CO2-bearing Fluids Research Articles

Origin and Characteristics of Ore-Forming Fluids of the Abu Gaharish Orogenic Gold Deposits, Central Eastern Desert, Egypt: Evidence from Alteration Geochemistry, Mineral Chemistry and Fluid Inclusions

AbstractThe Abu Gaharish mineralization comprises Au-rich NNE-trending quartz veins, and their surrounding shear zone is found hosted within a Neoproterozoic Sn-W-bearing monzogranite pluton and intersects the metavolcano-sedimentary assemblage at its eastern contact. The ore mineralogy consists of pyrite, galena, chalcopyrite, sphalerite, and gold, with secondary vanadinite occurring after galena and hematite after pyrite. Paragenesis reveals two generations of pyrite and galena, where gold formed mainly during the early sulfidation stage and mobilized upon later deformation events and incipient recrystallization. Mass balance calculations on the alteration zones reveal that the inputs upon alteration included Al2O3, Fe2O3, K2O, MgO, P2O5 W, Rb, Cu, Zn, Pb, V, Cr, Mo, Co, Sn, As, and U, whereas the outputs comprised SiO2, Na2O, CaO, MnO, Sr, Ba, Zr, Y, Th, Nb, and Ni, respectively, in decreasing order. The low contents of granitophile elements (such as Mo, Sn, and W) in the quartz veins at Abu Gaharish suggest that the gold-sulfide-quartz veins have no linkage with granitoid intrusion. However, the enrichment of these elements in the proximal alteration zone is attributed to their leaching by hydrothermal fluids from anomalous zones. The fluid inclusion data observed in quartz showcases the existence of CO2-bearing low-salinity fluids mixed with Mg, Na, and K chlorides under mesothermal conditions during the ore deposition process. This aligns with the formation of orogenic gold deposits as a consequence of the metamorphic devolatilization of the adjacent metavolcano-sedimentary succession. The characteristics of mineralizations at Abu Gaharish display resemblances to orogenic gold deposits and refute the intrusion-related model.

Experimental constraints on serpentinite carbonation in the presence of a H2O–CO2–NaCl fluid

Serpentinite carbonation contributes to the deep carbon (C) cycle. Recently, geophysical and numerical studies have inferred considerable hydrothermal alteration in plate bending faults, opening the possibility of significant C storage in the slab mantle. However, there is a lack of quantitative determination of C uptake in serpentinized mantle rocks. Here, we experimentally constrain serpentinite carbonation in H2O–CO2–NaCl fluids to estimate C uptake in hydrated mantle rocks. We find that serpentinite carbonation results in the formation of talc and magnesite along the serpentinite surface. The presence of porous reaction zones (49.2% porosity) promotes the progress of carbonation reactions through a continuous supply of CO2-bearing fluids to the reaction front. Added NaCl effectively decreases the serpentinite carbonation efficiency, particularly at low salinities (< 5.0 wt%), which is likely attributed to the reduction in fluid pH and the transport rate of reactants, and the increase in magnesite solubility. Based on previous and our experiments, we fit an empirical equation for the reaction rate of serpentinite carbonation. Extrapolation of this equation to depths of plate bending fault systems suggests that serpentinite carbonation may contribute to an influx of up to 7.3–28.5 Mt C/yr in subduction zones. Our results provide new insights into serpentinite carbonation in environments with high fluid salinities and potentially contribute to the understanding of the C cycle in subduction zones.

Carbonatization and silicification of ophiolitic ultramafic rocks and formation of gold-bearing listvenites in the Arabian-Nubian shield: A case study from the Al-Barramiya district

Late Neoproterozoic mantle section in the Gabal Al-Barramiya area, the northwestern corner of the Arabian-Nubian Shield (ANS), contains variably serpentinized peridotites that are highly altered along shear zones and thrust planes to form gold-bearing listvenites. They can be categorized into carbonate listvenite, silica-carbonate listvenite and silica listvenite (birbirite). Carbonate listvenite is characterized by the presence of schistosity and deformation fabrics similar to the host serpentinites, but such fabrics are absent in the silica-carbonate and silica listvenites, suggesting that they postdate carbonate listvenite and serpentinization. The presence of listvenites along shears zones and the presence of relics of serpentine and Cr-spinel reflects their formation through metasomatism of ultramafic rocks by hydrothermal fluids circulating along the thrust faults. Silica-carbonate listvenite is characterized by the presence of fuchsite and is enriched in Zn, Pb, Cu, Ag, and Au. Rare earth element (REE) contents differ between the studied listvenites. Silica -carbonate listvenite has the lowest total REE (∑₌0.98–2.56 ppm), whereas the silica listvenite contains the highest total of REE (∑ ₌ 15.70–21.42 ppm). Based on the above, carbonate listvenite is the earliest to form by the infiltration of CO2–bearing fluids released during serpentinization of the original fore-arc peridotite slab, followed by formation of silica-carbonate listvenite due to the activities of SiO2–saturation and CO2-bearing fluids released during ophiolite obduction. Fuchsite in silica-carbonate listvenite formed as a result of metasomatic reactions of Si- and K-rich fluids with Cr-spinel due to hydrothermal alteration of serpentinized peridotite. Silica listvenite formed at the final stage by the silicification of the early formed silica-carbonate listvenite. Listvenitization of the mantle section of the Al-Barramiya ophiolite led to concentration of Au, Pb, Zn, Cu and Ag. The silica-carbonate listvenite contains higher concentration of gold (899–2199 ppb) than the carbonate listvenite (119–191 ppb) and silica listvenite (156–233 ppb).

Influence of coal rock on tight sandstone reservoirs in coal seam roofs: A case study of the lower jurassic in the Taibei sag, Turpan-Hami Basin, China

After shale gas, coalbed methane and gas hydrate, coal measure gas has become an important new unconventional resource, for which exploration to depths of >3000 m are taking place in China. However, owing to unusual geological conditions and as yet inadequate exploration technology the current level of exploration is low. The acidic water medium in coal-bearing strata affects the diagenesis of adjacent tight sandstone reservoirs, thereby influencing reservoir quality. However, the current understanding of the impact mechanism of coal seams on neighboring tight reservoirs is insufficient, constraining the further exploration of coal measure gas. In order to reveal the influence of coal rock on a tight sandstone reservoir in its roof, we study the coal-bearing strata of the Xishanyao Formation in the Taibei Sag of the Turpan-Hami Basin using cast thin sections, physical property tests, XRD analysis, carbon and oxygen isotopes, high-pressure mercury intrusion and low-temperature N2 adsorption. The carbonate cement in the sandstone reservoir of the coal seam roof was formed by the decarboxylation of organic acid. The organic acid, containing CO2 generated by coal rock hydrocarbon generation, has modified the tight sandstone reservoir of the coal seam roof via dissolution. This has improved the physical properties and pore throat structure of the tight sandstone reservoir close to the coal-sandstone interface. The amount of improvement extends to about 2 m into the sandstone. During the upward transport of fluid, the pre-existing carbonate cement dissolves and then precipitates, which causes the CO2 generated by the organic acid decarboxylation to exchange carbon with the carbon isotopes in the pre-existing carbonate cement. Due to the slow upward diffusion rate and limited diffusion distance of the CO2-bearing fluids, the carbonate cement exhibits gradually heavier δ13CPDB values with increasing distance from the coal-sandstone interface.

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

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

Lithological discrimination of the Fawakhir-Atalla belt in the Central Eastern Desert of Egypt based on Landsat-9 remote sensing data, airborne gamma-ray spectrometry, field and petrographic investigations with implications on the evolution of the Arabian Nubian Shield

The Central Eastern Desert (CED) is a key territory for understanding the evolution of the Arabian Nubian Shield (ANS) in Egypt as it contains Cryogenian-Tonian ensimatic supracrustal assemblages, such as ophiolitic and arc volcanic rocks, as well as gold deposits. So, it has been the subject of extensive studies over the last two decades. However, the lithological mapping of the Fawakhir-Atalla belt, located west of the Meatiq gneiss dome (infrastructure) of the CED, is still debated, as the magmatic texture of some rocks was partially obscured owing to the shearing and alteration related to the Najd Fault System, mantle CO2-bearing fluid, and igneous activity in the final stage of the Pan-African Orogeny. In this regard, integrated studies of airborne gamma-ray spectrometry and Landsat-9 satellite imagery processing techniques, as well as field and petrographic investigations, have been used for the lithological mapping of the belt. The results led to the following sequence; ophiolitic rocks > island arc assemblages > older granitoids (syn-tectonic subduction-related) > Hammamat Group (molasse-type origin) > post-Hammamat felsite > younger granite (post-tectonic suture-related). The applied color composite images, selective band ratios, and image transformation techniques show a clear distinction between rock units. Older granitoids are tonalite to quartz diorite, while younger granites are monzo-to syenogranite. They are well-discriminated from each other using band ratios, and younger granites have the highest K, eU, and eTh values coherent with the post-Hammamat felsite. The image enhancement and image transformation techniques show a clear discrepancy between the mélange rocks and Hammamat conglomerates. Mélange rocks are composed of fragments embedded in a foliated matrix, while Hammamat conglomerates are grain-supported with pebbles of volcanic source and have higher K, eU, and eTh values. Volcanic rocks in the belt are not a part of the Dokhan series as they are metamorphosed with a composition range from meta-basalts to meta-rhyolite, and show mainly aphanitic to infrequently porphyritic textures, which are typical of island arc metavolcanics.

High-precision analysis of carbon isotopic composition for individual CO2 inclusions via Raman spectroscopy: Addressing issues arising from the laser-heating effects

The carbon isotopic composition of carbon dioxide fluid inclusions trapped within minerals reflects the origin and evolution of the CO2-bearing fluids and melts. Recently, we developed a highly accurate method using Raman spectroscopy to determine the carbon isotopic composition of CO2 fluid inclusions, by simultaneously collecting 13CO2 and hot bands at a controlled temperature, and using the peak height ratio of 13CO2 and one of hot bands near 1410 cm−1 (HR) to determine δ13C value. This microanalytical technique enables precise measurements of the δ13C values of different CO2 fluid inclusions within zoned mineral crystals to reveal the multiple-stages evolution of CO2-bearing fluids and melts. However, when studying fluid inclusions hosted within high laser heating coefficient minerals such as olivine and pyroxene in mantle xenoliths, local temperature near the inclusions will be higher than the temperature controlled by heating-cooling stage. To address this issue, we examined the effects of laser heating on CO2 isotopic standard samples sealed in the silica capillary, and developed a novel procedure to determine the δ13C values of natural fluid inclusions by using two CO2 standard samples with known carbon isotopic compositions. The proposed workflow successfully determines the δ13C values of natural CO2 inclusions, with an average deviation of 0.58 ‰ between the measurements and the model.

Origin of Zn-Pb Mineralization of the Vein Bt23C, Bytíz Deposit, Příbram Uranium and Base-Metal Ore District, Czech Republic: Constraints from Occurrence of Immiscible Aqueous–Carbonic Fluids

The mineralogical, fluid inclusion, and stable isotope (C, O) study was conducted on a Late Variscan Zn-Pb vein Bt23C, Příbram uranium and base-metal district, Bohemian Massif, Czech Republic. The vein is hosted by folded Proterozoic clastic sediments in exo-contact of a Devonian-to-Lower-Carboniferous granitic pluton. Siderite, dolomite-ankerite, calcite, quartz, baryte, galena, sphalerite, V-rich mica (roscoelite to an unnamed V-analogue of illite), and chlorite (chamosite) form the studied vein samples. The banded texture of the vein was modified by the episodic dissolution of earlier carbonates and/or sphalerite. Petrographic, microthermometric, and Raman studies of fluid inclusions proved a complicated fluid evolution, related to the activity of aqueous fluids and to an episode involving an aqueous–carbonic fluid mixture. Homogenization temperatures of aqueous inclusions decreased from ~210 to ~50 °C during the evolution of the vein, and salinity varied significantly from pure water up to 27 wt.% NaCl eq. The aqueous–carbonic fluid inclusions hosted by late quartz show highly variable phase compositions caused by the entrapment of accidental mixtures of a carbonic and an aqueous phase. Carbonic fluid is dominated by CO2 with minor CH4 and N2, and the associated aqueous solution has a medium salinity (6–14 wt.% NaCl eq.). The low calculated fluid δ18O values (−4.7 to +3.6‰ V-SMOW) suggest a predominance of surface waters during the crystallization of dolomite-ankerite and calcite, combined with a well-mixed source of carbon with δ13C values ranging between −8.2 and −10.5‰ V-PDB. The participation of three fluid endmembers is probable: (i) early high-temperature high-salinity Na&gt;Ca-Cl fluids from an unspecified “deep” source; (ii) late low-salinity low-temperature waters, likely infiltrating from overlying Permian freshwater partly evaporated piedmont basins; (iii) late high-salinity chloridic solutions with both high and low Ca/Na ratios, which can represent externally derived marine brines, and/or local shield brines. The source of volatiles can be (i) in deep crust, (ii) from interactions of fluids with sedimentary wall rocks and/or (iii) in overlying Permian piedmont basins containing, in places, coal seams. The event dealing with heterogeneous CO2-bearing fluids yielded constraints on pressure conditions of ore formation (100–270 bar) as well as on the clarification of some additional genetic aspects of the Příbram’s ores, including the reasons for the widespread dissolution of older vein fill, the possible re-cycling of some ore-forming components, pH changes, and occasionally observed carbon isotope shift due to CO2 degassing.

Discovery, geological setting and mineralization of the Shuvuutai molybdenum deposit, central-southern Mongolia

We document the newly discovered Shuvuutai Molybdenum (Mo) porphyry deposit located in the central-east Mongolian volcanic/-plutonic belt of the southern Altaids. The deposit is characterized by quartz vein- and veinlet-disseminated-type Mo ore bodies mainly hosted in a Late Permian-Early Triassic granitic intrusion. In this study, we provide a detailed study that integrates detailed geology with petrographic, mineralogic, geochemical, and geochronologic date to determine the tectonic setting of the deposit. Fluid inclusion analysis is used to reconstruct the fluid evolution history of the Shuvuutai Mo mineralization system and to understand the origin of the deposit. The ore bodies occur mainly as veins, lenses, and pods in positions from inner intrusions through contact zones to the host rocks distal to causative intrusions. The host rocks are variable in lithology, including granites, porphyries, volcanic breccias and tuffs, and sedimentary rocks. Outward from ore bodies to host rocks, the wall rock alteration is zoned from potassic (K-feldspar-quartz-mica), through phyllic (quartz-sericite-chlorite-epidote), to propylitic or argillic alterations. Two samples from porphyry stock intrusions at Shuvuutai were selected for U–Pb zircon geochronology and trace element composition studies, including the ore-hosting monzodiorite porphyry and quartz syenite porphyry. Our new ages are consistent with, or slightly postdate published zircon U-Pb ages of early phase of monzodiorite porphyry (268–232 Ma) and the main phase of quartz syenite porphyry (251.6 ± 1.7 Ma). Hydrothermal mineralization generally includes four stages, from early to late, represented by (1) potassic feldspar-quartz veins or veinlets, (2) quartz-molybdenite stockworks, (3) quartz-sulfide stockworks, and (4) quartz ± carbonate veins or veinlets. The ore-forming fluids were initially magmatic in origin and show high-temperature and high-salinity, containing daughter mineral and CO2-bearing fluid inclusions; and eventually evolved to low-temperature, low-pressure, low-salinity and CO2-poor meteoric water. S isotopic compositions of sulfides from the Shuvuutai Mo porphyry deposit indicate that the source of the ore-forming material was derived from the felsic magma. The Central-Eastern Mongolian volcanic-plutonic belt continues from Mongolia into northeast China, where similar Mo deposits are not yet recognized, suggesting that a new exploration strategy, based on the characteristics and history of the Shuvuutai discovery, is needed for the Chinese segment of the Altaids.

Carbonates and intermediate-depth seismicity: Stable and unstable shear in altered subducting plates and overlying mantle

A model for intermediate-depth earthquakes of subduction zones is evaluated based on shear localization, shear heating, and runaway creep within thin carbonate layers in an altered downgoing oceanic plate and the overlying mantle wedge. Thermal shear instabilities in carbonate lenses add to potential mechanisms for intermediate-depth seismicity, which are based on serpentine dehydration and embrittlement of altered slabs or viscous shear instabilities in narrow fine-grained olivine shear zones. Peridotites in subducting plates and the overlying mantle wedge may be altered by reactions with CO2-bearing fluids sourced from seawater or the deep mantle, to form carbonate minerals, in addition to hydrous silicates. Effective viscosities of magnesian carbonates are higher than those for antigorite serpentine and they are markedly lower than those for H2O-saturated olivine. However, magnesian carbonates may extend to greater mantle depths than hydrous silicates at temperatures and pressures of subduction zones. Strain rates within altered downgoing mantle peridotites may be localized within carbonated layers following slab dehydration. A simple model of shear heating and temperature-sensitive creep of carbonate horizons, based on experimentally determined creep laws, predicts conditions of stable and unstable shear with strain rates up to 10/s, comparable to seismic velocities of frictional fault surfaces. Applied to intermediate-depth earthquakes of the Tonga subduction zone and the double Wadati-Benioff zone of NE Japan, this mechanism provides an alternative to the generation of earthquakes by dehydration embrittlement, beyond the stability of antigorite serpentine in subduction zones.

Comparative Experiments on the Role of CO2 in the Gold Distribution between Pyrite and a High-Salinity Fluid

Experimental studies were conducted to identify the physical and chemical features of gold’s behaviour in hydrothermal processes linked to ore formation and involving CO2 in oxidized deposits. With the aid of the autoclave method, in a temperature range of between 200 and 400 °C, the isochoric dependences of the PVT parameters of concentrated sulphate chloride fluids were plotted, both in the presence and absence of CO2. Our experiments established that concentrated sulphate–chloride fluids (22 wt % Na2SO4 + 2.2 wt % NaCl) that lack CO2 are characterized by a wide supercritical temperature range, with homogenization temperatures of between 250 and 325 °C. In the presence of CO2, the same type of fluids showed heterogenization at a molar fraction of XCO2 = 0.18 (t = 192 °C, P = 176 bar). The process of homogenization for these low-density and high-salinity fluids was impossible at temperatures between 375 and 400 °C and at pressures between 600 and 700 bar. The behaviour of gold was studied during its interaction with a basic composition fluid of sulphate–chloride. We applied the autoclave method under the conditions of a simultaneous synthesis of pyrite and gold dissolution (metallic Au), at a temperature of 340 °C and at a pressure of 440 bar. High Au concentrations (up to 4410 ppm of Au in CO2-bearing fluids) were attained at high gold solubilities (up to 13.5 ppm in the presence of CO2), owing to the process of Au reprecipitation within the pyrite phase. We did not detect Au in the pyrite when we used the XRD or SEM methods, which suggested that it might be present as invisible gold. High values of the distribution coefficient (KD = CAu(solid)/CAu(solution)) in the fluids lacking (KD = 62) and bearing CO2 (KD = 327) empirically confirmed the possibility that gold concentrates in pyrite in structurally non-binding forms.

Helvine Mineralization in Devonian-Carboniferous Skarns of the Oriental Pampean Ranges, Córdoba, Argentina: Mineralogy and Nature of Ore-Forming Fluids

AbstractHelvine [Be3Mn2+4(SiO4)3S] occurs in less than one meter-sized spotty concentrations in some calcic skarns of Córdoba province, Argentina. The local geology, mineral chemistry, paragenetic mineral associations, and the evolution of helvine mineralizing fluids were studied from two selected localities (i.e., the Chingolo scheelite mine and Casa la Plata). Helvine from the Chingolo scheelite mine occurs in idiomorphic crystals up to 15 cm long, partially intergrown with spessartine-rich garnet, and in part or totally included in vug-filling spar calcite in the prograde garnet-vesuvianite skarn zone developed between replaced aplite-pegmatite dikes and calcic phlogopite-bearing marbles. Helvine from Casa la Plata occurs abundantly in vein-like, fluorite-rich garnet-vesuvianite skarn associations, where tetrahedrons up to 2 cm long occur preferentially included in fluorite in an illite-sericite-chlorite strongly replaced schist. The composition of helvine from both localities does not differ from other worldwide known compositions. Associated garnet from both localities is enriched in molar subcalcic garnet, largely as spessartine. Clinochlore is a conspicuous phase that occurs both as late infills and/or replacing phases in both the Chingolo scheelite mine and Casa la Plata. Primary fluid inclusions from helvine of both localities suggest that helvine deposited from moderate to high temperature and salinity aqueous fluids of likely magmatic origin. In both localities a late influx of gas-rich, CO2-bearing, moderate temperature, and moderate to low salinity fluid was trapped as secondary fluid inclusions. At the Chingolo scheelite mine, CO2-bearing fluids likely originated from decarbonation along the skarnification reaction front distanced from the prograde zone at lower temperature. In both studied areas, the latest trapped secondary fluids were of lower temperature and lower salinity. Pressure-corrected homogenization temperatures between 1.8 and 2.0 kbar sustain trapping temperatures for primary fluid inclusions within the 510–610 °C range for both localities. In the Chingolo scheelite mine, helvine formed at the contact zone between Ordovician aplite-pegmatites and Cambrian marbles that differentially reacted with infiltrated distal metasomatic-hydrothermal Be-bearing fluids fractionated from evolved granitic facies and/or pegmatites of the neighboring Devonian to Carboniferous Achala Batholith. Calculated δ18OH2O in equilibrium with garnet at ∼575 °C yielded δ18OH2O = 11.1 or 12.2‰. These heavy δ18OH2O values may derive from a magmatic fluid source possibly enriched in 18O from marbles or any other metasedimentary country rock during skarnification. This interpretation is supported by δ18OH2O values (8.3 to 10.1‰) and heavy δD values (−21.6 to −20.6‰) from retrograde epidote of other neighboring scheelite mines related to the Chingolo scheelite mine. The presence of beryl partially replaced by bertrandite + K-feldspar, non-paragenetically associated with helvine, confirms that early prograde crystallization conditions switched from a high temperature, subaluminous environment to a lower temperature, aluminous and increasingly acidic environment toward the retrograde skarn stage. At Casa la Plata, Cambrian schists and marble-amphibolite were also skarnified after the circulation of Be-bearing fluids derived from an epizonal Carboniferous granite (Capilla del Monte pluton) and its pegmatite dike swarm, which share parental links with the Achalian magmatism. The major Be supply for both studied localities should be attributed to Devonian and Carboniferous postorogenic to extensional peraluminous A-type granitic magmatism, which is the major source of beryllium not only for the Pampean Ranges but for the whole country.

High-precision analysis of carbon isotopic composition for individual CO2 inclusions via Raman spectroscopy to reveal the multiple-stages evolution of CO2- bearing fluids and melts

The carbon isotopic composition of CO2 inclusions trapped in minerals reflects the origin and evolution of CO2-bearing fluids and melts, and records the multiple-stages carbon geodynamic cycle, as CO2 took part in various geological processes widely. However, the practical method for determination isotope composition of individual CO2 inclusion is still lacking. Developing a microanalytical technique with spatial resolution in micrometers to precisely determinate the δ13C value of individual CO2 inclusion, will make it possible to analyze a tiny portion of a zoning mineral crystal, distinguish the differences in micro-scale, and possible to find many useful information that could not be obtained with the bulk extraction and analysis techniques. In this study, we systematically collected Raman spectra of CO2 standards with different δ13C values (−34.9 ‰ to 3.58 ‰) at 32.0 °C and from ∼7.0 MPa to 120.0 MPa, and developed a new procedure to precisely determinate the δ13C value of individual CO2 inclusion. We investigated the relationship among the Raman peak intensity ratio, δ13C value, and CO2 density, and established a calibration model with high accuracy (0.5 ‰−1.5 ‰), sufficient for geological application to distinguish different source of CO2 with varying δ13CO2. As a demonstration, we measured the δ13C values and the density of CO2 inclusions in the growth zones of alkali basalt-hosted corundum megacrysts from Changle, Shandong Province. We found the significant differences of density and δ13C between the CO2 inclusions in the core of corundum and those inclusions in the outer growth zones, the δ13C value decreases from core to rim with decreasing density: δ13C values are from −7.5 ‰ to −9.2 ‰ for the inclusions in the core, indicating the corundum core was crystallized from mantle-derived magmas; from −13.5 ‰ to −18.5 ‰ for CO2 inclusions in zone 1 and from −16.5 ‰ to –22.0 ‰ for inclusions in zone 2, indicating the outer zones of corundum grew in a low δ13C value environment, resulted from an infilling of low δ13C value fluid and/or degassing of the ascending basaltic magma.

Role of carbonaceous material in gold precipitation for orogenic gold deposits: A case study of the Bangbu gold deposit in southern Tibet, China

Carbonaceous material (CM) is widely distributed at the Bangbu orogenic gold deposit in vein-hosted and disseminated ores, as well as wall rocks. Despite being closely ore-related, the CM nature and genesis, as well as its possible role in gold metallogeny, remain unclear. Hence, we investigate the role of five ore-related CM types (CM1-4 and methane, which coexist with three pyrite generations of Py1-Py3) by integrating petrographic observation, Raman spectroscopy, LA-ICP-MS, fluid inclusion microthermometry, and thermodynamic modeling. CM1 only occurs in disseminated ores and is overprinted by large euhedral Py1 with median 5.28 ppm Au. Raman spectroscopy analysis shows that CM1 has undergone high-temperature regional metamorphism (∼510 °C). Geochemical modeling shows that Au precipitation in Py1 can be attributed to the fluid-rock interactions of CM1 and Au-bearing ore fluids, which future leads to the host rock alteration and CM1 consumption. CM2 occurs with large subhedral Py2 and hydrothermal sericite in quartz veins, and gold exists as native gold and as Au+ in pyrite. Py2 consists of Py2a with median 0.44 ppm Au and Py2b with median 49.80 ppm Au. Raman spectroscopy of CM2 experienced a temperature of ∼455 °C, much higher than the main ore stage fluid inclusion homogenization temperature (167–247 °C). Meanwhile, methane is commonly found in CO2-bearing fluid inclusions in the quartz closely associated with Py2 and CM2. Geochemical modeling shows that methane can be a more efficient reductant than CM2 and is capable of reducing Au-bisulfide to native gold. CM3 intergrows with fine Au-poor subhedral Py3 (median 1.00 ppm Au) in randomly-oriented “black sinuous” veins within vein-type ores. The CM3 formation temperature is calculated as ∼290 °C. During the sulfidation processes, H2S and CO2 from the ore fluids may have reacted with Fe-bearing minerals, precipitating CM3 and Py3. The loss of aqueous H2S would destabilize Au-bisulfide complexes, which is the secondary gold precipitation mechanism proposed for this deposit. CM4 occurs in the wall rocks and have similar structural features with structure-bound semi-graphite observed by petrology, indicating that the formation process is different from that of other CM types. This is supported by the Raman geothermometric results of CM4 (formation temperature ∼388 °C). Additionally, no spatial association was observed between CM4, auriferous sulfides, and native gold. In conclusion, our study proposed the most likely roles of CM in gold precipitation in this deposit, which bears important implications for better understanding of the processes that lead to the formation of high-grade ores.

Permeability and Mechanical Response of Granite after Thermal and CO2 Bearing Fluid Hydro-Chemical Stimulation

The large scale extraction of geothermal energy can reduce CO2 emissions. For hot dry rocks, the key to successful utilization depends on the efficiency of reservoir reconstruction. The chemical and thermal stimulation methods are always used in geothermal reservoir reconstruction except in hydraulic fracturing with high fluid injection pressure, which is believed to reduce the seismic hazard by applying before the high-pressure hydraulic fracturing stimulation. However, at the laboratory scale, there are still very limited experimental studies illustrating the combined effects of chemical and thermal stimulation on the permeability and mechanical properties of granite, which is regarded as the main type of hot dry rock. In this paper, comparative stimulation experiments were carried out, including thermal/cold stimulation, CO2 bearing solution hydro-chemical stimulation, combined thermal and CO2 bearing fluid stimulation. By means of nuclear magnetic resonance analysis, permeability test and triaxial compression test, the changes of the micro-structure, permeability and mechanical properties of granite under various stimulation conditions were analyzed. The experimental results show that, compared with the single thermal stimulation and CO2 bearing fluid hydro-chemical stimulation, the superposition effect of thermal and CO2 bearing fluid hydro-chemical stimulation can increase the number of micro-fractures in granite more effectively, thus increasing the permeability, while the elastic modulus and compressive strength decrease. Moreover, the cooling mode on the granite also has a certain influence on the stimulation effect. After water-cooling on the heated granite (300 °C), combined with the CO2 bearing fluid stimulation (240 °C, 20 MPa), the permeability of granite is the highest, increasing by 17 times that of the initial state, and the porosity also increases by 144.4%, while the elastic modulus and compressive strength decrease by 14.3% and 18.4%, respectively. This implies that the deterioration of mechanical properties due to the micro-fractures increased by the thermal and chemical stimulation can enhance the fluid conductivity and heat extraction of granite. The methods in this paper can provide a reference for the combined application of thermal and chemical stimulation technology in artificial reservoir reconstruction of hot dry rocks.

Contrasting alteration textures and geochemistry of allanite from uranium-fertile and barren granites: Insights into granite-related U and ion-adsorption REE mineralization

AbstractAllanite is an important rare earth element (REE)-U-bearing mineral in granites, and it can act as a metal source for the formation of some hydrothermal uranium deposits and ion-adsorption REE deposits. To investigate the potential of allanite as a mineral probe of granite-related uranium mineralization processes and the formation of ion-adsorption REE deposits, we present textures, geochemistry, and in situ U-Pb isotope data for allanite from the fertile Changjiang granite associated with the Changjiang uranium ore field and barren Jiufeng granite in the Zhuguangshan batholith, South China. Alteration of allanite in the Changjiang granite is characterized by the altered domains with lower backscattered electron (BSE) intensities than the unaltered domains and replacement by other secondary minerals such as REE fluorocarbonates, calcite, fluorite, thorite, clay minerals, quartz, chlorite, and epidote. Crystals from the Jiufeng granite were partly replaced by the altered domains appearing darker in BSE images and minor REE fluorocarbonates. The darker domains of the Changjiang and Jiufeng allanite grains have higher Fe3+/(Fe3++Fe2+) ratios and U concentrations than those of the brighter domains, indicating that the alteration of allanite was probably related to more oxidized fluids. This study suggests that the Changjiang granite might have been subjected to the influx of F- and CO2-bearing fluids.The brighter domains of the Changjiang and Jiufeng allanite grains have weighted mean 207Pb-corrected 206Pb/238U ages of 156.7 ± 4.3 Ma and 161.6 ± 5.3 Ma, respectively, consistent with the corresponding zircon 206Pb/238U ages of 156.1 ± 1.4 Ma and 159.8 ± 1.8 Ma. The darker domains of the Changjiang allanite grains yield a weighted mean 206Pb/238U age of 141.4 ± 5.6 Ma, which overlaps within error the timing of a uranium mineralization event (~140 Ma) in the Changjiang uranium ore field and the age of a crustal extension event (140–135 Ma) in South China. The BSE images and elemental maps reveal that rare earth elements such as La and Ce have been released from the Changjiang allanites during alteration and were precipitated as REE-fluorocarbonates that are susceptible to chemical weathering, which sets the stage for the formation of an ion-adsorption REE deposit. Our study suggests that the regional crustal extension might have played an important role in the formation of both granite-related uranium and ion-adsorption REE deposits in South China, as it could have triggered alteration or breakdown of REE-U-bearing minerals in source rocks.

Ore genesis of the Narenwula quartz-vein type W polymetallic deposit in the southern Great Xing’an Range W belt, NE China: Constraints from wolframite geochronology and individual fluid inclusion analysis

The Narenwula deposit, situated in the southern Great Xing’an Range W belt, is a large-scale quartz-vein type W polymetallic deposit in NE China. The mineralization is spatially associated with Late Jurassic monzogranite and granite porphyry. In this study, we present detailed description of the ore geology, wolframite in-situ U-Pb dating, and fluid inclusion analyses including microthermometry, laser Raman spectra, and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) microanalyses to precisely constrain the timing of ore formation, origin and evolution of ore-forming fluids as well as metal precipitation mechanisms. In-situ U-Pb dating of hydrothermal wolframite yields a W mineralization age of 136.4 ± 2.0 Ma (1σ, MSWD = 1.3), which is ∼14 Ma younger than the zircon U-Pb ages of W-bearing granitoids, indicating the W-bearing granitoids are not genetically related to the W mineralization at Narenwula. The hydrothermal process can be divided into four stages: stage I is characterized by abundant wolframite (I), which is the dominant stage of W mineralization; stage II is featured with the development of wolframite (II) together with minor amounts of pyrite and chalcopyrite; stage III is the predominant stage of sulfide mineralization; and stage Ⅳ is characterized by lack of sulfide or wolframite and occurrence of quartz, carbonate, and fluorite. Cathodoluminescence analysis of quartz further revealed four generations of quartz, corresponding to the four hydrothermal stages. Four types of fluid inclusions were distinguished for quartz, including CO2-rich (C1-type), CO2-bearing (C2-type), liquid-rich (l-type), and brine (B-type) fluid inclusions. Fluid inclusion microthermometry shows a decrease in homogenization temperatures and salinities from the early to late stages. The ranges of the homogenization temperature for stages I to Ⅳ are 440–280, 320–240, 260–180, and 200–160 ℃, respectively, and the ranges of salinities for stages II to Ⅳ are 2.9–17.8, 1.4–10.2, and 0.4–6.7 wt% NaCl equiv., respectively. The salinities of fluid inclusions from stage I have a bimodal distribution in the ranges of 9.6–17.4 and 31.1–35.6 wt% NaCl equiv. Individual fluid inclusion LA-ICP-MS analyses suggest a magmatic source for the fluids of all stages, evidenced by the high Rb and Mn concentrations, high Rb/Na, K/Na, Cs/Na, Li/Na, and Zn/Na ratios, which are distinctly different from those of basinal brines. The Rb/Sr and K/Rb ratios of fluid inclusions are similar to those of Late Mesozoic highly fractionated W-mineralized granitoids in NE China, indicating that the metallogenic parent rocks at Narenwula are highly evolved. In combination with evidence of consistent Cs/Rb and Cs/(Na + K) ratios of fluid inclusions from all stages, we suggest that the mineralizing fluids originated from an underlying, geochemically uniform, and highly fractionated granitic magma. Fluid immiscibility and fluid-rock interaction (especially greisenization) are the main mechanisms for wolframite precipitation, whereas natural cooling of fluids may be subordinate. Fluid inclusion data provide evidence that the addition of meteoric water to the magmatic-hydrothermal fluid initiated at the sulfide mineralization stage, and the fluid dilution and cooling due to fluid mixing played an important role in the process of sulfide precipitation. This study highlights that W and base metals (e.g., Cu, Pb, Zn) in ore-forming fluids display different migration and precipitation progresses, the knowledge of which is important for elucidating multi-stage ore-forming processes of quartz-vein type W polymetallic deposits in NE China.

AN UNUSUAL EARLY EOCENE, SYNCOLLISIONAL CARBONATITE COMPLEX AND RELATED RARE EARTH ELEMENT DEPOSIT IN THE INDIA-ASIA COLLISION ZONE, NORTHWESTERN VIETNAM

Abstract Carbonatite-related rare earth element (REE) deposits, the most significant source of REEs globally, are normally generated in extensional settings, such as intracontinental rifts, mantle plume-related environments, or postcollisional orogens. Syncollisional orogens represent overall compressional regimes, so carbonatites and related REE deposits are rarely identified in such a setting. However, this study reports an anomalous syncollisional carbonatite-related REE deposit, Dong Pao, in the India-Asia collision zone in northwestern Vietnam. The Dong Pao deposit is dated at ca. 52 to 51 Ma through zircon and bastnäsite Th-U-Pb chronometers. The ore-hosting carbonatites were emplaced as stocks with associated syenite. The carbonatite-syenite complex is significantly enriched in light REEs, Ba, and Sr and depleted in high-field strength elements, and has high (87Sr/86Sr)i ratios (&amp;gt;0.707) and low εNd(t) values (–6.5 to –5.6). These geochemical signatures imply that the carbonatite-syenite complex was derived from partial melting of subcontinental lithospheric mantle previously metasomatized and fertilized by REE- and CO2-bearing fluids. Timing of the REE-rich carbonatite-syenite complex indicates that it was related to a far-field stress within the early Eocene main-collision stage at 52 to 51 Ma rather than the late-collision stage at 42 to 35 Ma as previously thought. Collisional tectonism involving block rotation and fault activation are interpreted to have induced disturbance of the lithosphere mantle and created localized, transtensional/extensional environments oblique to the trend of the orogen that facilitated emplacement of the REE-rich carbonatitic magmas. Dong Pao appears to be the first identified, high-tonnage REE deposit that formed in the syncollisional geodynamic setting. Such a finding highlights that tectonic disturbance of an REE-rich lithosphere mantle distal to collision sutures has the potential to generate REE deposits, even during prominent convergence and collision of continents. As such, it defines additional search spaces for exploration of other REE orebodies of this style in complex collisional orogens.

Infiltration of volatile-rich mafic melt in lower crustal peridotites provokes lower crustal earthquakes

We document well-preserved extensional shear zones in a rift-related lower-crustal magmatic conduit system, the Reinfjord Ultramafic Complex. Deformation along the shear zones led to seismic events below the seismogenic zone of continental rifts (10–15 kbar and 850–1150 °C), similar to events observed along the East African Rift today. Processes leading to failure of the weakened rocks caused extremely high strain. We mapped pseudotachylytes along a network of millimeter to meter-scale transtensional shear zones associated with gabbronoritic dykes, and a 2 km long low-angle extensional shear zone. Deformation, initiated through priming of the rock by magmatic fluids, exploited subgrains and microfractures in olivine, with CO2-bearing fluids leading to volume expanding reactions (olivine + diopside + CO2 = dolomite + enstatite), enhancing olivine fracturing. Fragmentation of the olivine grains and the addition of weaker phases facilitated strain localization and increased the strain rate by two orders of magnitude through grain size reduction (Sørensen et al., 2019). Sudden failure under transient brittle conditions formed pseudotachylytes. We conclude that failure along shear zones in lower crustal continental rifts is possible without remote stress events, in the presence of pre-existing textural and structural heterogeneities and events of volatile fluid infiltration.

Poromechanical analysis of oil well cements in CO2-rich environments

Wells drilled in carbon storage sites could be converted to potential leakage pathways in the presence of CO2-bearing fluids and under the impact of the changes occurring in underground stress. To test this hypothesis, in this study, the behavior of Class G oil well cement in contact with supercritical CO2 has been investigated. The cement cores were cured under lime-saturated water for 28 days at a temperature of 20 ∘C and under atmospheric pressure. Subsequently, they were exposed to supercritical CO2 under a pressure of 20 MPa and at a temperature of 90 ∘C for 30 days. The penetration depth of the carbonation front and the change in the poromechanical properties of the cement core were measured against time. A numerical modeling exercise has also been conducted to simulate the alteration within the cement cores. The results presented in this study show that the precipitation of calcium carbonates reduces the porosity within the outermost layers of the cement cores. This phenomenon shifts the main pore size class towards smaller sizes. In contrast to expectations, the reduction in porosity does not improve the overall strength of the cement specimens. The observed reduction in the strength of the cement specimens might be associated with either the amorphous structure of the precipitated carbonates or the weak bonding between them and the solid walls of the pores and the high degradation of calcium silicate hydrates.