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Speleology in Kazakhstan

Shakalov on 04 Jul, 2018
Hello everyone!   I pleased to invite you to the official site of Central Asian Karstic-Speleological commission ("Kaspeko")   There, we regularly publish reports about our expeditions, articles and reports on speleotopics, lecture course for instructors, photos etc. ...

New publications on hypogene speleogenesis

Klimchouk on 26 Mar, 2012
Dear Colleagues, This is to draw your attention to several recent publications added to KarstBase, relevant to hypogenic karst/speleogenesis: Corrosion of limestone tablets in sulfidic ground-water: measurements and speleogenetic implications Galdenzi,

The deepest terrestrial animal

Klimchouk on 23 Feb, 2012
A recent publication of Spanish researchers describes the biology of Krubera Cave, including the deepest terrestrial animal ever found: Jordana, Rafael; Baquero, Enrique; Reboleira, Sofía and Sendra, Alberto. ...

Caves - landscapes without light

akop on 05 Feb, 2012
Exhibition dedicated to caves is taking place in the Vienna Natural History Museum   The exhibition at the Natural History Museum presents the surprising variety of caves and cave formations such as stalactites and various crystals. ...

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That subterranean is beneath the land surface [16].?

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Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
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Calculating flux to predict future cave radon concentrations, Rowberry, Matt; Marti, Xavi; Frontera, Carlos; Van De Wiel, Marco; Briestensky, Milos
Microbial mediation of complex subterranean mineral structures, Tirato, Nicola; Torriano, Stefano F.F;, Monteux, Sylvain; Sauro, Francesco; De Waele, Jo; Lavagna, Maria Luisa; D’Angeli, Ilenia Maria; Chailloux, Daniel; Renda, Michel; Eglinton, Timothy I.; Bontognali, Tomaso Renzo Rezio
Evidence of a plate-wide tectonic pressure pulse provided by extensometric monitoring in the Balkan Mountains (Bulgaria), Briestensky, Milos; Rowberry, Matt; Stemberk, Josef; Stefanov, Petar; Vozar, Jozef; Sebela, Stanka; Petro, Lubomir; Bella, Pavel; Gaal, Ludovit; Ormukov, Cholponbek;
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Your search for thermochemical sulfate reduction (Keyword) returned 7 results for the whole karstbase:
DISLOCATION OF THE EVAPORITIC FORMATIONS UNDER TECTONIC AND DISSOLUTION CONTROLS - THE MODEL OF THE DINANTIAN EVAPORITES FROM VARISCAN AREA (NORTHERN FRANCE AND BELGIUM), 1993, Rouchy J. M. , Groessens E. , Laumondais A. ,
Within the Franco-Belgian segment of the Hercynian orogen, two thick Dinantian anhydritic formations are known, respectively in the Saint-Ghislain (765 m) and Epinoy 1 (904 m) wells. Nevertheless, occurrences of widespread extended breccias and of numerous pseudomorphs of gypsum/anhydrite in stratigraphically equivalent carbonate deposits (boreholes and outcrops), suggest a larger extent of the evaporitic conditions (fig. 1, 2). The present distribution of evaporites is controlled by palaeogeographical differentiation and post-depositional parameters such as tectonics and dissolution. These latter have dissected the deposits formerly present in all the structural units. By using depositional, diagenetic and deformational characters of these formations, the article provides a model for the reconstruction of a dislocated evaporitic basin. This segment of the Hercynian chain is schematically composed of two main units (fig. 1, 3) : (1) the autochthonous or parautochthonous deposits of the Namur synclinorium, (2) the Dinant nappe thrusted northward over the synclinorium of Namur. The major thrust surface is underlined by a complex fault bundle (faille du Midi) seismically recognized over more than 100 km. A complex system of thrust slices occurs at the Hercynian front. Except for local Cretaceous deposits, most of the studied area has been submitted to a long period of denudation since the Permian. Sedimentary, faunistic and geochemical data argue for a marine origin of the brines which have generated the evaporites interbedded with marine limestones. Sedimentary structures. - The thick evaporitic formations are composed of calcium-sulfates without any clear evidence of the former presence of more soluble salts (with the exception of a possible carbonate-sulfate breccia in the upper part of the Saint-Ghislain formation). As in all the deeply buried evaporitic formations, the anhydrite is the main sulfate component which displays all the usual facies : pseudomorphs after gypsum (fig. 4A, B), nodular and mosaic (fig. 4C), laminated. The gypsum was probably an important component during the depositional phase despite the predominant nodular pattern of the anhydrite. Early diagenetic nodular anhydrite may have grown during temporary emersion of the carbonates (sabkha environments), but this mechanism cannot explain the formation of the whole anhydrite. So, most of the anhydrite structures result from burial-controlled gypsum --> anhydrite conversion and from mechanical deformations. Moreover, a complex set of diagenetic processes leads to various authigenic minerals (celestite, fluorite, albite, native sulfur, quartz and fibrous silica) and to multistaged carbonate <> sulfate replacements (calcite and dolomite after sulfate, replacive anhydrite as idiomorphic poeciloblasts, veinlets, domino-like or stairstep monocrystals...). These mineral transformations observed ill boreholes and in outcrops have diversely been controlled during the complex evolution of the series as : depositional and diagenetic pore-fluid composition, pressure and temperature changes with burial, bacterial and thermochemical sulfate reduction, deep circulations favored by mechanical brecciation, mechanical stresses, role of groundwater during exhumation of the series. Deformational structures. - A great variety of deformational structures as rotational elongation, stretching, lamination, isoclinal microfolding, augen-like and mylonitic structures are generated by compressive tectonic stresses (fig. 4D to J). The similarities between tectonic-generated structures and sedimentary (lamination) or diagenetic (pseudo-nodules) features could lead lo misinterpretations. The calcareous interbeds have undergone brittle deformation the style and the importance of which depend of their relative thickness. Stretching, boudins, microfolds and augen structures F, H. I) affect the thin layers while thicker beds may be broken as large fractured blocks dragged within flown anhydrite leading to a mylonitic-like structure (fig, 4G). In such an inhomogeneous formation made of interlayered ductile (anhydrite) and brittle (carbonate) beds, the style and the intensity of the deformation vary with respect to the relative thickness of each of these components. Such deformational features of anhydrite may have an ubiquitous significance and can result either from compressive constraints or geostatic movements (halokinesis). Nevertheless, some data evidence a relation with regional tangential stresses: (1) increase of the deformation toward the bottom of the Saint-Ghislain Formation which is marked by a deep karst suggesting the presence of a mechanical discontinuity used as a drain for dissolving solutions (fig. 3, 4); (2) structural setting (reversed series, internal slidings) of the Epinoy 1 formation under the Midi thrust. However, tectonic stresses also induce flowing deformations which have contributed to cause their present discontinuity. It can be assumed that the evaporites played an active role for the buckling of the regional structure as detachment or gliding layers and more specifically for the genesis of duplex structures. Breccia genesis. - Great breccia horizons are widely distributed in outcrops as well as in the subsurface throughout the greater part of the Dinant and Namur units (fig. 2). The wide distribution of pseudomorphosed sulfates in outcrops and the stratigraphical correlation between breccia and Saint-Ghislain evaporitic masses (fig. 2) suggest that some breccia (although not all) have been originated from collapse after evaporites solution. Although some breccia may result from synsedimentary dissolution, studied occurrences show that most of dissolution processes started after the Hercynian deformation and, in some cases, were active until recently : elements made of lithified and fractured limestones (Llandelies quarries) (fig. 5A), preservation of pseudomorphs of late replacive anhydrite (Yves-Gomezee) (fig. 5B, C), deep karst associated with breccia (Douvrain, Saint Ghislain, Ghlin boreholes) (fig. 3, 4, 5D)). Locally, the final brecciation may have been favored by a mechanical fragmentation which controlled water circulations (fig. 5E). As postulated by De Magnee et al. [19861, the dissolution started mostly after the Permian denudation and continued until now in relation with deep circulations and surface weathering (fig. 6). So, the above-mentioned occurrences of the breccia are logically explained by collapse after dissolution of calcium-sulfates interbeds of significant thickness (the presence of salt is not yet demonstrated), but other Visean breccia may have a different origin (fig. 5F). So, these data prove the extension of thick evaporitic beds in all the structural units including the Dinant nappe, before dissolution and deformation. Implications. - Distribution of Visean evaporites in northern France and Belgium is inherited from a complicated paleogeographic, tectonic and post-tectonic history which has strongly modified their former facies, thicknesses and limits (fig. IA, 6). Diversified environments of deposition controlled by both a palaeogeographical differentiation and water level fluctuations led to the deposition of subaqueous (gypsum) or interstitial (gypsum, anhydrite) crystallization. Nevertheless, most of the anhydrite structures can be interpreted as resulting from burial conversion of gypsum to anhydrite rather than a generalized early diagenesis in sabkha-like conditions. Deformation of anhydrite caused by Hercynian tangential stresses and subsequent flow mechanisms, have completed the destruction of depositional and diagenetic features. The tectonic deformations allow us to consider the role of the evaporites in the Hercynian deformations. The evaporites supplied detachment and gliding planes as suggested for the base of the Saint-Ghislain Formation and demonstrated by the structural setting of Epinoy 1 evaporites in reverse position and in a multi-system of thrust-slices below the Midi overthrust (fig. 7). So, although the area in which evaporation and precipitation took place cannot be exactly delineated in geographic extent, all the data evidence that the isolated thick anhydritic deposits represent relics of more widespread evaporites extending more or less throughout the different structural units of this Hercynian segment (fig. 1B). Their present discontinuity results from the combination of a depositional differentiation, mechanical deformations and/or dissolution

CHEMICAL-REACTION PATH MODELING OF ORE DEPOSITION IN MISSISSIPPI VALLEY-TYPE PB-ZN DEPOSITS OF THE OZARK REGION UNITED-STATES MIDCONTINENT, 1994, Plumlee G. S. , Leach D. L. , Hofstra A. H. , Landis G. P. , Rowan E. L. , Viets J. G. ,
The Ozark region of the U.S. midcontinent is host to a number of Mississippi Valley-type districts, including the world-class Viburnum Trend, Old Lead Belt, and Tri-State districts and the smaller Southeast Missouri barite, Northern Arkansas, and Central Missouri districts. There is increasing evidence that the Ozark Mississippi Valley-type districts formed locally within a large, interconnected hydrothermal system that also produced broad fringing areas of trace mineralization, extensive subtle hydrothermal alteration, broad thermal anomalies, and regional deposition of hydrothermal dolomite cement. The fluid drive was provided by gravity flow accompanying uplift of foreland thrust belts during the Late Pennsylvanian to Early Permian Ouachita orogeny. In this study, we use chemical speciation and reaction path calculations, based on quantitative chemical analyses of fluid inclusions, to constrain likely hydrothermal brine compositions and to determine which precipitation mechanisms are consistent with the hydrothermal mineral assemblages observed regionally and locally within each Mississippi Valley-type district in the Ozark region. Deposition of the regional hydrothermal dolomite cement with trace sulfides likely occurred in response to near-isothermal effervescence of CO2 from basinal brines as they migrated to shallower crustal levels and lower confining pressures. In contrast, our calculations indicate that no one depositional process can reproduce the mineral assemblages and proportions of minerals observed in each Ozark ore district; rather, individual districts require specific depositional mechanisms that reflect the local host-rock composition, structural setting, and hydrology. Both the Northern Arkansas and Tri-State districts are localized by normal faults that likely allowed brines to rise from deeper Cambrian-Ordovician dolostone aquifers into shallower carbonate sequences dominated by limestones. In the Northern Arkansas district, jasperoid preferentially replaced limestones in the mixed dolostone-limestone sedimentary packages. Modeling results indicate that the ore and alteration assemblages in the Tri-State and Northern Arkansas districts resulted from the flow of initially dolomite-saturated brines into cooler limestones. Adjacent to fluid conduits where water/rock ratios were the highest, the limestone was replaced by dolomite. As the fluids moved outward into cooler limestone, jasperoid and sulfide replaced limestone. Isothermal boiling of the ore fluids may have produced open-space filling of hydrothermal dolomite with minor sulfides in breccia and fault zones. Local mixing of the regional brine with locally derived sulfur undoubtedly played a role in the development of sulfide-rich ore runs. Sulfide ores of the Central Missouri district are largely open-space filling of sphalerite plus minor galena in dolostone karst features localized along a broad anticline. Hydrothermal solution collapse during ore deposition was a minor process, indicating dolomite was slightly undersaturated during ore deposition. No silicification and only minor hydrothermal dolomite is present in the ore deposits. The reaction path that best explains the features of the Central Missouri sulfide deposits is the near-isothermal mixing of two dolomite-saturated fluids with different H2S and metal contents. Paleokarst features may have allowed the regional brine to rise stratigraphically and mix with locally derived, H2S-rich fluids

Geology and Geochemistry of the Reocin Zinc-Lead Deposit, Basque-Cantabrian Basin, Northern Spain, 2003, Velasco Francisco, Herrero Jose Miguel, Yusta Inaki, Alonso Jose Antonio, Seebold Ignacio, Leach David,
The Reocin Zn-Pb deposit, 30 km southwest of Santander, Spain, occurs within Lower Cretaceous dolomitized Urgonian limestones on the southern flank of the Santillana syncline. The Reocin deposit is one of the largest known strata-bound, carbonate-hosted, zinc-lead deposits in Europe. The total metal endowment of the deposit, including past production and remaining reserves, is 62 Mt of ore grading 8.7 percent Zn and 1.0 percent Pb. The epigenetic mineralization consists of sphalerite and galena, with lesser marcasite and trace pyrite with dolomite as gangue. Microprobe analyses of different generations of dolomite revealed nonstoichiometric compositions with various amounts of iron (up to 14 mol % of FeCO3). Replacement of host dolomite, open-space filling of fractures, and cementation of breccias derived from dissolution collapse are the principal types of ore occurrence. Detailed cross-section mapping indicates a stratigraphic and structural control on the deposit. A stratiform morphology is present in the western part of the orebody (Capa Sur), whereas mineralization in the eastern part is highly discordant but strata bound (Barrendera). Stratigraphic studies demonstrate that synsedimentary tectonic activity, related to the rifting of the North Atlantic (Bay of Biscay), was responsible for variation in sedimentation, presence of unconformities (including paleokarsts), local platform emergence and dolomitization along the N60 fault trend. In the Reocin area, two stages of dolomitization are recognized. The first stage is a pervasive dolomitization of the limestone country rocks that was controlled by faulting and locally affected the upper part of the Aptian and the complete Albian sequence. The second dolomitization event occurred after erosion and was controlled by karstic cavities. This later dolomitization was accompanied by ore deposition and, locally, filling of dolomite sands and clastic sediments in karstic cavities. The circulation of hydrothermal fluids responsible for sulfide deposition and the infilling of karst cavities were broadly contemporaneous, indicating a post-Albian age. Vitrinite reflectance data are consistent with previously measured fluid inclusion temperatures and indicate temperatures of ore deposition that were less than 100{degrees}C. Carbon and oxygen isotopic data from samples of regional limestone, host-rock dolostone and ore-stage dolomite suggest an early hydrothermal alteration of limestone to dolostone. This initial dolomitization was followed by a second period of dolomite formation produced by the mixing of basinal metal-rich fluids with local modified seawater. Both dolomitization events occurred under similar conditions from fluids exhibiting characteristics of basinal brines. The{delta} 34S values of sulfides are between -1.8 and .5 per mil, which is consistent with thermochemical sulfate reduction involving organic matter as the main source of reduced sulfur. Galena lead isotope compositions are among the most radiogenic values reported for Zn-Pb occurrences in Europe, and they are distinct from values reported for galena from other Basque-Cantabrian deposits. This suggests that a significant part of the lead was scavenged from the local underlying Asturian sediments. The stratigraphic and structural setting, timing of epigenetic mineralization, mineralogy, and isotopic geochemistry of sulfide and gangue minerals of the Reocin deposit are consistent with the features of most of Mississippi Valley-type ore deposits

Australian Zn-Pb-Ag Ore-Forming Systems: A Review and Analysis, 2006, Huston David L. , Stevens Barney, Southgate Peter N. , Muhling Peter, Wyborn Lesley,
Zn-Pb-Ag mineral deposits are the products of hydrothermal ore-forming systems, which are restricted in time and space. In Australia, these deposits formed during three main periods at ~2.95, 1.69 to 1.58, and 0.50 to 0.35 Ga. The 1.69 to 1.58 Ga event, which accounts for over 65 percent of Australia's Zn, was triggered by accretion and rifting along the southern margin of Rodinia. Over 93 percent of Australia's Zn-Pb-Ag resources were produced by four ore-forming system types: Mount Isa (56% of Zn), Broken Hill (19%), volcanic-hosted massive sulfide (VHMS; 12%), and Mississippi Valley (8%). Moreover, just 4 percent of Australia's land mass produced over 80 percent of its Zn. The four main types of ore-forming systems can be divided into two 'clans,' based on fluid composition, temperature, and redox state. The Broken Hill- and VHMS-type deposits formed from high-temperature (>200{degrees}C) reduced fluids, whereas the Mount Isa- and Mississippi Valley-type deposits formed from low-temperature (<200{degrees}C), H2S-poor, and/or oxidized fluids. The tectonic setting and composition of the basins that host the ore-forming systems determine these fluid compositions and, therefore, the mineralization style. Basins that produce higher temperature fluids form in active tectonic environments, generally rifts, where high heat flow produced by magmatism drives convective fluid circulation. These basins are dominated by immature siliciclastic and volcanic rocks with a high overall abundance of Fe2. The high temperature of the convective fluids combined with the abundance of Fe2 in the basin allow inorganic sulfate reduction and leaching of sulfide from the country rock, producing reduced, H2S-rich fluids. Basins that produce low-temperature fluids are tectonically less active, generally intracratonic, extensional basins dominated by carbonate and variably mature siliciclastic facies with a relatively low Fe2 abundance. In these basins, sediment maturity depends on the paleogeography and stratigraphic position in an accommodation cycle. Volcanic units, if present, occur in the basal parts of the basins. Because these basins have relatively low heat flow, convective fluid flow is less important, and fluid migration is dominated by expulsion of basinal brines in response to local and/or regional tectonic events. Low temperatures and the lack of Fe2 prevent in-organic sulfate reduction during regional fluid flow, producing H2S-poor fluids that are commonly oxidized (i.e., {sum}SO4 > {sum}H2S). Fluid flow in the two basin types produces contrasting regional alteration systems. High-temperature fluid-rock reactions in siliciclastic-volcanic-dominated basins produce semiconformable albite-hematite-epidote assemblages, but low-temperature reactions in carbonate-siliciclastic-dominated basins produce regional K-feldspar-hematite assemblages. The difference in feldspar mineralogy is mostly a function of temperature. In both basin types, regional alteration zones have lost, and probably were the source of, Zn and Pb. The contrasting fluid types require different depositional mechanisms and traps to accumulate metals. The higher temperature, reduced VHMS- and Broken Hill-type fluids deposit metals as a consequence of mixing with cold seawater. Mineralization occurs at or near the sea floor, with trapping efficiencies enhanced by sub-surface replacement or deposition in a brine pool. In contrast, the low-temperature, oxidized Mount Isa- and Mississippi Valley-type fluids precipitate metals through thermochemical sulfate reduction facilitated by hydrocarbons or organic matter. This process can occur at depth in the rock pile, for instance in failed petroleum traps, or just below the sea floor in pyritic, organic-rich muds

Sulfur isotopic composition and the source of dissolved sulfur species in thermo-mineral springs of the Cerna Valley, Romania, 2010, Wynn Jonathan G. , Sumrall Jonathan B. , Onac Bogdan P.

Documenting the source and processes controlling dissolved sulfur (S) mineralization in thermo-mineral waters of the Cerna Valley, Romania is important to understanding speleogenesis in this karst region, in addition to understanding hydrogeological controls, therapeutic qualities and sustainability of the region's historic spas. Stable S and carbon (C) isotopic results reported here elucidate controls on redox processes, the source of dissolved S mineralization, and sulfur-bearing mineral precipitation in this unique karst hydrothermal system. At reservoir temperatures that occur in the Cerna Valley aquifers, it is likely that thermochemical sulfate reduction (TSR) is the dominant S reduction pathway. However the apparent isotope enrichment that we observed between coexisting dissolved sulfate and sulfide is higher than normally associated with TSR—a fact that likely reflects rapid redox cycling at low grade hydrothermal temperatures. δ13C values of dissolved inorganic carbon (DIC) are consistent with TSR using methane as an electron donor. δ34S values of total dissolved S (sum of sulfide and sulfate) in all springs sampled and particularly in those for which closed-system conditions can be demonstrated, is greater than + 16‰, consistently pointing to dissolved S that derives from marine-derived sulfate mineral sources. To this combined S–C isotope data set, we apply a model of Rayleigh distillation which describes exponentially increasing δ34S values of a diminishing sulfate reservoir during TSR, and linearly decreasing δ13C values of DIC indicating mixing of C from the electron donor involved in TSR. Comparison of our results to this model shows two distinct stages of TSR during transport of fresh water from karst aquifers towards the local geothermal anomaly. In an up-gradient group of springs and wells, incomplete TSR progress that is limited by energy from electron donors is evident from: low concentrations of dissolved sulfide with low δ34S values (as low as − 21.9‰), a large balance of remaining as SO42− similar in isotopic composition to its source ( + 17.4‰), and δ13C values showing little methane-derived DIC. Conversely, in a downstream group of springs and wells, excess concentration of methane provides abundant energy for near-complete TSR, and this near complete reaction progress is evident from: high δ34S values of remaining SO42− (up to + 71.8‰), high dissolved sulfide concentrations (> 32 mg/L as S2−) with δ34S values that take on the approximate isotopic signature of the total dissolved S (mean + 17.4‰), and low δ13C values of additional DIC derived from methane (as low as − 30‰). Thus the unique hydrogeology of the Cerna Valley allows the observation of two end-members of TSR (energy- and sulfate-limited) demonstrating wide boundary conditions of stable isotopic composition of dissolved S and C produced by TSR in a single natural system.


Tracing the sources of cave sulfates: a unique case from Cerna Valley, Romania, 2011, Onac Bogdan P. , Wynn Jonathan G. , Sumrall Jonathan B.

In order to reliably distinguish between different genetic processes of cave sulfate formation and to quantify the role of thermo-mineral waters on mineral deposition and cave morphology, it is critical to understand sulfur (S) sources and S transformations during hydrological and speleogenetic processes. Previous work has shown that sulfuric acid speleogenesis (SAS) often produces sulfate deposits with 34S-depleted isotopic signatures compared to those of the original source of S in sulfate rocks. However, 34S-depleted isotopic composition of S-bearing minerals alone does not provide enough information to clearly distinguish SAS from other speleogenetic processes driven by carbonic acid, geothermal heat, or other processes. The isotopic composition (δ18O and δ34S) of sulfate minerals (mainly gypsum) from seven caves of the Cerna Valley (Romania) defines three distinct populations, and demonstrates that the δ34S values of SAS-precipitated cave sulfates depend not only on the source of the S, but also on the H2S:SO4 2− ratio during aqueous S species reactions and mineral precipitation. Population 1 includes sulfates that are characterized by relatively low δ34S values (−19.4 to −27.9‰) with δ18O values between 0.2 and 4.3‰ that are consistent with oxidation of dissolved sulfide produced during methane-limited thermochemical sulfate reduction (TSR) that presently characterizes the chemistry of springs in the upper Cerna Valley. Population 2 of cave sulfates has 34S enriched δ34S values (14.3 to 19.4‰) and more 18O-depleted δ18O values (from −1.8 to −10.0‰). These values argue for oxidation of dissolved sulfide produced during sulfate-limited TSR that presently characterizes the chemistry of springs further downstream in the Cerna Valley. The δ18O values of cave sulfates from Population 1 are consistent with oxidation under more oxic aqueous conditions than those of Population 2. δ34S values of cave sulfates within Population 3 (δ34S: 5.8 to 6.5‰) may be consistent with several scenarios (i.e., pyrite oxidation, oxidation of dissolved sulfide produced during methane-limited TSR coupled with O2-limited oxidation during SAS). However, comparatively 18O-enriched δ18OSO4 values (11.9 to 13.9‰) suggest the majority of this sulfate O was derived from atmospheric O2 in gas-phase oxidation prior to hydration. Thus, the combined use of oxygen- and sulfur-isotope systematics of sulfate minerals precipitated in a variety of cave settings along Cerna Valley may serve as an example of how more complex cave systems can be deconvoluted to allow for more complete recognition of the range of processes and parameters that may be involved in SAS.


The fate of CO2 derived from thermochemical sulfate reduction (TSR) and effect of TSR on carbonate porosity and permeability, Sichuan Basin, China, 2015, Hao Fang, Zhang Xuefeng, Wang Cunwu, Li Pingping, Guo Tonglou, Zou Huayao, Zhu Yangming, Liu Jianzhang, Cai Zhongxian

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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