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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. ...

Did you know?

That goly karst is (russian.) see naked karst.?

Checkout all 2699 terms in the KarstBase Glossary of Karst and Cave Terms

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KarstBase a bibliography database in karst and cave science.

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 h2s (Keyword) returned 81 results for the whole karstbase:
Showing 16 to 30 of 81
Microbiology and geochemistry in a hydrogen-sulphide-rich karst environment, 2000, Hose Louise D. , Palmer Arthur N. , Palmer Margaret V. , Northup Diana E. , Boston Penelope J. , Duchene Harvey R. ,
Cueva de Villa Luz, a hypogenic cave in Tabasco, Mexico, offers a remarkable opportunity to observe chemotrophic microbial interactions within a karst environment. The cave water and atmosphere are both rich in hydrogen sulphide. Measured H2S levels in the cave atmosphere reach 210 ppm, and SO2 commonly exceeds 35 ppm. These gases, plus oxygen from the cave air, are absorbed by freshwater that accumulates on cave walls from infiltration and condensation. Oxidation of sulphur and hydrogen sulphide forms concentrated sulphuric acid. Drip waters contain mean pH values of 1.4, with minimum values as low as 0.1.The cave is fed by at least 26 groundwater inlets with a combined flow of 200-300 l/s. Inlet waters fall into two categories: those with high H2S content (300-500 mg/l), mean PCO2=0.03-0.1 atm, and no measurable O2; and those with less than 0.1 mg/l H2S, mean PCO2=0.02 atm, and modest O2 content (up to 4.3 mg/l). Both water types have a similar source, as shown by their dissolved solid content. However, the oxygenated water has been exposed to aerated conditions upstream from the inlets so that original H2S has been largely lost due to outgassing and oxidation to sulphate, increasing the sulphate concentration by about 4%. Chemical modelling of the water shows that it can be produced by the dissolution of common sulphate, carbonate, and chloride minerals.Redox reactions in the cave appear to be microbially mediated. Sequence analysis of small subunit (16S) ribosomal RNA genes of 19 bacterial clones from microbial colonies associated with water drips revealed that 18 were most similar to three Thiobacilli spp., a genus that often obtains its energy from the oxidation of sulphur compounds. The other clone was most similar to Acidimicrobium ferrooxidans, a moderately thermophilic, mineral-sulphide-oxidizing bacterium. Oxidation of hydrogen sulphide to sulphuric acid, and hence the cave enlargement, is probably enhanced by these bacteria.Two cave-enlarging processes were identified. (1) Sulphuric acid derived from oxidation of the hydrogen sulphide converts subaerial limestone surfaces to gypsum. The gypsum falls into the cave stream and is dissolved. (2) Strongly acidic droplets form on the gypsum and on microbial filaments, dissolving limestone where they drip onto the cave floors.The source of the H2S in the spring waters has not been positively identified. The Villahermosa petroleum basin within 50 km to the northwest, or the El Chichon volcano [small tilde]50 km to the west, may serve as source areas for the rising water. Depletion of 34S values (-11.7[per mille sign] for sulphur stabilized from H2S in the cave atmosphere), along with the hydrochemistry of the spring waters, favour a basinal source

Vein and Karst Barite Deposits in the Western Jebilet of Morocco: Fluid Inclusion and Isotope (S, O, Sr) Evidence for Regional Fluid Mixing Related to Central Atlantic Rifting, 2000, Valenza Katia, Moritz Robert, Mouttaqi Abdellah, Fontignie Denis, Sharp Zachary,
Numerous vein and karst barite deposits are hosted by Hercynian basement and Triassic rocks of the western Jebilet in Morocco. Sulfur, oxygen, and strontium isotope analyses of barite, combined with fluid inclusion microthermometry on barite, quartz, and calcite were used to reveal the nature and source of the ore-forming fluids and constrain the age of mineralization. The{delta} 34S values of barite between 8.9 and 14.7 per mil are intermediate between the sulfur isotope signatures of Triassic evaporites and Triassic-Jurassic seawater and lighter [IMG]f1.gif' BORDER='0'>, probably derived from the oxidation of dissolved H2S and leaching of sulfides in the Hercynian basement. The 87Sr/86Sr ratios of barite between 0.7093 and 0.7130 range between the radiogenic strontium isotope compositions of micaceous shale and sandstone and the nonradiogenic isotopic signature of Triassic to Jurassic seawater and Cambrian limestone. The{delta} 18O values of barite between 11 and 15 per mil (SMOW) support mixing between two or more fluids, including Late Triassic to Jurassic seawater or a water dissolving Triassic evaporites along its flow path, hot basinal, or metamorphic fluids with{delta} 18O values higher than 0 per mil and/or meteoric fluids with{delta} 18O values lower than 0 per mil. The general trend of decreasing homogenization temperatures and initial ice melting temperatures with increasing salinities of H2O-NaCl {} CaCl2 fluid inclusions trapped in barite, quartz, and calcite indicates that a deep and hot basinal fluid with salinities lower than 6 wt percent NaCl equiv might have mixed with a cooler surficial solution with a mean salinity of 20 wt percent NaCl equiv. Calcium was leached from the Cambrian limestone and the clastic and mafic volcanic rocks of the Hercynian basement. Alkali feldspars and micas contained in the Cambrain sandstones provided most of the Ba to the hydrothermal system. Vein and karst deposits are modeled as a two-component mixing process in which the temperature and the S and Sr isotope composition of the end members changed during the 220 to 155 Ma interval. The hot basinal fluid remained volumetrically dominant during the entire mineralization process. Differences in mean S, O, and Sr isotope compositions among the barite families are interpreted as reflecting differences in mineralization age. Most barite deposits formed before the Kimmeridgian, except for north-south-oriented vein barite, karst barite, and barite cement in the conglomeratic Upper Jurassic, which were deposited later, possibly around 155 Ma. Similar genetic processes have been described for late Paleozoic to Mesozoic F-Ba vein deposits in western Europe. The vein and karst barite in the western Jebilet of Morocco reveals a wide-scale regional mineralization event related to Central Atlantic rifting

Depositional Facies and Aqueous-Solid Geochemistry of Travertine-Depositing Hot Springs (Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, U.S.A.), 2000, Fouke Bw, Farmer Jd, Des Marais Dj, Pratt L, Sturchio Nc, Burns Pc, Discipulo Mk,
Petrographic and geochemical analyses of travertine-depositing hot springs at Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, have been used to define five depositional facies along the spring drainage system. Spring waters are expelled in the vent facies at 71 to 73{degrees}C and precipitate mounded travertine composed of aragonite needle botryoids. The apron and channel facies (43-72{degrees}C) is floored by hollow tubes composed of aragonite needle botryoids that encrust sulfide-oxidizing Aquificales bacteria. The travertine of the pond facies (30-62{degrees}C) varies in composition from aragonite needle shrubs formed at higher temperatures to ridged networks of calcite and aragonite at lower temperatures. Calcite 'ice sheets', calcified bubbles, and aggregates of aragonite needles ('fuzzy dumbbells') precipitate at the air-water interface and settle to pond floors. The proximal-slope facies (28-54{degrees}C), which forms the margins of terracette pools, is composed of arcuate aragonite needle shrubs that create small microterracettes on the steep slope face. Finally, the distal-slope facies (28-30{degrees}C) is composed of calcite spherules and calcite 'feather' crystals. Despite the presence of abundant microbial mat communities and their observed role in providing substrates for mineralization, the compositions of spring-water and travertine predominantly reflect abiotic physical and chemical processes. Vigorous CO2 degassing causes a unit increase in spring water pH, as well as Rayleigh-type covariations between the concentration of dissolved inorganic carbon and corresponding {delta}13C. Travertine {delta}13C and {delta}18O are nearly equivalent to aragonite and calcite equilibrium values calculated from spring water in the higher-temperature ([~]50-73{degrees}C) depositional facies. Conversely, travertine precipitating in the lower-temperature (<[~]50{degrees}C) depositional facies exhibits {delta}13C and {delta}18O values that are as much as 4{per thousand} less than predicted equilibrium values. This isotopic shift may record microbial respiration as well as downstream transport of travertine crystals. Despite the production of H2S and the abundance of sulfide-oxidizing microbes, preliminary {delta}34S data do not uniquely define the microbial metabolic pathways present in the spring system. This suggests that the high extent of CO2 degassing and large open-system solute reservoir in these thermal systems overwhelm biological controls on travertine crystal chemistry

Sulfuric acid, hypogene karst in the Guadalupe mountains of New Mexico and West Texas, USA, 2000, Hill C. A.
Carlsbad Cavern, Lechuguilla Cave, and other caves in the Guadalupe Mountains are probably the worlds best examples of karst formed by sulfuric acid in a hypogene setting. Four episodes of karstification have occurred in these mountains from Late Permian time to the present, the sulfuric acid episode being the last of these four. Sulfuric acid karst can be recognized by its large passage size, ramiform-spongework pattern, horizontal passages connected by deep pits and fissures, location beneath structural and stratigraphic traps, gypsum and native sulfur deposits, and the sulfuric-acid/H2S indicator minerals endellite, alunite, natroalunite, and tyuyamunite. Guadalupe caves formed in a diffuse-flow aquifer regime where caves may have acted as mixing chambers for hypogene-derived H2S and meteoric-derived fresh water. How cave hydrology has been related to regional hydrology during the late-Tertiary to present is poorly understood. Sulfuric acid karst is an integral part of H2S-degassing hydrocarbon basins which also can contain economic sulfur and Mississippi Valley-type ore deposits.

By-Product Materials related to H2S-H2SO4-Influenced Speleogenesis of Carlsbad, Lechuguilla, and Others Caves of the Guadalupe Mountains, New Mexico, 2001, Polyak, V. J. , Provencio, P.

Geomicrobiology and redox geochemistry of the karstified Miocene gypsum aquifer, Western Ukraine: A study from Zoloushka Cave., 2001, Andrejchuk V. N. , Klimchouk A. B.
The gypsum karst of the western Ukraine developed largely under artesian conditions. The Miocene aquifer is presently entrenched and dewatered over much of the territory, while it remains confined in the zone adjacent to the Carpathian Foredeep. The most prominent geochemical features of the Miocene aquifer system in the confined karst zone are: 1) the almost universal presence of a bioepigenetic calcite bed, enriched in the light carbon isotope, at the top of the gypsum (the "Ratynsky Limestone"), 2) the widespread sulfur mineralization associated with the above calcite bed (the region is one of the world's largest sulfur-bearing basins), and 3) high H2S and CO2 in the groundwater. Intense microbial sulfate-reduction processes occur in the gypsum in this zone. Zoloushka Cave is the third longest (92 km) and the largest by volume (more than 7 x 105 m3) gypsum cave in the world. It is a unique example of a young artesian cave that only during the Holocene became partly drained and during the last 50 years progressively dewatered due to a quarry operation. These rapid changes have induced a number of transitional geochemical processes, some of which appear to be bacterially mediated. Six groups of microorganisms have been identified in the cave. The paper discusses the aquifer geochemistry during the transitional stage in the light of the microbiological studies.

Geomicrobiology and redox geochemistry of the karstified Miocene gypsum aquifer, western Ukraine: The study from Zoloushka Cave, 2001, Andrejchuk Vn, Klimchouk Ab,
The gypsum karst of the western Ukraine developed largely under artesian conditions. The Miocene aquifer is presently entrenched and dewatered over much of the territory, while it remains confined in the zone adjacent to the Carpathian Foredeep. The most prominent geochemical features of the Miocene aquifer system in the confined karst zone are: (1) the almost universal presence of a bioepigenetic calcite bed, enriched in the light carbon isotope, at the top of the gypsum (the 'Ratynsky Limestone'), (2) the widespread sulfur mineralization associated with the above calcite bed (the region is one of the world's largest sulfur-bearing basins), and (3) high H2S and CO2 in the groundwater. Intense microbial sulfate-reduction processes occur in the gypsum in this zone. Zoloushka Cave is the third longest (92 km) and the largest by volume (more than 7 x 10(5) m(3)) gypsum cave in the world. It is a unique example of a young artesian cave that only during the Holocene became partly drained and during the last 50 years progressively dewatered due to a quarry operation. These rapid changes have induced a number of transitional geochemical processes, some of which appear to be bacterially mediated. Six groups of microorganisms have been identified in the cave. Our article discusses the aquifer geochemistry during the transitional stage in the light of the microbiological studies

The hypogenic caves: a powerful tool for the study of seeps and their environmental effects, 2002, Forti P, Galdenzi S, Sarbu Sm,
Research performed in caves has shown the existence of significant effects of gas seeps, especially CO2 and H2S, within subterranean voids. Carbon dioxide causes important corrosive effects and creates characteristic morphologies (e.g., bell-shaped domes, bubble's trails), but is not involved in the deposition of specific cave minerals. On the other hand, in carbonate environments, hydrogen sulfide when oxidized in the shallow sections of the aquifer generates important corrosion effects and is also responsible for the deposition of specific minerals of which gypsum is the most common.Studies performed in the last few years have shown that H2S seeps in caves are associated with rich and diverse biological communities, consisting of large numbers of endemic species. Stable isotope studies (carbon and nitrogen) have demonstrated that these hypogean ecosystems are entirely based on in situ production of food by chemoautotrophic microorganisms using energy resulting from the oxidation of H2S.Although located only 20 m under the surface, Movile Cave does not receive meteoric waters due to a layer of impermeable clays and loess that covers the Miocene limestone in which the cave is developed. In the Frasassi caves, where certain amounts of meteoric water seep into the limestone, the subterranean ecosystems are still isolated from the surface. As the deep sulfidic waters mix with the oxigenated meteoric waters, sulfuric acid limestone corrosion is accelerated resulting in widespread deposition of gypsum onto the cave walls.Both these caves have raised a lot of interest for biological investigations regarding the chemoautotrophically based ecosystems, demonstrating the possibility of performing such studies in environments that are easily accessible and easy to monitor compared to the deep-sea environments where the first gas seeps were discovered

Gypsum deposits in the Frasassi Caves, central Italy, 2003, Galdenzi, S. , Maruoka, T.
The Frasassi Caves are hypogenic caves in central Italy, where H2S-rich groundwater flows in the lowest cave level. Near the water table, the H2S is converted to sulfuric acid by biotic and abiotic processes, which have enhanced cave development. The sulfate generally deposits above the water table as a replacement gypsum crust coating limestone walls or as large gypsum crystals. Although the oxidation of sulfide also occurs below the water table, sulfate saturation is not achieved, therefore, sulfate does not precipitate below the water table. In the upper dry levels of the cave, three main types of ancient gypsum deposits occurs: (1) replacement crusts, similar to the presently forming deposits of the active zone, (2) microcrystalline large and thick floor deposits, and (3) euhedral crystals inside mud. The study of the depositional setting and the analysis of sulfur isotopes in the gypsum and groundwater clearly demonstrate that all the sampled gypsum in the cave formed by H2S oxidation above the water table. Some fraction of small sulfur isotopic differences between H2S in the water and gypsum can be explained by isotopic fractionation during abiotic and/or biotic oxidation of H2S.

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

Evolution of hydraulic conductivity by precipitation and dissolution in carbonate rock, 2003,

The evolution of hydraulic conductivity and flow patterns, controlled by simultaneous  precipitation and dissolution in porous rocks, was examined in a series of laboratory  experiments. Linear flow experiments were performed in columns of crushed calcareous  sandstone by injecting different concentrations of HCl/H2SO4 mixtures at various flow  rates. The effect of simultaneous calcium carbonate dissolution and gypsum precipitation  was analyzed. Changes in head gradient, recorded at specific time intervals during the  experiments, were used to calculate overall hydraulic conductivity of each column. The  effluent acid was analyzed for Ca2+ and SO4  2_ concentrations in order to calculate porosity  changes during the experiments. After each experiment, the rock sample was retrieved and  sectioned in order to study the pore space geometry, micromorphology, and mineral  concentrations. Arange of injected H+/SO4  2_ ratios and flow rates was identified which leads  to oscillations in the effective hydraulic conductivity of the evolving carbonate rock  samples. Because the dissolution of calcium carbonate is a mass transfer limited process,  higher flow rates cause a more rapid dissolution of the porous medium; in such cases, with  dissolution dominating, highly conductive flow wormholes were observed to develop.  At slower flow rates, no wormhole formation was observed, but the porosity varied in  different parts of the columns. Analysis of the sectioned parts of the column, after each  experiment, showed that total porosity increased significantly by dissolution of carbonate  mineral near the inlet of the column and decreased along the interior length of the column by  gypsum precipitation. These findings are in qualitative accordance with conceptual  understanding of such phenomena

Microbial contributions to cave formation: New insights into sulfuric acid speleogenesis, 2004, Engel As, Stern La, Bennett Pc,
The sulfuric acid speleogenesis (SAS) model was introduced in the early 1970s from observations of Lower Kane Cave, Wyoming, and was proposed as a cave-enlargement process due to primarily H2S autoxidation to sulfuric acid and subaerial replacement of carbonate by gypsum. Here we present a reexamination of the SAS type locality in which we make use of uniquely applied geochemical and microbiological methods. Little H2S escapes to the cave atmosphere, or is lost by abiotic autoxidation, and instead the primary H2S loss mechanism is by subaqueous sulfur-oxidizing bacterial communities that consume H2S. Filamentous 'Epsilonproteobacteria' and Gammaproteobacteria, characterized by fluorescence in situ hybridization, colonize carbonate surfaces and generate sulfuric acid as a metabolic byproduct. The bacteria focus carbonate dissolution by locally depressing pH, compared to bulk cave waters near equilibrium or slightly supersaturated with calcite. These findings show that SAS occurs in subaqueous environments and potentially at much greater phreatic depths in carbonate aquifers, thereby offering new insights into the microbial roles in subsurface karstification

'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

Mineralogical and Stable Isotope Studies of Kaolin Deposits: Shallow Epithermal Systems of Western Sardinia, Italy, 2005, Simeone R. , Dilles J. H. , Padalino G. , Palomba M. ,
Large kaolin deposits hosted by Miocene silicic pyroclastic rocks in northwestern Sardinia represent hydrothermal alteration formed within 200 m of the Miocene paleosurface. Boiling hydrothermal fluids ascended steeply dipping faults that are enveloped by altered rock. The broadly stratiform kaolin deposits constitute advanced argillic alteration that was produced in a steam-heated zone near the paleosurface overlying the deeper hydrothermal systems. The deeper zones represent two distinct types of epithermal systems: weakly acidic (inferred low-sulfidation) systems at Tresnuraghes and acidic (high-sulfidation) systems at Romana. Tresnuraghes is characterized at depth by chalcedony {} quartz {} barite veins within a 50-m-wide zone of K-feldspar-quartz-illite alteration and overlying local occurrences of chalcedony sinter, which define the paleosurface. Kaolin deposits near the paleosurface are characterized by zonation outward and downward from an inner shallow zone of kaolinite 1T-opal {} dickite {} alunite (<20-{micro}m-diam grains) to an outer deeper kaolinite 1M-montmorillonite-cristobalite. This zonation indicates formation by descending acidic fluids. The system evolved from ascending weakly acidic or neutral fluids that boiled to produce H2S-rich vapor, which condensed and oxidized within the near-surface vadose zone to form steam-heated acid-sulfate waters and kaolin alteration. At Romana, veins at depth contain chalcedony or quartz and minor pyrite and are enclosed in up to 20-m-wide zones of kaolinite 1T-quartz alteration. Near hydrothermal vents along the paleosurface, chalcedonic silica is enclosed within a zone of kaolinite 1T-alunite (<50-{micro}m-diam grains)-quartz-opal {} dickite {} cristobalite. Kaolin quarries near the paleosurface display outward and downward zoning to kaolinite 1T-opal {} cristobalite and then to montmorillonite-kaolinite 1T {} opal, consistent with formation by descending low pH fluid. The siliceous and advanced argillic alteration along steep conduits formed from acidic ascending magmatic-hydrothermal fluids, whereas the near-surface kaolin formed from steam-heated meteoric waters. Alteration mineral assemblages and stable isotope data provide evidence of the temperature and source of hydrothermal fluids. Barite from Tresnuraghes (average{delta} 18O = 17.1{per thousand},{delta} 34S = 18.8{per thousand}), one alunite sample from Romana ({delta}18O = 12.0{per thousand},{delta} D = -3{per thousand},{delta} 34S = 16.7{per thousand}), and quartz from both localities ({delta}18O = 15.9-22.0{per thousand}) formed in hydrothermal feeders. Source fluids were likely mixtures of meteoric water and minor magmatic fluid, similar to other epithermal systems. Kaolinite-dickite minerals from the kaolin deposits ({delta}18O = 16.6-21.4{per thousand},{delta} D = -43 to -53{per thousand}) formed from steam-heated meteoric water having{delta} D = - 20 per mil, consistent with the presence of anomalous Hg and fine-grained Na- and Fe-poor alunite. The laterally extensive kaolin deposits in Sardinia, and possibly similar deposits elsewhere in the world, appear to represent the uppermost parts of large hydrothermal systems that may be prospects for gold at depth

The Geomicrobiology of Ore Deposits, 2005, Southam G. , Saunders James A. ,
Bacterial metabolism, involving redox reactions with carbon, sulfur, and metals, appears to have been important since the dawn of life on Earth. In the Archean, anaerobic bacteria thrived before the Proterozoic oxidation of the atmosphere and the oceans, and these organisms continue to prosper in niches removed from molecular oxygen. Both aerobes and anaerobes have profound effects on the geochemistry of dissolved metals and metal-bearing minerals. Aerobes can oxidize dissolved metals and reduced sulfur, as well as sulfur and metals in sulfide minerals can contribute to the supergene enrichment of sulfide ores, and can catalyze the formation of acid mine drainage. Heterotrophic anaerobes, which require organic carbon for their metabolism, catalyze a number of thermodynamically favorable reactions such as Fe-Mn oxyhydroxide reductive dissolution (and the release of sorbed metals to solution) and sulfate reduction. Bacterial sulfate reduction to H2S can be very rapid if reactive organic carbon is present and can lead to precipitation of metal sulfides and perhaps increase the solubility of elements such as silver, gold, and arsenic that form stable Me-H2S aqueous complexes. Similarly, the bacterial degradation of complex organic compounds such as cellulose and hemicellulose to simpler molecules, such as acetate, oxalate, and citrate, can enhance metal solubility by forming Me organic complexes and cause dissolution of silicate minerals. Bacterially induced mineralization is being used for the bioremediation of metal-contaminated environments. Through similar processes, bacteria may have been important contributors in some sedimentary ore-forming environments and could be important along the low-temperature edges of high-temperature systems such as those that form volcanogenic massive sulfides

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