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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]

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 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 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]

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]

• 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]

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]

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]

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]

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]

• 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]

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]

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]

Calcite veins at outcrop in the Mesozoic, oil-bearing Wessex Basin, UK, have been studied using field characterization, petrography, fluid inclusions and stable isotopes to help address the extent, timing and spatial and stratigraphic variability of basin-scale fluid flow. The absence of quartz shows that veins formed at low temperature without an influence of hydrothermal fluids. Carbon isotopes suggest that the majority of vein calcite was derived locally from the host rock but up to one quarter of the carbon in the vein calcite came from CO2 from petroleum source rocks. Veins become progressively enriched in source-rock-derived CO2 from the outer margin towards the middle, indicating a growing influence of external CO2. The carbon isotope data suggest large-scale migration of substantial amounts of CO2 around the whole basin. Fluid inclusion salinity data and interpreted water-δ18O data show that meteoric water penetrated deep into the western part of the basin after interacting with halite-rich evaporites in the Triassic section before entering fractured Lower and Middle Jurassic rocks. This large-scale meteoric invasion of the basin probably happened during early Cenozoic uplift. A similar approach was used to reveal that, in the eastern part of the basin close to the area that underwent most uplift, uppermost Jurassic and Cretaceous rocks underwent vein formation in the presence of marine connate water suggesting a closed system. Stratigraphically underlying Upper Jurassic mudstone and Lower Cretaceous sandstone, in the most uplifted part of the basin, contain veins that resulted from intermediate behaviour with input from saline meteoric water and marine connate waters. Thus, while source-rock-derived CO2 seems to have permeated the entire section, water movement has been more restricted. Oil-filled inclusions in vein calcite have been found within dominant E-W trending normal faults, suggesting that these may have facilitated oil migration. [ABSTRACT FROM AUTHOR]

Structures in Cretaceous strata in the Devils River Uplift of west Texas include folds, thrust faults, and bedding-parallel veins indicative of contractional deformation in a thrust faulting stress regime. In this study we analyze a series of small-wavelength (meters to tens of meters) folds in roadcut exposures northwest of Del Rio, Texas. The folds have WNW-ESE dominant trends, gently plunging axes, and are gentle to tight with upright to inclined axial surfaces of variable vergence. These structures are interpreted as detachment folds, with detachments within volcanic ash or mudrock beds. Observed thickening in anticline cores was by ductile flow of volcanic ash or mudrock, small-scale folding, and thrust or reverse faulting. Bed-perpendicular calcite veins are common and in some cases are offset by flexural slip on fold limbs, indicating that folding occurred after brittle failure and extension vein formation in lithified rock. Although rare, bed-parallel calcite veins are also present in the exposure and indicative of a thrust faulting stress regime. Occasional normal and reverse or thrust faults are also present in the exposures. Fluid inclusion analysis of vein cements from extension fractures and faults yielded homogenization temperatures of 71–101 °C, and estimated trapping depths of 2.2–3.5 km prior to and coeval with folding. We interpret these folds as having formed during NNE-SSW directed Laramide shortening (∼80–40 Ma) in a thrust-faulting stress regime with >2 km of overburden, rather than as either penecontemporaneous with deposition or after exhumation by caliche formation, as previously interpreted. • Analyses of small-wavelength folds in Devils River Uplift, west Texas. • Folds are typically detached above volcanic ash or mudrock beds. • Calcite veins offset by flexural-slip on fold limbs – bed-parallel veins rare. • Vein fluid inclusions trapped at 71–101 °C, and depths of 2.2–3.5 km. • Folds record NNE-SSW directed Laramide shortening. [ABSTRACT FROM AUTHOR]

This study integrates field structural data, petrographic and geochemical (δ18O, δ13C, Δ 47 , 87Sr/86Sr, and elemental composition) analyses and U–Pb dating of calcite veins cutting the Bóixols-Sant Corneli anticline (Southern Pyrenees) in order to date and to investigate the spatio-temporal relationships between fluid flow and fold evolution. This E-W trending anticline grew from Late Cretaceous to Paleocene at the front of the Bóixols thrust sheet deforming pre-growth and growth sedimentary sequences. U–Pb dating reveals Late Cretaceous to late Miocene deformation ages, which agree with the age of growth strata deposition and the sequence of deformation interpreted from field and microstructural data. Dates coeval (71.2 ± 6.4 to 56.9 ± 1.4 Ma) and postdating (55.5 ± 1.2 to 27.4 ± 0.9 Ma) Upper Cretaceous to Paleocene growth strata are interpreted to record: (i) the growth of the Bóixols-Sant Corneli anticline during the Bóixols thrust emplacement, and (ii) the tightening of the anticline during the southern tectonic transport of the South-Central Pyrenean Unit. Other ages (20.8 ± 1.2 to 9.0 ± 4.6 Ma) postdate the folding event and have been associated with the collapse of the Bóixols-Sant Corneli anticline. The geochemistry of calcite veins indicates that the fluid flow behavior varied across the Bóixols-Sant Corneli anticline through its growth, showing a compartmentalized fluid system. In the hinge of the anticline and in the upper Santonian to middle Campanian syn-orogenic sequence along the footwall of the Bóixols thrust, the similar petrographic and geochemical features between all calcite cements and host rocks point towards a locally-derived or well-equilibrated fluid system. Contrarily, along large faults such as the Bóixols thrust, and in the anticline limbs, the geochemistry of vein cements indicates a different scenario. Cements in large faults yielded the lightest δ18O values, from −8 to −14 ‰VPDB, and variable enrichment in δ13C, 87Sr/86Sr, elemental composition and δ18O fluid. This is interpreted as the migration of fluids, through fault zones, that evolved from distinct fluid origins. Cements in the fold limbs exhibit δ18O and δ13C between −8 and −6 ‰VPDB and between −10 and + 2 ‰VPDB, respectively, the lowest Sr contents and the lowest precipitation temperatures, suggesting that the anticline limbs recorded the infiltration and evolution of meteoric waters. The paleohydrological system in the Bóixols-Sant Corneli anticline was restricted to the Bóixols thrust sheet. The Upper Triassic evaporitic basal detachment likely acted as a lower fluid barrier, preventing the input of fluids from deeper parts of the Pyrenean crustal thrust system. This study provides a well-constrained absolute timing of fracturing and fluid flow during basin inversion and folding evolution and highlights the suitability of U–Pb geochronology to refine the age of fractures and veins and their sequential evolution in orogenic belts. • Twenty-three new U-Pb dates provide a well-constrained timing of deformation in an anticline that preserves pre-, syn- and post-folding fractures that do not exhibit a symmetrical orientation with respect to the fold axis, which have important implications for the interpretation of fold-fracture systems. • We further constrain the age and duration of fold evolution in the Bóixols-Sant Corneli anticline. • The geochemistry of calcite veins reveals that the fluid flow behavior varied across the different structural positions of the Bóixols-Sant Corneli anticline, evidencing a compartmentalized fluid system. • The paleohydrological system in the Bóixols-Sant Corneli anticline only involves fluids sourced above the detachment levels, which may act as a lower boundary for the fluid system, preventing the input of fluids from deeper parts of the belt. [ABSTRACT FROM AUTHOR]

We analyzed from meso-to microscale the chemical interaction (e.g., bleaching) between deep fluids and carbonate rocks in pelagic limestones exposed along the seismically active Gubbio normal fault (Northern Apennines), exhumed from ca. 2 km depth. Bleaching is enhanced by the exploitation of inherited stylolitic seams by fluids and is favored by the progressive leaching and mobilization of primary components (i.e., Ca, Fe, Pb, and Cu) and the precipitation of authigenic baryte due to temperature and/or redox potential contrast. Analysis of fluid inclusions trapped in calcite veins in the damage zone precipitated from a H 2 O–NaCl-bearing fluid(s), with low salinity (1.22–2.57 wt%NaCleq) and a range of trapping temperature between 107 °C and 185 °C, higher than the host rock peak T conditions. Analysis of fluid inclusions and noble gases from syn-kinematic calcite and mineralogy of altered rocks suggests a mixed contribution between crustal-derived fluids with diagenetic fluids containing sulphates and CO 2. We speculate that bleaching is a by-product of the circulation of such aggressive fluids with mixed contributions, likely mobilized during seismic event(s) and injected into the damage zone at shallow depths. Such processes, affecting the chemical-physical properties of limestones, are generally underestimated and should be considered when modelling hydraulic connectivity in fractured carbonate reservoirs. • Fault-rocks heterogeneity in carbonate-bearing faults forms structural domains with distinct permeability. • Bleaching of carbonates in the Gubbio fault is tectonically controlled. • Host rock alteration occurs by dissolution of calcite and hematite and precipitation of authigenic baryte at the reaction front. • Bleaching as exhumed evidence of circulation of deep-derived CO 2 -rich fluids in seismic faults. [ABSTRACT FROM AUTHOR]

We present a structural, microstructural, and stable isotope study of a calcite vein mesh within the Cretaceous Natih Formation in the Oman Mountains to explore changes in fluid pathways during vein formation. Stage 1 veins form a mesh of steeply dipping crack-seal extension veins confined to a 3.5-m-thick stratigraphic interval. Different strike orientations of Stage 1 veins show mutually crosscutting relationships. Stage 2 veins occur in the dilatant parts of a younger normal fault interpreted to penetrate the stratigraphy below. The δ18O composition of the host rock ranges from 21.8‰ to 23.7‰. The δ13C composition ranges from 1.5‰ to 2.3‰. This range is consistent with regionally developed diagenetic alteration at top of the Natih Formation. The δ18O composition of vein calcite varies from 22.5‰ to 26.2‰, whereas δ13C composition ranges from −0.8‰ to 2.1‰. A first trend observed in Stage 1 veins involves a decrease of δ13C to compositions nearly 1.3‰ lower than the host rock, whereas δ18O remains constant. A second trend observed in Stage 2 calcite has δ18O values up to 3.3‰ higher than the host rock, whereas the δ13C composition is similar. Stable isotope data and microstructures indicate an episodic flow regime for both stages. During Stage 1, formation of a stratabound vein mesh involved bedding-parallel flow, under near-lithostatic fluid pressures. The 18O fluid composition was host rock-buffered, whereas 13C composition was relatively depleted. This may reflect reaction of low 13C CO2 derived by fluid interaction with organic matter in the limestones. Stage 2 vein formation is associated with fault-controlled fluid flow accessing fluids in equilibrium with limestones about 50 m beneath. We highlight how evolution of effective stress states and the growth of faults influence the hydraulic connectivity in fracture networks and we demonstrate the value of stable isotopes in tracking changes in fluid pathways. [ABSTRACT FROM AUTHOR]

A low-angle extensional fault system affecting the non metamorphic rocks of the carbonate dominated Tuscan succession is exposed in the Lima valley (Northern Apennines, Italy). This fault system affects the right-side-up limb of a kilometric-scale recumbent isoclinal anticline and is, in turn, affected by superimposed folding and late-tectonic high-angle extensional faulting. The architecture of the low-angle fault system has been investigated through detailed structural mapping and damage zone characterization. Pressure-depth conditions and paleofluid evolution of the fault system have been studied through microstructural, mineralogical, petrographic, fluid inclusion and stable isotope analyses. Our results show that the low-angle fault system was active during exhumation of the Tuscan succession at about 180°C and 5 km depth, with the involvement of low-salinity fluids. Within this temperature - depth framework, the fault zone architecture shows important differences related to the different lithologies involved in the fault system and to the role played by the fluids during deformation. In places, footwall overpressuring influenced active deformation mechanisms and favored shear strain localization. Our observations indicate that extensional structures affected the central sector of the Northern Apennines thrust wedge during the orogenic contractional history, modifying the fluid circulation through the upper crust and influencing its mechanical behavior. [ABSTRACT FROM AUTHOR]

Abstract: In fold-and-thrust belts, shortening is mainly accommodated by thrust faults which are preferential zones for recrystallisation and mass transfer. This study focuses on a detachment fault related to the emplacement of the Monte Perdido thrust unit in the southern Pyrenees. The studied fault zone consists of a 10 m thick intensively foliated phyllonite developed within the Millaris marls, of Eocene age. The lithological homogeneity of the hanging wall and footwall allows us to compare the Millaris marls outside the fault zone with the highly deformed marls located in the fault zone and to quantify the chemical, mineralogical and volumetric changes related to deformation processes along the fault. The Millaris marls are composed of detrital quartz, illite, chlorite, minor albite and pyrite, in a micritic calcite matrix. In the fault zone, the cleavage planes are marked by clay minerals and calcite ± chlorite veins attest to fluid–mineral interactions during deformation. The mineral proportions in all samples from both the fault zone and Millaris marls have been quantified by two methods: (1) X-ray diffraction and Rietveld refinement, and (2) bulk chemical analyses as well as microprobe analyses to calculate modal composition. The excellent agreement between the results of these two methods allows us to estimate mineralogical variations using a modification of the Gresens' equation. During fault activation, up to 45 wt% of calcite was lost while the amounts of quartz and chlorite remained unchanged. Illite content remained constant to slightly enriched. The mineralogical variations were coupled with a significant volume loss (up to 45%) mostly due to the dissolution of micritic calcite grains. Deformation was accompanied by pressure solution and phyllosilicates recrystallisation. These processes accommodated slip along the fault. They required fluids as catalyst, but they did not necessitate major chemical transfers. [Copyright &y& Elsevier]

The Paraná Basin, southern Brazil, has an atypical thermal and fluid history due to the occurrence of an episodic continental flood volcanism during the Early Cretaceous. So far, there are few data about the influence of this volcanic event on the paleotemperatures and paleofluids of the Paraná Basin sedimentary rocks. The Teresina Formation in the northern flank of the Ponta Grossa dyke swarm hosts high concentration of subsurface igneous rock bodies (sills and dykes), besides its covering by a hundreds meter thick volcanic rock cap. In this study, we used fluid inclusion analysis performed in horizontal and vertical calcite veins from the Teresina Formation and from a Late Cretaceous basic dyke to estimate paleotemperatures and to characterize the composition of diagenetic paleofluids. Homogenization temperatures of requilibrated fluid inclusions show that the Teresina Formation reached temperatures above 200 °C. Horizontal parallel bedding calcite veins from the Teresina Formation record low to high salinity (2–26 wt.% NaCl eq.) aqueous paleofluids. The prevalence of high salinity fluid inclusions associated with light hydrocarbon fluid inclusions indicates deep buried fluids. Fluid inclusions in vertical calcite vein from basic dyke comprise only low salinity aqueous fluids (0–3 wt.% eq.NaCl) interpreted as dominated by meteoric water. The recorded paleotemperatures are attributed to the heating by the Paraná volcanic event during the Early Cretaceous, with the thermal effect of the volcanic rock cap surpassing the effect of nearby sills and dykes. Estimated paleotemperatures higher than 200 °C would allow the generation of light liquid and gaseous hydrocarbons. Overpressured compartments in the Teresina Formation allowed the expulsion of buried pore fluids (high salinity aqueous fluids and hydrocarbons) to fracture systems, where they mixed with meteoric water. The input of meteoric water through fracture systems connected with the surface favored hydrocarbons degradation in the early stages of source rock maturation during the Early Cretaceous. [ABSTRACT FROM AUTHOR]

Abstract: During compressive events, deformation in sedimentary basins is mainly accommodated by thrust faulting and related fold growth. Thrust faults are generally rooted in the basement and may act as conduits or barriers for crustal fluid flow. Most of recent studies suggest that fluid flow through such discontinuities is not apparent and depends on the structural levels of the thrust within the fold-and-thrust belt. In order to constrain the paleofluid flow through the Jaca thrust-sheet-top basin (Paleogene southwest-Pyrenean fold-and-thrust belt) this study compares on different thrust faults located at different structural levels. The microstructures in the different fault zones studied are similar and consist of pervasive cleavage, calcite shear veins (SV1), extension veins (EV1) and late dilatation veins (EV3). In order to constrain the nature and the source of fluids involved in fluid-rock interactions within fault zones, a geochemical approach, based on oxygen and carbon stable isotope and trace element compositions of calcite from different vein generations and host rocks was adopted. The results suggest a high complexity in the paleohydrological behaviors of thrust faults providing evidence for a fluid-flow compartmentalization within the basin. Previous studies in the southern part of the Axial Zone (North of the Jaca basin) indicates a circulation of deep metamorphic water, probably derived from the Paleozoic basement, along fault zones related to the major basement Gavarnie thrust. In contrast, in northern part of the Jaca basin, the Monte Perdido thrust fault is affected by a closed hydrological fluid system involving formation water during its activity. The Jaca and Cotiella thrust faults, in turn, both located more to the south in the basin, are characterized by a composite fluid flow system. Indeed, stable isotope and trace element compositions of the first generations of calcite veins suggest a relatively closed paleohydrological system, whereas the late calcite vein generations, which are probably associated with the late tectonic activity of the basin, support a contribution of both meteoric and marine waters. Based on these results, a schematic fluid-flow model is presented. This model allows visualization of three main fluid flow compartments along a N–S transect. [Copyright &y& Elsevier]

Calcite is a common mineral precipitated within upper crustal fault zones and associated fractures, forming veins, mineral cements and fault coatings. It has the potential to be dated using several radioisotopic systems if parent/daughter isotope abundances are suitable for the currently available analytical techniques. U-Pb dating can be most readily achieved using the in-situ laser ablation technique, which has led to a rapid growth area in the U-Pb dating of calcite. The ability to constrain the timing of fault slip hinges critically on the ability to confidently link calcite precipitation to fault movement and/or spatially and temporally associated fracture opening which requires careful microstructural and petrographic documentation. We discuss the varying reliability of different fracture fill types to make these links, and demonstrate that crack-seal-slip fills associated with faults are the most suitable for unambiguously linking calcite growth to phases of fault slip. Previous applications of the U-Pb and U-Th methods to natural examples at a range of temporal and spatial scales are reviewed, in particular their implications for the timescales of faulting and for the rates of fracture-filling. We then highlight the main limitations of the method, and provide a brief commentary on future directions. [Display omitted] • The application of calcite geochronology to the timing of mineralization directly associated with faulting is reviewed. • Examples at a range of timescales are presented. • Limitations and future directions are highlighted. [ABSTRACT FROM AUTHOR]

We combine structural and microstructural data with stable and clumped isotopes of syntectonic calcite veins or slickenfibers of five thrust and four strike-slip faults to characterize the paleofluid circulation in the Jura fold-and-thrust belt, eastern France. Syn-tectonic fluid circulation occurred along high permeability networks of breccias, foliated fault rocks, and discrete fault surfaces. At the regional scale, fluid circulation was dominated by cold meteoric fluids that infiltrated downward along both thrust and strike-slip faults, with various degrees of interaction with the carbonate host rocks. Fault-related mineralizations precipitated from fluids with δ ⁠18O values between −0.8‰ and − 7.8‰ (V-SMOW) at temperatures between 8 °C and 54 °C. The δ ⁠18O values of the paleofluids partly overlap those of modern meteoric waters of the region. The calcite mineralizations yielding the highest calculated δ ⁠18O paleofluid values are also the warmest ones and those with the heaviest carbon isotope signal, indicating strong host rock buffering and fluid heating at depth. A contribution of deep fluids from Permo-Triassic rocks cannot be excluded, but not likely. This could be related to the presence of Middle Jurassic Opalinus Clay Formation, which acted as a regional low-permeability barrier in the sedimentary succession. This can create two different fluid circulation systems characterized by warm and partly basement-derived fluids and by cold meteoric fluids, respectively, below and above the Middle Jurassic Opalinus Clay Formation. Results from this study can be used for modeling fluid circulation at the regional scale in carbonate-dominant foreland fold-and-thrust belts elsewhere in the world. [Display omitted] • Meteoric water circulated in thrust and strike-slip faults of the Jura fold-and-thrust belt. • Meteoric water channelized along high-permeability fault rocks. • Clays are regional low-permeability barrier for deep fluid upwelling. • Calcite precipitated in veins and slickenfibers at temperatures between 8 and 35 °C. • Tectonic deformation and fluid circulation occurred at depths between 0 and 0.8 km. [ABSTRACT FROM AUTHOR]

Abstract: The emplacement of calcite-filled veins perpendicular to the Dead Sea Fault Zone in northern Israel reflects strain partitioning during transpression. We present structural, geochemical, and U–Th geochronological data that constrain the mechanism, conditions and timing of vein formation. Vein walls are strongly brecciated and commonly cemented with coarsely crystalline calcite, whereas calcite-filled veins are composed of wall-parallel bands of calcite crystals. Elongated blocky and fibrous calcite crystals grew perpendicular to the vein walls and are characterised by a truncate sealing-hiatus morphology, indicating episodes of partial or complete sealing of the fractures during calcite precipitation. Stable isotope and rare-earth element and yttrium (REY) analyses indicate that calcite-filled veins precipitated by karst processes, involving meteoric water and limited fluid-rock interactions. U–Th dating results show a prolonged history of vein growth. While some veins initiated prior to 500 ka, the majority of the veins were active between 358 and 17 ka. Age constraints on vein activity correspond to an ∼E–W regional shortening phase in this sector of the Dead Sea Fault Zone, associated with an increased component of convergence during the late-Pleistocene. [Copyright &y& Elsevier]

Abstract: The origin and evolution of CO2 inclusions and calcite veins in peridotite xenoliths of the Pannonian Basin, Hungary, were investigated by means of petrographic investigation and stable isotope analyses. The fluid inclusions recovered in paragenetic olivine and clinopyroxene belong to distinct populations: type A (texturally early) inclusions with regular shapes (often with negative crystal forms) forming intragranular trails; type B (texturally late) inclusions defining randomly oriented trails that reach grain boundaries. Type B inclusions are often associated with silicate melt (type C) inclusions. Stable carbon isotope compositions in inclusion-hosted CO2 were obtained by vacuum crushing followed by conventional dual inlet as well as continuous flow mass spectrometry in order to eliminate possible lab artifacts. Olivines, clino- and orthopyroxenes of the host peridotite have oxygen isotope compositions from 5.3 to 6.0‰ (relative to V-SMOW), without any relationship with xenolith texture. Some of the xenoliths contained calcite in various forms: veins and infillings in silicate globules in veins, secondary carbonate veins filling cracks and metasomatic veins with diffuse margins. The former two carbonate types have δ 13C values around –13‰ (relative to V-PDB) and low Sr contents (<0.5wt.%), whereas the third type,veins with high-temperature metasomatic features have a δ 13C value of –5.0‰ and high Sr contents up to 3.4wt.%. In spite of the mantle-like δ 13C value and the unusually high Sr content typical for mantle-derived carbonate, trace element compositions have proven a crustal origin. This observation supports the conclusions of earlier studies that the carbonate melt droplets found on peridotite xenoliths in the alkaline basalts represent mobilized sedimentary carbonate. The large δ 13C range and the 12C-enrichment in the carbonates can be attributed to devolatilization of the migrating carbonate or infiltration of surficial fluids containing 12C-rich dissolved carbon. Carbon isotope compositions of inclusion-hosted CO2 range from –17.8 to –4.8‰ (relative to V-PDB) with no relation to the amount of CO2 released by vacuum crushing. Low-δ 13C values measured by stepwise heating under vacuum suggest that the carbon component is pristine and not related to surficial contamination, and that primary mantle fluids with δ 13C values around –5‰ were at least partly preserved in the xenoliths. Tectonic reworking and heating by the basaltic magma resulted in partial CO2 release and local 13C-depletion. [Copyright &y& Elsevier]

Investigation of fault rocks is crucial for the evaluation of sealing properties of rock formations considered as oil and gas storage or for the disposal of heat-generating radioactive waste. Even in tight rock formations, fluid flow may concentrate along brittle faults. The present study focuses on the sealing properties of faulted Lower Cretaceous clay- and siltstones encountered in drill cores from the central and eastern Lower Saxony Basin (Germany). Our investigations are based on a multidisciplinary approach including microstructural, mineralogical-geochemical, stable isotope and biomarker analyses. The new data suggest that preexisting discontinuities and/or sedimentary heterogeneities played a significant role for the increase in fluid pressure and formation of mode I veins within low permeability claystones. High-strain domains of fault cores consist of fine-grained fault gouge. A scaly fabric of varying deformation intensity is present around larger faults. Calcite-precipitation in faults and complex mineralized veins, and the differences in trace element concentrations of various veins, reflect several phases of palaeofluid activity. Calcite precipitation in the fault rocks led to elevated amounts of Mn, Ba and/or Sr. Isotope signatures indicate a local carbonate source for the origin of thin calcite coatings of fault planes, but a more complex palaeofluid interaction for the larger faults and for complex veins, consistent with the microfabrics. Biomarker signatures reveal the presence of mature hydrocarbons pointing to hydrocarbon migration in sections where steep, only weakly mineralized faults occur. The new results suggest that faulted claystones represent critical zones with a potentially reduced barrier capability consistent with published data. • Deformation in Lower Cretaceous clay- and siltstones is localized along brittle fault zones. • The position of small scale faults is related to structural or sedimentary heterogeneities. • Migration of hydrocarbons along faults and veins through overlying clay- and siltstones. • Mineralizations seal the faults, but potentially promote overpressure around the sealed section. [ABSTRACT FROM AUTHOR]

The Late Permian coal measures in the Bowen Basin, Australia, are extensively mineralized with calcite as cleat infilling and veins. This study utilised strontium and samarium‑neodymium isotope analyses as well as rare earth element and yttrium (REY) composition of vein calcites, from two boreholes in a faulted and intruded area within the Jellinbah Thrust Zone, to investigate the origin and timing of calcite precipitation. All samples showed low Sr isotopic ratios that overlapped the range typical of mantle materials, suggesting that fluids were derived from the mantle. The calcite veins in core from Dingonose 14, with two exceptions, exhibit very similar Sr isotopic ratios yet have large variations in REY patterns and a wide range in Sm–Nd ratios. These samples defined an isochron corresponding to an age of 174 ± 11 Ma, which may record the timing of fluid mobilization from the deeply buried part of the foreland basin during the Early and Middle Jurassic, prior to subsequent extension and uplift in the Late Cretaceous. This fluid event may be a response to the Gondwana supercontinent break-up during the Early-Middle Jurassic. Various thermal and chemical conditions resulted in the different REY patterns of calcite in Dingonose 14 core. Calcite veins in Summit 3 core showed extremely similar REY patterns and Sr isotopic ratios but different Sm–Nd isotopic compositions relative to Dingonose 14 core, with no Sm–Nd isochron able to be resolved. The structural geology of the Summit 3 locality is complex, having overturned beds and large veins of prismatic quartz present in addition to calcite, and potential for multiple periods of veining to have occurred. Hence the lack of Sm–Nd isotopic equilibrium for the Summit 3 samples is most likely due to multiple fluid events. [ABSTRACT FROM AUTHOR]

• Frontal thrusts act as a conduit for infiltration of meteoric-derived fluids. • Calcite precipitation occurred at temperatures between 10° and 54 °C. • Layer-parallel shortening and shear occurred during folding. • Pressure-solution, frictional sliding, and veining occurred during thrusting. • Slow deformation along thrust is consistent with aseismic growth of Jura anticline. Structural mapping and microstructural analyses are combined with stable, clumped, and radiogenic isotopes to unravel deformation mechanisms and syntectonic fluid flow during upward propagation along the frontal thrust (Fuans thrust) of the internal part of the Jura fold-and-thrust belt. The Fuans thrust cuts through Upper Jurassic-Lower Cretaceous carbonate deposits, branches into two splays, and generates a system of fault-propagation folds. Folding was accomodated by layer-parallel shortening and layer-parallel shear, which generated flexural slip along bedding surfaces, stylolites, and foliated fabric in marly limestone interbeds. Thrusting was characterized by cycles of mutually overprinting pressure-solution and brittle processes, such as frictional sliding and fracturing/veining. This generated foliated tectonites in marls and limestones without significant cataclasis of the host rock. Pressure-solution and micrometer slip along slickenfibers are evidence of aseismic slip, in agreement with the ongoing aseismic growth of anticlines in the Jura fold-and-thrust, while crackle-like vein texture may account for episodic seismic fracturing. Geochemical data show that Fuans thrust acted as a conduit for the downward infiltration of meteoric-derived fluids, which channeled along foliated tectonites during syntectonic fluid flow. Calcite mineralizations precipitated at temperatures between 54 °C and 10 °C, showing an increased contribution of organic carbon from soils in colder paleofluids. This indicates a progressive opening of the system, characterized by a more efficient and extensive meteoric fluids circulation. Considering the highest recorded temperature of 54 °C and assuming the modern geothermal gradient of 30 °C/km, thrusting in the study outcrop initiated at a burial depth of at least ∼1.4 km. [ABSTRACT FROM AUTHOR]