Low-temperature Hydrothermal Fluids Research Articles

Hydrothermal alteration mechanisms of an Archaean metamorphic buried hill and the models for reservoir zonation, Bozhong depression, Bohai Bay Basin, China

Multiple metamorphic buried-hill hydrocarbon reservoirs have been recently discovered in the Bozhong Depression, Bohai Bay Basin. Among them, the buried-hill reservoirs in the BZ13, BZ19 and BZ26 regions have the largest condensate gas reserve in eastern China. The hydrocarbon-bearing reservoir has a large thickness with a maximum of ∼1 km, making the oil-equivalent reserve exceed 5 × 108 tons. This study used petrography, isotopes, gas composition, zircon U–Pb geochronology, X-ray diffraction, electronic probe and hydrothermal dissolution experiments to discuss the formation mechanisms of the metamorphic buried-hill reservoirs. The results indicate that the reservoirs 500 m below the surface of the buried hill have been significantly altered by the mantle-derived CO2. This is supported by the carbon isotope of CO2, He isotope of the helium gas, strong negative excursions in δ18OPDB, positive excursions in δ13CPDB, Co/Ni ratio greater than 1 in pyrite and secondary characteristic minerals such as dawsonite. Hydrothermal dissolution experiments using CO2 result in the precipitation of kaolinite, ankerite and quartz cements, which is consistent with petrographic observation. The mantle-derived CO2 reacts with feldspars, hornblende, biotite and carbonates, creates secondary dissolution pores and significantly improves reservoir quality. Moreover, partial carbonate cements exhibit negative excursions in δ13CPDB and the depletion of light rare earth elements, indicating the influence of organic acids-bearing low-temperature hydrothermal fluids. Therefore, three development models illustrating the formation of metamorphic buried-hill reservoirs were proposed. This study may serve as a reference for the hydrocarbon exploration in metamorphic buried-hill reservoirs.

Formation of Ediacaran stromatolitic cherts through a combination of biogenic and abiotic processes: New insights from the Bohemian Massif

Stromatolites are remarkable organosedimentary laminated structures that grow gradually through time due to the activity of microorganisms, mostly algae and cyanobacteria. The appearance of stromatolites in formations as old as ∼ 3.7 Ga represents the earliest macroscopic traces of life on Earth. Yet, the biogenic origin of some presumed stromatolites has been questioned as abiotic processes (e.g., fluid precipitation, diagenesis and metamorphism) can also be responsible for the formation of stromatolite-like textures. This is especially true in case of pervasively silicified stromatolites (stromatolitic cherts) that have rarely been reported from Neoproterozoic successions. Here, we present a detailed study of the Ediacaran stromatolitic cherts from the Blovice accretionary complex (Bohemian Massif) that combines petrography, trace element and Si–O isotopic compositions and Raman spectroscopy of organic matter to decipher the complex processes leading to their formation and evaluate the biogenicity of their precursor. Textural evidence (i.e. the presence of pseudomorphs after carbonate/evaporate and micro-ooids, variable thickness and spacing of organic-rich laminae) as well as trace element/isotopic compositions argue for a multi-stage formation of stromatolitic cherts. The primary carbonaceous stromatolitic precursors first formed in shallow-water lagoons with variable salinity at seamount slopes, were then fragmented by surface processes (erosion, mass wasting), and finally silicified by low-temperature hydrothermal fluids. The primary biogenic character of stromatolitic textures is evidenced by the non-equidistant alternation of dark (organic matter-rich) and light laminae with markedly different oxygen isotopic compositions reflecting probably seasonal cycles during stromatolite deposition, enrichment of bio-essential elements (e.g., Cu, Zn, Co and Mn) in dark laminae, and Raman spectra of organic matter indicative for variably matured kerogens. The presence of late-stage diagenetic modifications might be related to subsequent burial and low-grade metamorphism of stromatolitic cherts within the accretionary wedge.

Genesis of the Beizhan Iron Deposit in Western Tianshan, China: Insights from Trace Element and Fe-O Isotope Compositions of Magnetite

The Beizhan iron deposit (468 Mt at an average grade of 41% Fe) is the largest iron deposit in the Awulale iron metallogenic belt of Western Tianshan, northwest China. The high-grade magnetite ores are hosted in the Carboniferous volcanic rocks with extensive development of skarn alteration assemblages. While considerable progress has been made in understanding the characteristics of Beizhan and its genetic association with volcanic rocks, the genetic models for ore formation are poorly constrained and remain controversial. This study combines detailed petrographic investigations with in situ LA-ICP-MS analyses of trace elements and Fe-O isotope compositions of magnetite to elucidate the origin of magnetite and the conditions of ore formation. The trace element concentrations in magnetite unveil intricate origins for various ore types, implying the precipitation of magnetite from both magmatic and hydrothermal fluids. The application of the Mg-in magnetite thermometer (TMg-mag) reveals a notable temperature divergence across different magnetite varieties, spanning from relatively higher temperatures in magmatic brecciated magnetite (averaging ~641 and 612 °C) to comparatively lower temperatures in hydrothermal platy magnetite (averaging ~552 °C). The iron isotopic composition in massive and brecciated magnetite grains, characterized by lighter δ56Fe values (ranging from −0.078 to +0.005‰ and −0.178 to −0.015‰, respectively), suggest a magmatic or high-temperature hydrothermal origin. Conversely, the heavier δ56Fe values observed in platy magnetite (+0.177 to +0.200‰) are attributed to the influence of pyrrhotite, signifying late precipitation from low-temperature hydrothermal fluids. Additionally, the δ18O values of magnetite, ranging from +0.6 to +4.6‰, provide additional evidence supporting a magmatic–hydrothermal origin for the Beizhan iron deposit. Overall, the identified genetic associations among the three magnetite types at Beizhan provide valuable insights into the evolution of ore-forming conditions and the genesis of the deposit. These findings strongly support the conclusion that the Beizhan iron deposit underwent a process of magmatic–hydrothermal mineralization.

Hydrothermal amorphous silica, barite and orpiment from the crater area of seamount (SM-13) off Nicobar island, Andaman sea: Indications for the development of a new hydrothermal field

The Andaman sea characterized by trench-arc-backarc elements (Andaman-Nicobar island-arc, the Andaman back-arc spreading center, the seamount complex, and the back-arc basin) is a complex active basin and is known for hydrothermal activity in some of the seamounts (subaerial and submarine) of the volcanic arc. In the present study, 13 submarine seamounts (SM1- SM13) in the southern Andaman volcanic arc, extending from 6°47′N: 94°43′E to 7° 56′ N: 94° 2.47′E, were surveyed onboard RV Sindhu Sadhana (November 2021) to find the evidences for the hydrothermal activity. Out of the 13 seamounts, at one crater seamount (SM-13) we have observed evidence for hydrothermal activity characterized by plumes rich in dissolved gases (mainly CO2) in the water column, live chemosymbiotic organisms (Bathymodiolus species), and neoforming minerals such as amorphous silica, barite and orpiment. We observed two plumes rich in dissolved gases (mainly CO2), called GP1 and GP2, in the water column at two different water depths i.e. 400 and 380 mbsl respectively. Geochemical analysis of the water samples shows enhanced TCO2 concentrations within the plumes rich in dissolved gases (mainly CO2) observed in sub-bottom profiler data, however, the dissolved methane concentrations do not show any enrichment when compared with ambient seawater concentrations. Apart from the enhancement in the TCO2 concentrations, pH and total alkalinity data also show fluctuations within the same depth zone which may be attributed to the hydrothermal plume exhausting from the crater seamount. The occurrence of live chemosymbiotic organism Bathymodiolus species indicate an active and continuous supply of H2S. The precipitation of neoforming hydrothermal minerals such as amorphous silica, tabular barite, and orpiment on the surface of the rock samples further supports the hydrothermal activity. Previous studies carried out in 2007 have reported hydrothermal ferromanganese oxides precipitated from low-temperature hydrothermal fluids (Surya prakash et al., 2012) and inferred SM-13 as a dormant submarine volcano (Kamesh Raju et al., 2012). However, after 14 years, we observe volatile emissions to the water column, hydrothermal mineral precipitation and live chemosymbiotic organisms from the same seamount. These observations of the present study infer development of a new hydrothermal field in the least explored Andaman Sea. This study adds up a new active site to the global hydrothermal inventory which may allow better estimation of global hydrothermal flux and its role in oceanic elemental cycle.

Magnetite geochemistry and mineralogy of iron skarn in the southern Wag Water Belt, Jamaica: Implications for ore genesis

The Mavis Bank iron skarn mineralisation is located within a Paleocene to Eocene rift system typified by terrestrial and marine deposits, and extensive lava flows and subvolcanic intrusions of adakitic composition. Iron occurs primarily as massive, lenticular magnetite bodies at the contact between the intrusions and calcic Fe skarn (metasomatised limestone) which grades into a low-grade marble with disseminated magnetite. Magnetite is also disseminated in shales and lavas located within the main mineralised zones. Skarn mineralogy is poorly developed in both the endoskarn and the exoskarn with only minor occurrence of diopside. Retrograde and alteration minerals, such as epidote, chlorite, and hematite, are more common. Sulphides are rare, highly altered, and dominated by pyrite, pyrrhotite, and minor chalcopyrite. Petrographic analysis, including micro-XRF-EDS mapping of polished thin sections, shows that massive magnetite and calcic Fe skarns have minor disseminated Ti and S phases along with trace amounts of Cu and Co. Scanning electron microscope-backscattered electron (SEM-BSE) imaging of the exoskarn highlights the extent of retrograde alteration and later supergene weathering, and the presence of dissolution and reprecipitation features.The in situ trace element composition of magnetite in massive magnetite and calcic Fe skarn was determined using LA-ICP-MS. The results, when plotted on multi-element and discriminant diagrams, including Ni/(Cr + Mn) vs Ti + V, Ca + Al + Mn vs Ti + V, Ti vs V, and Ti vs Ni/Cr, are generally consistent with the geochemical signatures of skarn deposits worldwide. The mineralogy and trace element signatures suggest that the skarn deposit was formed at relatively shallow levels by low temperature hydrothermal fluids with high fO2 and fS. In addition, δ18O values of 6.6 and 7.1 ‰ obtained from massive magnetite are typical of infiltrative skarns and are consistent with a mixture of magmatic and meteoric water, and limestone oxygen isotope signatures.

The Kaolin and Bentonite Deposit of Tamame De Sayago (Zamora, Spain): Mineralogy, Geochemistry, and Genesis

A geological, mineralogical, and geochemical characterization of the Tamame de Sayago (Zamora, Spain) deposit was carried out with the aim of knowing the conditions that facilitated the genesis in the same deposit of kaolinite and smectites. The alteration processes affecting a Variscan granite were deduced throughout the study of a very wide group of representative samples by X-ray diffraction (XRD), scanning electron microscopy (SEM), chemical analyses of major, minor, and trace elements, as well as δ18O, δ34S stable isotope and K/Ar dating analyses. In addition, 2D and 2.5D graphs of the kaolinite and smectite isoconcentrations were obtained from core data. According to the color and texture, two different clayey rock types were identified and named as homogeneous alteration zones (ZAHO) and heterogeneous alteration zones (ZAHE). The ZAHO are regoliths in which the granite texture is preserved, and the feldspars are almost completely kaolinized. In the ZAHE, the original texture of the granitic rock is lost, and the main clay mineral is smectite. The mineralogical composition is similar, with kaolinite, smectite, mica, quartz, scarce feldspar, and occasionally natroalunite and APS (aluminum-phosphate-sulphate); however, the mineral concentration varies considerably because ZAHO are rich in kaolin areas whereas ZAHE are bentonitic areas. Both rock types contain numerous veins and nodules. The weathering of the Paleozoic granite alongside the absence of sedimentation during the Mesozoic led to the formation of kaolinite that is preserved in ZAHO materials. Nonetheless, during the Cretaceous–Tertiary transit, the conditions of tectonic stability varied. Late Variscan faults reactivated which allowed the percolation of Mg- and Ca-rich hydrothermal fluids through the already kaolinized granite, increasing the alteration of the primary silicates and leading to the formation of smectites in ZAHE materials. The amount of smectites is greater closer to the faults. The stable isotopes indicate the meteoric nature of the low-temperature hydrothermal fluids. The K/Ar data obtained from the natroalunite of veins indicate that those hydrothermal fluids circulated in different pulses from 66.4 ± 1.7 to 58.8 ± 1.5 Ma, as a minimum. Those ages are coincident with the first formation stages of the Duero Basin.

Formation of hydrothermal ferromanganese oxides from the Daigo-Kume Knoll in the middle Okinawa Trough, Japan

Many active hydrothermal sites resulting from active volcanism have been recognized in the Okinawa Trough, a nascent back-arc basin. Despite its importance for understanding whole hydrothermal circulation, low-temperature (LT) hydrothermal activity, which precipitates ferromanganese (Fe–Mn) oxides, has not been actively studied compared to high-temperature (HT) hydrothermal activity, which forms sulfide deposits. Therefore, in this study, we investigated the origin and formation of Fe–Mn oxides obtained from the outer rim of the Daigo-Kume Knoll caldera in the middle Okinawa Trough based on their chemical and mineral compositions. Composed of birnessite and todorokite, the Fe–Mn oxide samples contain low levels of trace elements, indicating their precipitation from LT hydrothermal fluids. This is the first report of hydrothermal activity at the Daigo-Kume Knoll. Based on an independent component analysis of elemental mapping data, it was determined that the hydrothermal activity consisted of two stages: a primary hotter LT hydrothermal fluid (roughly 30 °C–150 °C) that altered silicate debris and precipitated mainly Fe oxides, and a secondary colder LT hydrothermal fluid (roughly 30 °C) that precipitated mainly Mn oxides without alteration. The growth rate, estimated from the chemical composition, and the thickness of the Fe–Mn oxide samples indicated that the duration of the hydrothermal activity was about 17.7–29.5 kyr. In contrast to their LT hydrothermal origin, the high Mo/Mn ratio of the Fe–Mn oxide samples suggested that the LT hydrothermal fluids that precipitated the Fe–Mn oxide samples might be originally produced by HT water–rock interactions.

Hydrothermal alteration of basalts in the ultramafic-associated Tianxiu Vent Field, Carlsberg Ridge

The Tianxiu vent field (TVF) is the first active ultramafic-associated hydrothermal field to be discovered at the termination of a detachment fault on the slow-spreading Carlsberg Ridge. Most hydrothermal chimneys in the TVF are developed on the basaltic apron. This paper presents mineralogical, petrological, and geochemical data for altered basalts in and surrounding the TVF. The basalt samples can be classified into seafloor-weathered and hydrothermally altered (i.e., slightly saponite-altered, highly saponite-altered, and silicified) types. At the periphery of the TVF, the basalts have experienced seafloor weathering, which has resulted in slight mineralogical and geochemical changes. In the TVF, most basalts have interacted with diffuse low-temperature hydrothermal fluids, leading to variable degrees of saponite alteration. As the distance from the vents decreases, basaltic glass, olivine, and pyroxene are progressively replaced by saponite; Zn, Cu, Co, and U are enriched; and Ca and Mn are depleted. Magnesium, Fe, and Li have been lost due to olivine replacement by saponite, and have been gained due to pyroxene replacement by saponite. In the fluid flow conduits, the basalts have interacted with focused medium- to high-temperature fluids, which has led to the replacement of saponite by opal; depletion in Mg, Fe, Li, and rare earth elements; and enrichment in Zn, Cu, Co, and U. We propose a new hydrothermal alteration model for basalts in an ultramafic-associated vent field. Based on a comparison with mafic-hosted vent fields along mid-ocean ridges, we propose that: (1) the permeable host rocks promote lateral fluid flow, widespread mixing with cold seawater, and pervasive low-temperature hydrothermal alteration; and (2) H2S-poor reducing fluids reduce the solubility of U and inhibit the precipitation of Fe, leading to high Cu/Fe and Zn/Fe ratios, and high U concentrations. The hydrothermal alteration model for the TVF is applicable to similar vent fields and can guide exploration for seafloor massive sulfide deposits along slow-spreading ridges.

Monazite-(Gd), a new Gd-dominant mineral of the monazite group from the Zimná Voda REE–U–Au quartz vein, Prakovce, Western Carpathians, Slovakia

AbstractMonazite-(Gd), ideally GdPO4, is a new mineral of the monazite group. It was discovered near Prakovce-Zimná Voda, ~23 km WNW of Košice, Western Carpathians, Slovakia. It forms anhedral domains (≤100 μm, mostly 10–50 μm in size), in close association with monazite-(Sm), Gd-bearing xenotime-(Y), Gd-bearing hingganite-(Y), fluorapatite and uraninite. All these minerals are hosted in a REE–U–Au quartz–muscovite vein, hosted in phyllites in an exocontact to granites. The density calculated using the average empirical formula and unit-cell parameters is 5.55 g/cm3. The average chemical composition measured by means of electron microprobe is as follows (wt.%): P2O5 29.68, As2O5 0.15, SiO2 0.07, ThO2 0.01, UO2 0.04, Y2O3 1.30, La2O3 3.19, Ce2O3 6.93, Pr2O3 1.12, Nd2O3 10.56, Sm2O3 17.36, Eu2O3 1.49, Gd2O3 22.84, Tb2O3 1.57, Dy2O3 2.27, CaO 0.21, total 99.67. The corresponding empirical formula calculated on the basis of 4 oxygen atoms is: (Gd0.30Sm0.24Nd0.15Ce0.10La0.05Dy0.03Y0.03Tb0.02Eu0.02Pr0.02Ca0.01)0.98P1.01O4. The ideal formula is GdPO4. The monazite-type structure has been confirmed by micro-Raman spectroscopy and selected-area electron diffraction. Monazite-(Gd) is monoclinic, space group P21/n, a = 6.703(1) Å, b = 6.914(1) Å, c = 6.383(1) Å, β = 103.8(1)°, V = 287.3(1) Å3 and Z = 4. The middle REE enrichment of monazite-(Gd) is shared with the associated Gd-bearing xenotime-(Y) to ‘xenotime-(Gd)’ and Gd-bearing hingganite-(Y). This exotic REE signature and precipitation of Gd-bearing mineral assemblage is a product of selective complexing and enrichment in middle REE in low-temperature hydrothermal fluids by alteration of primary uraninite, brannerite and fluorapatite on a micro-scale. The new mineral is named as an analogue of monazite-(La), monazite-(Ce), monazite-(Nd) and monazite-(Sm) but with Gd dominant among the REE.

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 > 3.5%, graphitized organic matter > 25%, and resistivity < 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.

Andrieslombaardite, RhSbS, a new platinum-group mineral from the platiniferous Onverwacht Pipe, Republic of South Africa

Abstract A hundred years after the discovery of the Merensky Reef in 1924, it is appropriate to present the new mineral andrieslombaardite in honour of Andries Frederik Lombaard who was instrumental in its discovery. Andrieslombaardite, RhSbS, was first described as an unknown mineral from placer deposits associated with the Tulameen Alaskan-Uralian type complex, British Colombia, Canada (Raicevic and Cabri, 1976) but has since been reported from several other deposits including the platiniferous Driekop, Mooihoek, and Onverwacht pipes in the eastern Bushveld Complex, South Africa. The mineral and the name were approved by the Commission on New Minerals Nomenclature and Classification (CNMNC) of the International Mineralogical Association (IMA no. 2022-076) based on data in the co-type samples from Onverwacht and a co-type sample from the Yubdo stream, Birbir River, Ethiopia. Andrieslombaardite in the Onverwacht sample is a single 8 x 20 μm grain attached to laurite in a matrix of altered silicate and Fe-oxyhydroxide minerals. In the Yubdo samples, there are many grains of pale brownish gray andrieslombaardite up to 25 x 55 μm in size, included in Pt-Fe alloys, some associated with erlichmanite, and others attached to bornite and chalcopyrite. The reflectance values (R%) measured in air and in oil at the COM wavelengths are 48.3 and 33.0 (470 nm), 49.3 and 34.0 (546 nm), 51.0 and 35.9 (589 nm), and 51.8 and 36.7 (650 nm). The colour values x, y, Y, λd, and Pe in air are 0.317, 0.322, 50.3, 580, and 3.2, and in oil are 0.319, 0.324, 35.6, 579, and 4.5. The composition of andrieslombaardite is ideally RhSbS, but it contains variable amounts of Fe, Pt, Pd, and Ir that may substitute for Rh. The mineral is cubic with unit-cell dimensions of a = 6.0278(4) Å, V = 219.01(6) Å3 and Z = 4. It was synthesised at 400 and 550°C using stoichiometric elemental amounts. It is a member of the cobaltite group. The mineralisation of the intrusive dunite pipes was probably introduced at high temperatures, under magmatic conditions. The primary assemblages were to a certain degree overprinted and redistributed by low-temperature hydrothermal fluids. The Pt-Fe alloys from Yubdo containing PGM inclusions such as andrieslombaardite in the Yubdo-Alaskan-type complex were formed at some post-magmatic stage owing to PGE remobilisation during hydrothermal or metamorphic episodes.

Tourmalines in the Namacotche Li-Cs-Ta granitic pegmatite group, Mozambique: crystal chemistry and origin

The field work, backscattered electron images and detailed microanalyses of three generations of tourmaline from the Namacotche LCT pegmatites allows de distinction between the compositional magmatic and hydrothermal tourmalines. The generation 1 occurs in the outer intermediate zone of the pegmatite. It consists of zoned crystals with an oscillatory inner core of foitite and schorl, an outer core of schorl and an Fe-rich fluor-elbaite rim. Unzoned Fe-rich fluor-elbaite crystals occur in the inner intermediate zone of the pegmatite. All the crystals are derived by fractionation of a (Al, Li, B)-rich pegmatite melt. However, the rim of zoned crystals and some compositions of unzoned crystals show evidence of hydrothermal fluids, as they plot outside the fractionation trends. The zoned fluor-elbaite crystals of the generation 2 are from the inner intermediate zone of the pegmatite. They have a pink core and a green rim. The rim has higher YFe2+, Na, F contents YFe2+/(YFe2++Licalc.) value and lower Si, YAl, Licalc. and X-site vacancy contents, X-vacancy/(Na+X-vacancy) value than the core. Both zones are hydrothermal. The rim is an overgrowth. The fluor-elbaite gemmy crystals of the generation 3 occur in sheared breccia blasts and clasts with a cookeite matrix. They depend mainly on the fluid-rich hydrothermal environment of low temperatures (280-150ºC). Some from the cycle a may result from the dissolution of magmatic tourmaline crystals of the generation 1 from the sheared outer and inner intermediate zones of the pegmatite due to reaction with late fluids in chemical disequilibrium, followed by growth of tourmaline with low temperature hydrothermal fluids. The evolution from the cycle a to the cycle b and to the cycle c of the generation 3 implies that the hydrothermal reacting fluids were undergoing fractionation and becoming richer in Li and poorer in Fe2+ during the late hydrothermal crystallization of the pegmatites.

Hydrothermal alteration and corresponding reservoir significance of the Permian Emeishan basaltic lavas, west Sichuan, China

Reservoir spaces, such as vesicles, ‘secondary’ amygdales, dissolution caverns and geodes, are widely developed in the Emeishan basaltic lavas in the Zhoudaping section, Leshan, west Sichuan, China. The dissolution characteristics, cementation sequences, hydrothermal activity stages, as well as fluid types, and their effects on the reservoir capacity were investigated for each stage. Macroscopically, the dissolution features present as irregular dissolution zones, which are characterised by a light red colour. Microscopically, in the dissolved zone, the cementation-filling minerals are associated with complex fill sequences, such as quartz/laumontite/chlorite–chlorite/saponite–epidote/celadonite–cryptocrystalline chlorite–laumontite/calcite/quartz. The U–Pb geochronology shows that the age of chlorite fill in amygdales is 235.3 ± 19.6 Ma; the coarse-crystalline quartz inside dissolution caverns/geodes, 124.47 ± 5.63 to 123.84 ± 5.63 Ma; and the siliceous mineral-filled amygdales, 118.34 ± 3.70 to 114.08 ± 3.76 Ma, which correspond to the early Late Triassic and the mid–late Early Cretaceous, respectively. Combined with geochemical characteristics of post-dissolution fill, the amygdales are affected by two stages of hydrothermal activity: chlorite filling of the amygdales corresponds to post-magma hydrothermal fluids during the early Late Triassic, and the siliceous mineral-fill in amygdales corresponds to deep-sourced hydrothermal fluids during the mid–late Early Cretaceous. The geodes/dissolution caverns result from a single stage of hydrothermal activity related to the mid–late Early Cretaceous deep-source low-temperature hydrothermal fluid. The Late Triassic post-magma hydrothermal fluids are generally destructive to pores, and tectonic-related dissolution of deep-sourced hydrothermal fluids has a positive effect on the formation of reservoir spaces, greatly enhancing fluid storage and flow capacities of the volcanic lavas. We recommend the multi-stage hydrothermal dissolution during Late Triassic–Early Cretaceous and faults, fractures and columnar joints be the focus of hydrocarbon exploration. KEY POINTS The reservoir spaces developed in the Zhoudaping section, such as amygdales, dissolution caverns and geodes, were controlled by different stages and types of hydrothermal alteration. Amygdales are the product of two hydrothermal events, which correspond to post-magma hydrothermal fluids during the early Late Triassic and the deep-sourced hydrothermal fluids of the mid–late Early Cretaceous. Geodes/dissolution caverns are affected by deep-source low-temperature hydrothermal fluids in the mid–late Early Cretaceous. The multi-stage hydrothermal dissolution during the Late Triassic–Early Cretaceous and faults, fractures and columnar joints should be the focus of hydrocarbon exploration.

Mohammadabad Manganese deposit, southwest Sabzevar basin, Iran: Evidence of sea-floor exhalation and geochemical studies in the late Cretaceous volcano-sedimentary sequence

The southwest Sabzevar basin in northeast Iran is one of the most important areas for volcanogenic stratiform manganese deposits. The Mohammadabad Mn deposit, found in this basin, is hosted by the upper late Cretaceous marly tuffs in a region that has an active history of tectonism. Their geology, mineralogy and geochemistry, including major, trace and rare earth elements (REE), are described in this work. The main ore minerals include pyrolusite, psilomelane, cryptomelane, with minor braunite and manganite. Four styles of manganese mineralization are recognized: (1) layered; (2) nodular; (3) disseminated; and (4) replacement to massive. Regardless of style, pyrolusite, psilomelane, and cryptomelane usually tend to parallel the stratification of sediments, while braunite veins occur in high angle fractures. The replacement of radiolarian and foraminiferal fossils by manganese minerals during diagenesis near the seawater-sediment interface suggests that mineralization occurred in oxygen-rich conditions under the influence of low-temperature hydrothermal fluids. The geochemistry of trace elements of manganese oxides and rare earth elements gives clear evidence of hydrothermal-exhalative origin for Mohammadabad deposit. In general, ore minerals have Co/Ni ratios above 0.12, and U/Th ratios vary from 0.13 to 11.29. The presence of negative Eu anomalies in manganese minerals shows that the ore-forming fluids were generally low-temperature and oxic during mineral formation. In-situ mineralogy studies based on SEM-EDS have distinguished syngeneic and diagenetic Mn systems during the formation of manganese mineralization. The Mohammadabad deposit is considered a typical case of volcanic hydrothermal exhalative-diagenetic Mn mineralization, in which minerals deposited when hydrothermal fluid was released from oxic to dysoxic water columns.

Hydrothermal fluid signatures of the Yulong porphyry Cu-Mo deposit: Clues from the composition and U-Pb dating of W-bearing rutile

AbstractHydrothermal rutile (TiO2) is a widely distributed accessory mineral in hydrothermal veins or alteration assemblages of porphyry deposits and provides important information for further understanding hydrothermal fluid signatures. This study determines the geochemical composition and U-Pb dates of hydrothermal rutile from the Yulong porphyry Cu-Mo deposit in east Tibet, China. Three types of TiO2 polymorphs have been identified based on their Raman spectroscopic, textural, and chemical characteristics. (1) Brookite and anatase pseudomorphs after titanite in a fine-grained matrix, indicating low-temperature hydrothermal fluids destabilizing primary Ti-bearing minerals during argillic alteration (type-I). (2) Elongated and prismatic rutile present in hydrothermal veins or in clusters in accompanying alteration envelope characterized by weak zoning (type-II). And (3) rutile intergrown with sulfides in hydrothermal veins, characterized by well-developed patchy and sector zoning (type-III). In contrast to the type-I and type-II TiO2 polymorphs, tungsten is enriched in backscattered bright patches and sector zones in type-III rutile, which is due to the substitution of W6+ in the Ti4+ octahedral site. The mechanism of the enrichment of tungsten is effectively driven by the halogen-rich (F, Cl) aqueous fluids during hydrothermal mineralization. In situ U-Pb dating of the type-III rutile yields a lower intercept age of 41.8 ± 1.2 Ma, which brackets the timing of the Cu-Mo mineralization. The relationship between rutile textures and composition indicates that W-bearing rutile can serve as a recorder of hydrothermal processes in porphyry Cu deposits.

Formation of the Rock Canyon Creek carbonate-hosted REE–F–Ba deposit, British Columbia, Canada: Constraints from Mg-Sr isotopes of dolomite, calcite, and fluorite

The Rock Canyon Creek REE–F–Ba deposit is a carbonate-hosted REE deposit located in the Alkaline Province of British Columbia, Canada, which hosts most REE mineralization. It shares tectonic, stratigraphic and structural similarities with nearby Mississippi Valley-type deposits. To constrain the dolomitization and mineralization processes, the δ26Mg, 87Sr/86Sr, and elemental compositions of dolomite, calcite, and fluorite were determined. The δ26Mg values of dolomite from the unmineralized zone (−1.83 ‰ and −1.67 ‰) are consistent with marine evaporative dolomite, but those from the mineralized zone (−0.97 ‰ to −0.17 ‰) are higher and more variable. The linear 87Sr/86Sr–Sr/Mg relationships, both in the dolomite and calcite from the unmineralized zone, suggest dolomitization in an evaporative marine environment. The high δ26Mg values with large variation and the non-stoichiometric Ca/Mg ratios in the dolomite from the mineralized zone suggest that this dolomite interacted with a relatively low-temperature hydrothermal fluid (<200 °C). Considering the Na, Ca, Sr, Ba, and LREE-enrichment and low 87Sr/86Sr signature in the dolomite from the mineralized zone as well as mineral paragenesis in the deposit, the most plausible scenario for the formation of the deposit is that marine-evaporitic dolomite re-equilibrated with basinal fluids along permeable zones, and at a later stage, carbohydrothermal REE-bearing fluids infiltrated into the Rock Canyon Creek brecciated zone and deposited the REE mineralization. Late-stage, post-mineralization calcite veins and iron oxides formed in the upper part of the deposit under supergene conditions, as suggested by combination of textural observations, REE patterns, and differences in isotopic compositions between dolomite and calcite from the mineralized zone. This study demonstrates that δ26Mg, 87Sr/86Sr, and element/Mg ratios in carbonate minerals are useful for characterizing mineralizing fluids in carbonate-hosted deposits, and discriminating mineralization-related dolomite from marine evaporative dolomite and unmineralized hydrothermal dolomite.

Gadolinium-dominant monazite and xenotime: Selective hydrothermal enrichment of middle REE during low-temperature alteration of uraninite, brannerite, and fluorapatite (the Zimná Voda REE-U-Au quartz vein, Western Carpathians, Slovakia)

AbstractA hydrothermal quartz vein with REE-U-Au mineralization in the Zimná Voda (Gemeric Unit, Western Carpathians, Slovakia) is associated with contact metamorphism between Permian granites and host phyllites and metaquartzites. It contains unique REE minerals of the monazite and xenotime groups. Monazite-(Ce), monazite-(Nd), monazite-(Sm), and Gd-dominant monazite [“monazite-(Gd)”], along with xenotime-(Y) to Gd-dominant xenotime [“xenotime-(Gd)”] and Gd-rich hingganite-(Y) show heterogeneous compositions and reflect a strong fractionation trend toward the enrichment of MREE (Sm to Dy), particularly Gd. Here, the gadolinium abundance reported in “monazite-(Gd)” (≤23.4 wt% Gd2O3) and Gd-rich xenotime-(Y) to “xenotime-(Gd)” (≤28.7 wt% Gd2O3) and accompanied by Gd-rich hingganite-(Y) (≤15.8 wt% Gd2O3), is among the highest Gd concentrations ever reported in natural minerals. The Gd-richest compositions show the following formulas: (Gd0.31Sm0.24 Nd0.15Ce0.10La0.05Dy0.03Y0.03…)0.98PO4 [“monazite-(Gd)”], (Gd0.36Y0.32Dy0.13Sm0.08Tb0.05…)0.98 (P0.96As0.04)1.00O4 [“xenotime-(Gd)”] and (Y0.71Gd0.43Dy0.23Sm0.22Tb0.06Er0.04Nd0.06…Ca0.06)1.96 (☐0.87Fe0.132+)1.00(Be1.82B0.18)2.00(Si1.90As0.10)2.00O8(OH1.70O0.30)2.00 [hingganite-(Y)]. The MREE-rich monazites, xenotimes, and hingganite-(Y) precipitated in response to the alteration of primary uraninite, brannerite, and fluorapatite by low-temperature hydrothermal fluids of heterogeneous compositions on a microscale. These are responsible for the strong enrichment of individual MREE, especially Gd in the secondary minerals. This is accompanied by the advancing development of the W-type tetrad effect on REE through monazite species. The substantial incorporation of Gd into both REE-selective monazite and xenotime structures that are accompanied by LREE vs. HREE segregation indicates the possibility of differently sized REE3+ miscibility in REEPO4 solid solutions, as well as the stabilization of the Gd-rich orthophosphate structure by substitution of the remaining A-site cations with smaller HREE+Y in the xenotime-type, and/or larger LREE in the monazite-type structure.

Uranium in Chinese coals: Concentration, spatial distribution, and modes of occurrence

Uranium in coals is an environmental radionuclide with resource utilization value. To comprehensively understand the prevalence of uranium in Chinese coals, the concentration, spatial distribution, and modes of occurrence were analyzed based on the data acquired from 1326 coal samples. Chinese coals are relatively rich in uranium, with the arithmetic and weighted average concentrations of 3.08 and 2.38 mg/kg, respectively. The regions with high uranium enrichment in coals are Guizhou, Guangxi, Yunnan, Sichuan and Chongqing, which are mainly located in southwestern China. The uranium was more enriched in Late Permian coal and medium-to-high metamorphic coal. Organic matter is the main carrier of uranium in coals, followed by silicates and sulfides. The factors affecting uranium enrichment in coal at the national scale include magma intrusions, volcanic ash, seawater influence, low-temperature hydrothermal fluids, and paleoclimate. This paper provides a reference for further research on environmental management and resource utilization of uranium in Chinese coals.

Petrological and micrometer-scale geochemical constraints on chert origins in the Dengying Formation, Yangtze Block, South China: Implications for Late Ediacaran hydrothermal activity and tectonic setting

The Ediacaran–Cambrian (E–C) transition was a key interval in geological history. Chert was widely distributed in the Yangtze Block at the end of the Ediacaran and may have recorded important information about the coevolution of earth systems in this period. Five lithofacies of chert were identified in the northern margin of the Yangtze Platform. Breccias with crustiform chert were formed by hydrothermal fracturing of dolomite to form breccias in vents, which were immediately immersed and crusted by a silicon-rich fluid. This silicon-rich fluid was deposited directly onto the inner walls of the conduits to form chert linings. The silicon-rich fluid filled the water-fractured fissures to form spider-veinlet chert and then mixed with residual seawater in primary pores of the bedding to form void-filling cherts. Finally, the dolomite far away from the conduits was replaced by the silicon-rich fluid, forming chert bands. In the vents, there are typical hydrothermal mineral assemblages of quartz, pyrite, barite, Fe–Mn metal microparticles, and saddle dolomite and these assemblages contain abnormally high-temperature inclusions. The rare-earth element (REE-Y) patterns of void-filling chert, crustiform chert, and saddle dolomite show that they originated from normal seawater influenced by a low-temperature hydrothermal fluid, silicon-rich hydrothermal fluid, and high-temperature hydrothermal fluid, respectively. The trace element ratios and Si isotope contents of chert also show that deposition was mainly caused by hydrothermal solutions. All these data indicate that the various types of cherts at the top of the Dengying Formation near the synsedimentary fault zone constitute typical siliceous sinter. There was massive upward migration of silicon-rich hydrothermal fluids from depth to the seafloor during the E–C transition, which resulted in abnormally silicon-rich seawater and a widespread distribution of various cherts in the Yangtze Block. The identification of siliceous sinter in synsedimentary faults indicates an intense extension of the northern margin or even of the entire Yangtze Block during the E–C transition. This may be related to the combined effects of slab pull on the western side and rollback on the northeastern side of the Yangtze Block during the convergence of Gondwana.

Genetic model for early Cambrian reef limestone-hosted Pb-Zn deposits in the world-class Huayuan orefield, South China: New insights from mineralogy, fluorite geochemistry and sulfides in situ S-Pb isotopes

The Xiangxi-Qiandong metallogenic belt (>300 Mt sulfide ores @∼4.0 wt% Pb + Zn), located at the southeastern margin of the Yangtze Block, is one of the important Pb-Zn producers in China. Although carbonate-hosted Pb-Zn deposits in this district have attracted great attention during past decades, many issues, particularly the ore genesis and geodynamic setting, remain unclear. In this study, we take the Limei and Yutang deposits as typical case studies, using detailed geology, rare earth elements and yttrium (REY) geochemistry of fluorite and sulfides in situ S-Pb isotopes, to propose a new model for early Cambrian reef limestone-hosted Pb-Zn deposits in the district. REY contents (0.47 to 8.67 ppm; mean = 3.99 ppm) in fluorite from Limei and Yutang slightly deplete in LREE and HREE relative to MREE, indicating that the REEs and metals were transported predominantly as chloride complexes in a low-temperature (<200 °C) hydrothermal fluid with high saline. New δ34S values of sulfides (+27.66 to + 35.46‰ in Limei and + 24.80 to + 36.07‰ in Yutang) imply that S2- was originated from evaporite sulfate within ore-hosting strata via thermo-chemical reduction (TSR) as the presence of reducing agents (bioclastic limestone and organic matter). In situ δ34S values show a slightly large range (variation up to 11.27‰) and vary significantly within single grain (up to 4.60‰), which may be inherited from the S composition of H2S in the original fluid. In situ Pb isotopic ratios of sulfides from Limei (206Pb/204Pb = 18.001–18.269, 207Pb/204Pb = 15.645–15.796 and 208Pb/204Pb = 38.243–38.597) and Yutang (206Pb/204Pb = 18.135–18.384, 207Pb/204Pb = 15.714–15.924 and 208Pb/204Pb = 38.347–38.874) positively correlates in Pb-Pb diagrams, indicating the mineralizing metals are mainly derived from Proterozoic basement rocks with an amount of contribution from early Cambrian sedimentary rocks. Mineralogy, fluorite REY geochemistry and sulfides in situ S-Pb isotopes together with previously reported mineralization ages suggest that the mixing of metal-rich fluid from basement rocks and the H2S-rich fluid originated from ore-hosting strata plays an important role in forming the Pb-Zn deposits of Limei and Yutang. This study provides a typical example for better understanding the genesis and geodynamic setting of MVT deposits in the foreland basin, South China.