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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 angle of repose is the natural slope of unsupported granular material [16].?

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Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
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Featured articles from other Geoscience Journals
Karst environment, Culver D.C.
Mushroom Speleothems: Stromatolites That Formed in the Absence of Phototrophs, Bontognali, Tomaso R.R.; D’Angeli Ilenia M.; Tisato, Nicola; Vasconcelos, Crisogono; Bernasconi, Stefano M.; Gonzales, Esteban R. G.; De Waele, Jo
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 fluid inclusion (Keyword) returned 62 results for the whole karstbase:
Showing 16 to 30 of 62
Hydrothermal speleogenesis: its settings and peculiar features, 2000, Dublyansky Y. V.
Three major settings of hydrothermal karst development are: endokarst, deep-seated karst, and shallow karst. Endokarst develops at great depth, where the pressure exceeds the strength of the rock and voids can exist only if they are filled with overpressured fluid, which prevents them from collapse. In the deep-seated setting hydrothermal karst develops in response to changes of pressure and temperature of upwelling fluids. Two large zones: (1) zone of carbonate dissolution and (2) zone of carbonate precipitation form within hydrothermal systems. The shallow setting encompasses the interface between thermal and low-temperature waters or the zone near the upper surface of thermal waters. Four major conditions, which create and enhance solutional capacity in hydrothermal systems are: (1) elevated temperature gradients (for carbonated waters); (2) elevated rate of discharge (for carbonated waters); (3) oxidation of hydrogen sulfide; and (4) mixing waters of contrasting chemistry. These features readily occur in the shallow hydrothermal karst setting; the largest hydrothermal caves are formed there. Morphologies and dimensions of hydrothermal caves range from pores, individual rooms, and single conduit caves to large three-dimensional mazes. Cave deposits hold clues as to their origin in their mineralogy, morphology, chemistry, isotopic properties, and fluid inclusion temperatures.

Geochemical study of calcite veins in the Silurian and Devonian of the Barrandian Basin (Czech Republic): evidence for widespread post-Variscan fluid flow in the central part of the Bohemian Massif, 2000, Suchy V. , Heijlen W. , Sykorova I. , Muchez Ph. , Dobes P. , Hladikova J. , Jackova I. , Safanda J. , Zeman A.

Carbonate fracture cements in limestones have been investigated by fluid inclusion and stable isotope analysis to provide insight into fluid evolution and deformation conditions of the Barrandian Basin (Silurian–Devonian) of the Czech Republic. The fractures strike generally north–south and appear to postdate major Variscan deformation. The most common fracture cement is calcite that is locally accompanied by quartz, natural bitumen, dolomite, Mn-oxides and fluorite. Three successive generations of fracture-filling calcite cements are distinguished based on their petrographical and geochemical characteristics. The oldest calcite cements (Stage 1) are moderate to dull brown cathodoluminescent, Fe-rich and exhibit intense cleavage, subgrain development and other features characteristic of tectonic deformation. Less tectonically deformed, variable luminescent Fe-poor calcite corresponds to a paragenetically younger Stage 2 cement. First melting temperatures, Te, of two-phase aqueous inclusions in Stages 1 and 2 calcites are often around 2208C, suggesting that precipitation of the cements occurred from H2O–NaCl fluids. The melting temperature, Tm, has values between 0 and 25.88C, corresponding to a low salinity between 0 and 8.9 eq. wt% NaCl. Homogenization temperatures, Th, from calcite cements are interpreted to indicate precipitation at about 708C or less. No distinction could be made between the calcite of Stages 1 and 2 based on their fluid inclusion characteristics. In some Stage 2 cements, inclusions of highly saline (up to 23 eq. wt% NaCl) brines appear to coexist with low-salinity inclusions. The low salinity fluid possibly contains Na-, K-, Mg- and Ca-chlorides. The high salinity fluid has a H2O–NaCl–CaCl2 composition. Blue-to-yellow-green fluorescing hydrocarbon inclusions composed of medium to higher API gravity oils are also identified in some Stages 1 and 2 calcite cements. Stage 1 and 2 calcites have d 18O values between 213.2‰ and 27.2‰ PDB. The lower range of the calculated d 18O values of the ambient fluids (23.5‰ to 1 2.7‰ SMOW) indicate precipitation of these cements from deeply circulating meteoric waters. The presence of petroleum hydrocarbon inclusions in some samples is interpreted to reflect partial mixing with deeper basinal fluids. The paragenetically youngest Stage 3 calcite cement has only been encountered in a fewveins.These calcites are characterised by an intensely zoned luminescence pattern, with bright yellow and non-luminescent zones. Inclusions of Mn-oxides and siliceous sinters are commonly associated with Stage 3 calcite, which is interpreted to have precipitated from shallower meteoric waters. Regional structural analysis revealed that the calcite veins of the Barrandian basin belong to a large-scale system of north–south-trending lineaments that run through the territory of the Czech Republic. The veins probably reflect episodes of fluid migration that occurred along these lineaments during late stages of the Variscan orogeny

Diagenesis and porosity evolution of the Upper Silurian-lowermost Devonian West Point reef limestone, eastern Gaspe Belt, Quebec Appalachians, 2001, Bourque Pa, Savard Mm, Chi G, Dansereau P,
Diagenetic analysis based on cathodoluminescence petrography, cement stratigraphy, carbon and oxygen stable isotope geochemistry, and fluid inclusion microthermometry was used to reconstruct the porosity history and evaluate the reservoir potential of the Upper Silurian-Lower Devonian West Point limestone in the eastern part of the Gaspe Belt. The West Point limestone was investigated in two areas: 1) In the Chaleurs Bay Synclinorium, the limestone diagenesis of the lower and middle complexes of the Silurian West Point Formation was affected by repeated subaerial exposure related to late Ludlovian third-order eustatic low-stands, which coincided with the Salinic block tilting that produced the Salinic unconformity. The Anse McInnis Member (middle bank complex) underwent freshwater dissolution, and mixed marine and freshwater cementation during deposition. Concurrently, the underlying Anse a la Barbe and Gros Morbe members (lower mound and reef complex) experienced dissolution by fresh water percolating throughout the limestone succession. Despite this early development of karst porosity, subsequent meteoric-influenced cementation rapidly occluded all remaining pore space in the Gros Morbe, Anse a la Barbe, and Anse McInnis limestones. In contrast, the overlying Colline Daniel Member limestone (upper reef complex) does not show the influence of any freshwater diagenesis. Occlusion of its primary porosity occurred during progressive burial and was completed under a maximum burial depth of 1.2 kin. 2) In the Northern Outcrop Belt, the diagenesis of the Devonian pinnacle reefs of the West Point Formation followed a progressive burial trend. The primary pores of the reef limestone were not completely occluded before the reefs were buried at a significant depth (in some cases, to 6 km). Therefore, hydrocarbon migration in subsurface buildups before primary porosity occlusion might have created reservoirs. Moreover, the presence of gaseous hydrocarbons in Acadian-related veins attests to a hydrocarbon source in the area

Symposium Abstract: Palaeohydrology in the Eastern mediterranean from speleothem fluid inclusion D/H analyses, 2003, Mcgarry S. , Barmatthews M. , Matthews A. , Ayalon A.

Sedimentologic, diagenetic and tectonic evolution of the Saint-Flavien gas reservoir at the structural front of the Quebec Appalachians, 2003, Bertrand R, Chagnon A, Malo M, Duchaine Y, Lavoie D, Savard Mm,
The Beekmantown Group (Lower Ordovician) of the Saint-Flavien reservoir has produced 162x106 m3 (5.7 bcf) of natural gas between 1980 and 1994. The conversion of the field into gas storage was initiated in 1992 and the pool became operational in 1998. Integration of structural and sedimentologic features, carbonate and organic matter petrography and geochemistry for 13 drill holes is used to define a tectonic-sedimentologic-diagenetic model for porosity evolution in these reservoir dolostones. The Beekmantown Group consists of numerous fifth-order shallowing-upward cycles 1.0 to 7.0 m thick (average of 2.4 m). Each cycle consists of a basal shale deposited during the initial flooding of the platform which was subsequently covered by a shoaling succession of subtidal and intertidal limestones to intertidal dolostones. Early dolomitization has produced intercrystalline porosity and preserved some moldic pores in the intertidal facies. Near surface, post-dolomite karstification has created vugs that were subsequently filled by early marine calcite fibrous cement based on the {delta}18O and {delta}13C ratios of calcite. Early burial elements consist of horizontal stylolites, pyrite and sphalerite. Late migrated bitumen was thermally altered or vaporized as native coke under deep burial conditions exceeding 240{degrees}C, partly due to overthrusting of Appalachian nappes. Under these conditions, breccias and fractures were generated and subsequently filled with K-feldspar, quartz, illite, and xenomorphic and poikilotopic calcite. The {delta}18O of the poikilotopic calcite and homogenization temperature of coeval fluid inclusions indicate formation under high temperatures (Th about 260{degrees}C). Horizontal shear zones and marcasite-rich vertical stylolites were produced during folding and thrusting. Dissolution has preferentially affected late fracture-filling calcite and generated most of the actual porosity during or soon after the Taconian Orogeny. The relationship between the occurrence of smectite and this type of porosity indicates the low temperature condition of this dissolution (T <100{degrees}C). Porosity in the Saint-Flavien reservoir has been mostly produced by fracture-controlled, late to post-Taconian dissolution of early to late calcite in the intertidal dolomitic slightly porous facies at the top of rhythmic cycles that compose the Beekmantown Group

Origin and Significance of Postore Dissolution Collapse Breccias Cemented with Calcite and Barite at the Meikle Gold Deposit, Northern Carlin Trend, Nevada, 2003, Emsbo P, Hofstra Ah,
The final event in a complicated hydrothermal history at the Meikle gold deposit was gold deficient but caused extensive postore dissolution of carbonate, collapse brecciation, and precipitation of calcite and barite crystals in the resulting cavities. Although previously interpreted to be part of the Carlin-type hydrothermal system, crosscutting relationships and U-Th-Pb geochronology constrain this hydrothermal event to late Pliocene time (ca. 2 Ma), nearly 36 Ma after ore formation. Mineralogic, fluid inclusion, and stable isotope data indicate that postore hydrothermal fluids were reduced, H2S-rich, unevolved meteoric waters ({delta}18O = -17{per thousand}) of low temperature (ca. 65{degrees}C). The{delta} 18O values of barite and calcite indicate that these minerals were in isotopic equilibrium, requiring that barite SO4 was derived from the oxidation of reduced sulfur; however, preexisting sulfides in breccia cavities were not oxidized. The{delta} 34S (15{per thousand}) values of barite are higher than those of local bulk sulfide and supergene alunite indicating that SO4 was not derived from supergene oxidation of local sulfide minerals. The 15 per mil {delta}34S value suggests that the H2S in the fluids may have been leached from sulfur-rich organic matter in the local carbonaceous sedimentary rocks. A reduced H2S-rich fluid is also supported by the bright cathodoluminescence of calcite which indicates that it is Mn rich and Fe poor. Calcite has a narrow range of {delta}13C values (0.3-1.8{per thousand}) that are indistinguishable from those of the host Bootstrap limestone, indicating that CO2 in the fluid was from dissolution of the local limestone. These data suggest that dissolution and brecciation of the Bootstrap limestone occurred where H2S-rich fluids encountered more oxidizing fluids and formed sulfuric acid (H2SO4). Intense fracturing in the mine area by previous structural and hydrothermal events probably provided conduits for the descent of oxidized surface water which mixed with the underlying H2S-rich waters to form the dissolving acid. The surface-derived fluid apparently contained sufficient oxygen to produce H2SO4 from H2S but not enough to alter pyrite to Fe oxide. Although H2S is an important gold-transporting ligand, the temperature was too low to transport a significant amount of gold. The presence of analogous calcite- and barite-lined cavities in other Carlin-type deposits suggests that the generation (and oxidation) of H2S-rich meteoric waters was a common phenomenon in north-central Nevada. Previous sulfur isotope studies have also shown that the Paleozoic sedimentary rocks were the principal source of H2S in Devonian sedimentary exhalative-type, Jurassic intrusion-related, Eocene Carlin-type, and Miocene low-sulfidation gold deposits in the region. The similar sulfur source in all of these systems suggests that basin brines, magmatic fluids, and meteoric waters all evolved to be H2S-rich ore fluids by circulation through Paleozoic sedimentary rocks. Thus, although not directly related to gold mineralization, the recent hydrologic history of the deposit provides important clues to earlier ore-forming processes that were responsible for gold mineralization

Geology of the Beltana Willemite Deposit, Flinders Ranges, South Australia, 2003, Groves Iain M. , Carman Cris E. , Dunlap W. James,
Beltana is a high-grade hypogene willemite deposit hosted in Lower Cambrian carbonate rocks in the Arrowie basin, northern Flinders Ranges, South Australia. It is situated adjacent to a major growth fault on the basin margin. Ooid grainstone units of the Woodendinna Dolomite and units of Archaeocyathid-rich Wilkawillina Limestone are the main host lithologies. Lead minerals in subeconomic quantities are also present in karstic collapse breccias surrounding the willemite orebodies. Mineralization is structurally controlled and associated with brecciation and extensive hematite-rich hydrothermal zincian dolomitization. Ore minerals include willemite and coronadite with lesser mimetite, hedyphane, and smithsonite. Late-stage gangue minerals include manganocalcite, dolomite, and minor quartz. The texture of willemite is heterogeneous, resulting from various depositional mechanisms such as partial to massive replacement of the carbonate host rock, internal sedimentation, fracture fill, brecciation, and vein fill. On the periphery of the deposit, smithsonite formed by weathering of willemite. Beltana is centered on a karstic collapse breccia that extends at least 100 m vertically, formed in part through corrosion by acidic ore solutions. The geochemical signature of the orebody includes high levels of Zn, Pb, Cd, As, and Mn. Notably, silver is absent from the deposit and sulfur concentrations are low (<20 ppm). Fluid inclusion studies yield a low minimum temperature range of ore deposition between 50{degrees} and 170{degrees}C. K-Ar dating of coronadite associated with the willemite orebody indicates an age of formation of ~ 435 {} 5 Ma. Premining resources of willemite ore were 850,000 t at 36 percent Zn, and an associated body of subeconomic lead contained more than 800,000 t at 8.9 percent Pb, 3.9 percent Zn and 1 percent As. The deposit has some similarities with Mississippi Valley-type deposits but differs in ore and alteration mineral assemblages

Carbonate-Hosted Zn-Pb Deposits in Upper Silesia, Poland: Origin and Evolution of Mineralizing Fluids and Constraints on Genetic Models, 2003, Heijlen Wouter, Muchez Philippe, Banks David A. , Schneider Jens, Kucha Henryk, Keppens Eddy,
Microthermometric and crush-leach analyses of fluid inclusions in ore and gangue minerals of the Upper Silesian Zn-Pb deposits, Poland, along with first results of Rb-Sr geochronology on sulfides, provide important constraints on the paleohydrogeologic and metallogenetic models for the origin of these ores. The analyzed samples comprise two generations of dolomite, two generations of sphalerite, galena, and late calcite. The two dolomite generations and the late calcite were also analyzed for their oxygen and carbon isotope compositions, allowing a characterization of the mineralizing fluids. The ore-forming fluids represent highly saline (20-23 wt % CaCl2 equiv) Na-Ca-Cl brines, episodically introduced into the Triassic host carbonates. They had an oxygen isotope composition of ~0 per mil V-SMOW. Their Na-Cl-Br content (molar Na/Br and Cl/Br ratios between 99 and 337 and between 248 and 560, respectively) suggests that they originated by evaporation of seawater, which most likely occurred in the Permian-Triassic. The relative concentrations of potassium (molar K/Cl between 0.0147 and 0.0746) and lithium (molar Li/Cl between 0.0004 and 0.0031) further indicate that the fluids significantly interacted with siliciclastic rocks. The ionic and calculated oxygen isotope compositions of the fluids indicate that they were more evolved than present-day brines in the Upper Silesian coal basin, and the present-day brines show more extensive mixing with low-salinity fluids. The first results of direct Rb-Sr dating of ore-stage sulfides yield an isochron model age of 135 {} 4 Ma for the mineralizing event. This is consistent with hydrothermal activity and ore formation in Upper Silesia occurring in response to Early Cretaceous crustal extension preceding the opening of the northern Atlantic Ocean. The data presented support a model in which bittern brines migrated down into the deep subsurface and evolved into mineralizing fluids owing to extensive water-rock interaction. They were episodically expelled along deeply penetrating faults during the Early Cretaceous to form Zn-Pb deposits in the overlying Mesozoic carbonate rocks

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

Fluid inclusion and stable isotopic evidence for early hydrothermal karstification in vadose caves of the Nizke Tatry Mountains (Western Carpathians), 2004, Orvosova M. , Hurai V. , Simon K. , Wiegerova V. ,
Hydrothermal paleokarst cavities with calcite crystals up to 20 cm in diameter were found in two caves of the Nizke Tarry Mountains developed in Triassic limestone and dolomite of the Guttenstein type. In both caves, older zones of tectonic and hydrothermal activity have been overprinted by vadose speleogenesis. According to fluid inclusion microthermometry data, prismatic-scalenoliedral calcite from the Silvo ova Diera Cave has precipitated at temperatures between similar to60 and 101degreesC from low salinity aqueous solutions (less than or equal to0.7 wt. % NaCl eq.). Carbon and oxygen isotope profiling revealed significant delta(13)C decrease accompanied by slight delta(18)O increase during growth of calcite crystals. The negatively correlated carbon and oxygen isotope data cannot be interpreted in terms of any geologically reasonable models based on equilibrium isotopic fractionation. Fluid inclusion water exhibits minor decrease of deltaD values from crystal core (-31 %o SMOW) to rim (-41 %(0) SMOW). Scalenohedral calcite from the NovA Stanisovska Cave has precipitated at slightly higher temperatures 63-107degreesC from aqueous solutions with salinity : less than or equal to2.7 % NaCl eq. The positively correlated trend of delta(13)C and delta(18)O values is similar to common hydrothermal carbonates. The fluid inclusion water deltaD values differ significantly between the crystal core (-50 %(0) SMOW) and rim (- 11 %o SMOW). The calcite crystals are interpreted as representing a product of an extinct hydrothermal system, which was gradually replaced by shallow circulation of meteoric water. Fossil hydrothermal fluids discharged along Alpine uplift-related NNW-SSE-trending faults in Paleogene-pre-Pliocene times. Increased deuterium concentration in the inclusion water compared to recent meteoric precipitation indicates a warmer climate during the calcite crystallization

Concepts and models of dolomitization: a critical reappraisal, 2004, Machel Hans G. ,
Despite intensive research over more than 200 years, the origin of dolomite, the mineral and the rock, remains subject to considerable controversy. This is partly because some of the chemical and/or hydrological conditions of dolomite formation are poorly understood, and because petrographic and geochemical data commonly permit more than one genetic interpretation. This paper is a summary and critical appraisal of the state of the art in dolomite research, highlighting its major advances and controversies, especially over the last 20-25 years. The thermodynamic conditions of dolomite formation have been known quite well since the 1970s, and the latest experimental studies essentially confirm earlier results. The kinetics of dolomite formation are still relatively poorly understood, however. The role of sulphate as an inhibitor to dolomite formation has been overrated. Sulphate appears to be an inhibitor only in relatively low-sulphate aqueous solutions, and probably only indirectly. In sulphate-rich solutions it may actually promote dolomite formation. Mass-balance calculations show that large water/rock ratios are required for extensive dolomitization and the formation of massive dolostones. This constraint necessitates advection, which is why all models for the genesis of massive dolostones are essentially hydrological models. The exceptions are environments where carbonate muds or limestones can be dolomitized via diffusion of magnesium from seawater rather than by advection. Replacement of shallow-water limestones, the most common form of dolomitization, results in a series of distinctive textures that form in a sequential manner with progressive degrees of dolomitization, i.e. matrix-selective replacement, overdolomitization, formation of vugs and moulds, emplacement of up to 20 vol% calcium sulphate in the case of seawater dolomitization, formation of two dolomite populations, and -- in the case of advanced burial -- formation of saddle dolomite. In addition, dolomite dissolution, including karstification, is to be expected in cases of influx of formation waters that are dilute, acidic, or both. Many dolostones, especially at greater depths, have higher porosities than limestones, and this may be the result of several processes, i.e. mole-per-mole replacement, dissolution of unreplaced calcite as part of the dolomitization process, dissolution of dolomite due to acidification of the pore waters, fluid mixing (mischungskorrosion), and thermochemical sulphate reduction. There also are several processes that destroy porosity, most commonly dolomite and calcium sulphate cementation. These processes vary in importance from place to place. For this reason, generalizations about the porosity and permeability development of dolostones are difficult, and these parameters have to be investigated on a case-by-case basis. A wide range of geochemical methods may be used to characterize dolomites and dolostones, and to decipher their origin. The most widely used methods are the analysis and interpretation of stable isotopes (O, C), Sr isotopes, trace elements, and fluid inclusions. Under favourable circumstances some of these parameters can be used to determine the direction of fluid flow during dolomitization. The extent of recrystallization in dolomites and dolostones is much disputed, yet extremely important for geochemical interpretations. Dolomites that originally form very close to the surface and from evaporitic brines tend to recrystallize with time and during burial. Those dolomites that originally form at several hundred to a few thousand metres depth commonly show little or no evidence of recrystallization. Traditionally, dolomitization models in near-surface and shallow diagenetic settings are defined and/or based on water chemistry, but on hydrology in burial diagenetic settings. In this paper, however, the various dolomite models are placed into appropriate diagenetic settings. Penecontemporaneous dolomites form almost syndepositionally as a normal consequence of the geochemical conditions prevailing in the environment of deposition. There are many such settings, and most commonly they form only a few per cent of microcrystalline dolomite(s). Many, if not most, penecontemporaneous dolomites appear to have formed through the mediation of microbes. Virtually all volumetrically large, replacive dolostone bodies are post-depositional and formed during some degree of burial. The viability of the many models for dolomitization in such settings is variable. Massive dolomitization by freshwater-seawater mixing is a myth. Mixing zones tend to form caves without or, at best, with very small amounts of dolomite. The role of coastal mixing zones with respect to dolomitization may be that of a hydrological pump for seawater dolomitization. Reflux dolomitization, most commonly by mesohaline brines that originated from seawater evaporation, is capable of pervasively dolomitizing entire carbonate platforms. However, the extent of dolomitization varies strongly with the extent and duration of evaporation and flooding, and with the subsurface permeability distribution. Complete dolomitization of carbonate platforms appears possible only under favourable circumstances. Similarly, thermal convection in open half-cells (Kohout convection), most commonly by seawater or slightly modified seawater, can form massive dolostones under favourable circumstances, whereas thermal convection in closed cells cannot. Compaction flow cannot form massive dolostones, unless it is funnelled, which may be more common than generally recognized. Neither topography driven flow nor tectonically induced ( squeegee-type') flow is likely to form massive dolostones, except under unusual circumstances. Hydrothermal dolomitization may occur in a variety of subsurface diagenetic settings, but has been significantly overrated. It commonly forms massive dolostones that are localized around faults, but regional or basin-wide dolomitization is not hydrothermal. The regionally extensive dolostones of the Bahamas (Cenozoic), western Canada and Ireland (Palaeozoic), and Israel (Mesozoic) probably formed from seawater that was pumped' through these sequences by thermal convection, reflux, funnelled compaction, or a combination thereof. For such platform settings flushed with seawater, geochemical data and numerical modelling suggest that most dolomites form(ed) at temperatures around 50-80 {degrees}C commensurate with depths of 500 to a maximum of 2000 m. The resulting dolostones can be classified both as seawater dolomites and as burial dolomites. This ambiguity is a consequence of the historical evolution of dolomite research

Hydrothermal mixing, carbonate dissolution and sulfide precipitation in Mississippi Valley-type deposits, 2004, Corbella M, Ayora C, Cardellach E,
A large number of Mississippi Valley-Type (MVT) deposits are located within dissolution zones in carbonate host rocks. Some genetic models propose the existence of cavities generated by an earlier event such as a shallow karstification, that were subsequently filled with hydrothermal minerals. Alternative models propose carbonate dissolution caused by the simultaneous precipitation of sulfides. These models fail to explain either the deep geological setting of the cavities, or the observational features which suggest that the dissolution of carbonates and the precipitation of minerals filling the cavities are not strictly coeval. We present a genetic model inspired by the textural characteristics of MVT deposits that accounts for both the dissolution of carbonate and precipitation of sulfides and later carbonates in variable volumes. The model is based on the mixing of two hydrothermal fluids with a different chemistry. Depending on the proportion of the end members, the mixture dissolves and precipitates carbonates even though the two mixing solutions are both independently saturated in carbonates. We perform reactive transport simulations of mixing of a regional groundwater and brine ascending through a fracture, both saturated in calcite, but with different overall chemistries (Ca and carbonate concentrations, pH, etc). As a result of the intrinsic effects of chemical mixing, a carbonate dissolution zone, which is enhanced by acid brines, appears above the fracture, and another zone of calcite precipitation builds up between the cavity and the surrounding rock. Sulfide forms near the fracture and occupies a volume smaller than the cavity. A decline of the fluid flux in the fracture would cause the precipitation of calcite within the previously formed cavities. Therefore, dissolution of carbonate host rock, sulfide precipitation within the forming cavity, and later filling by carbonates may be part of the same overall process of mixing of fluids in the carbonate host rock

Palaeo-climate reconstruction from stable isotope variations in speleothems: a review, 2004, Mcdermott, F.

Speleothems are now regarded as valuable archives of climatic conditions on the continents, offering a number of advantages relative to other continental climate proxy recorders such as lake sediments and peat cores. They are ideal materials for precise U-series dating, yielding ages in calendar years, thereby circumventing the radiocarbon calibration problems associated with most other continental records. Stable isotope studies in speleothems have shifted away from attempting to provide palaeo-temperature reconstructions to the attainable goal of providing precise estimates for the timing and duration of major O isotope-defined climatic events characterised by high signal to noise ratios (e.g. glacial/interglacial transitions, Dansgaard–Oeschger oscillations, the ‘8200- year’ event). Unlike the marine records, speleothem data sets are not ‘tuned’, and their independent chronology offers opportunities to critically assess leads and lags in the climate system, that in turn can provide important insights into forcing and feedback mechanisms. Improved procedures for the extraction and measurement of stable isotope ratios in fluid inclusions trapped in speleothems are likely to provide, in the near future, a much enhanced basis for the quantitative interpretation of O isotope ratios in speleothem calcite. The latter developments open up once again the tantalising prospect of palaeo-temperature estimates, but more importantly perhaps, provide a direct test for a new generation of general circulation models whose hydrological cycles will incorporate the ‘water isotopes’. The literature is reviewed briefly to provide for the reader a sense of the current state-of-the-art, and to provide some pointers for future research directions

Cavity-based secondary mineralization in volcanic tuffs of Yucca Mountain, Nevada: a new type of the polymineral vadose speleothem, or a hydrothermal deposit?, 2005, Dublyansky Y. V. , Smirnov S. Z.
Secondary minerals (calcite, chalcedony, quartz, opal, fl uorite, heulandite, strontianite) residing in open cavities in the Miocene rhyolite tuffs of Yucca Mountain, Nevada have been interpreted by some researchers as "speleothemic" formations, deposited as a result of downward infiltration of meteoric waters (DOE, 2001, Whelan et al., 2002). The major mineral of the paragenesis, calcite, shows spectacular trend of the textural and crystal morphology change: from anhedral granular occurrences, through (optional) platelet, bladed and scepter varieties, to euhedral blocky morphologies. The trend is consistent with the overall decrease in the supersaturation of the mineral forming solution. Stable isotope properties of calcite evolve from 13C-enriched (?13C = +4 to +9 PDB) at early stages of growth to 13C-depleted (-5 to -10 ) at late stages. The non-cyclic character of the isotope record and extreme variations of isotopic values argue against the meteoric origin of mineral forming fluids. The ?13C >4 PDB require isotope partitioning between dissolved CO2 and CH4, which is only possible in reducing anoxic environment, but not in aerated vadose zone. Fluid inclusions studied in calcite, quartz and fluorite revealed that the minerals were deposited from thermal solutions. The temperatures were higher at early stages of mineral growth (60 to 85oC) and declined with time. Most late-stage calcites contain only all-liquid inclusions, suggesting temperatures less than ca. 35-50oC. Minerals collected close to the major fault show the highest temperatures. Gases trapped in fluid inclusions are dominated by CO2 and CH4; Raman spectrometry results suggest the presence of aromatic/cyclic hydrocarbon gases. The gas chemistry, thus, also indicates reduced (anoxic) character of the mineral forming fluids. Secondary minerals at Yucca Mountain have likely formed during the short-term invasion(s) of the deep-seated aqueous fluids into the vadose zone. Following the invasion, fluids, initially equilibrated with the deep (reduced, anoxic) environment, evolved toward equilibrium with the new environment (cooling, degassing, mixing with shallow oxidizing waters, etc.). While some features of mineralization are compatible with the "speleothemic" or "meteoric infiltration" model, most of the evidence does not lend itself to rational explanation within this model.

'Sour gas' hydrothermal jarosite: ancient to modem acid-sulfate mineralization in the southern Rio Grande Rift, 2005, Lueth V. W. , Rye R. O. , Peters L. ,
As many as 29 mining districts along the Rio Grande Rift in southern New Mexico contain Rio Grande Rift-type (RGR) deposits consisting of fluorite-barite sulfide-jarosite, and additional RGR deposits occur to the south in the Basin and Range province near Chihuahua, Mexico. Jarosite occurs in many of these deposits as a late-stage hydrothermal mineral coprecipitated with fluorite, or in veinlets that crosscut barite. In these deposits, many of which are limestone-hosted, jarosite is followed by natrojarosite and is nested within silicified or argillized wallrock and a sequence of fluorite-barite sulfide and late hematite-gypsum. These deposits range in age from similar to 10 to 0.4 Ma on the basis of Ar-40/Ar-39 dating of jarosite. There is a crude north-south distribution of ages, with older deposits concentrated toward the south. Recent deposits also occur in the south, but are confined to the central axis of the rift and are associated with modem geothermal systems. The duration of hydrothermal jarosite mineralization in one of the deposits was approximately 1.0 my. Most Delta(18)O(SO4)-OH values indicate that jarosite precipitated between 80 and 240 degrees C, which is consistent with the range of filling temperatures of fluid inclusions in late fluorite throughout the rift, and in jarosite (180 degrees C) from Pena Blanca, Chihuahua, Mexico. These temperatures, along with mineral occurrence, require that the jarosite have had a hydrothermal origin in a shallow steam-heated environment wherein the low pH necessary for the precipitation of jarosite was achieved by the oxidation of H2S derived from deeper hydrothermal fluids. The jarosite also has high trace-element contents (notably As and F), and the jarosite parental fluids have calculated isotopic signatures similar to those of modem geothermal waters along the southern rift; isotopic values range from those typical of meteoric water to those of deep brine that has been shown to form from the dissolution of Permian evaporite by deeply circulating meteoric water. Jarosite delta(34)S values range from -24 parts per thousand to 5 parts per thousand, overlapping the values for barite and gypsum at the high end of the range and for sulfides at the low end. Most delta(34)S values for barite are 10.6 parts per thousand to 13.1 parts per thousand and many delta(34)S values for gypsum range from 13.1 parts per thousand to 13.9 parts per thousand indicating that a component of aqueous sulfate was derived from Permian evaporites (delta(34)S = 12 2 parts per thousand). The requisite H2SO4 for jarosite formation was derived from oxidation of H2S which was likely largely sour gas derived from the thermochemical reduction of Permian sulfate. The low delta(34)S values for the precursor H2S probably resulted from exchange deeper in the basin with the more abundant Permian SO42-- at similar to 150 to 200 degrees C. Jarosite formed at shallow levels after the PH buffering capacity of the host rock (typically limestone) was neutralized by precipitation of earlier minerals. Some limestone-hosted deposits contain caves that may have been caused by the low pH of the deep basin fluids due to the addition of deep-seated HF and other magmatic gases during periods of renewed rifting. Caves in other deposits may be due to sulfuric acid speleogenesis as a result of H2S incursion into oxygenated groundwaters. The isotopic data in these 'sour gas' jarosite occurrences encode a recod of episodic tectonic or hydrologic processes that have operated in the rift over the last 10 my. (c) 2004 Elsevier B.V. All rights reserved

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