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Aiming at understanding the source of the fluids that mineralizing within seismically active fault zones, we investigate the noble gas isotopes (i.e., helium (He), neon (Ne), and argon (Ar)) in the fluid inclusions (FIs) trapped in the calcite veins sampled along high‐angle fault zones of the Contursi hydrothermal basin, southern Italy. The latter basin lies in close vicinity of the MW = 6.9, 1980 Irpinia earthquake and exposes numerous fault scarps dissecting Mesozoic shallow‐water carbonates. The analyses of noble gases (He, Ne, Ar) are conducted to identify the origin of the volatiles circulating along the faults at the time of calcite precipitation. Then, outcomes of this discussions are compared with currently outgassing of deep‐sourced CO2 coupled to mantle‐derived He in that area, whose output is larger than those from some volcanic areas worldwide. The results indicate that He in FIs is dominated by a crustal radiogenic component (4He), and by an up to 20% of a mantle‐derived component (3He), with a highest isotopic signature of 1.38 Ra. This value is consistent with the highest percentage of mantle‐derived He associated to high‐flux CO2 gas emission in the investigated area (1.41 Ra). We propose that the variability of the He isotopic signature measured in primary FIs can result from early trapping of fluid inclusions or post trapping processes and seismic activity that modify the pristine He isotopic signature (i.e., derived from the crust and/or mantle) in groundwater along the faults during periods of background seismicity. Such investigations are fundamental to understand fluid migration in fault systems and the role of fluids in processes of earthquake nucleation. Key Points: Paleofluids in the studied seismogenic fault derive from the mixing between crustal and mantle (∼20%) derived fluidsThe variability of the He isotopic signature registered in fluid inclusions results from either early trapping processes (due to past possible earthquakes events) or post trapping processes by addition of radiogenic 4He produced within fractured calcite veins over time (vein aging)The pristine mantle source has been active in the Irpinia area (southern Italy) for at least 1 Ma based on the post trapping process [ABSTRACT FROM AUTHOR]

Abstract Aiming at understanding the source of the fluids that mineralizing within seismically active fault zones, we investigate the noble gas isotopes (i.e., helium (He), neon (Ne), and argon (Ar)) in the fluid inclusions (FIs) trapped in the calcite veins sampled along high‐angle fault zones of the Contursi hydrothermal basin, southern Italy. The latter basin lies in close vicinity of the MW = 6.9, 1980 Irpinia earthquake and exposes numerous fault scarps dissecting Mesozoic shallow‐water carbonates. The analyses of noble gases (He, Ne, Ar) are conducted to identify the origin of the volatiles circulating along the faults at the time of calcite precipitation. Then, outcomes of this discussions are compared with currently outgassing of deep‐sourced CO2 coupled to mantle‐derived He in that area, whose output is larger than those from some volcanic areas worldwide. The results indicate that He in FIs is dominated by a crustal radiogenic component (4He), and by an up to 20% of a mantle‐derived component (3He), with a highest isotopic signature of 1.38 Ra. This value is consistent with the highest percentage of mantle‐derived He associated to high‐flux CO2 gas emission in the investigated area (1.41 Ra). We propose that the variability of the He isotopic signature measured in primary FIs can result from early trapping of fluid inclusions or post trapping processes and seismic activity that modify the pristine He isotopic signature (i.e., derived from the crust and/or mantle) in groundwater along the faults during periods of background seismicity. Such investigations are fundamental to understand fluid migration in fault systems and the role of fluids in processes of earthquake nucleation.

Lamellar calcite veins are prevalent in carbonate-rich, lacustrine dark shale. The formation mechanisms of these veins have been extensively debated, focusing on factors such as timing, depth, material source, and driving forces. This paper examines dark lacustrine shale lamellar calcite veins in the Paleogene strata of Dongying Depression, using various analytical techniques: petrography, isotope geochemistry, cathodoluminescence, inclusion thermometry, and electron probe micro-analysis. Two distinct types of calcite veins have been identified: granular calcite veins and sparry calcite veins. These two types differ significantly in color, grain structure, morphology, and inclusions. Through further investigation, it was observed that vein generation occurred from the shallow burial period to the maturation of organic matter, with a transition from granular calcite veins to sparry calcite veins. The granular calcite veins exhibit characteristics associated with the shallow burial period, including plastically deformed laminae and veins, the development of strawberry pyrite, the absence of oil and gas, weak fractionation in oxygen isotopes, and their contact relationship with sparry calcite veins. These granular calcite veins were likely influenced by the reduction of sulfate bacteria. On the other hand, sparry calcite veins with fibrous grains are antitaxial and closely linked to the evolution and maturation of organic matter. They contain oil and gas inclusions and show a distribution range of homogenization temperature between 90 °C and 120 °C and strong fractionation in oxygen isotopes, indicating formation during the hydrocarbon expulsion period. The carbon isotope analysis of the surrounding rocks and veins suggests that the material for vein formation originates from the shale itself, specifically authigenic micritic calcite modified by the action of methanogens. The opening of horizontal fractures and vein formation is likely driven by fluid overpressure resulting from undercompaction and hydrocarbon expulsion. Veins may form rapidly or through multi-stage composite processes. Early veins are predominantly formed in situ, while late veins are a result of continuous fluid migration and convergence. Furthermore, the veins continue to undergo modification even after formation. This study emphasizes that the formation of lamellar calcite veins in shale is a complex diagenetic process influenced by multiple factors: biology, organic matter, and inorganic processes, all operating at various stages throughout the shale's diagenetic history. [ABSTRACT FROM AUTHOR]

Abstract The damage behavior of limestone rock masses containing calcite mineral filling under uniaxial compression experimental conditions is unclear, and the fracture mechanism of the rock masses needs to be further explored. In this study, uniaxial compression tests were conducted on limestone rock specimens containing veined calcite by combining acoustic emission and digital image correlation techniques. The effects of veined calcite on the generation and development of cracks on the surface of the specimens until the formation of macroscopic penetration and the strength properties of the rock mass were analyzed. The results showed that the transversely distributed veined calcite caused significant stress concentrations in the rock specimens. The longitudinally distributed veined calcite caused cracks in the specimens or influenced the expansion path of the longitudinal principal cracks. The final damage pattern of the specimens didn’t differ significantly from that of conventional rock masses due to the presence of veined calcite. The presence of the veined calcite had effect on the uniaxial compressive capacity of the rock, but the load variation process of the specimen with time still conformed to the load variation pattern during the uniaxial compressive test of conventional rocks.

Abstract From core observations of shales of the Niutitang formation in the northern part of Guizhou Province, China, calcite was often found to act as a natural fracture filler and affect the extension of fractures in hydraulic fracturing. Therefore, it is crucial to understand the tensile mechanical behavior of shales by calcite veins. In this paper, by computed tomography scanning of shales containing calcite veins of different dip angles from the Niutitang formation, a three‐dimensional numerical model reflecting the internal fine structure of the shale was constructed. Direct tensile numerical simulations were carried out to investigate the effect of calcite veins at different angles on the fine‐scale damage process and mechanical properties of shale. The experimental results show that the tensile capacity of the shale increases with the increase in calcite veins. Depending on the dip angle of the calcite vein, the damage pattern of the shale is divided into three types of damage: pull‐off damage along the calcite vein, jagged damage, and horizontal damage perpendicular to the loading method. At high dip angles, the shale damage is more intense and the fracture network more complex. The temporal and spatial characteristics of the acoustic emissions provide a good indication of the microscopic behavior of the shale specimens during the damage process. The box dimension method was used to calculate the fractal dimension of the shale specimens at the final damage, and it was found that the damage was more intense and the fracture network was more complex at high dip angles, and there was an angular threshold.

The Middle Permain Maokou Formation (P2m) is a new region of natural gas exploration in the Sichuan Basin, is characterized by bioclastic limestone with localized dolomitization, and karst fractured-vuggy reservoirs. Currently, on the gas source, hydrocarbon accumulation process and control factors in the Sichuan Basin during the Permian are lacking. To bridge this gap, herein, we identified the filling sequence minerals inside the pores/vugs, along with the oil charge of the Maokou Formation using drill cores, thin sections, oil inclusion analysis, and U-Pb dating of calcite cements. The results showed that the reservoir space of the Maokou Formation was predominated by the residual dissolved pores/vugs, fractures, and dissolved fractures. The pores/vugs underwent four stages of mineral filling by very fine-fine (-crystalline, CC1) calcite ^ fine-medium calcite (CC2: from 256.4 ± 1.7 to 244.1 ± 6.3 Ma) ^ fibrous calcite (FC; -183.9 ± 8.2 Ma) ^ coarse-macro calcite (CC3; -171.5 ± 5.3 Ma). Combined with the homogenization temperature and salty of fluid inclusion, we considered that three stages of oil charge were present in the Maokou Formation reservoirs. The first stage involved the formation of paleo-oil reservoirs during the Late Permian to Early Triassic, corresponding to the high-maturity aqueous inclusions in CC2, with a homogenization temperature of 106.7°C-137.8°C. At that time, the oil generation from the Lower Cambrian Qiongzhusi Formation rocks peaked, and the generated hydrocarbons migrated upward into the Maokou Formation through the strike-slip faults in the basin center. The second stage involved the formation of paleo-oil reservoirs during the Early Jurassic. The Permian source rocks reached the oil generation window with hydrocarbon expulsion, which was consistent with the oil inclusions in FC. The third stage involved the formation of paleo-gas reservoirs during the Middle Jurassic to Early Cretaceous, corresponding to the high-density methane inclusions and bitumen inclusions occurring in CC3, with the homogenization temperature peaking at 151.9°C-178°C. The natural gas in the Middle Permian of the Central Sichuan Basin is predominantly sourced from the Lower Cambrian Qiongzhusi Formation mudstone and partially from the source rocks of the Middle Permian, indicating a significant source-reservoir conduit of the strike-slip faults in the basin center. The findings provide considerable baseline data to advance further research in the Sichuan Basin. [ABSTRACT FROM AUTHOR]

From core observations of shales of the Niutitang formation in the northern part of Guizhou Province, China, calcite was often found to act as a natural fracture filler and affect the extension of fractures in hydraulic fracturing. Therefore, it is crucial to understand the tensile mechanical behavior of shales by calcite veins. In this paper, by computed tomography scanning of shales containing calcite veins of different dip angles from the Niutitang formation, a three‐dimensional numerical model reflecting the internal fine structure of the shale was constructed. Direct tensile numerical simulations were carried out to investigate the effect of calcite veins at different angles on the fine‐scale damage process and mechanical properties of shale. The experimental results show that the tensile capacity of the shale increases with the increase in calcite veins. Depending on the dip angle of the calcite vein, the damage pattern of the shale is divided into three types of damage: pull‐off damage along the calcite vein, jagged damage, and horizontal damage perpendicular to the loading method. At high dip angles, the shale damage is more intense and the fracture network more complex. The temporal and spatial characteristics of the acoustic emissions provide a good indication of the microscopic behavior of the shale specimens during the damage process. The box dimension method was used to calculate the fractal dimension of the shale specimens at the final damage, and it was found that the damage was more intense and the fracture network was more complex at high dip angles, and there was an angular threshold. [ABSTRACT FROM AUTHOR]

The Middle Permain Maokou Formation (P2m) is a new region of natural gas exploration in the Sichuan Basin, is characterized by bioclastic limestone with localized dolomitization, and karst fractured-vuggy reservoirs. Currently, on the gas source, hydrocarbon accumulation process and control factors in the Sichuan Basin during the Permian are lacking. To bridge this gap, herein, we identified the filling sequence minerals inside the pores/vugs, along with the oil charge of the Maokou Formation using drill cores, thin sections, oil inclusion analysis, and U-Pb dating of calcite cements. The results showed that the reservoir space of the Maokou Formation was predominated by the residual dissolved pores/vugs, fractures, and dissolved fractures. The pores/vugs underwent four stages of mineral filling by very fine-fine (-crystalline, CC1) calcite → fine-medium calcite (CC2: from 256.4 ± 1.7 to 244.1 ± 6.3 Ma) → fibrous calcite (FC; ∼183.9 ± 8.2 Ma) → coarse-macro calcite (CC3; ∼171.5 ± 5.3 Ma). Combined with the homogenization temperature and salty of fluid inclusion, we considered that three stages of oil charge were present in the Maokou Formation reservoirs. The first stage involved the formation of paleo-oil reservoirs during the Late Permian to Early Triassic, corresponding to the high-maturity aqueous inclusions in CC2, with a homogenization temperature of 106.7°C–137.8°C. At that time, the oil generation from the Lower Cambrian Qiongzhusi Formation rocks peaked, and the generated hydrocarbons migrated upward into the Maokou Formation through the strike-slip faults in the basin center. The second stage involved the formation of paleo-oil reservoirs during the Early Jurassic. The Permian source rocks reached the oil generation window with hydrocarbon expulsion, which was consistent with the oil inclusions in FC. The third stage involved the formation of paleo-gas reservoirs during the Middle Jurassic to Early Cretaceous, corresponding to the high-density methane inclusions and bitumen inclusions occurring in CC3, with the homogenization temperature peaking at 151.9°C–178°C. The natural gas in the Middle Permian of the Central Sichuan Basin is predominantly sourced from the Lower Cambrian Qiongzhusi Formation mudstone and partially from the source rocks of the Middle Permian, indicating a significant source-reservoir conduit of the strike-slip faults in the basin center. The findings provide considerable baseline data to advance further research in the Sichuan Basin.

The 8# coal seam in the Benxi Formation of the southeastern margin of the Ordos Basin is a deep coal seam with abundant coalbed methane resources. Calcite veins are commonly developed within the 8# coal seam, and their formation processes and mechanisms have significant implications for the enrichment of deep coalbed methane. Genesis of the calcite veins was analyzed to reveal the impact of the calcite veins formation on coalbed methane accumulation, with an integrated application of petrographic study by thin section, cathodoluminescence analysis, carbon-oxygen isotope analysis, and homogeneous temperature measurements of fluid inclusions. The research findings indicate that the calcite veins in the 8# coal seam can be classified into three stages: C1, C2, and C3. The diagenetic fluids of C1 primarily originated from contemporaneous seawater. The fluids responsible for the formation of C2 primarily consist of organic fluids enriched in biogenic gas, whereas the fluids contributing to the formation of C3 are primarily associated with liquid hydrocarbons originated form decarboxylation of organic matter. Furthermore, the development of both C2 and C3 is influenced by deep hydrothermal fluids resulting from tectonic heating events during the Early Cretaceous. By combining analysis of the hydrocarbon accumulation history and burial history in the study area, it has been established that C2 formation occurred during the Late Triassic to Early Jurassic, while C3 formation took place during the Late Jurassic to Early Cretaceous. The exploration and production practices in the study area have firmly established the crucial significance of the formation and evolution of calcite veins within the 8# coal seam for the migration and accumulation of coalbed methane. The research outcomes provide valuable insights for the exploration of deep coalbed methane enrichment areas. [ABSTRACT FROM AUTHOR]

• Polyphase tectonics shapes hydrothermal pathways in fractured Devonian carbonates. • Exhumed analogue of low-enthalpy geothermal reservoir reveals structural complexities. • Hydrothermal carbonate vein analyses unveil long-lived hydrothermal fluid pathways. • Proposal of geothermal exploration targets in strike slip tectonic settings. This study examines the impact of polyphase tectonics on the development of structurally controlled hydrothermal fluid pathways in carbonate geothermal reservoirs. Our case study focuses on hydrothermal carbonate veins and vein-filled faults in Devonian carbonates from the North Rhine-Westphalia region in western Germany, currently being explored as a potential low-enthalpy geothermal reservoir at depths of 4–5 km. These veins, which can be up to 20 m thick, are subvertical and strike NNW, N, or ESE. They exhibit pinch-and-swell undulating geometries, faulted vein-wall contacts, and occasional fillings of hydrothermal breccias. Vein-filled normal faults show hybrid shear-dilatant openings, with fault tips characterized by horsetail vein terminations. The textures, orientations, and age of the veins suggest their formation at low confining pressures and at depths < 2 km during the Post-Variscan East-West extension. Orthogonal North- and East-striking strike slip faults, inherited from the Variscan orogeny, were likely reactivated during post-Variscan extension, with a significant dilatant component that formed the observed veins. In the Ruhr Basin, the dilation tendency analysis indicates that NNW-striking veins or joints are optimally oriented for re-opening under the current strike-slip stress regime, characterized by NNW-trending maximum horizontal stress. The intersections of fractures may currently create moderately SSE-plunging linear zones of enhanced fluid flow. The main uncertainty regards the presence of similar structures at geothermal reservoir depths of ∼4–5 km in the Middle Devonian carbonates underneath the Ruhr Basin. As the study veins are likely to have formed at depths <2 km, the existence of analogous dilatant conduits at greater depths remains speculative. Eventually, we propose that zones characterized by open discontinuities and channelized fluid flow in carbonate geothermal reservoir in strike-slip tectonic settings can be: (a) dilational jogs between overlapping strike-slip faults, (b) bends along faults, and (c) strike-slip fault terminations with horsetail extensional structures. These zones can also be prone to enhanced karstification. [ABSTRACT FROM AUTHOR]

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We applied field structural data and isotope geochemical (δ13C, δ18O and 87Sr/86Sr) analyses to understand the relationship among calcite veins, fault damage zones and carbonate host rocks in a thrust fault damage zone in the Achado quarry, Irecê Basin in the São Francisco Craton, NE Brazil. Our results reveal three hydrological packages with different rheological behaviours in a stratified carbonate succession. The upper package includes the Achado fault damage zone that is characterised by interlayered dolomitised grainstones and mudstones. These rocks display high positive δ13C values (10‰–13‰), negative δ18O values (mean −6.34‰) and radiogenic (87Sr/86Sr) isotope values (0.70885–0.71519). A second package is marked by a cataclastic brittle shear zone lateral parallel to dolograinstones bedding. These rocks show low to positive δ13C values (−3.41‰ to +8.85‰), more positive δ18O values (mean −3.73‰) and radiogenic (87Sr/86Sr) isotope values (0.71039–0.71373). The lower package is characterised by well‐preserved pristine limestone succession that shows δ13C values ranging between −0.46‰ and +3.17‰, mean δ18O = −5.41‰ and less radiogenic 87Sr/86Sr values (0.70762–0.70818). In contrast to the upper and intermediate packages, rocks from the lower one exhibit very low permeability and behaved as a seal for fluid migration. Fluid flow occurred several times during basin evolution, for example along syn‐rift fault damage zones, bedding‐parallel carbonate breccia, thrust faults, cataclastic shear zones, synorogenic conjugate shear fractures or joints and opening mode I fracture‐fill calcite veins. These fractures allowed pervasive fluid flow in the porous intermediate cataclastic shear zone where fluids flowed and formed veins, as diffuse fluid flow in randomly oriented fracture swarms, or channelised fluid flow in aligned fracture corridors. They record significant centimetre‐scale to km‐scale hydrological behaviour within carbonate layers. Most carbonates that are associated with veins, fault damage zones and hydraulic breccia were formed by fluids of the same origin with low δ13C (−6.0 to −2.0‰) and δ18O (−6.0 to −8.5‰) values, and more radiogenic 87Sr/86Sr values compared to the carbonate host rocks. [ABSTRACT FROM AUTHOR]

U-Pb dating and geochemical analyzes (δ18O, δ13C, Δ47, 87Sr/86Sr and elemental composition) have been applied to fracture-filling calcite veins and host carbonates from the Bóixols-Sant Corneli anticline, which developed along the front of the Bóixols thrust sheet in the Southern Pyrenees. This robust dataset is used to determine: (i) the absolute timing of fracturing and mineralization from fluid flow; (ii) the age and duration of fold evolution; and (iii) the variations and implications of fluid behavior across the anticline, as has been described in the article “Spatio-temporal variation of fluid flow behavior along a fold: The Bóixols-Sant Corneli anticline (Southern Pyrenees) from U–Pb dating and structural, petrographic, and geochemical constraints – Marine and Petroleum Geology (2022) (Muñoz-López et al., 2022).In this new contribution, we present the raw data that have been analyzed and discussed in the related research article and, also, the whole elemental and REE composition of calcite veins and host carbonates that has not been published yet. These data may be used to unravel the age and origin of veins, to understand their sequential evolution in orogenic belts and to compare our results with those obtained in similar settings worldwide.

The Silurian hydrocarbon accumulation research in the southeastern Sichuan Basin lacks evidence of the hydrocarbon accumulation and destruction stages in reservoirs. Bitumen and calcite veins that were developed in the Shiniulan Formation had recorded the information of the fluid evolution in reservoirs and have important implications for fluid activities and hydrocarbon accumulation processes in the Dingshan area, southeast Sichuan Basin. Based on analysis of petrographic, trace element, fluid inclusion and laser Raman spectroscopy of the calcite veins, this research determines the timing and origin of the paleo-fluids formed the calcite veins; recovers the paleo-pressure of the methane inclusions, and reveals the petroleum system evolution and controlling factors of the Shiniulan Formation. The results indicate that two phases of calcite veins were developed in the Shiniulan Formation, and oil charging happened before the formation of the two phases of the calcite veins. The first phase of calcite veins were formed at ~127 Ma under relative reduction conditions, with the forming fluid sourcing from the diagenetic fluid of the same strata, which show brown-red cathode luminescence colors. The second phase calcite veins were formed at ~83 Ma under relative oxidation conditions, showing brown-yellow cathode luminescence colors. Oil generation peak of the Longmaxi source rocks, which were the main source of the Shiniulan reservoirs, was from ~190 Ma to ~150 Ma. Oil to gas cracking happened at ~135 Ma. The trapping pressure of methane inclusions is 51.77-57.46 MPa, and the pore fluid pressure coefficient is 1.26-1.40. Since the Yanshanian period, a series of tectonic movements have taken place in the Dingshan area, which uplifts and lead to erosion and fracturing of the Dingshan area is accounts for the destruction of the Shiniulan gas reservoirs.

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The high-angle, structural genetic calcite veins of the Ordovician in the Shunnan-Gucheng area in the Tarim Basin provide a convenient study of fluid properties, hydrocarbon migration, and accumulation events in the fault zone of this area. Based on detailed core investigation, studies on fluid inclusions in calcite veins and comparison of geochemical characteristics of limestone matrix and calcite veins were carried out. Multiple types of hydrocarbons inclusion (e.g., dry asphalt inclusion,three-phase hydrocarbon inclusion, oil and water inclusion,gas-rich inclusion) were found in calcite veins. Furthermore, the coexisted aqueous inclusions with the gas–liquid phase had a high homogenization temperature (130–160 °C). The distribution characteristics of 18O-depleted (δ18O: −13.1‰ to −8.7‰), 87Sr-enriched (87Sr/86Sr: 0.708 879 to 0.710 432), relatively high total Rare Earth Elements (REEs), and positive Europium Anomalies indicated that the structural origin of calcite veins was mainly derived from the dissolution of surrounding rocks and diagenetic-hydrocarbon fluids. Participation signs of meteoric water were not proved. The rich hydrocarbon inclusions in the calcite veins indicated that the north-east strike-slip fault zone in the Shunnan-Gucheng area is an essential channel for hydrocarbon migration and accumulation.

Securing and managing underground water resources requires a good knowledge of the structure, texture and connections of the reservoir, in order to develop realistic and reliable hydrogeological models. On the coastline of the Gulf of Lion Margin (S. France), the Balaruc-les-Bains deep karst reservoir is subjected to interactions between fresh, marine and deep thermal waters, respectively. Water resource usage for drinking, spa resort, and fish-farming raises important economic and social issues. These were addressed by an integrated research program, involving drilling of an exploratory borehole across the Jurassic carbonate reservoir. This contribution analyses the 750 m cores, in order to (i) characterise the architecture and evolution of the karst reservoir and (ii) investigate the paleo-fluids circulations, witnessed by calcite and dolomite mineralization in the fractures, karst cavities, and as cement of tectonic beccia. The structure of the reservoir is characterised by the superposition of several aquifers separated by marly intervals. At shallow level, the initial grainstone is incompletely dolomitized in metre-thick intervals, while limestone in the 210–340 m interval was completely dolomitized at an early stage. Dolomite has been subjected to penetrative extensional cataclastic deformation, while the preserved limestone is affected by normal faulting, resulting from NNE–SSW extension. Distinct types of karsts have been documented, from the top of the reservoir (paleo-lapiaz filled with Burdigalian marine marls), down to 500 m depth (paleo-endokarst filled with continental silts). The upper reservoir (75–150 m) is intensely karstified, and includes 0.1 to 1 m-wide cavities, where present day water fluxes are documented. Analyses of calcite and dolomite crystallisation under natural light and cathodoluminescence indicate precipitation from distinct fluids: formation water in chemical equilibrium with the host rock, water rich in oxides and hydroxides, ascending hydrothermal fluid and corrosive water of meteoric origin. Alternate dolomitization and calcitization observed in the upper reservoir suggests alternate flows of karstic freshwater and marine salt-water. Vertical, metre-long and centimetre wide open cracks are presently used for large water flows; several generations of syntaxial calcite growth provide evidence for varying chemistry of the circulating fluids. Structural cross cutting relationships allowed us to establish a relative chronology of events, which can be correlated with the regional geodynamic evolution. The study reveals that the present-day reservoir architecture results from the superimposition of structures formed during the Early Cretaceous extension, Maastrichtian-Eocene Pyrenean shortening, and Oligocene rifting of the Gulf of Lion. The reservoir was also shaped by successive karstification episodes and marine transgressions. Although the present-day hydrological system is controlled by, and reactivates structures inherited from a long-term evolution, it is characterised by frequent turn-overs of the water flow, tuned by high-frequency external forcings such as sea-level changes driven by Pleistocene glacio-eustasy, or varying precipitation rates.

The preservation of natural gas can be easily dismissed by late crustal deformations, which are often concealed by fracture-filling calcite vein networks. This study introduces a novel approach to confine the timeframe of natural gas-leakage processes by employing coupled in situ U–Pb dating and clumped isotope (Δ 47) analysis of late-fracture calcite veins associated with brittle deformation in caprock/unconventional reservoirs during basin uplift. Specifically, Δ 47 and U–Pb data were acquired for fracture calcite veins that formed in high-angle or vertical fractures within the early Silurian shale reservoirs of the Southeastern Sichuan Basin in China. Absolute U–Pb ages revealed two distinct calcite precipitation events at 6.89 ± 0.18 and 3.55 ± 0.11 Ma, respectively. The primary mechanism for shale gas escape from early Silurian shale reservoirs was the leakage of natural gas through activated high-angle faults that had remained unsealed since at least 6.89 Ma. At approximately 3.55 Ma, the overlying weathered layer was lifted to the surface of the Earth, facilitating the connection between meteoric water and shale reservoirs through activated fractures. Natural gas leakage occurred concurrently with meteoric water infiltration, and a non-linear mixing effect between methanogenesis and meteoric water, as well as intense ventilation along the water-bearing fracture surface, is identified as the cause of delayed late-fracture calcite precipitation, leading to an abnormal δ13C of calcite vein (up to +22.1‰). This approach holds significant implications for assessing natural-gas preservation in uplifted basins worldwide. • Late crustal movements can mask natural gas risks, challenging preservation assessments. • Combined U–Pb dating and clumped isotope analysis on calcite veins show timing of natural gas leakage events at 6.89 Ma and 3.55 Ma. • Lifting of weathered layer connected meteoric water to shale reservoirs, causing natural gas leakage and abnormal calcite precipitation. [ABSTRACT FROM AUTHOR]

In this study, we describe the characteristics of tectonic stylolites and related veins affecting a low-porosity micritic limestone (Jurassic carbonates, Les Matelles, South of France) in order to unravel the conditions of initiation and interaction between pressure-solution and fracturing in such rock. Field description, various petrographic and microstructural investigations (cathodoluminescence, SEM imaging, EBSD analysis), and petrophysical/geochemical analyses (Hg porosimetry, XRD, EPMA) are used. We document that pressure-solution initiates at micropores and propagates along calcite grain contacts, connecting surrounding stylolite micro-segments, and progressively concentrates insoluble material such as clays and siliceous particles. The dissolved material is evacuated to the veins where the newly-formed porous space is progressively filled by calcite cement. These deformation processes are strictly restricted to the stylolitic interface and veins, as no modification of porosity or grain deformation is detected in the neighboring host rock. This is due to the low-permeability of the surrounding host rock impeding the evacuation of dissolved material and fluids through interstitial porosity around the pressure-solution zone, leading to overpressure and veins formation. The water release and microporosity caused by diagenesis of the clay fraction (smectite-illite transformation) are discussed as key diagenetic processes instigating the conditions of pressure-solution initiation, then tectonic stylolite formation in low-porosity limestones. • The pressure-solution process is restricted to the stylolitic interface. • Stylolites propagate along grain contact and concentrate insoluble material. • Soluble material is evacuated to the vein formed by hydraulic fracturing. • The material transfer from stylolite to vein is a closed system. • Clay diagenesis releasing water and porosity allows the pressure-solution initiation. [ABSTRACT FROM AUTHOR]

The lack of effective paleogeothermometers restricts the study of the thermal history of carbonate strata. Carbonate clumped isotope thermometry and in-situ U–Pb dating are appropriate for reconstructing the thermal history of carbonate strata. Herein, this study analyzed clumped isotope compositions and U–Pb ages of calcite fabrics, including micrite matrix and veins, from Permian carbonate strata in the eastern Sichuan Basin. U–Pb dating of the micrite matrix was performed to rule out the influence of recrystallization and determine the diagenetic age of the samples. Clumped isotope temperatures of the four micrite matrix samples ranged from 102 °C to 137 °C. The maximum paleotemperature derived from a solid-state reordering model was between 210 °C and 220 °C. From all four samples, three calcite veins yielded crystallization temperatures corresponding to 160 ± 10 °C, 60 ± 10 °C, and 29 ± 4 °C, as determined by clumped isotope and solid-state reordering model analyses. In-situ U–Pb dating provided corresponding crystallization ages of 159 ± 17 Ma, 256.6 ± 5.5 Ma, and 17.86 ± 0.8 Ma. The crystallization ages and temperatures of the three calcite veins align well with the thermal history of the Permian strata, indicating a high degree of accuracy. This study introduces a new strategy for reconstructing the thermal history of carbonate strata. The thermal history can be quantified using the constraints of the crystallization ages and temperatures from different stages of calcite veins or cements. This approach is suitable for determining the maturation progress of the source rock and conducting oil and gas exploration in petroliferous basins. • Permian strata's maximum paleotemperature simulated by clumped isotope is 210–220 °C. • Solid-state reordering model can get the calcite vein's crystallization temperature. • Calcite veins are essential to reconstructing the thermal history of carbonate strata. [ABSTRACT FROM AUTHOR]

The distribution of oxygen isotopes between calcite and fluid inclusions has demonstrated utility for reconstructing near-surface calcite precipitation temperatures. For calcite that formed at depth, however, the resilience of this paleothermometer to diagenetic oxygen isotope alteration is poorly constrained. Clumped isotopes also document calcite precipitation temperatures and are similarly vulnerable to diagenetic alteration. Post-entrapment isotope exchange between calcite and fluid-inclusions could alter the calcite-fluid oxygen isotope distribution (α c-fi), as well as the clumped isotope composition (Δ 47) of calcite, and therefore these two seemingly independent paleo-thermometers are potentially linked via the same alteration process. Using closed-system batch fractionation equations, we have modelled various scenarios of oxygen isotope exchange between water and host-rock during burial, as well as internal oxygen isotope exchange between calcite and fluid inclusions during exhumation. Assuming both paleo-thermometers record concordant temperatures at the time of vein formation, our models predict that if a fraction of calcite is available for isotopic interaction with fluid inclusions, the fluid inclusion and clumped isotope-derived paleothermometers yield discrepant temperature estimates after exhumation. We show that the fluid inclusion thermometer is more sensitive to isotopic alteration than the clumped isotope thermometer and that the mass balance of oxygen between calcite and fluid inclusions determines the sensitivity of both paleothermometers as well as the vulnerability of fluid inclusions (δ18O fi) to diagenetic overprinting. We applied coupled clumped isotope and fluid inclusion measurements on calcite veins from the External Albanides (Albania), which were formed at depth and subsequently exhumed, in order to compare natural samples to our isotope exchange model. These veins show strongly discrepant calcite-water equilibrium temperatures and clumped isotope temperatures, suggesting the fraction of calcite available for isotope exchange with internal fluids may indeed be a key parameter of diagenetic alteration during exhumation. Even though the clumped isotope temperatures of our samples appear to be insensitive towards internal oxygen isotope exchange, our model predicts that at low burial temperatures, the carbonate clumped isotope thermometer may be susceptible to alteration by diagenetic isotope exchange with fluid inclusions under certain conditions. [ABSTRACT FROM AUTHOR]

Based on the published data of pillow lava-hosted mineralized veins, this study compares post-magmatic fracturing, fluid flow, and secondary mineralization processes in the Troodos and Izu–Bonin supra-subduction zone (SSZ) and discusses the crucial factors for the development of distinct vein types. Thin section and cathodoluminescence petrography, Raman spectroscopy, fluid inclusion microthermometry, and trace element and isotope (87Sr/86Sr, δ18O, δ13C, Δ47) geochemistry indicate that most veins consist of calcite that precipitated from pristine to slightly modified seawater at temperatures < 50 °C. In response to the mode of fracturing, fluid supply, and mineral growth dynamics, calcites developed distinct blocky (precipitation into fluid-filled fractures), syntaxial (crack and sealing), and antitaxial (diffusion-fed displacive growth) vein microtextures with vein type-specific geochemical signatures. Blocky veins predominate in all study areas, whereas syntaxial veins represent subordinate structures. Antitaxial veins occur in all study areas but are particularly abundant in the Izu–Bonin rear arc where the local geological setting was conducive of antitaxial veining. The temporal framework of major calcite veining coincides with the onset of extensional faulting in the respective areas and points to a tectonic control on veining. Thus, major calcite veining in the Troodos SSZ began contemporaneously with volcanic activity and extensional faulting and completed within ~ 10–20 Myr. This enabled deep seawater downflow and hydrothermal fluid upflow. In the Izu–Bonin forearc, reliable ages of vein calcites point to vein formation > 15 Myr after subduction initiation. Therefore, high-T mineralization (calcite, quartz, analcime) up to 230 °C is restricted to the Troodos SSZ. [ABSTRACT FROM AUTHOR]

Abstract International Ocean Discovery Program Expeditions 352 and 351 drilled into the Western Pacific Izu‐Bonin forearc and rear arc. The drill cores revealed that the forearc is composed of forearc basalts (FAB) and boninites and the rear arc consists of FAB‐like rocks. These rocks are pervaded by calcite veins. Blocky vein microtextures enclosing host rock fragments dominate in all locations and suggest hydrofracturing and advective fluid flow. Significant diffusion‐fed and crystallization pressure‐driven antitaxial veining is restricted to the rear arc. The lack of faults and presence of an Eocene sedimentary cover in the rear arc facilitated antitaxial veining. Rare earth element and isotopic (δ18O, δ13C, 87Sr/86Sr, and Δ47) tracers indicate varying parental fluid compositions ranging from pristine to variably modified seawater. The most pristine seawater signatures are recorded by FAB‐hosted low‐T (95% seawater and

Serpentinization and calcite precipitation of mantle peridotites exhumed along detachment faults at the slow- to ultraslow-spreading centers can provide important clues to the hydrothermal alteration processes. The Tianxiu hydrothermal field is a new-found active and ultramafichosted hydrothermal vent site along the Carlsberg Ridge, Northwest Indian Ocean. Two types of calcite veins are recognized in serpentinized harzburgite samples collected from the seafloor at the water depth of 3 500 m (3.67°N/63.83°E) and 400 m north of Tianxiu hydrothermal field. Calcite veins I occur in the fractures that cut through mesh texture in the highly serpentinized harzburgite, while calcite veins II precipitate within the mesh texture in the relatively weaker serpentinized harzburgite. Both veins show similar δ13CPDB (+0.54‰ and +0.58‰) but different δ18OPDB(−16.67‰ and +4.46‰) values, suggesting that they were derived from the same carbon source but precipitated at different temperatures. Taking the deep seawater temperature of 2 °C as the precipitation temperature of the calcite veins I, the equilibrium δ18OV-SMOW of calcite-precipitating fluid was calculated to be 1.78‰, which is close to the average δ18OV-SMOW value (1.74‰) of vent fluid samples from the ultramafic-hosted hydrothermal systems worldwide. The formation temperature of calcite veins II is inferred to be approximately 134 °C, based on the calculated δ18OV-SMOW above. The temperature differences of calcite precipitation probably resulted from the fluid cooling conductively and mixing with seawater along the presumed fractures during slow upflow. The low-temperature calcite postdates the mesh texture, while the high-temperature calcite may precipitate under relatively low water/rock ratios, alkaline and reduced conditions among the mesh texture, which is revealed by the geochemical models. Therefore, it is suggested that they both have been influenced by hydrothermal fluids and the sampling site is near the discharge zone of hydrothermal circulation. [ABSTRACT FROM AUTHOR]

International Ocean Discovery Program Expeditions 352 and 351 drilled into the Western Pacific Izu‐Bonin forearc and rear arc. The drill cores revealed that the forearc is composed of forearc basalts (FAB) and boninites and the rear arc consists of FAB‐like rocks. These rocks are pervaded by calcite veins. Blocky vein microtextures enclosing host rock fragments dominate in all locations and suggest hydrofracturing and advective fluid flow. Significant diffusion‐fed and crystallization pressure‐driven antitaxial veining is restricted to the rear arc. The lack of faults and presence of an Eocene sedimentary cover in the rear arc facilitated antitaxial veining. Rare earth element and isotopic (δ18O, δ13C, 87Sr/86Sr, and Δ47) tracers indicate varying parental fluid compositions ranging from pristine to variably modified seawater. The most pristine seawater signatures are recorded by FAB‐hosted low‐T (<30 °C) vein calcites. Their 87Sr/86Sr ratios intersect the 87Sr/86Sr seawater curve at ~35–33 and ~22 Ma. These intersections are interpreted as precipitation ages, which concur with Pacific slab rollback. Boninite‐hosted low‐T (<30 °C) vein calcites precipitated from seawater that was modified by fluid‐rock interactions. Mixing calculations yield a mixture of >95% seawater and <5% basaltic 87Sr/86Sr. In the rear arc, low‐T rock alteration lowered the circulating seawater in δ18O and 87Sr/86Sr. Thus, vein calcites precipitated from modified seawater with up to 20–30% basaltic 87Sr/86Sr at temperatures up to 74 ± 12 °C. These results show how the local geology and vein growth dynamics affect microtextures and geochemical compositions of vein precipitates. Plain Language Summary: Our knowledge of the oceanic crust relies on crustal pieces uplifted above sea level and sampling by dredging, diving, and drilling expeditions. Since uplift may involve the alteration and destruction of original geological features, International Ocean Discovery Program Expeditions 352 and 351 drilled into the Izu‐Bonin forearc and rear arc crust (Western Pacific), revealing rocks unaffected by these processes. The volcanic rocks in these drill cores are characterized by fractures through which seawater percolated from which calcium carbonate (calcite) precipitated (veining). By analyzing crystal shapes, elemental and isotopic compositions of vein calcites, this research project investigated the causes of fracturing, the geochemical composition of the percolating fluids, and the calcite formation temperatures. In the forearc calcites formed at temperatures <30 °C in fractures that opened due to high fluid pressures. These calcites precipitated from fluids ranging from unmodified seawater to seawater that was weakly modified by fluid‐rock interaction. Most seawater‐derived calcites formed between ~35 and ~33 million years. In the rear arc calcites precipitated at temperatures up to 74 °C from seawater that was modified by low‐temperature fluid‐rock interaction during which elements and isotopes were exchanged. The rear arc geology facilitated fluid diffusion and fracture‐independent veining. Key Points: In the Izu‐Bonin forearc vein calcites precipitated at <30 °C from pristine to weakly modified seawater in hydrofracturesCalcite veining (max. 74 °C) in the rear arc is characterized by weak to moderate fluid‐rock interaction, diffusive and advective fluid flowA sedimentary cover and the lack of faults facilitated diffusion‐fed and crystallization pressure‐driven antitaxial veining in the rear arc [ABSTRACT FROM AUTHOR]

Evidence of episodic fluid overpressure events noted in samples from the San Andreas Fault Observatory at Depth (SAFOD) have remained largely uncorrelated in terms of their collective significance for seismic history of the fault zone. The compositional and microstructural correlations sought in this study could shed light on questions about potential for major seismic events in the creeping segment of the SAF in central California. We used quantitative energy dispersive spectroscopy (EDS), Cathodoluminescence (CL) and Scanning Electron Microscope (SEM) imaging, and electron backscatter diffraction (EBSD) analysis to acquire geochemical and microstructural data from a suite of twenty SAFOD core samples including the damage zone and the active core of the fault. The results indicate intermittent coseismic fluid overpressure events that overprint the background aseismic creep across the fault. Analysis of trace elements and deformation in the coseismic calcite vein generations and their associated hydrothermal mineral phases indicate progressive uplift and exhumation followed by an asymmetric incursion of meteoric water into the damage zone. The same analysis suggests that the actively creeping intervals act as permeability barriers. Our results are in overall agreement with recent studies of the SAF in central California that indicate large seismic events have occurred intermittent with aseismic creep in recent geological time or suggest future potential for such events. [ABSTRACT FROM AUTHOR]

Many low-permeability, hydrocarbon-bearing rocks are productive for petroleum because natural fractures enhance hydrocarbon delivery to wellbores. Exploration and development decisions often must be made in the face of uncertainty about the presence and properties of natural fractures at scales of beds, field and plays, and how they contribute to production. Fractures patterns in subsurface rocks are challenging to predict or characterize owing to the difficulty in obtaining representative samples of fractures and the sparse set of tools for reconstructing how and when fractures grow during sedimentary basin evolution. In this study, we investigate bed-parallel fracture diagenesis in the Vaca Muerta shales (Argentina) based on a set of calcite vein collected from core across a thermal maturity sequence that ranges from the oil to dry gas window. We characterize these samples using secondary ions mass spectrometry (SIMS) measurements of stable isotope ratios, carbonate clumped isotope geothermometry and fluid inclusion analysis. These measurements precisely reconstruct the evolution of fluid geochemistry, temperature and pore fluid pressure during fracture opening. Here we show that within each studied site, all bedding parallel fibrous veins calcite formed at similar ranges of temperature. The fracture mineralization temperature increases substantially at the basin scale, from 90 °C to 120 °C, correlated with host-rock thermal maturity. We compare our constraints on carbonate and fluid temperature with apatite fission track thermal models and find that most of the fractures of the Vaca Muerta shales have formed in a relatively early stage of subsidence of the basin (c.a. 90 to 70 Ma). These ages estimations are consistent with recently published U–Pb ages on calcite veins from the outcropping area (117–61 Ma). The presence of petroleum inclusions (oil, condensate, and gas) in most of the vein's calcite fibers from cores also provides clear evidence that fracture formation was contemporaneous or posterior with petroleum generation, constraining the timing of catagenesis in the Vaca Muerta. Reconstructed paleo pressures conditions of veins formation from fluid inclusion analysis highlight significant fluid overpressure in the shale interval, which likely contributed to fracture initiation and growth. Preserved apparent Δ 47 temperatures in fibrous veins carbonates mineralization evolves gradually from 130 °C to 175 °C with increasing host rock thermal maturity. These clumped-isotope-based temperatures are systematically higher than trapping temperatures of associated fluid inclusions; one interpretation of this observation is that carbonate clumped isotope compositions re-equilibrated to near maximum burial conditions by solid-state isotopic re-ordering, yielding a record of the maximum burial temperature the shale unit experienced. The combination of paleothermometry techniques used in this study illustrates the importance of simultaneously exploring several independent geothermometers, particularly the informative combination of fluid inclusion and clumped isotope constraints, which provides a means of understanding the complex diagenesis of old sedimentary rocks that have experienced burial temperatures in the oil and gas thermal windows. • Paired clumped isotope paleothermometry and fluid inclusion analyses for time–temperature evaluation for natural fractures in the VMF. • Direct relationship between hydraulic fracturing intensity and the level of organic catagenesis (maturity) • PVT modelling of aqueous-HC fluid inclusions indicate that calcite precipitation under fluid overpressure. • Combination of FI and Δ 47 geothermometry indicate altered (reset) Δ 47 compositions during burial. [ABSTRACT FROM AUTHOR]

Calcite veins hosted in pillow lavas of the Late Cretaceous Troodos suprasubduction zone ophiolite provide insights into the timing and physicochemical environment of postmagmatic fracturing and fluid circulation through oceanic crust. This study presents rare earth element and yttrium (REE+Y) concentrations, δ13C, δ18O, 87Sr/86Sr, and clumped isotopic (Δ47) compositions of vein calcites in order to investigate their fluid sources, formation temperatures, and precipitation ages. These geochemical data are combined with microtextural analyses. Intersections of 87Sr/86Sr ratios of vein calcites with the Sr isotope seawater curve suggest two distinct calcite veining phases. Major calcite veining within an interval of ~10 Myr after crust formation is characterized by microtextures that point to extensional fracturing related to crack and sealing, host rock brecciation, and advective fluid flow. These vein calcites show REE+Y characteristics, 87Sr/86Sr ratios, and clumped isotopic compositions indicative of precipitation from seawater at <50 °C. Extended fluid residence times intensified fluid‐rock interactions and lowered Y/Ho ratios of some blocky vein calcites, whereas crack and sealing resulted in pristine seawater signatures. Low 87Sr/86Sr ratios of localized high‐temperature blocky vein calcites point to the involvement of hydrothermal fluids. These calcites show Mn‐controlled oscillatory growth zonations that probably developed in a closed system out of equilibrium. Later calcite veining (<75 Ma) may have coincided with rotation and/or uplift of the Troodos ophiolite. Microtextures of these vein calcites indicate fluid diffusion and fracture‐independent crystallization pressure‐driven veining. Their variably modified seawater signatures resulted from diffusion‐related fluid interaction with hydrothermal sediments. Plain Language Summary: The Troodos ophiolite (Cyprus) formed as oceanic crust 92 million years ago along a mid‐ocean ridge above a young subduction zone before it was uplifted to its present position 2,000 m above sea‐level. Therefore, the Troodos ophiolite constitutes a suitable research object to understand the formation and alteration of oceanic crust. Subsequent to its formation, the oceanic crust underwent structural and mineralogical changes. This investigation explores the age, chemical and physical conditions of these changes using an elemental and isotopic approach. Seawater entered the oceanic crust through fractures and in cases exchanged elements and isotopes with ambient rocks. Calcium carbonate (calcite) precipitated from these waters at temperatures mostly <50 °C and filled fractures. These structures are termed veins. A few vein calcites formed at temperatures up to ~220 °C and show distinguishable zones that developed automatically without external input. The principal mineralization finished ~10 million years after the onset of oceanic crust formation. Later calcite mineralization, less than 75 million years ago, is characterized by diffusive fluid flow and fibrous calcites. The crystallization of these calcite fibers pushed the rock aside. As a result of their different origins, calcites have specific crystal shapes, distinct elemental and isotopic characteristics. Key Points: The Troodos oceanic crust experienced a 10‐Myr‐long major phase of predominantly low‐temperature blocky and syntaxial calcite veiningOscillatory growth‐zoned high‐temperature blocky vein calcites precipitated from hydrothermal fluids in a closed system out of equilibriumLow‐temperature diffusion‐fed antitaxial vein calcites precipitated after the major veining phase from seawater that interacted with umbers [ABSTRACT FROM AUTHOR]

Vein mineralization observed in boreholes, quarries and outcrops of Upper Permian and Mesozoic sediments in the Thuringian Syncline, Germany, was investigated for the first time by petrography, electron microprobe analysis and stable isotope analysis. The objective was a characterization of paleo-fluid systems within this basin. Veins are mostly restricted to NW-SE trending fault systems and comprise carbonates (calcite, dolomite), minor sulfates (gypsum/anhydrite, celestite, barite), and rarely sulfides. They are variably distributed within the Late Paleozoic to Mesozoic succession. Calcite vein mineralization occurs in almost all Triassic strata, though dominating in the Lower Muschelkalk subgroup (mu). Gypsum/anhydrite veins occur in the Middle Keuper subgroup (km), Middle Muschelkalk subgroup (mm), Middle and Upper Buntsandstein subgroup (sm, so) as well as in the Upper Permian (Zechstein). Sulfate and carbonate isotope analyses indicate that most vein mineralization dominantly crystallized from intraformational fluids within the Upper Permian and Triassic sediments. Crystallization from descending meteoric waters was observed especially for calcite veins in the Lower Muschelkalk, but also for gypsum/anhydrite veins in the Upper Buntsandstein. Mineralization from ascending, carbonate-pH-buffered, warm waters was restricted to individual parts of the southern, deep reaching main border fault zone of the Thuringian Syncline. Mixing and fault crossing fluid movements are subordinate within the Thuringian Syncline. We conclude that no large scale cross-formational fluid flow occurred in Thuringian Syncline over the last millions of years. • No large scale cross-formational fluid flow within Thuringian Syncline • Precipitation first and foremost from intraformational fluids • Close to the surface mineralization subordinately from descending meteoric water • Locally indications for ascending, warmer fluids along the main fault system [ABSTRACT FROM AUTHOR]

The continent is the second largest carbon sink on Earth's surface. With the diversification of vascular land plants in the late Paleozoic, terrestrial organic carbon burial is represented by massive coal formation, while the development of soil profiles would account for both organic and inorganic carbon burial. As compared with soil organic carbon, inorganic carbon burial, collectively known as the soil carbonate, would have a greater impact on the long-term carbon cycle. Soil carbonate would have multiple carbon sources, including dissolution of host calcareous rocks, dissolved inorganic carbon from freshwater, and oxidation of organic matter, but the host calcareous rock dissolution would not cause atmospheric CO2 drawdown. Thus, to evaluate the potential effect of soil carbonate formation on the atmospheric pCO2 level, different carbon sources of soil carbonate should be quantitatively differentiated. In this study, we analyzed the carbon and magnesium isotopes of pedogenic calcite veins developed in a heavily weathered outcrop, consisting of limestone of the early Paleogene Guanzhuang Group in North China. Based on the C and Mg isotope data, we developed a numerical model to quantify the carbon source of calcite veins. The modeling results indicate that 4–37 wt% of carbon in these calcite veins was derived from atmospheric CO2. The low contribution from atmospheric CO2 might be attributed to the host limestone that might have diluted the atmospheric CO2 sink. Nevertheless, taking this value into consideration, it is estimated that soil carbonate formation would lower 1 ppm atmospheric CO2 within 2000 years, i.e., soil carbonate alone would sequester all atmospheric CO2 within 1 million years. Finally, our study suggests the C–Mg isotope system might be a better tool in quantifying the carbon source of soil carbonate. [ABSTRACT FROM AUTHOR]

Abstract The dissolution of marine shales and its influence on reservoir physical properties was revealed based on shale samples from the Ordovician-Silurian Wufeng and Longmaxi Formations in the southeast of the Sichuan Basin, China. Three kinds of gas storage spaces were formed by dissolution, including intergranular dissolution (InterD) pores, intragranular dissolution (IntraD) pores and dissolution microfractures (DmF). The diameters of the InterD and IntraD are 10.2–72.4 μm and 0.13–1.52 μm, respectively. The apertures of the DmF are between 0.5 and 11.2 μm. The dissolution effect resulted in a diagenetic environment for quartz cementation and a material basis for calcite veins. The main controlling factors of the dissolution effect are the mineral constituent content in the matrix, the amount of organic matter and the strata burial rate. Dissolution pores and fractures play important roles in shale gas enrichment and migration. The porosity of shale reservoirs with DmF is twice the porosity of reservoirs without DmF, and the spaces formed by dissolution pores and fractures are well connected. A new model for shale gas flow in shale reservoirs was proposed, which provides a new understanding for the connection between organic material pores, and the results can be used for shale reservoirs worldwide. Highlights • Calcite veins are effective channels for shale flow. • Dissolution pores and dissolution fractures play an important role in the transfusion of shale gas. • Three main controlling factors of dissolution in shale reservoirs are given. • A new model for shale gas flow in shale reservoirs is proposed. [ABSTRACT FROM AUTHOR]

The extensional Val Roveto Fault, which is the longest exhumed potentially-seismogenic structure of central Apennines, Italy, is examined to constrain earthquake-related fluid circulation and fluid sources within shallow carbonate-hosted faults. The study focuses on fault-related comb and slip-parallel veins that are calcite-filled and cut through the principal surface of the Val Roveto Fault. We observe multiple crack-and-seal events characterized by several veining episodes, probably related to different slip increments along the fault plane. We show that vein calcite precipitated in Late Pleistocene time below the present-day outcrop level at a maximum depth of ∼350 m and temperatures between 32 and 64 °C from meteoric-derived fluids modified by reactions with crustal rocks and with a mantle contribution (up to ∼39%). The observed warm temperatures are not compatible with a shallow (≤∼350 m) precipitation depth, which, in this region, is dominated by circulation of cold meteoric water and/or shallow groundwater. Based on structural–geochemical data, we propose that deep-seated crust–mantle-derived warm fluids were squeezed upward during earthquakes and were hence responsible for calcite precipitation at shallow depths in co-seismic comb and slip-parallel fractures. As comb- and slip-parallel veins are rather common, particularly along seismogenic extensional faults, we suggest that further studies are necessary to test whether these veins are often of co-seismic origin. If so, they may become a unique and irreplaceable tool to unravel the seismic history of hazardous active faults. [ABSTRACT FROM AUTHOR]

Billi et al. (2017) proposed a new interpretation for the origin and internal structure of thermogene travertine deposits. On the basis of evidence from two quarries located in southern Tuscany (Italy), they interpreted some travertine beds as calcite veins and argued that undulating travertine beds formed by syn -diagenetic (i.e. non-tectonic) folding that was caused by laterally-confined volume expansion caused by incremental veining. They assumed that such a process causes changes to the rock properties, including porosity reduction, rock strengthening, and age rejuvenation. The interpretations by Billi et al. (2017) challenge and question the current understanding and interpretation of thermogene travertine deposits. This understanding, based on numerous studies since the 1980s, is that these deposits form from thermal water flowing downslope, and precipitating calcium carbonate. Here, we explain how the comparison with active depositional systems is essential for the understanding the origin of structures in older, inactive travertine deposits, such as those studied by Billi et al. (2017). We further argue that the three-dimensional setting of travertine deposits should be taken into account in order to discuss the possible development of secondary structures. Indeed travertine deposition on slopes typically leads to the formation of terraced morphologies with pools bordered by rounded rims and separated from each other by steep walls. The resulting three-dimensional structures can be misinterpreted as asymmetric folds in two-dimensional views (i.e., in saw-cut walls of quarry). In this paper we debate the interpretations offered by Billi et al. (2017) and their criteria to recognise syn -diagenetic, non-tectonic folds in travertine deposits, and explain why many of their ideas are questionable. [ABSTRACT FROM AUTHOR]

The Chingshui geothermal field, a moderate-temperature and water-dominated hydrothermal system, was the site of the first geothermal power plant in Taiwan. Many geological, geophysical and geochemical studies using more than 21 drilled wells have been performed since the 1960s. However, there are still controversies regarding the heat and fluid sources due to the tectonically complicated geological setting. To clarify the heat and fluid sources, we analyzed clumped isotopes with carbon and oxygen isotopic compositions of calcite scaling in geothermal wells and veins on outcrops and calculated the δ 18 O values of the source fluids. Two populations of δ 18 O values were calculated: −5.8 ± 0.8‰ VSMOW from scaling in the well and −1.0 ± 1.6‰ to 10.0 ± 1.3‰ VSMOW from outcropping calcite veins, indicative of meteoric and magmatic fluid sources, respectively. Meanwhile, two hydrothermal reservoirs at different depths have been identified by magnetotelluric (MT) imaging with micro-seismicity underneath this area. As a result, we propose a two-reservoir model: the shallow reservoir provides fluids from meteoric water for the scaling sampled from wells, whereas the deep reservoir provides magmatic fluids from deep marble decarbonization recorded in outcropping calcite veins. [ABSTRACT FROM AUTHOR]

The Jabal Qusaybah Anticline, in north Oman, is affected by syn-folding strike-slip and extensional fault zones developed during foreland deformation ahead of the Northern Oman Mountains thrust wedge, in Cenozoic times. Migration of fluids in fault-damage zones is recorded in complex calcite vein networks. By employing the microthermometric and compositional microanalysis of the fluid inclusions (crush-leach), two distinct generations of veins have been studied. The aim was to determine the source of elevated salinity in fluids involved in their cementation and explain their compositional evolution through fluid-rock interactions. The ionic ratios (Na/Br and Cl/Br) obtained from crush-leach analysis give supporting evidence that the elevated salinity of fluid inclusions in both vein groups originated from an evaporated seawater beyond the onset of halite precipitation (residual brines). The results reveal a gradual increase in salinity of the fluids, F/Cl molar ratios, as well as Li/Cl molar ratios. These results imply the progressively increasing contribution of evaporitic residual brines and fluids that interacted with, or were derived from siliciclastic rocks. We suggest that the most likely origin of the former fluids is provided by residual brines associated with precipitation of the Ara evaporites (Cambrian). The regional driving mechanism for such a significant fluid migration is believed to be compaction-driven upward flow that was channeled into faults and fractures during major deformational events. [ABSTRACT FROM AUTHOR]

Calcite veins in carbonate fracture have been investigated by petrographic, fluid inclusion, geochemical analyses and coupled with basin modeling techniques to provide useful insights into fluid activity and deformation conditions of the Cambrian to Triassic Shizhu synclinorium from the western region of Mid-Yangtze, central China. The results of the fluid inclusion microthermometry show a wide range of homogenization temperatures (78.6-215.5 °C) and salinities (0.18-23.11 wt.% NaCl equivalent), indicating the formation under diverse fluid conditions. All the calcite veins have negative Ce anomalies, which are the typical characteristic of marine carbonate sediments; it is therefore plausible that calcite veins were precipitated from the marine basin fluid. The stable carbon iso-topic compositions of calcites ( δ C=-2.5‰-4.26‰) and host limestones ( δ C=-3.56‰-5.80‰) are very similar with a correlation coefficient of 0.86, however, four calcites from the Lower Permian and Lower Triassic show lower δ C values relative to the host limestones, and they are depleted in total REE concentrations (ΣREE ratio varies from 0.74 to 2.06), suggesting the derivation of dissolved carbon from marine carbonates hosting the calcite veins and, less commonly, from the degradation of organic matter. Calculated δ O of the fluids-precipitating calcites ( δ O=-0.41‰-14.42‰), Sr/Sr ratios varying in the range of coeval seawater and the distinct REE pattern simultaneously suggest calcite-forming fluids in each stratigraphic unit could have formed from the involvement of fluids that originated from coeval seawater and evolved through different degrees of water rock interaction. However, the presence of more radiogenic Sr/Sr ratios than coeval seawater and pronounced positive Eu anomalies in calcites of Lower to Middle Ordovician rocks indicate that terrestrial input from upper strata mudstone and siliciclastic rocks could be involved in the precipitation of the Ordovician calcite. Fluid-inclusion data combined with burial and thermal history modeling indicate there was large-scale flow of evolved basinal fluids through the carbonate formation fractures spanning a time frame from 135 to 50 Ma (Early Cretaceous-Eocene). Therefore, the geochemical characteristics of calcite veins can provide the basis for deformation events in Late Yanshanian and Early Himalayan orogeny. [ABSTRACT FROM AUTHOR]

• Use clumped isotope thermometry combined with their bulk isotopic compositions to reconstruct thermal structures in geothermal system. • Identify the magmatic/metamorphic origin for heat sources underneath the Tuchang-Jentse Geothermal Field. • Rhombic calcites in the open cracks inherit concentrated δ18O fluid values derived from meteoric origin and heated at current reservoir temperatures. • Prove clumped isotope thermometer could provide precise temperature estimation for drill cuttings in the carbonate-dominated system during the exploration period. Temperature and oxygen isotope composition of fluids, which are critical for reconstructing thermal structures and characterizing hydrothermal fluids in a geothermal system, can be obtained using carbonate clumped isotope analysis. Ideally, carbonate clumped isotope compositions (Δ47) recording the thermal fluid temperatures and compositions for fault-associated veins and rhombic calcite crystals inside open cracks demonstrate previous tectonic activities and present reservoir conditions, respectively. We studied the clumped isotope geochemistry of veins and travertines in outcrops and cuttings from exploration wells in the Tuchang–Jentse geothermal field in Taiwan. The Δ47-based temperatures (Δ47-T; 161 − 8 + 8 to 238 − 14 + 16 °C) and calculated δ18O fluid values (+2.0 to +5.0‰) of vein calcites were the highest, indicating mixing of the magmatic/metamorphic fluids with the meteoric water after water–rock interaction in the deep thermal fluid cycle and migration to shallow areas by fault activity. Rhombic calcites with high Δ47-T (142 − 6 + 6 to 185 − 4 + 5 °C) and low calculated δ18O fluid (−9.1 to −5.3‰) correspond to downhole temperatures and measured δ18O fluid of thermal fluids in the exploration wells, respectively, suggesting that the latest thermal fluid was of meteoric water origin. Travertines near faults have low calculated δ18O fluid (−8.9 to −1.0‰) and Δ47-T that are above air temperatures (32 − 9 + 9 to 95 − 9 + 10 °C), implying that the local groundwater was subsequently heated by or mixed with deep fluid. Carbonate clumped isotope thermometry application demonstrates that the carbonate clumped isotope thermometer not only precisely estimates temperature in the carbonate-dominated system using drill cutting samples during the exploration phase, but also reveals the spatial and temporary evolution of geothermal fluids used as a reference for future site selection planning. [ABSTRACT FROM AUTHOR]

The San Andreas Fault Observatory at Depth (SAFOD), near Parkfield, California, is a borehole drilled through two active deforming zones of the San Andreas fault, the Southwest Deforming Zone (SDZ) and the Central Deforming Zone (CDZ). These zones accommodate displacement by seismic slip and aseismic creep. Elevated fluid pressures and fluid–rock interactions have been proposed to explain the low apparent strength and aseismic creep observed, but the origin of the fluids and existence of high fluid pressures remains uncertain. We use clumped-isotope thermometry and δ 18 O–δ 13 C compositions of calcite in veins to constrain the origin of paleofluids and compare these results to the isotopic composition of modern-day pore fluids from the SAFOD borehole and nearby areas. We observe that: (1) calcite vein temperatures vary from 81 to 134 °C, which overlaps the current ambient borehole temperatures of 110–115 °C at sampled depths; (2) vein calcite is not in carbon isotope equilibrium with modern-day pore fluids; (3) the δ 18 O values of paleofluids close to the SDZ and CDZ, calculated from vein δ 18 O and temperature data, are not in equilibrium with local modern-day pore waters but approach equilibrium with modern pore waters far from these zones; and (4) syntectonic vein calcite is only in C- and O-isotopic equilibrium with their host rocks within the SDZ and CDZ. Spatial patterns of δ 18 O and δ 13 C show little evidence for across-fault fluid-flow. Clumped isotope temperatures are consistent with locally-derived fluid sources, but not with continuous or episodic replenishment of fluids from shallow sedimentary brines or deep fluid sources. Our findings are compatible with flow of meteoric fluids from the southwestern damage zone into the SDZ and CDZ, which would have favored the formation of weak phyllosilicates and contributed to the present day weakness of the two actively deforming zones. [ABSTRACT FROM AUTHOR]

Solid bitumen in calcite veins in Natih limestone on the southern flank of the Jebel Akhdar Anticline provide evidence for at least two previously unrecognized petroleum migration events in the Oman Mountains. We present field observation of bituminous calcite veins combined with microscopy using highly polished thin sections. This allows imaging of solid bitumen in reflected light and study of its microstructural context in transmitted light. Straight and en échelon, black impregnated, bedding-normal Natih A calcite veins strike 110°. They formed as one of the earliest structures in an extensional stress regime at the end of Cretaceous (Turonian–Santonian) either by flexure of the Arabian plate (Wasia–Aruma break) or by subsidence during subduction. The veins always contain planar arrays of small (< 10 μm) intracrystal solid bitumen inclusions and may contain angular mosaic type solid bitumen associated with white, solid bitumen-free calcite and/or round, homogeneous type solid bitumen. The solid bitumen formed in multiple events and were most likely derived from the Natih B source rocks. During the first migration event, microfracturing during obduction of the Semail ophiolite and emplacement of the Hawasina thrust sheets in Santonian–Campanian times formed pathways for oil into the veins. Mosaic type solid bitumen formed during further vein growth. It has a higher solid bitumen reflectance (BR r = 3.40–3.76%) combined with a high optical anisotropy compared to the underlaying thermally overmature Natih B source rock (BR r = 3.10–3.14%). The higher reflectance of mosaic type solid bitumen is interpreted to result from deformation and does not reflect maximum burial temperatures which are inferred to have been about 225 °C. The second migration event is indicated by low-reflective homogeneous type solid bitumen with palaeotemperatures (BR r = 0.86–0.92%; about 145 °C) lower than maximum burial. It occurs along pressure solution seams which cross-cut the veins showing that this is the latest event in the paragenetic sequence, interpreted to have formed after lateral intraformational oil migration from the active Natih oil kitchen located approximately 40 km SW of the study area during doming and uplift of the Oman Mountains in Oligocene to Pliocene times. [ABSTRACT FROM AUTHOR]