp2, and Sp3 directly record the ore-forming processes, and the mineralization of silver shows an evolution trend from simple sulfides to complex sulfosalts. LA-ICP-MS trace element analyses showed that the Sp1 contains low content of silver and other trace elements (Fe, Mn, Sn, Cu, and Pb), indicating an anoxic to an euxinic environment. Stage 2 contributed largely to the silver endowment, with relatively high silver content in sphalerite or Ag-bearing mineral inclusions in Sp2a, Sp2b, and galena. Most of the silver minerals were deposited during stage 3, with sulfide and sulfosalt assemblages (e.g., pyrargyrite + canfieldite + tetrahedrite with minor pyrrhotite) replacing Sp2b. Selenium is significantly enriched in Sp3 and selenium-rich canfieldite from Stage 3. Sulfur isotopes determined by in situ LA-multicollector (MC)-ICP-MS analyses of sphalerite vary significantly from −9.6 to 2.2 ‰ (δ34SSp1 = -4.1 ∼ 1.1 ‰; δ34SSp2 = -4.2 ∼ 2.2 ‰; δ34SSp3 = -9.6 ∼ -2 ‰). Sulfur was possibly derived from the magmas forming the granite porphyry (δ34S = 1.4 ‰) and the magmatic sulfur reservoir was oxidized by mixing with the Dashizhai stratum sulfur (δ34S: −4.9 to −6.5 ‰). This resulted in lowering of the fluid δ34S value during the deposition of Sp3. The textural, chemical and isotopic data indicate distinct ore-forming episodes at Shuangjianzishan. We suggest that the deposition of abundant Ag-bearing minerals was induced by a new volume of Ag-rich ore-forming fluids and triggered by extensive decompression and cooling during Stage 3. The sulfur isotope and chemical geothermometers suggest the involvement of relatively high-temperature (>330 °C) hydrothermal fluid during Stage 2. Unlike a single cooling mineralization process, the superposition of relatively high-temperature mineralizing fluids may be an important factor in the large-scale Ag-Pb-Zn mineralization at Shuangjianzishan.

Genesis of the Longwanggou iron deposit in the Yudongzi Complex, South China: Implications for the redox state of seawater at the onset of the Great oxidation Event

Banded iron formations (BIFs) deposited during the onset of the Great Oxidation Event (GOE) are crucial to understanding fundamental changes in the redox conditions of Earth’s surface environments, however, they are poorly understood in South China. Here, we investigate the petrographic, geochronological, and geochemical characteristics of a set of continuous magnetite quartzite samples from a drill core through the Longwanggou iron deposit in the Yudongzi Complex, South China. These magnetite quartzite samples exhibit diagnostic features of BIFs — 1) they comprise alternating magnetite and quartz layers at the centimeter–millimeter scales, 2) they are dominantly composed of SiO2 + Fe2O3T (87.8–95.8 wt%, average = 91.4 wt%), and 3) they are characterized by shale-normalized rare earth elements plus yttrium patterns similar to seawater. The maximum depositional age of the Longwanggou BIF (i.e., magnetite quartzite) is constrained to ca. 2.49 Ga based on U–Pb dating of detrital zircon grains from chlorite schist that is intercalated with the BIF. The metamorphic complex of the Yudongzi Complex that hosts the BIF was intruded by ca. 2.5–2.45 Ga granitoid gneisses, indicating that the BIF must be older than 2.45 Gyr. Accordingly, the depositional age of the Longwanggou BIF is constrained to ca. 2.49–2.45 Ga, coincident with the onset of the GOE. The positive Eu anomalies (1.3–4.2; average = 2.2) that occur throughout BIF samples suggest a continuous flux of submarine, high-temperature hydrothermal fluids to the ocean at the Archean–Proterozoic boundary. Based on elemental mass balance, the proportion of submarine, high-temperature hydrothermal fluids that contributed to the deposition of the BIF was less than 0.1%. Unlike BIFs deposited during the GOE, the Longwanggou BIF samples lack negative Ce anomalies, suggesting that the water column in which the BIF was deposited was at least locally anoxic during the onset of the GOE. Identification of the Longwanggou BIF provides new constraints for the Precambrian evolution of South China and lays the foundation for further study of the environmental changes at the Archean–Proterozoic boundary.

Chronolgy and Geochemistry of the Sijiaying Iron Deposit in Eastern Hebei Province, North China Craton: Implications for the Genesis of High-Grade Iron Ores

The Sijiaying iron deposit is located in the Eastern Hebei area of the southern section of the northern margin of the North China Craton (NCC) and is the largest single iron deposit in China. The deposit contains many banded iron formations (BIFs) and was proven to have more than 3 million tons of high-grade iron ore resources. This study carried out geochemistry and zircon U–Pb analysis of normal-grade iron ore, high-grade iron ore, and wall rock (biotite–leptynite, chlorite–sericite schist) in the Sijiaying deposit and discussed the genesis and metallogenic age of high-grade iron ore. BIFs have low concentrations of Al2O3 and TiO2 and high field strength element (HFSE) depletion, indicating almost no contamination via terrestrial debris. The standardized post-Archean Australian shale (PAAS) rare earth element (REE) distribution pattern indicates that the iron formation exhibits positive Eu, Y, and heavy rare earth element (HREE) anomalies and lacks negative Ce anomalies, indicating that the Sijiaying BIF was enriched with iron sources via high-temperature hydrothermal fluids from the seabed and deposited in an anoxic ancient marine environment. In addition, geological field work identified two types of high-grade iron ore in the mining area: primitive sedimentary and hydrothermally altered high-grade iron ore. Further ore geochemical research showed that the primitive sedimentary-type iron ore is similar in geochemistry to the BIF. In addition to low Eu/Eu* values, the hydrothermally altered high-grade iron ore shows geochemical characteristics similar to those of the BIF, suggesting that they share the same iron source but did not form at the same time. The total large ion lithophile element (LILE) (Sr, Ba, Pb) contents in primitive sedimentary-type high-grade iron ore are higher than those in hydrothermally altered high-grade iron ore, indicating that LILEs are carried away via fluids during the hydrothermal alteration process in normal-grade iron ore. The geochemical characteristics of biotite–leptynite and chlorite–sericite schist include high contents of SiO2 and Al2O3, light rare earth elements (LREEs), LILE enrichment (Rb, Ba, Sr, Zr), and HFSE depletion (Nb, Ta, P, Ti), characteristics that are similar to island arc volcanic rocks. The reconstruction of the original rock indicates that the wall rock is a product of volcanic sedimentary cycles in an island arc setting. Zircon cathodoluminescence images and LA–ICP–MS zircon U–Pb dating can be divided into four age groups (3283 Ma, 2547 Ma, 2500 Ma, and 2407 Ma), which correspond to the earliest volcanic activity in eastern Hebei, the main mineralization age of the Sijiaying BIF (the mineralization age of primitive sedimentary high-grade iron ore), a regional tectonic–metamorphic event, and the occurrence of migmatization (the mineralization age of hydrothermally altered high-grade iron ore), respectively. Therefore, the Sijiaying BIF and primitive sedimentary high-grade iron ores were deposited and mineralized at 2547 Ma, and the iron orebody was later altered via the hydrothermal solution at 2407 Ma, forming large-scale high-grade iron ores.

Influence of Low-Temperature Hydrothermal Events and Basement Fault System on Low-Resistivity Shale Reservoirs: A Case Study from the Upper Ordovician to Lower Silurian in the Sichuan Basin, SW China

High graphitization is responsible for low-resistivity shale development with poor reservoir quality. This paper provides an explanation of organic matter graphitization and determines the impact of high graphite content on low-resistivity shale reservoir quality at the Wufeng-Longmaxi Formation in the Southern Sichuan Basin. Fine veins are frequently developed at shale samples with Ro &gt; 3.5%, graphitized organic matter &gt; 25%, and resistivity &lt; 5 Ω•m, which are dominated by three mineral assemblages: brunsvigite, barite-hyalophane-barium feldspar-potassium feldspar-anhydrite, and calcite-ankerite. These filling minerals are characterized by an Eu positive anomaly and high Ba, Fe, and Mn contents, suggesting that low-resistivity shale was modified by magmatic-related low-temperature hydrothermal fluid. Temperature measurements of brine inclusions and a semi-empirical geothermometer of chlorite show that low-temperature hydrothermal fluid experienced the chlorite stage (150–180 °C), the low-sulfidation stage (120–150 °C), and the low-temperature calcitization stage. Paleozoic fault systems and late Permian hydrothermal activities associated with the Emeishan mantle plume control the graphitization of low-resistivity shale. The water formation and seawater infiltrated into the deep crust along the Paleozoic basement faults under gravity, developing alkaline hot brine through mantle plume heating and then causing a water-rock reaction with basement rocks. They migrated upward along deep and large Paleozoic faults through convective thermal circulation in the Tiangongtang area, the Shuanglong-Luochang area, and the Xuyong area. Cation exchange and redox reactions occurred during the interaction between high-temperature hydrothermal fluid and cool wall rocks. The migration of alkaline hot brine via the Wufeng-Longmaxi shale introduced a subsequent water-rock reaction, resulting in the development of hydrothermal mineral assemblages that intricately filled fractures. It increased formation temperature and enhanced thermal maturity and graphitization of organic matter at the Wufeng-Longmaxi low-resistivity shale, resulting in a wide distribution of low-resistivity shale at the Changning Block.

Fe-Si-C isotope constraints on the genesis of iron ores in Gongchangling iron deposit in northeastern China

The Gongchangling iron deposit is an oxide-facies Algoma-type banded iron formation (BIF) and one of the most representative iron deposits in northeastern China. We present new data from petrological, whole-rock geochemical, and Fe-Si-O isotope compositional data from the Gongchangling BIFs to constrain the origin of ore-forming materials and mineralization processes. The low Al2O3 and TiO2 contents in iron ores indicate that the sources of the BIFs were not contaminated by terrigenous clastic sediments. The Gongchangling BIFs are characterized by depletions in LREEs and 30Si and enrichments in HREEs, with positive Eu and Y anomalies. Given these and the Fe isotope results, we conclude that both high-temperature hydrothermal fluid and seawater contributed to the formation of the BIFs and that a mixture of seawater and ~ 0.1 % hydrothermal fluid, which percolated and dissolved the submarine volcanic rocks, provided the ore-forming materials. Combining the Ce anomalies, enrichments in heavy Fe isotopes and low δ13C compositions, we conclude that the fO2 of Archean seawater was limited. Integrated petrographic and geochemical evidence indicates that the high-grade iron ores from the Gongchangling BIFs experienced incomplete oxidation and low amounts of Fe precipitation in a marine environment and that dissimilatory iron reduction and metamorphic hydrothermal fluid played important roles.

Tracing hydrothermal mineral thenardite in geysers/hot springs of North-western Himalayan belt, Ladakh Geothermal Province, India by hydrogeochemistry, fluid-mineral equilibria and isotopic studies

The present study highlights the first evidence of hydrothermal mineral Thenardite (Na2SO4) from Puga geothermal area, North-western Himalayan belt in Ladakh Geothermal Province, India, which is unequivocal evidence for the presence of high-temperature hydrothermal fluid activity from one of the thickest crust areas of the Earth. The Puga geothermal belt illustrates a fault-bounded hydrothermal system with a clearly defined conductive zone, coinciding with Kiagar Tso fault typically exemplifying a shallow-level medium enthalpic geothermal reservoir. The hydrogeochemistry suggests that thermal and non-thermal waters are of Na-Cl-HCO3 and Ca-Mg-HCO3 type, respectively, with neutral to near alkaline pH. The silica and cation geothermometry reveal sub-surface temperatures around 150 °C and 250 °C, respectively, at shallow depth; however, >250 °C is anticipated at the deepest levels (~3 km). Stable isotope (δD and δ18O) studies explicate depletion of isotopic content for thermal waters over Puga river water and radiogenic isotope (3H) suggests matured thermal waters with ongoing water-rock interactions. The recharge altitude estimation and physiographic studies put forth that geothermal reservoir is recharged with the ice masses located at an altitude of 6458 m above mean sea level (msl) in the west of Puga valley, probably from the highest peak of Polokong La mountain. The two key processes participating in regulation of proportions of the dissolved salts in the thermal waters are silicate weathering and ion-exchange kinetics. The powder X-ray diffraction study reveals a major occurrence of hydrothermal mineral thenardite in the hot spring deposits for the first time along with huge encrustations of trona, borax, calcite and elemental sulfur. The high-temperature fluids encounter thenardite, pyrite, and jarosite-bearing minerals in basement rock causing enrichment of SO42− and Cl− in geothermal waters. The temperature-dependent speciation modelling (50 °C–200 °C) for major ion Na+ reveals the composition of the reservoir fluid (~150 °C): Na+ > NaCO3− > NaSO4− > NaHCO3 > NaF > NaOH. A conceptual evolution model of thermal waters involving the recharge-deep circulation-mixing-discharge of thermal springs is hence put forth in the study using various hydrogeochemical insights.

Studies on geochemical characteristics and biomineralization of Cambrian phosphorites, Zhijin, Guizhou Province, China.

Phosphate rocks, an important ore resource in Guizhou Province, China, are mainly hosted within the Sinian Doushantuo Formation and the Cambrian Meishucun Formation. In addition, the phosphate rocks of the Cambrian Meishucun Formation are rich in biological fossils. Although numerous studies investigating the genesis of phosphate deposits have been performed, the relationship between biological activity and the formation of phosphate deposits in the lower Cambrian Meishucun Formation has not been convincingly explained. This study focuses on the biological fossil assemblage, the characteristics of phosphorus, and the relationship between biological and phosphorus enrichment of the lower Cambrian phosphorites. The primary objectives of our study are to analyze the role of organisms in the formation of phosphorites, restore the phosphorus-formation environment of the Cambrian Meishucun Formation, and construct a sedimentary model of the phosphorites in the Meishucun Formation. The results indicate that there is a significant positive correlation between biological activity and the deposition of phosphorites, that is, the higher the degree of biological enrichment and differentiation, the stronger the deposition. The geochemical analysis of several profiles in the Zhijin phosphorite block shows that the phosphorite block was deposited in an oxygen-rich environment and was affected by a high-temperature hydrothermal fluid. Upwelling ocean currents supplied abundant phosphorus and other nutrients, which provided the conditions for small shells and algae to flourish. Biochemical activity was a crucial factor in the deposition of the phosphorite.

Boron and Oxygen Isotope Systematics of Two Hydrothermal Systems in Modern Back-Arc and Arc Crust (PACMANUS and Brothers Volcano, W-Pacific)

AbstractA better characterization of subsurface processes in hydrothermal systems is key to a deeper understanding of fluid-rock interaction and ore-forming mechanisms. Vent systems in oceanic crust close to subduction zones, like at Brothers volcano and in the eastern Manus basin, are known to be especially ore rich. We measured B concentrations and isotope ratios of unaltered and altered lava that were recovered from drilling sites at Brothers volcano and Snowcap (eastern Manus basin) to test their sensitivity for changing alteration conditions with depth. In addition, for Brothers volcano, quartz-water oxygen isotope thermometry was used to constrain variations in alteration temperature with depth. All altered rocks are depleted in B compared to unaltered rocks and point to interaction with a high-temperature (&amp;gt;150°C) hydrothermal fluid. The δ11B values of altered rocks are variable, from slightly lower to significantly higher than those of unaltered rocks. For Brothers volcano, at the Upper Cone, we suggest a gradual evolution from a fluid- to a more rock-dominated system with increasing depth. In contrast, the downhole variations of δ11B at Snowcap as well as δ11B and δ18O variations at the NW Caldera (Site U1530) of Brothers volcano are suggested to indicate changes in water-rock ratios and, in the latter case, also temperature, with depth due to permeability contrasts between different lithology and alteration type boundaries. Furthermore, δ11B values from the NW Caldera (Site U1527) might point to a structural impact on the fluid pathway. These differences in the subseafloor fluid flow regime, which ranges from more pervasive and fluid-controlled to stronger and controlled by lithological and structural features, have significant influence on alteration conditions and may also impact metal precipitation within the sea floor.

The Paleoproterozoic Zhaigou banded iron formation in the Fuping Complex, North China Craton: Geochemistry, geochronology and implications for genesis and tectonic setting

Precambrian Banded iron formations (BIFs) provide important insights on the chemical composition of ancient seawater, as well as the tectonic setting of their formation. The Precambrian BIFs deposits in the North China Craton are widely distributed in the Archean greenstone belts and are composed predominantly of Neoarchean Algoma-type including those in the Anshan-Benxi and eastern Hebei areas of the Eastern Block, together with minor Paleoproterozoic Superior-type BIFs in the southern segment of the trans-North China Orogen. The Zhaigou BIF deposit is associated with Paleoproterozoic Wanzi supracrustal sequence and amphibolite in the Fuping Complex in central North China Craton. Here, we present petrological, geochronological and geochemical data of the meta-sedimentary rocks, BIF ores and amphibolites from the Zhaigou BIF deposit in the Fuping Complex for the first time to constrain the formation age, source characteristics and depositional setting, and evaluate the redox states of the Paleoproterozoic seawater. Whole-rock geochemical data show that the BIF ores are enriched in HREE with low (La/Yb)PAAS values (0.037–0.073), and exhibit positive Eu (3.34–6.21) and Pr (1.05–1.10) anomalies. The PAAS-normalized REY patterns resemble 1:100 mixture of high-temperature hydrothermal fluid and seawater, indicating the involvement of the two end members. In combination with whole-rock geochemical data of BIF ores, trace elements of magnetite and U-Pb ages of detrital zircons from the meta-sedimentary rocks, we propose that crustal components from the Fuping TTG gneiss also contributed to the BIFs. The geochemical features suggest that the protolith of amphibolite is basalt formed in island arc setting. The negative Ce anomaly (Ce/Ce* = 0.81 ∼ 0.90) indicates the deposition of the Zhaigou BIF ore in an oxidizing environment. Zircon U-Pb data on the BIF ore yield weighted mean 207Pb/206Pb ages of 2028 ± 33 Ma and 1874 ± 52 Ma, representing the formation age of the Zhaigou BIF deposit and the subsequent metamorphic event, respectively. The Zhaigou BIF deposit belongs to the Algoma-type which shows close association with the Paleoproterozoic sedimentary sequence and basaltic magmatism in oceanic island arc setting. The Paleoproterozoic seawater forming the Zhaigou deposit was oxidized after the Great Oxygenation Event (GOE) during the terrane assembly in the trans-North China Orogen.

The genetic link between iron oxide-apatite and iron skarn mineralization in the Beizhan deposit, Western Tianshan, NW China: Evidence from magnetite and gangue mineral geochemistry

• We identify coexisting IOA ore and iron skarn ore in the Beizhan deposit. • IOA and iron skarn ore could form from a single magmatic-hydrothermal system. Multiple types of deposits could form from a single magmatic hydrothermal system. Thus, identification of the temporal, spatial and genetic link among different styles of deposits is crucial to understand the evolution of magmatic-hydrothermal systems and helpful in ore deposit exploration. Iron oxide-apatite (IOA) ores sometimes coexist with iron skarn ores in the same region, but whether these two iron ore styles could form from the single magmatic-hydrothermal system remains poorly understood. The Beizhan deposit is the largest-scale iron deposit (468 Mt, with an average of 41% Fe) in the Awulale Metallogenetic Belt (AMB) in Western Tianshan, and was previously considered to be submarine volcanic-hosted iron deposit or iron skarn deposit. In this study, we identify coexisting IOA ore and iron skarn ore in the orebody proximal to a dioritic-granitic intrusion in the Beizhan deposit. Combined with the geochemistry of magnetite and gangue minerals, we suggest that the IOA ores are consistent with formation from a high-temperature hydrothermal fluid sourced from a dioritic magma. In contrast, the iron skarn mineralization originated from a relatively low-temperature and more evolved hydrothermal fluid compared with the IOA ores. We propose the consecutive precipitation of an evolving magmatic-hydrothermal system during the two stages of iron mineralization at Beizhan, that resulted through compositional evolution of the fluid during magma differentiation. The coexisting two ore types identified in the Beizhan deposit provides insights into the evolution of the intermediate-felsic magmatic-hydrothermal systems and the genetic model of the similar ore type associations in the other deposits.

Petrography and geochemistry of the iron-rich rocks in the banded iron formation of the Chilpi Group, Central India: Implications on the level of oxygen in the Paleoproterozoic atmosphere before the “Proterozoic iron ore gap”

The Chilpi Group (2050–1850 Ma) in the Bastar Craton contains Banded Iron Formation (BIF) deposited immediately after the Great Oxidation Event but before the “Proterozoic iron ore gap”. Baseline geochemical data generated from this crucial period of Earth's history representing the transition from an initial high productivity period followed by productivity collapse, thereby delaying the evolution of biota, are interpreted in terms of the redox state of the ocean and atmospheric oxygen content. Presence of chamosite, greenalite and siderite in the ironstones of the Chilpi Group, identified during present analysis, provide valuable information regarding the redox state of the shallow sea. Geochemical analyses reveal high concentrations of Fe2O3total and SiO2 (average ~ 87.85 wt%) in iron-rich bands. Trace elements commonly enriched in detrital phases (e.g. Sc, Hf, Nb, Th and Zr) show good correlation with total REE concentration, but these have concentration below the cut-off limit defined for detrital sediments (except 3 samples). Higher concentration of these elements in greenalite/chamosite-rich samples indicates accumulation of these elements in greenalite/chamosite during primary precipitation. Most of the samples have low concentrations of Al2O3 (<5 wt%) and TiO2 (<0.5 wt%), but some chamosite-bearing samples show enrichments of Al2O3 (up to ~20 wt%). Post-Archean Australian Shale normalised rare earth elements with Y (REEY) patterns, showing a superchondritic Y/Ho ratio (average 32.15) and positive La, Gd and Y anomalies, indicate the preservation of seawater like signatures. Though a low positive Eu-anomaly, and Al/(Al + Fe + Mn) versus Fe/Ti plot suggest seawater signature with possible mixing of hydrothermal fluids and/or <10 % detrital components, preservation of seawater signatures and no involvement of high-temperature hydrothermal fluids are deduced from Eu/Sm versus Sm/Yb and Eu/Sm versus Y/Ho patterns. The Eu/Sm and Y/Ho ratios lower than the seawater and a mixing trend away from oceanic hydrothermal solution indicate possible mixing of freshwater with seawater for the observed REEY patterns. Redox-sensitive trace element ratios indicate a dysoxic to suboxic-anoxic condition in the depositional basin. Presence of oolitic textures and occurrence of chamosite support the shallow water (<60 m water depth) and anoxic condition in the depositional basin. The oxygen content of 10−3–10−5 times the present atmospheric level in the atmosphere is inferred for the period during the deposition of the BIF.

The Depositional Mechanism of Hydrothermal Chert Nodules in a Lacustrine Environment: A Case Study in the Middle Permian Lucaogou Formation, Junggar Basin, Northwest China

Although chert deposits are limited in geological distribution, their geological and geochemical characteristics can provide important information to reconstruct paleoenvironmental and diagenetic processes. For the Permian period, cherts are utilized to trace global silicon cycles and hydrothermal activities in relation to the Permian Chert Event. In Northwest China, Permian chert nodules have recently been discovered in both the southeastern and northwestern margins of the Junggar Basin. We conducted an analysis of the mineralogy, petrology and geochemistry of chert nodules of the Lucaogou Formation in the southeastern margin of the Junggar Basin to identify silicon sources and determine the precipitation mechanism of chert nodules. As evidenced by petrology, the chert nodules were mainly composed of crypto-microcrystalline silica (94.33% on average), with development of a soft-sediment deformation structure, indicating the synsedimentary deposition of silicon. Proven by trace elements, high Eu/Eu* ratios (average 2.14), low total rare earth element content (average 6.03 ppm), low LaN/YbN ratios (average 0.17) and low Y/Ho ratios (average 25.25) in chert nodules supports the hydrothermal source of silicon. The wide distribution of authigenic metal-bearing minerals and the significant positive Eu anomalies observed suggest that the chert depositions in the Lucaogou Formation intermittently received high-temperature (&gt;250 °C) hydrothermal fluids, likely associated with the initiation of the Bogda Rift in the middle Permian. Following rapid cooling down and differential compaction, siliceous sediments dehydrated and deformed, finally forming chert nodules.

The effect of high-temperature alteration of oceanic crust on the potassium isotopic composition of seawater

High-temperature hydrothermal alteration of oceanic crust is one of the two main sources of potassium (K) to the oceans, with modern flux estimates ranging roughly from ∼8 to 30 % of the K flux from rivers. Despite the role of high-temperature hydrothermal fluids in the global seawater K budget, little is known about its effect on the K isotopic composition of the oceans. Here we present stable K isotope measurements (δ41KSRM3141a) of globally distributed high-temperature hydrothermal fluids from three mid-ocean ridge systems: the East Pacific Rise (n = 21), the Juan de Fuca Ridge (n = 34), and the Mid-Atlantic Ridge (n = 18). We find a strong correlation between δ41K and Mg/K ratios, consistent with conservative mixing between a high-temperature hydrothermal fluid (i.e., Mg = 0) and seawater as fluids ascend to the seafloor and/or due to seawater entrainment during sampling. The δ41K of end-member hydrothermal fluids is found to range between −0.80 ‰ and 0.07 ‰, with an average value of −0.36 ± 0.30 ‰ (2σ, n = 38). Most (∼76 %) of the variability in end-member fluid δ41K compositions observed here can be explained by high-temperature fluid-rock K exchange, with little (∼0.2 ‰) to no K isotope fractionation between hydrothermal fluid and altered crust. Larger deviations from the average end-member hydrothermal fluid value are likely to result from processes other than high-temperature fluid-rock exchange, such as (1) low-temperature hydrothermal reactions during fluid recharge, (2) reaction of fluids with local sedimentary sources, and (3) phase separation. The K contents of end-member fluids vary considerably, from ∼1 to 38 mM, thus a K-weighted average of −0.37 ± 0.24 ‰ (2σ, n = 38) is estimated to represent the δ41K composition of the global hydrothermal K flux. Our results suggest that K sourced from axial hydrothermal alteration does not contribute to the elevated 41K/39K of seawater compared to bulk silicate Earth (BSE). In addition, subduction of oceanic crust altered under high-temperature conditions is unlikely to be a significant source of K isotopic heterogeneity to Earth’s mantle.

A submarine hydrothermal origin of banded iron formations from Archean Kiriburu-Meghahatuburu iron ore deposit, Singhbhum Craton, eastern India

The high-grade (>62 wt% Fe) iron ores of Kiriburu-Meghahatuburu deposit (KMID) of the Singhbhum-Orissa region, eastern India are mainly hosted by banded hematite Jasper (BHJ) and shale. These BIFs belong to oxide facies (hematite ± martite) iron formations without sulfidic/carbonitic signatures. These BIFs have low concentrations of Al2O3 (0.86 wt%), TiO2 (0.13 wt%) and trace HFSE [(high field strength elements such as Zr (13 ppm), Hf (0.30 ppm), Ta (5 ppm), Pb (7 ppm) and Th (0.45 ppm)], reflecting minor amounts of clastic contamination. The SiO2-Zr/TiO2 ratios and the binary plots between certain trace elements, e.g., Hf-Zr and Zr-Y indicate clastic contamination derived from various sources. The weak positive chondrite normalized Eu anomaly (average 1.13) in BHJ, associated with low V (7 ppm) and Ni (17 ppm) contents are analogous to the Superior-type BIFs worldwide, and are consistent with deposition in a submarine hydrothermal environmental setting under low oxygenated environment. Positive Eu anomalies and the Y/Ho vs Eu/Sm relationships indicate mixing of seawater with a small amount of high-temperature hydrothermal fluids (<0.1 %). Based on the field studies, ore mineralogical and geochemical signatures, a “polygenic-supergene- hydrothermal” model has been proposed for the genesis of Kiriburu-Meghahatuburu BIFs that can be used in understanding the mineralogical variations in the iron ores and their genetic aspects at KMID which has implications for exploration.