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Blowing Spring Cave in northwestern Arkansas is representative of cave systems in the karst of the Ozark Plateaus, and stable isotopes of water (δ18O and δ2H) and inorganic carbon (δ13C) were used to quantify soil-water, bedrock-matrix water, and precipitation contributions to cave-spring flow during storm events to understand controls on cave water quality. water samples from recharge-zone soils and the cave were collected from March to May 2012 to implement a multicomponent hydrograph separation approach using δ18O and δ2H of water and dissolved inorganic carbon (δ13C–DIC). During baseflow, median δ2H and δ18O compositions were –41.6‰ and –6.2‰ for soil water and were –37.2‰ and –5.9‰ for cave water, respectively. Median DIC concentrations for soil and cave waters were 1.8 mg/L and 25.0 mg/L, respectively, and median δ 13C–DIC compositions were –19.9‰ and –14.3‰, respectively. During a March storm event, 12.2 cm of precipitation fell over 82 h and discharge increased from 0.01 to 0.59 m3 /s. The isotopic composition of precipitation varied throughout the storm event because of rainout, a change of 50‰ and 10‰ for δ2H and δ18O was observed, respectively. Although, at the spring, δ2H and δ18O only changed by approximately 3‰ and 1‰, respectively. The isotopic compositions of precipitation and pre-event (i.e., soil and bedrock matrix) water were isotopically similar and the two-component hydrograph separation was inaccurate, either overestimating (>100%) or underestimating (<0%) the precipitation contribution to the spring. During the storm event, spring DIC and δ13C–DIC de- creased to a minimum of 8.6 mg/L and –16.2‰, respectively. If the contribution from precipitation was assumed to be zero, soil water was found to contribute between 23 to 72% of the total volume of discharge. Although the assumption of negligible contributions from precipitation is unrealistic, especially in karst systems where rapid flow through conduits occurs, the hydrograph separation using inorganic carbon highlights the importance of considering vadose-zone soil water when analyzing storm chemohydrographs.
Dissolution processes in karst regions commonly involve (meteoric) water whose stable isotopic (O, H, C) composition is distinctly different from that of the paleowaters from which the host rock (limestone, dolostone) formed. This, in theory, should lead to isotopic alteration of the host rock beyond the active solution surface as the modern karst water is out of isotopic equilibrium with the carbonate rock. No such alteration has been reported, however, in epigenetic karst systems. In contrast, isotopic alteration, commonly referred to as isotopic halos or fronts, are known from various hypogene systems (ore deposits, active hydrothermal systems, etc.). These empirical observations suggest that stable isotope data may be a diagnostic tool to identify hypogene water-rock interactions particularly in cave systems whose origin is ambiguous.
We have been testing the applicability of this assumption to karst settings by studying the isotopic composition of carbonate host rocks in a variety of caves showing clear-cut hypogene morphologies. Cores drilled into the walls of cave chambers and galleries were studied petrographically and the C and O isotope composition was analyzed along these cores, which typically reached a depth of 0.5 to 1.2 m. We identified three scenarios: (a) no isotopic alteration, (b) a sigmoidal isotope front within a few centimeters of the cave wall, and (c) pervasive isotope alteration throughout the entire core length. Type (a) was found in caves where the rate of cave wall retreat apparently outpaced the rate of isotopic alteration of the wall rock (which is typical, for example, for sulfuric acid speleogenesis). Type (c) was observed in geologically young, porous limestone showing evidence of alteration zones up to 5 m wide. The intermediate type (b) was identified in hypogene karst cavities developed in tight limestone, dolostone and marble.
Our data in conjunction with evidence from speleothems and their geochemical and fluid-inclusion composition suggest that the spatial extent of the isotopic alteration front depends on the porosity and permeability, as well as on the saturation state of the water. Wider alteration zones primarily reflect a higher permeability. Shifts are most distinct for oxygen isotopes and less so for carbon, whereby the amplitude depends on a number of variables, including the isotopic composition of unaltered host rock, the isotopic composition of the paleofluid, the temperature, the water/rock ratio, the surface of water-rock contact, the permeability of the rock, and the time available for isotope exchange. If the other parameters can be reasonably constrained, then semi-quantitative temperature estimates of the paleowater can be obtained assuming isotopic equilibrium conditions.
If preserved (scenarios b and c), alteration fronts are a strong evidence of hypogene speleogenesis, and, in conjunction with hypogene precipitates, allow to fingerprint the isotopic and physical parameters of the altering paleofluid. The reverse conclusion is not valid, however; i.e. the lack of evidence of isotopic alteration of the cave wall rock cannot be used to rule out hypogene paleo-water-rock interaction.
Speleogenesis in iron ore caves may involve generation of porosity at depth with a later surficial phase associated with slope hydrological processes. The earlier phreatic phase results in morphological features similar to but much more irregular at wall and ceiling scale than what is observed in hypogene caves. Processes responsible for the generation of caves do not seem to follow normal karst geochemical paths, but instead occur through bacterially mediated redox reactions.
Numerical models of speleogenesis typically simulate flow and dissolution within single fractures or networks of fractures. Such models employ fracture flow and pipe flow equations to determine flow rates and only consider average velocities within each fracture segment. Such approximations make large scale simulations of speleogenesis tractable. However, they do not allow simulation of the formation and evolution of micro- or meso-scale cave passage morphologies. Such morphologies are frequently studied within a field setting and utilized for the interpretation of the speleogenetic processes that formed the cave. One classic example is the formation of scallops in cave streams with turbulent flow. Scallops are used to interpret past flow velocities and directions. However, a recent analysis of the theory of limestone dissolution in turbulent flow conditions suggests a discrepancy between theory and reality concerning the formation of limestone scallops (Covington, in review). Similarly, the only attempt to numerically simulate flute formation in limestone found that the flute forms were not stable (Hammer et al., 2011). Motivated by these puzzles, we are developing a computational fluid dynamics (CFD) framework for the simulation of the evolution of dissolution morphologies.
While this project was initially conceived to better understand dissolution in turbulent flow, the tools being developed are particularly well-suited to examine a variety of other questions related to cave morphology on the micro- and meso-scales. There has been significant recent discussion about the interpretation of features that are diagnostic of hypogenic or transverse speleogenesis, such as the morphological suite of rising flow defined by Klimchouk (2007). Other authors have suggested that such forms can be found in a variety of settings where confined flow is not present (Mylroie and Mylroie, 2009; Palmer, 2011). We propose that simulation of such forms using a CFD speleogenesis code will allow a more complete understanding of the connections between process and form, because in such simulations the processes occurring are well-known, well-defined, and also can be adjusted within controlled numerical experiments, where relevant parameters and boundary conditions are systematically varied.
The CFD framework we are developing is based on the Lattice Boltzman method (Chen and Doolen, 1998), which is a popular technique for modeling the mechanics of complex fluids, including fluid mixtures, reactive transport, porous media flow, and complex and evolving domain geometries. With this framework it is straightforward to simulate many of the processes occurring in hypogene settings, including complex fluid flows, dissolution, solute and heat transport, and buoyancy-driven flow. Furthermore, this modeling framework allows these processes to be coupled so that their interactions and feedbacks can be explored. With the suite of capabilities provided by this framework, we can begin to numerically simulate the processes occurring in hypogene speleogenesis, including the driving mechanisms and the role of buoyancy-driven flow and its relationship with the morphological suite of rising flow. In the spirit of a workshop, this work is presented as in-progress, in the hopes that it will stimulate discussion on potential applications of the model being developed.
Existing definitions of the term hypogene karst (hypogene speleogenesis) are not always consistent with the established meaning of the term hypogene in the Earth Sciences. They are commonly biased either toward geochemical or toward hydrogeological aspects of the phenomenon. It is proposed that hypogene karst is defined on the basis of the two properties: predominance of the deep-seated sources of aggressiveness of karst water, independent of the environment at the overlying or immediately adjacent surface; and recharge of soluble formation from below, independent of recharge from overlying or immediately adjacent surface
The carbon dioxide produced in the soil and dissolved in the percolation water is considered as the main agent for karstification in the carbonate rocks. Superficial morphologies and underground caves are product of the corrosion of the limestone, while carbonate speleothems is the other end member of the process.
Hypogene speleogenesis driven by deep seated fluids is the cave formation processes for the main karst systems in the Apennines of Italy. Hydrogen sulfide and endogenic carbon dioxide are the main agents for underground karst corrosion and the soil carbon dioxide plays a secondary rule. The limestone corrosion driven by hydrogen sulfide produces gypsum deposits in caves that could be assumed as the indicator of the hypogene speleogenesis. The action of endogenic carbon dioxide in the cave formation, especially if it operates at lower temperature, is not easy to detect and the resulting cave morphology is not helpful to recognize the cave formation process.
The main sources of carbon dioxide in the underground karst system in the Apennines of Italy can be related to different processes driven by the endogenic fluids emissions. The crustal regional degassing seems to be the prevalent source for carbon dioxide in the karst massifs with the main release in the groundwater. Hydrogen sulfide and methane oxidation, possibly mediated by bacteria activity, are other sources in the buried Cenozoic sediments. Releasing of carbon dioxide along the faults and in the fractures occurring in the carbonate rocks is an important source, especially in the seismically active area. Finally, thermogenic reactions with carbonate rocks are well known as one of the main production mechanism of carbon dioxide released in the atmosphere.
Data from carbon dioxide monitoring in several caves show a relevant contribution of the endogenic carbon dioxide (about 75 %) in the karst system which drives the speleogenesis reactions and shapes the underground morphologies.
The conduit system of mature karstified carbonate aquifers is typically characterised by a high hydraulic conductivity and does not impose a major flow constriction on catchment discharge. As a result, discharge at karst springs is usually flashy and displays pronounced peaks following recharge events. In contrast, some karst springs reported in literature display a discharge maximum, attributed to reaching the finite discharge capacity of the conduit system (flow threshold). This phenomenon also often leads to a non-standard recession behaviour, a so called “convex recession”, i.e. an increase in the recession coefficient during flow recession, which in turn might be used as an indicator for conduit restricted aquifers. The main objective of the study is the characterisation and modelling of those hydrogeologically challenging aquifers. The applied approach consists of a combination of hydrometric monitoring, a spring hydrograph recession and event analysis, as well as the setup and calibration of a non-linear reservoir model. It is demonstrated for the Auja spring, the largest freshwater spring in the Lower Jordan Valley. The semi-arid environment with its short but intensive precipitation events and an extended dry season leads to sharp input signals and undisturbed recession periods. The spring displays complex recession behaviour, exhibiting exponential (coefficient α) and linear (coefficient β) recession periods. Numerous different recession coefficients α were observed: ∼0.2 to 0.8 d−1 (presumably main conduit system), 0.004 d−1 (fractured matrix), 0.0009 d−1 (plateau caused by flow threshold being exceeded), plus many intermediate values. The reasons for this observed behaviour are the outflow threshold at 0.47 m3 s−1 and a variable conduit–matrix cross-flow in the aquifer. Despite system complexity, and hence the necessity of incorporating features such as a flow threshold, conduit–matrix cross-flow, and a spatially variable soil/epikarst field capacity, the developed reservoir model is regarded as relatively simplistic. As a number of required parameters were calculated from the hydrogeological analysis of the system, it requires only six calibration parameters and performs well for the highly variable flow conditions observed. Calculated groundwater recharge in this semi-arid environment displays high interannual variability. For example, during the 45-year simulation period, only five wet winter seasons account for 33% of the total cumulative groundwater recharge.
The abundance and variety of speleothems are undoubtedly among the remarkable features of Cova des Pas de Vallgornera, the longest cave system in Mallorca Island developed in the eogenetic karst of its southern coast. Due to the monotonous carbonate lithology of the area, most of the speleothems are composed of calcite and in a few cases aragonite, although other minerals are also represented (e.g., gypsum, celestine, barite.). However, in spite of the rather common mineralogy of the speleothems, its distribution results strongly mediated by the lithologic and textural variability linked to the architecture of the Upper Miocene reefal rocks. Apart from a vast majority of speleothem typologies that are ubiquitous all along the cave system, some particular types are restricted to specific sections of the cave. In its landward inner passages, formed in the low permeability back reef facies, a great variety of speleothems associated to perched freshwater accumulations stands out, as well as some non frequent crystallizations like for example cave rims. On the other hand, the seaward part of the cave (developed in the very porous reef front facies) hosts conspicuous phreatic overgrowths on speleothems (POS), which are discussed to show their applications to constrain sea level changes. The factors controlling the distribution of speleothems found in Cova des Pas de Vallgornera are discussed along the paper, focusing the attention on the lithologic, hydrogeologic and speleogenetic conditionings; at the same time some uncommon speleothems, not found in any other cave in Mallorca, are also documented from this locality. Finally, a cognizant endeavour has been undertaken to illustrate with photographs the most remarkable speleothem types represented in the cave.
Volumetric depletion of a subsurface body commonly results in the collapse of overburden and the formation of enclosed topographic depressions. Such depressions are termed sinkholes in karst terrains and pit craters or collapse calderas in volcanic terrains. This paper reports the first use of computed X-ray microtomography (?CT) to image analog models of small-scale (~< 2 km diameter), high-cohesion, overburden collapse induced by depletion of a near-cylindrical (“stock-like”) body. Time-lapse radiography enabled quantitative monitoring of the evolution of collapse structure, velocity, and volume. Moreover, ?CT scanning enabled non-destructive visualization of the final collapse volumes and fault geometries in three dimensions. The results illustrate two end-member scenarios: (1) near-continuous collapse into the depleting body; and (2) near-instantaneous collapse into a subsurface cavity formed above the depleting body. Even within near-continuously collapsing columns, subsidence rates vary spatially and temporally, with incremental accelerations. The highest subsidence rates occur before and immediately after a surface depression is formed. In both scenarios, the collapsing overburden column undergoes a marked volumetric expansion, such that the volume of subsurface depletion substantially exceeds that of the resulting topographic depression. In the karst context, this effect is termed “bulking”, and our results indicate that it may occur not only at the onset of collapse but also during progressive subsidence. In the volcanic context, bulking of magma reservoir overburden rock may at least partially explain why the volume of magma erupted commonly exceeds that of the surface depression.
Karst is the result of climatic and geohydrological processes, mainly in carbonate and evaporite rocks, during geological periods of Earth history. Dissolution of these rock formations over time has generated karst aquifers and environments of significant water and mineral resources. In addition, beautiful landscapes have been created which constitute natural parks, geosites, and caves. Due to their origin and nature, karstified areas require investigation with special techniques and methodology. International collaboration and discussions on advances in karst research are necessary to promote Karst Science. The International Symposium on Karst Aquifers is one of the worldwide events held periodically to specifically address karst environments. The symposium constitutes an ongoing international forum for scientific discussion on the progress made in research in karst environments. The first and second symposiums were organized in Nerja (near Malaga, Spain), in 1999 and 2002; the third and fourth symposiums were held in Malaga city in 2006 and 2010. The 5th International Symposium on Karst Aquifers (ISKA5) occurred in Malaga on during October 14–16, 2014. It was organized by the Centre of Hydrogeology University of Málaga (CEHIUMA) and the Spanish Geological Survey (IGME), in cooperation with UNESCO and the International Association of Hydrogeologists (IAH) Karst Commission. More than 100 contributions were received from 30 countries on five continents. Presentations made during the symposium and published in this book are a compendium of 70 of these manuscripts. Papers submitted by April 2014, were peer-reviewed and subsequently accepted by the Scientific Committee. Contributions are grouped into five sections:
• Methods Utilized to Study Karst Aquifers.
• Karst Hydrogeology.
• Mining and Engineering in Karst media.
• Karst Cavities.
• Karst Geomorphology and Landscape.
A large part of the contributions, 30 %, is related to Methods Utilized to Study Karst Aquifers. Several issues are addressed: methods for groundwater recharge assessment, dye tracer and stable isotope applications, analysis of hydrodynamic data and hydrochemistry, among others. Most contributions, 40 %, however, are on Karst Hydrogeology. These are primarily in connection with various topics such as numerical modeling in karst, floods, karst groundwater flow, protection of karst aquifers or pollution, and vulnerability in karst. Five percent of the published papers deal with Mining and Engineering in Karst Media. These papers are about tunnels, hydrogeological risks, and karst risk assessment in mining and civil engineering. Another section concerning Karst Cavities encompasses 15 % of the contributions. These chapters deal with corrosion and speleogenetic processes, speleothems, CO2 sources, the global carbon cycle in endokarst, and the study of past climate. Karst Geomorphology and Landscape constitutes the remaining 10 % of the contributions. These papers are related to karst features, wetlands, hypogene speleogenesis, geodiversity, and karstic geosites. The results of project work performed by karst specialists worldwide are described in the book. Included in it are experiences from pilot sites, methodologies, monitoring, and data analyses in various climatic, geological, and hydrogeological contexts. Material presented may be utilized for activities such as teaching and technical-professional applications particularly as they apply to the increasingly multidisciplinary nature of karst studies. Information provided may also be useful to decisions makers in making critical decisions regarding development in karst regions. Scientists and engineers and many of the lay public interested in karst environments will benefit from the contents
In scarcity of light and primary producers, subterranean ecosystems are generally extremely oligotrophic habitats, receiving poor supplies of degradable organic matter from the surface. Human direct impacts on cave ecosystems mainly derive from intensive tourism and recreational caving, causing important alterations to the whole subterranean environment. In particular, artificial lighting systems in show caves support the growth of autotrophic organisms (the so-called lampenflora), mainly composed of cyanobacteria, diatoms, chlorophytes, mosses and ferns producing exocellular polymeric substances (EPSs) made of polysaccharides, proteins, lipids and nucleic acids. This anionic EPSs matrix mediates to the intercellular communications and participates to the chemical exchanges with the substratum, inducing the adsorption of cations and dissolved organic molecules from the cave formations (speleothems). Coupled with the metabolic activities of heterotrophic microorganisms colonising such layer (biofilm), this phenomenon may lead to the corrosion of the mineral surfaces. In this review, we investigate the formation of biofilms, especially of diatom-dominated ones, as a consequence of artificial lighting and its impacts on speleothems. Whenever light reaches the subterranean habitat (both artificially and naturally) a relative high number of species of diatoms may indeed colonise it. Cave entrances, artificially illuminated walls and speleothems inside the cave are generally the preferred substrates. This review focuses on the diatom flora colonising subterranean habitats, summarizing the information contained in all the scientific papers published from 1900 up to date. In this review we provide a complete checklist of the diatom taxa recorded in subterranean habitats, including a total of 363 taxa, belonging to 82 genera. The most frequent and abundant species recorded in caves and other low light subterranean habitats are generally aerophilic and cosmopolitan. These are, in order of frequency: Hantzschia amphioxys, Diadesmis contenta, Orthoseira roeseana, Luticola nivalis, Pinnularia borealis, Diadesmis biceps and Luticola mutica. Due to the peculiarity of the subterranean habitats, the record of rare or new species is relatively common. The most important environmental factors driving species composition and morphological modifications observed in subterranean populations are analysed throughout the text and tables. In addition, suggestions to prevent and remove the corrosive biofilms in view of an environmentally sustainable cave management are discussed.
Principles of optimality provide an interesting alternative to modeling hydrological processes in detail on small scales and have received growing interest in the last years. Inspired by the more than 20 years old concept of minimum energy dissipation in river networks, we present a corresponding theory for subsurface flow in order to obtain a better understanding of preferential flow patterns in the subsurface. The concept describes flow patterns which are optimal in the sense of minimizing the total energy dissipation at a given recharge under the constraint of a given total porosity. Results are illustrated using two examples: two-dimensional flow towards a spring with a radial symmetric distribution of the porosity and dendritic flow patterns. The latter are found to be similar to river networks in their structure and, as a main result, the model predicts a power-law distribution of the spring discharges. In combination with two data sets from the Austrian Alps, this result is used for validating the model. Both data sets reveal power-law-distributed spring discharges with similar scaling exponents. These are, however, slightly larger than the exponent predicted by the model. As a further result, the distributions of the residence times strongly differ between homogeneous porous media and optimized flow patterns, while the mean residence times are similar in both cases.
Many speleothems can be assigned to one of two morphological groups: massive speleothems, which consist of compact bulks of material, and coralloids, which are domal to digitate in form. Faster growth on protrusions of the substrate occurs in the typical growth layers of coralloids (where those layers are termed “coralloid accretions”), but it is not observed in the typical layers of massive speleothems, which in contrast tend to smoothen the speleothem surface (and can therefore be defined as "smoothing accretions"). The different growth rates on different areas of the substrate are explainable by various mechanisms of CaCO3 deposition (e.g., differential aerosol deposition, differential CO2 and/or H2O loss from a capillary film of solution, deposition in subaqueous environments). To identify the causes of formation of coralloids rather than massive speleothems, this article provides data about d13C and d18O at coeval points of both smoothing and coralloid accretions, examining the relationship between isotopic composition and the substrate morphology. In subaerial speleothems, data show an enrichment in heavy isotopes both along the direction of water flow and toward the protrusions. The first effect is due to H2O evaporation and CO2 degassing during a gravity-driven flow of water (gravity stage) and is observed in smoothing accretions; the second effect is due to evaporation and degassing during water movement by capillary action from recesses to prominences (capillary stage) and is observed in subaerial coralloids. Both effects coexist in smoothing accretions interspersed among coralloid ones (intermediate stage). Thus this study supports the origin of subaerial coralloids from dominantly capillary water and disproves their origin by deposition of aerosol from the cave air. On the other hand, subaqueous coralloids seem to form by a differential mass-transfer from a still bulk of water towards different zones of the substrate along diffusion flux vectors of nutrients perpendicular to the isodepleted surfaces. Finally, this isotopic method has proved useful to investigate the controls on speleothem morphology and to obtain additional insights on the evolution of aqueous solutions inside caves.
Many speleothems can be assigned to one of two morphological groups: massive speleothems, which consist of compact bulks of material, and coralloids, which are domal to digitate in form. Faster growth on protrusions of the substrate occurs in the typical growth layers of coralloids (where those layers are termed “coralloid accretions”), but it is not observed in the typical layers of massive speleothems, which in contrast tend to smoothen the speleothem surface (and can therefore be defined as "smoothing accretions"). The different growth rates on different areas of the substrate are explainable by various mechanisms of CaCO3 deposition (e.g., differential aerosol deposition, differential CO2 and/or H2O loss from a capillary film of solution, deposition in subaqueous environments). To identify the causes of formation of coralloids rather than massive speleothems, this article provides data about d13C and d18O at coeval points of both smoothing and coralloid accretions, examining the relationship between isotopic composition and the substrate morphology. In subaerial speleothems, data show an enrichment in heavy isotopes both along the direction of water flow and toward the protrusions. The first effect is due to H2O evaporation and CO2 degassing during a gravity-driven flow of water (gravity stage) and is observed in smoothing accretions; the second effect is due to evaporation and degassing during water movement by capillary action from recesses to prominences (capillary stage) and is observed in subaerial coralloids. Both effects coexist in smoothing accretions interspersed among coralloid ones (intermediate stage). Thus this study supports the origin of subaerial coralloids from dominantly capillary water and disproves their origin by deposition of aerosol from the cave air. On the other hand, subaqueous coralloids seem to form by a differential mass-transfer from a still bulk of water towards different zones of the substrate along diffusion flux vectors of nutrients perpendicular to the isodepleted surfaces. Finally, this isotopic method has proved useful to investigate the controls on speleothem morphology and to obtain additional insights on the evolution of aqueous solutions inside caves.
This article discusses the role ofmethane in thermochemical sulfate reduction (TSR), the fate of TSR-derived CO2 and the effect of TSR on reservoir porosity and permeability, and the causes of the anomalously high porosity and permeability in the Lower Triassic soured carbonate gas reservoirs in the northeast Sichuan Basin, southwest China. The Lower Triassic carbonate reservoirs were buried to a depth of about 7000 m and experienced maximum temperatures up to 220 °C before having been uplifted to the present-day depths of 4800 to 5500 m, but they still possess porosities up to 28.9% and permeabilities up to 3360 md. The present-day dry gas reservoirs evolved from a paleo-oil accumulation and experienced varying degrees of TSR alteration as evidenced from the abundant sulfur-rich solid bitumens and varying H2S and CO2 concentrations. TSR occurred mainly within the oil and condensate/wet gas windows, with liquid hydrocarbons and wet hydrocarbon gases acting as the dominant reducing agents responsible for sulfate reduction, sulfur-rich solid bitumen and H2S generation, and calcite precipitation. Methane-dominated TSR was a rather late event and had played a less significant role in altering the reservoirs. Intensive H2S and CO2 generation during TSR resulted in calcite cementation rather than carbonate dissolution, which implies that the amount of water generated during TSR was volumetrically insignificant. 13C-depleted CO2 derived from hydrocarbon oxidation preferentially reacted with Ca2+ to form isotopically light calcite cements, and the remaining CO2 re-equilibrated with the 13C-enriched water–rock systems with its δ13C rapidly approaching the values for the host rocks, which accounted for the observed heavy and relatively constant CO2 δ13C values. The carbonate reservoirs suffered from differential porosity loss by TSR-involved solid bitumen generation and TSR-induced calcite and pyrite precipitation. Intensive TSR significantly reduced the porosity and permeability of the intervals expected to have relatively high sulfate contents (the evaporative-platform dolostones and the platform-margin shoal dolostones immediately underlying the evaporative facies). Early oil charge and limited intensity of TSR alteration, together with very low phyllosilicate content and early dolomitization, accounted for the preservation of anomalously high porosities in the reservoirs above the paleo-oil/water contact. A closed system seems to have played a special role in preserving the high porosity in the gas zone reservoirs below the paleo-oil/water contact. The closed system, which is unfavorable for deep burial carbonate dissolution and secondary porosity generation, was favorable for the preservation of early-formed porosity in deeply buried carbonates. Especially sucrosic and vuggy dolostones have a high potential to preserve such porosity.
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