Fluid-rock Reactions Research Articles

Fluid boiling during high-grade gold deposition in an epithermal gold-telluride deposit, Guilaizhuang, China

Boiling is a well-established mechanism for precious metal mineralization in low-sulfidation epithermal veins, and is considered a key process in the formation of high-grade bonanza zones in those systems. In contrast, the potential role of fluid boiling in the formation of epithermal gold-telluride veins associated with alkalic porphyries has rarely been discussed. The Guilaizhuang gold-telluride deposit, Shandong Province, China, is an ideal location to investigate the possible role of fluid boiling because the deposit comprises several distinct styles of orebodies, ranging from finely-disseminated gold mineralization hosted in carbonate rocks at depth, through to very high-grade mineralized breccia zones at shallower levels. Here, we examine the relationships between ore-forming fluids and mineralization styles in this deposit, based on paragenesis, vein textures and fluid inclusions. In the deeper carbonate-replacement style orebodies, we found no evidence of fluid boiling and, as such, alternative mechanisms such as fluid mixing or fluid-rock reactions were likely occurring. In contrast, the shallower, high-grade breccias show clear evidence of fluid boiling, which we infer contributed to the formation of exceptional bonanza zones. Our results thus indicate that fluid boiling can play a key role in precious metal mineralization in gold-telluride deposits, analogous to the low-sulfidation epithermal deposits. Furthermore, our results illuminate how contrasting mechanisms of gold mineralization in these deposits (i.e., boiling versus non-boiling) can give rise to the diversity and distribution of gold grades and reserves within an epithermal gold-telluride system.

Genesis of altered slate type ores in the Huangjindong gold deposit, Jiangnan Orogenic Belt, South China

Altered rock ores, closely associated with fluid-rock interactions, represent a typical mineralization style in hydrothermal gold deposits. In the Huangjindong gold deposit of the Jiangnan Orogenic Belt, South China, altered slate ores are generally characterized with bleaching, but the genesis remains not understood. Based on field work, petrographic observations and Tescan Integrated Mineral Analyzer (TIMA) analysis, the alteration of the slate can be defined as carbonatization-sericitization, characterized with the abundant siderite spots and sericite, as well as locally occurred cryptocrystalline quartz. Abundant gold-bearing sulfides are locally present in altered rocks, which constitute the altered slate ores. In altered slates, pyrite and arsenopyrite aggregate near carbonate spots, sharing similar geochemical compositions with those in quartz veins. These sulfides locally crosscut siderite grains, demonstrating that the carbonatization-sericitization alteration took place before gold mineralization. μ-XRF analysis and mass balance calculation show that Fe is not prominently gained or lost but aggregated to form siderite spots in the alteration zone. In addition, K contents increased during alteration, consistent with the presence of sericitization. Thermodynamic modeling of the dissolution of siderite manifests that the chemical reactions between siderite and S-Au-bearing fluids leads to the co-precipitation of gold, pyrite, arsenopyrite and quartz. Moreover, taking account of the siderite contents in altered slates and Au contents in sulfides, the water-rock interaction could generate altered slate ores with economic significance. These results show that large amounts of siderite spots are generated during the pre-mineralization fluid-rock reaction, and thus provide favorable chemical traps for gold mineralization. Abundant siderites contribute to gold mineralization by triggering sulfidation, which is the major genesis for the altered slate ores in the Huangjindong gold deposit.

Alteration and mineralization patterns in orogenic gold deposits: Constraints from deposit observation and thermodynamic modeling

Hydrothermal alteration and mineralization types of orogenic gold deposits display many variations depending on formation depths, types of host rock, compositions of ore fluids, spatial positions, fluid/rock ratios, and repetitive modifications during multiple fluid infiltrations in the complicated processes of fluid-rock interaction. Therefore, establishing holistic reference patterns of hydrothermal alteration with associated mineralization for the orogenic gold system is necessary. Based on the observation of typical orogenic gold deposits and thermodynamic simulation of fluid-rock reaction, the general features of proposed patterns include:(1)Orogenic ore fluids are capable of transporting sufficient gold from deep (5 kbar and 600°C) to shallow (1 kbar and 200°C) crustal levels, resulting in alteration and mineralization occurred in a much-varied depth. Only considering the effects of fluid-rock reaction and sulfidation, the formation of pyrrhotite and pyrite at relatively high and low P-T conditions, respectively, is the most important mechanism driving gold precipitation. In addition, the changes of fluid fO2 and pH can also trigger a decrease in the gold solubility in fluids.(2)Multiple waves of fluid infiltration are capable of dissolving the early-formedulfides and gold, and reprecipitate them in the distal alteration zones, which can explain the irregular gold concentration distribution patterns in wide alteration zones. The fluids under higher P-T conditions (5 kbar and 600°C and 3 kbar and 400°C) are more capable of dissolving early-formed sulfides and gold. Additionally, the later infiltrated fluids can transform early-formed pyrrhotite into pyrite.(3)The model of interactions between ore fluids and aluminosilicate rocks at varied P-T conditions indicates that the alteration mineral assemblages in hypozonal deposits (>12 km) mainly include biotite, amphibole, anorthite, K-feldspar, quartz, and pyrrhotite assemblages; that those in mesozonal deposits (6 to 12 km) are characterized by chlorite, calcite, quartz, muscovite, pyrite or pyrrhotite. The epizonal deposits (<6 km) commonly develop more abundant Fe-Mg bearing carbonates (e.g., dolomite, ankerite, and siderite), quartz, muscovite, and pyrite. The compositional variations of ore fluids and host rocks have important controls on the development of iron-oxides and carbonaceous material.(4) The alteration halo is relatively restricted under hypozonal to lower mesozonal conditions. However, broad carbonation develops under upper mesozonal to epizonal conditions, with Fe-Mg bearing carbonates and calcite distributed in proximal and distal zones, respectively.

Evaluation of chemical weathering proxies by comparing drilled cores versus outcrops and weathering history during the Permian–Triassic transition

Continental records of the Permian–Triassic boundary are characterized by intense chemical weathering, likely due to global warming and acid rainfall associated with volcanism. However, the weathering history throughout the late Permian has not been interrogated in time-equivalent continental successions because of the lack of stratigraphically continuous deposits. Here, we present comparative investigations of outcrops and drilled cores from upper Permian to lowest Triassic terrestrial deposits from the Taoshujing Section, South China. These sediments have a mafic-dominated source with insignificant sorting and recycling during deposition, as documented by the invariable TiO2/Al2O3, Zr/Ti, Th/Sc, Zr/Sc, and Cr/Th ratios, and low values of Th/Sc and Cr/Th ratios. However, different diagenetic effects on outcrops and drilled cores have generated counterintuitively low values of commonly used chemical weathering proxies. Potassium enrichment, recognized from the A-CN-K diagram produced for portions of the outcrop, is also verified by the strongly negative correlations between CIA, CIX, and the molar contents of K2O (r = −0.90 and −0.92, respectively), as well as clay mineralogy analysis. However, the reduced CIA, CIW, and PIA values for the drilled core samples primarily result from an insufficient subtracting of CaO in the secondary carbonates. Using two modified proxies (CIX and CPA), the decline observed in the lower Xuanwei Fm. was probably caused by the cooling climate during the early Wuchiapingian. Nevertheless, the lower values from the Kayitou Fm. to the basal Dongchuan/Feixianguan Fm. likely indicated weak chemical weathering intensity due to physical denudation and subsequent rapid deposition under rapid warming and short fluid-rock reaction time conditions. This weak chemical weathering might have been intensified by drier conditions and increased seasonality in the sediment source area and tectonics related to the closure of the eastern Tethys Ocean. Our work is the first comparative study on chemical weathering proxies for drilled core and outcrop samples from the Late Permian to Early Triassic, a time period which included the most severe bio-crisis and global environmental change in the Phanerozoic. These results highlight that non-weathering factor alterations on commonly used chemical weathering proxies are essential to evaluate with multiple techniques. Compared to the drilled cores, samples collected from the subsurface by excavation could not avoid later weathering alteration and should be used with caution to uncover the past chemical weathering history of an area.

Formation of the Banxi Sb deposit in Eastern Yangtze Block: Evidence from individual fluid inclusion analyses, trace element chemistry, and He-Ar-S isotopes

The Banxi Sb deposit (>100,000 t Sb metal with a grade of 0.02%–64.5% Sb (typically 15.3%–25.9% Sb) in the Eastern Yangtze Block is hosted in Neoproterozoic low-grade metamorphic clastic rocks of the Banxi Group. The deposit is characterized by vein-type Sb-only mineralization. Analyses of individual quartz-hosted fluid inclusions obtained by LA-ICP-MS identified Na as the most abundant cation (thousands to tens of thousands of ppm) in the ore-forming fluids of the Banxi Sb deposit, together with variable contents of K, Ca, Al, As, Fe and Sb (tens to thousands of ppm). Multiple chemical criteria, including high Na+/K+ (typically 3–15) and low Mn2+/Na+ (0.003–0.2) and Sr2+/Na+ (0.001–0.01) ratios of individual fluid inclusions, suggest that the fluids responsible for quartz and stibnite precipitation in the Banxi Sb deposit were likely dominated by basinal brines within low-grade metasedimentary rocks. Moreover, the extremely low 3He/4He ratios (0.001–0.048Ra) but relatively high 3He/36Ar (0.5 × 10−5–5.8 × 10−4) and 40Ar/36Ar ratios (323–1111 with an average of 737) of fluid inclusions trapped in ore-stage quartz further support a sedimentary origin of ore-forming fluids in this deposit. The positive and homogeneous sulfur isotopic values (δ34S = 8.0–9.5‰) of stibnite and arsenopyrite are comparable to those of sulfides in Proterozoic metasedimentary rocks (δ34S = 5.6–11.5‰), indicating these metasedimentary rocks may have served as the primary source of S for the Banxi Sb deposit. Combined with geological features and new trace element chemistry data for quartz and stibnite, we envisaged a new formation model for the Banxi Sb deposit that assumes that circulation of weakly alkaline basinal brines through faults under an extensional tectonic setting during the Early Cretaceous (∼130 Ma), mobilization of Sb and S from the underlying and host metasedimentary rocks and ascent of ore- forming fluids along faults, and ultimately precipitation of Sb minerals in or around fault/fracture zones as a result of the decreasing pH of the ore-forming fluids as well as sulfidation during fluid-rock reaction.

Age and genesis of the Lamahanshan Ag-Pb-Zn deposit, southern Great Xing'an Range, northeastern China: Constraints from sphalerite Rb-Sr dating, fluid inclusions and H-O-S-Pb isotopes

The Lamahanshan deposit in the eastern Central Asian Orogenic Belt (CAOB) is a newly-discovered Ag-Pb-Zn vein deposit in the southern Great Xing'an Range (GXR). Vein-type Ag-Pb-Zn orebodies are mainly hosted in the fracture zones of gneissic plagiogranite, granite porphyry, and quartz porphyry. Mineralization comprises four stages: (I) quartz-magnetite, (II) quartz-pyrite-chalcopyrite, (III) quartz-polymetallic sulfides, and (IV) quartz ± sphalerite. Sphalerite Rb-Sr dating yielded an isochron age of 137.7 ± 6.1 Ma, coeval with the regional Late Jurassic-Early Cretaceous Pb-Zn polymetallic mineralization. Three types of fluid inclusions (FIs), namely vapor-rich two-phase (LV-type), liquid-rich two-phase (VL-type), and daughter mineral-bearing three-phase (SL-type), are distinguished at Lamahanshan. Stage I and II contain all FI types with homogenization temperatures (Th) of 383–418 °C and 350–392 °C and salinities of 0.9–38.1 wt% and 0.7–35.0 wt%, respectively, whereas stage III contain VL- and LV-type FIs with Th = 318–349 °C and salinity = 0.7–10.5 wt%. Only VL-type FIs occur in stage IV, with Th of 271–320 °C and salinities of 4.3–7.8 wt%. The microthermometric and H-O isotope data (δ18OH2O = −9.4 to 0.9‰ and δD = −137.0 to −124.7‰) indicate that the ore-forming fluids were initially magmatic with later meteoric water incursion. Fluid boiling, cooling, fluid-rock reactions, and meteoric water mixing were the major ore precipitation mechanisms at Lamahanshan. The sulfide S (δ34S = 4.0–6.7‰), Sr ((87Sr/86Sr)i = 0.698957–0.700069), and Pb (206Pb/204Pb = 17.230–18.193, 207Pb/204Pb = 15.440–15.627, and 208Pb/204Pb = 37.664–38.407) isotopes also support that the metals were magmatic-derived. Integrating the available geological, mineralization, fluid inclusion, and H-O-S-Sr-Pb isotope evidence, we propose that the Lamahanshan deposit shares many similar features with distal magmatic-hydrothermal vein-type ores, and was formed in an extensional setting related to the Early Cretaceous Paleo-Pacific subduction rollback.

Hydrogeochemical evolution of formation waters responsible for sandstone bleaching and ore mineralization in the Paradox Basin, Colorado Plateau, USA

AbstractThe Paradox Basin in the Colorado Plateau (USA) has some of the most iconic records of paleofluid flow, including sandstone bleaching and ore mineralization, and hydrocarbon, CO2, and He reservoirs, yet the sources of fluids responsible for these extensive fluid-rock reactions are highly debated. This study, for the first time, characterizes fluids within the basin to constrain the sources and emergent behavior of paleofluid flow resulting in the iconic rock records. Major ion and isotopic (δ18Owater; δDwater; δ18OSO4; δ34SSO4; δ34SH2S; 87Sr/86Sr) signatures of formation waters were used to evaluate the distribution and sources of fluids and water-rock interactions by comparison with the rock record. There are two sources of salinity in basinal fluids: (1) diagenetically altered highly evaporated paleo-seawater-derived brines associated with the Pennsylvanian Paradox Formation evaporites; and (2) dissolution of evaporites by topographically driven meteoric circulation. Fresh to brackish groundwater in the shallow Cretaceous Burro Canyon Formation contains low Cu and high SO4 concentrations and shows oxidation of sulfides by meteoric water, while U concentrations are higher than within other formation waters. Deeper brines in the Pennsylvanian Honaker Trail Formation were derived from evaporated paleo-seawater mixed with meteoric water that oxidized sulfides and dissolved gypsum and have high 87Sr/86Sr indicating interaction with radiogenic siliciclastic minerals. Upward migration of reduced (hydrocarbon- and H2S-bearing) saline fluids from the Pennsylvanian Paradox Formation along faults likely bleached sandstones in shallower sediments and provided a reduced trap for later Cu and U deposition. The distribution of existing fluids in the Paradox Basin provides important constraints to understand the rock record over geological time.

New Opportunities and Untapped Scientific Potential in the Abyssal Ocean

The abyssal ocean covers more than half of the Earth’s surface, yet remains understudied and underappreciated. In this Perspectives article, we mark the occasion of the Deep Submergence Vehicle Alvin’s increased depth range (from 4500 to 6500 m) to highlight the scientific potential of the abyssal seafloor. From a geologic perspective, ultra-slow spreading mid-ocean ridges, Petit Spot volcanism, transform faults, and subduction zones put the full life cycle of oceanic crust on display in the abyss, revealing constructive and destructive forces over wide ranges in time and space. Geochemically, the abyssal pressure regime influences the solubility of constituents such as silica and carbonate, and extremely high-temperature fluid-rock reactions in the shallow subsurface lead to distinctive and potentially unique geochemical profiles. Microbial residents range from low-abundance, low-energy communities on the abyssal plains to fast growing thermophiles at hydrothermal vents. Given its spatial extent and position as an intermediate zone between coastal and deep hadal settings, the abyss represents a lynchpin in global-scale processes such as nutrient and energy flux, population structure, and biogeographic diversity. Taken together, the abyssal ocean contributes critical ecosystem services while facing acute and diffuse anthropogenic threats from deep-sea mining, pollution, and climate change.

Tin isotopes as geochemical tracers of ore-forming processes with Sn mineralization

AbstractTin is a key strategic metal and indispensable in the high-tech industry. Constraining the source of the mineralizing fluids, their pathways, and subsequent ore-forming process is fundamental to optimizing tin exploration and efficient mining operations. Here, we present trace element analysis, LAICP-MS mapping, and the first systematic high-precision in situ Sn isotope analysis of cassiterite from several tin deposits (i.e., Weilasituo, Baiyinchagan, Maodeng Sn-polymetallic deposits) in northeast China using UV-fs-LA-ICP-MS. We show that the distribution of trace elements in cassiterite from these localities reflects crystallization under disequilibrium conditions with coexisting fluids or melts, and it suggests intense fluid-rock reactions. Among the three deposits, cassiterite from the Maodeng Sn-Cu deposit has the heaviest weighted mean Sn isotope composition, with δ124/117Sn values ranging from 0.11 ± 0.04‰ to 0.62 ± 0.08‰. The Baiyinchagan Sn-Ag-Pb-Zn deposit displays the lightest isotope composition with δ124/117Sn values ranging from –1.43 ± 0.06‰ to –0.50 ± 0.04‰. While the Weilasituo Sn-W-Li-polymetallic deposit shows the largest spread in δ124/117Sn values, ranging from –0.66 ± 0.05‰ to 0.59 ± 0.03‰. The Sn isotope variability in these natural cassiterites is attributed to Sn isotope fractionation associated with the diversity of Sn mineralization pathways and different physicochemical conditions. Furthermore, the δ124/117Sn values of cassiterite from the Maodeng and Baiyinchagan deposits gradually decrease from early to late mineralization stages, suggesting that they were generated by Rayleigh fractionation during progressive mineral precipitation from a hydrothermal fluid. In contrast, heavy Sn isotope values in late-stage Weilasituo cassiterites are likely a result of disequilibrium fluid-rock interaction with external, wall-rock-derived fluids. Our results reveal that liquid-vapor partitioning or fluid-rock interaction may have more influence on Sn isotope fractionation between cassiterite and evolving ore-forming fluids than do magmatic differentiation, pH, pressure, and temperature during the formation of tin deposits. According to the tin isotopic data obtained so far from this study and published previously, we observe no relationship between the Sn isotope composition of cassiterite and the age of mineralization or tectonic setting. However, cassiterite displays heavier Sn isotope compositions than coexisting stannite (Cu2FeSnS4) regardless of the deposit type and depth of emplacement, suggesting that the redox state may influence Sn isotope fractionation. More importantly, we first recognize a general shift toward light Sn isotope compositions in cassiterite associated with decreasing Ti/Zr ratios, suggesting that Sn isotopes can be a robust tool for identifying the source of the mineralization. Furthermore, based on our Sn isotope data together with previous studies of fluid inclusion, we propose that the dominant Sn(II) species occur in early ore mineralization systems, then shifts to the Sn(IV) species in late stage due to redox change or higher Cl– activity. Tin isotopes may be a robust tool to trace the mineralization center and fluid pathways and to ascertain the mechanisms of metal precipitation.

Chemical and boron isotopic variations of tourmaline deciphering magmatic-hydrothermal evolution at the Gejiu Sn-polymetallic district, South China

The world-class Gejiu Sn-polymetallic district (southwest China), with ca. 3.27 Mt Sn metal, is a magmatic-hydrothermal deposit associated with the Late Cretaceous biotite granites; however, the magmatic and hydrothermal processes involved in its formation remain poorly understood. Tourmaline is a ubiquitous phase in the Gejiu district, and here we employ in-situ major, trace element, and boron isotope compositions of tourmaline to investigate the source and evolution of the mineralizing fluid, and late-magmatic and hydrothermal processes related to ore formation. Based on petrographic observations, four types of tourmaline are identified: i) late-magmatic tourmaline (Tur I) disseminated in the biotite granites, ii) hydrothermal tourmaline (Tur II) from quartz veins with fracture-filling structure in the biotite granites, iii) hydrothermal tourmaline (Tur IIIa-1, IIIa-2 and Tur IIIb-1, IIIb-2) from fluorite-quartz veins with typical replacement texture against the greisenized granites, among which Tur IIIb-2 is directly related to cassiterite formation, and iv) hydrothermal tourmaline (Tur IV) from sulfide-calcite veins hosted by proximal skarn. Tourmaline (Tur I to Tur III) from the granites belongs mostly to the alkali group and schorl-dravite solid-solution series, with Fe/(Fe + Mg) ranging from 0.83–1.00 for Tur I, 0.68–1.00 for Tur II, and 0.19–1.00 for Tur III, respectively. By contrast, Tur IV belongs mostly to the vacancy group and has foitite–Mg-foitite composition, with Fe/(Fe + Mg) of 0.10–1.00. Large variations of Fe/(Fe + Mg) as well as Na/(Na + Ca) in hydrothermal tourmaline (Tur II to Tur IV), are related to different degrees of interaction between B-rich fluids with host rocks (solidified granite or carbonate). Most trace elements in tourmaline do not correlate with Fe/(Fe + Mg) and Na/(Na + Ca) ratios, implying the trace element compositions are predominantly controlled by melt/fluid compositions and local fluid-rock reactions. Relative to late-magmatic Tur I, hydrothermal tourmaline (Tur II to Tur IV) is enriched in Sr and depleted in Nb, Ta, and (REE + Y), whereas their Li, Be, Sc, V, and Sn concentrations are largely overlapped. The δ11B values in different types of tourmaline fall in a narrow range from −17.8 to −13.7‰, in favor of B-rich fluids episodically exsolved from the granitic melt.Tin enrichment in both late-magmatic and hydrothermal tourmaline grains, especially in those (Tur IIIb) from Sn-mineralized veins, is related to magmatic differentiation and late-stage fluid exsolution. Among all types of tourmaline, Tur IIIb-2 coexisting with cassiterite has elevated Fe3+/(Fe3+ + Fe2+) ratios (mean 0.23), indicating that cassiterite precipitated under relatively oxidized conditions. The distinct chemical (i.e. high Mg, Ti, V, Sc, Sr, and Sn contents) and B-isotope compositions (slightly lower δ11B values of −17.8 to −15.0‰) in syn-ore Tur IIIb-2, combined with the co-occurrence of liquid- and vapor-rich inclusions triggered by fluid boiling in Sn-mineralized veins, suggest that fluid boiling and acid-consuming reaction could be major processes triggering cassiterite precipitation in the quartz vein and greisen. Overall, the chemical and B-isotope signatures of tourmaline are ideal tracers to unravel the magmatic-hydrothermal evolution in the Gejiu Sn-polymetallic district, which could be further employed as a potential prospecting guide for SnW deposits.

Eocene fault-controlled fluid flow and mineralization in the Paradox Basin, United States

Abstract Sedimentary rocks of the Paradox Basin of the Colorado Plateau (southwestern USA) record widespread manifestations of paleo–fluid flow and fluid-rock reactions including Cu, U-V, and Fe-Mn mineral deposits, Si and Ca metasomatism, hydrocarbon accumulations, and bleached sandstones. Many of these are spatially associated with faults. Here we show evidence for a widespread phase of fault-related fluid migration and mineralization at 41–48 Ma in the Paradox Basin. We measured K-Ar dates of multiple size fractions of clay-rich fault gouge, yielding statistically overlapping dates of authigenic (1Md) illite for the Salt Valley (47.0 ± 3.0 Ma), Kane Springs (47.7 ± 3.8 Ma), Cliffdweller (43.4 ± 4.6 Ma), Courthouse (41.9 ± 2.3 Ma), Lisbon Valley (45.3 ± 0.9 Ma), and GTO (48.1 ± 2.6 Ma) faults. The latter two have an illite Rb-Sr isochron age of 50.9 ± 3.5 Ma, and fault-adjacent bornite has a Re-Os isochron age of 47.5 ± 1.5 Ma. Authigenic illite from a paleo–oil reservoir near the Courthouse fault formed from the interaction of reduced fluids with oxidized red-bed sandstones at 41.1 ± 2.5 Ma. The Moab and Keystone faults have older authigenic illite ages of 59.1 ± 5.7 Ma and 65.2 ± 1.0 Ma, respectively. Our results show a close temporal relationship between fault gouge formation, red-bed bleaching, and Cu mineralization during an enigmatic time interval, raising questions about drivers of Eocene fluid flow.

The Diagenetic Alteration of the Carbonate Rocks from the Permian Qixia Formation as Response to Two Periods of Hydrothermal Fluids Charging in the Central Uplift of Sichuan Basin, SW China

The hydrothermal fluid–carbonate rock reaction is frequently regarded to occur in deep-burial diagenesis, and the hydrothermal dissolution is usually distributed and takes place along the faults. Previous studies have suggested that there was hydrothermal fluid activity locally in the Permian Qixia Formation in Sichuan Basin, likely related to the Emeishan basalt eruption. However, the effect of hydrothermal fluids on the carbonate rocks of the Qixia Formation in the central uplift of Sichuan Basin is still unclear. Based on the characteristics and geochemical parameters of the diagenetic minerals, this study aims to reveal the diagenetic alteration related to the hydrothermal fluid–rock reaction in the Qixia Formation and reestablish the diagenetic evolution by using the timing of diagenetic mineral precipitation. The methods include petrographic observation; trace and rare earth element (REE) analysis; C, O and Sr isotope measurement; fluid inclusion temperature measurement and cathodoluminescence analysis. According to the petrographic characteristics, the dolostones are mainly of crystalline structure, namely fine-medium crystalline dolostone, meso-coarse crystalline dolostone, and coarse crystalline dolostone, with the cathodoluminescence color becoming brighter in that order. The limestones from the Qixia Formation are of the bioclastic limestone type, with no cathodoluminescence color. Compared with dolostones, limestones have higher Sr content, lower Mn content, and heavier oxygen isotopes. With the crystalline size of dolostone becoming coarser, the oxygen isotopes of dolostones tend to become lighter. The meso-coarse crystalline dolostone has the highest Mn content and negative carbon isotope. Both limestones and dolostones have an obvious positive Eu anomaly in the Qixia Formation. However, the REE patterns of fine-medium crystalline dolostones are very different from those of meso-coarse crystalline dolostones. It is credible that there were two periods of hydrothermal fluid charging, with different chemical compositions. The first period of hydrothermal fluids could laterally migrate along the sequence boundary. Fine-medium crystalline dolostones were almost completely distributed below the sequence boundary and were dolomitized during the shallow burial period. As products of the hydrothermal fluid–dolostone reaction, the saddle-shaped dolomites in the meso-coarse crystalline dolostones were the evidence of the second period of hydrothermal fluids. As a result, the dolomitization model was established according to the timing of diagenetic mineral precipitation, which can improve that the geological understanding of the effect of hydrothermal fluid activities on the carbonate rocks in the Qixia Formation.

Synthetic Fluid Inclusions XXIV. In situ Monitoring of the Carbonation of Olivine Under Conditions Relevant to Carbon Capture and Storage Using Synthetic Fluid Inclusion Micro-Reactors: Determination of Reaction Rates

Ultramafic and mafic rocks are possible targets for CO2 sequestration via mineral carbonation. The determination of reaction kinetics and the factors that control mineralization are important in order to understand and predict how fast injected CO2 will react with host rocks to permanently isolate and store the carbon. Here we present experimental results of olivine carbonation experiments using synthetic fluid inclusions (SFI) as micro-reactors. The micro-reactor technique coupled with non-destructive Raman spectroscopy allows us to monitor the reaction progress in situ and in real time at elevated temperatures (50–200°C) and pressures (several 10's to a few hundred bars), and quantify the amount of CO2 consumed in the reaction using the Raman CO2 densimeter and mass-balance calculations. Results show a measurable decrease of CO2 density in the fluid inclusions as a result of the reaction between the CO2-bearing seawater-like aqueous solution and olivine. Magnesite formation was observed within hours at ≥100°C, while at 50°C magnesite nucleation and precipitation was only observed after a few weeks. Raman mapping and FIB-SEM analysis confirmed the formation of a non-continuous Si-rich layer on the inclusion wall and the presence of ferroan magnesite as a reaction product. Reaction rates [log J (mol/m−2 s−1)] obtained for olivine carbonation range between ~-8.4 at 50°C and −4.7 at 200°C, which is sufficiently rapid to be suitable for commercial CO2 injection projects. Reaction rates involving a seawater-like fluid were similar to rates published for high salinity solutions containing NaHCO3, and were faster compared to rates involving solutions with low salinity. Thus, CO2 injection into submarine environments might offer some advantages over CO2 storage in onshore basalts where the pores are likely to be filled with low salinity meteoric water. The application of the synthetic fluid inclusion technique, combined with non-destructive analytical techniques, is a promising tool to monitor rates of fluid-rock reactions in situ and in real time. Here, we have documented its application to experimentally study carbonation reactions in the olivine-H2O-CO2-NaCl-MgCl2 system.

Genesis of the Baimadong carbonate-hosted uranium deposit, Guizhou, SW China: Constrains from geology, fluid inclusions, and C-O isotopes

The Baimadong uranium deposit is situated in the Yangtze Craton, SW China, and is one of the most representative carbonate-hosted uranium deposits in China. Uranium mineralization has spatial and genetical relationships with black and red alterations that has been documented by previous studies. However, the signature, source, and evaluation of ore-forming fluids producing the alterations and mineralization remain poorly understood. Fluid inclusions hosted in different generations of hydrothermal calcite have been analyzed in this study, including Cal 1 (pre-ore stage), Cal 2 (early ore stage), and Cal 3 (main ore stage). Three types of fluid inclusions were identified: liquid-dominated biphase, vapor-dominated biphase, and vapor-only monophase. Based on fluid inclusion microthermometry using the FIA method, the fluids associated with Cal 2 are characterized by relatively higher temperature (∼243 ℃) and salinity (5.3 wt% NaCl equiv.) compared with fluids associated with Cal 1 (Th = ∼221 ℃; Salinity = 1.9 wt% NaCl equiv.) and Cal 3 (Th = ∼144 ℃; Salinity = 2.5 wt% NaCl equiv.). The results of stable isotopes (C, O, and S) indicate that the carbon in pre-ore stage fluids was dominantly originated from host marine carbonate rocks (δ13Cfluid-PDB = −3.0 to 0.5 ‰; δ18Ofluid-SMOW = 4.8 to 11.3 ‰), the carbon and sulfur in early ore-forming fluids were mainly derived from the Niutitang Formation with minor from deep crust (δ13Cfluid-PDB = −11.2 to −8.4 ‰; δ18Ofluid-SMOW = 7.9 to 11.4 ‰; δ34Sv-CDT = −11.3 to + 2.1 ‰), whereas the main ore-forming fluids were sourced from meteoric fluids (δ13Cfluid-PDB = −8.6 to −4.9 ‰; δ18Ofluid-SMOW = 0.4 to 8.6 ‰). These results reveal that redox reaction as well as fluid-rock reaction are key factors controlling the large-scale uranium mineralization at Baimadong. Combined with these observations, geological setting, and previous geochemical features, we suggest that tectonic system together with overprinting zone of black and red alterations are indicators for exploration of carbonate-hosted uranium deposit in South China and elsewhere worldwide.

Fluid inclusion evidence for the magmatic-hydrothermal evolution of closely linked porphyry Au, porphyry Mo, and barren systems, East Qinling, China

Abstract The Xiong’ershan district in central China hosts broadly coeval porphyry Au (Qiyugou deposit), porphyry Mo (Leimengou deposit), and barren (Huashan pluton) systems. The key controls on the ore potential and different mineralization styles in these systems are not well understood, with first-order differences in fluid chemistry and melt sources being the main alternatives. The fluid inclusion characteristics of all three porphyry systems have been studied using an integrated approach that combines field geology, petrography, microthermometry, and laser ablation–inductively coupled plasma–mass spectrometry analysis of single fluid inclusions. The results permit a reconstruction of the magmatic-hydrothermal evolution of the ore-forming fluids, and to elucidate whether specialized hydrothermal fluids strongly enriched in ore metals (i.e., Mo, Au, Cu) were essential to form the economically significant deposits. The fluid compositions across the three hydrothermal stages from the Qiyugou Au deposit remain approximately the same over time, suggesting that progressive magma fractionation, fluid-rock reaction along fluid path, and mineral precipitation had a limited effect on fluid composition. The syn-ore stage fluids of the Leimengou Mo deposit are characterized by higher Cs/Na, Sr/Na, and B/Na, but lower K/Na and Cl/Na ratios, and also have salinities and homogenization temperatures distinct from the earlier fluids. This demonstrates that Mo mineralization was caused by a second pulse of fluid input from a highly fractionated felsic magma subsequent to the pre-ore stage. At the Huashan barren pluton, fluids from phase II have higher Cs/Na, B/Na, Li/Na, and Rb/Na ratios with lower homogenization temperatures than fluids occurring in porphyritic rocks of phase III, reflecting a higher degree of magma fractionation of this plutonic complex. The Huashan pluton does not host economic mineralization which is likely caused by the low ore metal tenor, inefficient fluid extraction from the melt, or the flat-roof geometry preventing accumulation of a large volume of fluid in the apical part. The Au tenor of the Qiyugou deposit was most likely contributed by mantle-derived material of higher Mg/Na, Fe/Na, Pb/Na, and Zn/Na ratios. Taken together, the metal charged magmatic-hydrothermal fluids, steeply dipping geometry, and small volume of the porphyry stocks all suggest that a much larger magma chamber feeding the porphyry systems should be present at deeper levels with good potential for Mo mineralization below the current level of exposure at Qiyugou deposit.

A meso-mechanical approach to time-dependent deformation and fracturing of partially saturated sandstone

In the present paper, we investigate how water acts to weaken rock in two complementary ways: mechanically through the generalized effective stress principle, and chemically through time-dependent rock-fluid reactions that allow subcritical crack growth. These processes, together with capillary suction and stress corrosion , were incorporated into a three-dimensional discrete element grain-based model to investigate both the time-independent and the time-dependent mechanical behavior of partially saturated sandstone at the mesoscale . The capillary parameters related to capillary suction and subcritical parameters related to stress corrosion in the model were calibrated to match the deformation behavior of partially saturated sandstone observed in laboratory. Following this calibration, numerical simulations of partially saturated sandstone with different levels of saturation were performed in uniaxial compression. The simulations show that both the peak strength and elastic modulus of the sandstone decrease as a function of increasing saturation and that the relationships between these properties can be expressed by negative exponential functions. The simulations are in good agreement with the experimental results. Second, the long-term brittle deformation of partially saturated sandstone with different levels of saturation under a constant stress level was modeled. The results show that time-to-failure during brittle creep decreases, and the initial strain and the minimum creep strain rate increases, as a function of increasing saturation, as also observed in laboratory. The simulations also highlight the formation of tensile cracks as the main deformation mechanism during brittle creep. Finally, brittle creep in partially saturated sandstone samples with different levels of saturation was studied under different stress levels. These simulations show that the minimum creep strain rate and the time-to-failure as a function of stress can be well described by exponential relations. We conclude that the proposed model permits a deeper understanding of time-independent and time-dependent deformation and failure of partially saturated sandstone at the mesoscale.

Rare earth element precipitation induced by non-redox transformation of magnetite to hematite: Microtextural and geochemical evidence from the Kamthai carbonatite complex, western India

Hydrothermal rare earth element (REE) precipitation in carbonatite is generally attributed to increase in pH or decrease in temperature when REE-bearing acidic fluids interact with carbonates. Here, we document microtextures comprising intergrowth of bastnäsite, hydroxyl-parisite, röntgenite, synchysite, and pyrochlore, with calcite that pseudomorphically replaces patches of hematite with cellular boxwork-type structure, in calciocarbonatites from the Kamthai alkaline complex in western India. The nature of the REE mineralization grades from proximal bastnäsite-dominated to distal hydroxyl-parisite dominated in the boxworks. The microtextural relations and trace element chemistry of hematite, magnetite and calcite, and C-O isotope composition of carbonate are suggestive of extensive low-temperature hydrothermal alteration of the carbonatites. The hematite boxwork structure and the REE mineral-calcite intergrowths often have squarish outlines and are interpreted to have pseudomorphed primary magnetite during fluid-rock interaction. We propose a new mechanism of REE precipitation in magnetite-rich carbonatites involving influx of acidic hydrothermal fluids, which scavenged the REE and other trace elements from magmatic carbonates and apatite. These acidic fluids were responsible for the protonation of magnetite and leaching out of Fe2+, converting them to hematite through a non-redox transformation. The reaction results in 32% volume reduction for every mole of magnetite consumed, generating significant rock porosity, which further aided and abetted fluid-rock reaction and hydrothermal alteration. More importantly, it consumed proton, which increased the fluid pH triggering precipitation of bastnӓsite-group minerals (including bastnӓsite, parasite, röntgenite, synchysite). Close to the magnetite-hematite reaction front, fluor-dominated bastnӓsite-group minerals (mainly bastnӓsite) appear, while away from such fronts, mineralization was enriched in hydroxyl-bastnӓsite group minerals (mainly parisite) as a consequence of decreasing activity of F‐ and/or increasing activity of OH‐ with the progress of magnetite-to-hematite transformation.

Formation mechanisms of paleokarst and karst collapse columns of the Middle Cambrian-Lower Ordovician carbonates in Huainan coalfield, Northern China

Karst water in the Middle Cambrian-Lower Ordovician carbonates is the ecological resources and domestic water in the Huainan coalfield (Anhui Province, China), but it also directly threatens the safe production of coal mines due to the development of paleokarst and karst collapse columns (KCCs). Most of the Middle Cambrian-Lower Ordovician carbonates in Northern China experienced multistage tectonic movements and were affected by multi-type corrosive fluids, but very few studies focused on the effect of multistage fluid-rock reaction on the formation of paleokarst and KCCs. To investigate the formation mechanisms and characteristics of paleokarst and KCCs, this study integrated petrographic studies, isotope geochemistry (C and O) and minor elements (Ba, Mn, and Sr), and clarified the sources and types of corrosive fluids. Through this study, meteoric water, formation water, hydrothermal fluids, and mixing fluids were determined as the four main types of corrosive fluids that formed pores, vugs, fractures, caves, and KCCs in the Middle Cambrian-Lower Ordovician carbonates. The meteoric dissolution is controlled by carbonic acid solution recharge conditions which affect the karst development in the Cambrian and Ordovician paleoweathering crusts and local carbonate outcrops. Hydrothermal fluids with high-temperature, high-pressure and high-corrosivity can develop a strong hydrothermal pore-fracture system in the Cambrian carbonate, which is the reason that KCCs can develop in the Cambrian strata in the Huainan coalfield. The mixing dissolution is controlled by sulfuric acid dissolution and usually occurs in the water tables and the fault and fracture zones, which are conducive to the development of caves and KCCs. In addition to the above four corrosive fluids, the development of paleokarst and KCCs in the Huainan area is also controlled by stratigraphic lithology and geological structures, especially for faults and fractures, which are the main migration channels of corrosive fluids. An evolution model of paleokarst and KCCs was established, providing a plausible interpretation for better understanding of the spatial distribution of paleokarst and KCCs. In practice, this study provides critical references for predicting the spatial distribution of paleokarst and KCCs in Northern China coalfields, as well as the exploration and development of karst water around the world.

Simulation of CO2 mineral trapping and permeability alteration in fractured basalt: Implications for geologic carbon sequestration in mafic reservoirs

Basalt formations are potentially attractive targets for carbon capture and sequestration (CCS) on the basis of favorable CO2-water-rock reactions, which result in permanent CO2 isolation through mineral trapping. Recent pilot-scale experiments in Iceland and Washington state, USA, provide promising results that indicate rapid carbon mineralization occurs within basalt reservoirs. Nevertheless, transitioning these pilot-scale results to large-scale industrial CCS operations is fraught with uncertainty because fluid flow in basalt formations is governed by fracture-controlled hydraulic properties that are highly heterogeneous and difficult to map in situ. This uncertainty is exacerbated by feedbacks between multi-phase fluid dynamics (CO2 and water) and fluid-rock reactions, which may result in a reinforcing feedback comprising CO2 mineralization, permeability alteration, and fluid mobility. To begin to understand the feedbacks between multi-phase fluid flow and mineralization in fractured basalt, this study uses reactive transport simulation methods to model CO2 infiltrating a meter-scale, synthetic basalt fracture overlying a storage reservoir while accounting for porosity change due to mineralization and its corresponding effect on permeability and fluid mobility. Results show that (i) carbonate and clay mineralization tends to occur downgradient of a fracture intersection, (ii) mineralization reduces porosity, which leads to permeability reduction and slows free-phase CO2 migration, (iii) stronger porosity-permeability coupling increases the proportion of mineralized carbon while reducing CO2 mass that can enter fracture, which may lead to self-sealing behavior as fluid mobility approaches nil, and (iv) errors caused by unknown porosity-permeability relationships are small in comparison to errors that arise by omitting mineralization-induced permeability reduction when simulating CO2 sequestration scenarios in basalt reservoirs.

Genesis of carbonatite and associated U–Nb–REE mineralization at Huayangchuan, central China: Insights from mineral paragenesis, chemical and Sr-Nd-C-O isotopic compositons of calcite

The Huayangchuan deposit in the North Qinling alkaline province of Central China is a unique carbonatite-hosted giant U–Nb–REE polymetallic deposit. The mineralization is characterized by the presence of betafite, monazite, and allanite as the main ore minerals, but also exhibit relatively high budgets of heavy rare earth elements (HREE = Gd–Lu and Y). The origin of carbonatites has long been controversial, thus hindering our understanding of the genesis of the deposit. Here, we conducted an in-situ trace elemental, Sr–Nd isotopic, and bulk C–O isotopic analyses of multi-type calcites in the deposit. Two principal types (Cal-I and Cal-II), including three sub-types (Cal-I-1, Cal-I-2 and Cal-I-3) of calcites were identified based on crosscutting relationships and calcite textures. Texturally, Cal-I calcites in carbonatites display cumulates with the grain size decreasing from early coarse- (Cal-I-1) to medium- (Cal-I-2) and late fine-grained (Cal-I-3), whereas Cal-II calcites coexist with zeolite displaying zeolite–calcite veinlets. Geochemically, Cal-I calcites contain relatively high REE(Y) (151–2296 ppm), Sr (4947–9566 ppm) and Na (29–390 ppm) contents, characterized by right- to left-inclined flat distribution patterns [(La/Yb)N = 0.2–4.2] with enrichment of HREE(Y) (136–774 ppm), whereas Cal-II calcites display low REE, Sr and undetectable Na contents, characterized by a right-inclined distribution pattern [(La/Yb)N = 13.5, n = 16]. The U–Nb–REE mineralization, accompanied with intense and extensive fenitization and biotitization, is mainly associated with the Cal-I-3 calcites which show flat to relatively left-inclined flat REE distribution patterns [(La/Yb)N = 0.2–1.0]. Isotopic results show that Cal-I calcites with mantle signatures are primarily igneous in origin, whereas Cal-II are hydrothermal, postdating the U–Nb–REE mineralization. Cal-I calcites (Cal-I-1, Cal-I-2 and Cal-I-3) from mineralized and unmineralized carbonatites, displayed regular changes in REE, Na and Sr contents, but similar trace element distribution patterns and Sr–Nd-C-O isotopic signatures, indicating that these carbonatites originated from the same enriched mantle (EM1) source by low-degree partial melting of HREE-rich carbonated eclogites related to recycled marine sediments. The combination of trace elements and Sr-Nd isotopic composition of calcites further reveals that these carbonatites have undergone highly differentiated evolution. Such differentiation is conducive to the enrichment of ore-forming elements (U–Nb–REE) in the late magmatic–hydrothermal stages owing to extensive ore-forming fluids exsolved from carbonatitic melts. The massive precipitation of the U–Nb–REE minerals from ore-forming hydrothermal fluids may have been triggered by intense fluid–rock reactions indicated by extensive and intense fenitization and biotitization. Therefore, the Huayangchuan carbonatite-related U-Nb-REE deposit may have formed by a combination of processes involving recycled U–Nb–REE–rich marine sediments in the source, differentiation of the produced carbonatitic magmas, and subsequent exsolution of U–Nb–REE–rich fluids that precipitated ore minerals through reactions with wall rocks under the transitional tectonic regime from compression to extension at the end of Late Triassic.