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Enviroscan Ukrainian Institute of Speleology and Karstology

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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 strath terrace is an erosional remnant of an elevated broad river valley [16].?

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

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What is Karstbase?



Browse Speleogenesis Issues:

KarstBase a bibliography database in karst and cave science.

Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
See all featured articles
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 gases (Keyword) returned 37 results for the whole karstbase:
Showing 1 to 15 of 37
Evaluation of Carbon Dioxide and Oxygen Data in Cave Atmospheres using the Gibbs Triangle and the Cave Air Index, 1982,
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Halbert, Erik J. M.

Water Vapour determines the volume percentage of component gases in cave atmospheres. This is particularly significant in foul air caves where carbon dioxide and oxygen concentrations are measured and used to diagnose foul air types. The variation in atmospheric composition brought about by systematic change in carbon dioxide and oxygen levels is examined and shown on the Gibbs triangle. The current three foul air types are readily identifiable in this visualisation of data, and the boundaries of these types are mapped. Further, these diverse data can be combined into a Cave Air Index by which foul air atmospheres may be assigned to type in a rapid and objective manner. The use of these concepts in evaluation of published data on Wellington and Bungonia Caves and with mine and soil data is shown.

Gypsum Trays in Torgac Cave, New Mexico, 1998,
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Doran, L. M. , Hill, C. A.
Mount St. Helens is an active dacitic volcano, which is currently in a semi-dormant state after a catastrophic explosive eruption in May 1980. A dacite dome occupies the crater and plugs the volcanic vent. The crater area has been progressively covered by a layer of snow, firn, and glacier ice since as early as 1986. Heat, steam, and volcanic gases from the crater fumaroles melted over 2415 meters of cave passage in the crater ice mass. The caves are in approximate balance with the present geothermal heat release. Future changes in the thermal activity will influence the dimensions, location, ceiling, wall, and wall ablation features of these caves. Cave passages are located above fumaroles and fractures in and adjacent to the crater lava dome. Cave passages gradually enlarge by ablation, caused by outside air circulation and by geothermal sources beneath the ice. The passages form a circumferential pattern around the dome, with entrance passages on the dome flanks. Passages grow laterally and vertically toward the surface, spawning ceiling collapse.

Lava tube remelt by radiant heat and burning gasses., 1998,
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Allred Kevin
Some volcanologists assume that interior surfaces of hot lava tubes can commonly he remelted by burning gases and radiant heat. Pending further data, this appears to be unlikely.

Chemoautotrophic microbial mats in submarine caves with hydrothermal sulphidic springs at Cape Palinuro, Italy, 1998,
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Mattison R. G. , Abbiati M. , Dando P. R. , Fitzsimons M. F. , Pratt S. M. , Southward A. J. , Southward E. C. ,
Observations were made on the distribution, morphology, and chemoautotrophic potential of microbial mats found in submarine caves of dolomitized limestone which contain hydrothermal sulphidic springs at Cape Palinuro, Italy. The distribution of microbial mats is closely associated with the flow of hydrothermal fluid from springs whose activity is intermittent and initiated during low tide. Fluid emitted from active springs in the Grotta Azzurra has a maximum temperature of 24.6 degrees C and is enriched in dissolved sulfur species (H2S, S2O32-) and dissolved gases (CH4, CO2). However, it is depleted in NaCl and dissolved O-2, in comparison with ambient seawater. This fluid is less dense and rises above the ambient seawater to form a visible thermocline and chemocline separating both lavers in the submarine caves. Microbial mats were attached to rock surfaces immersed in fluid above the chemocline and were differentiated into brown and white forms. Brown mats were composed of trichomes (4.2 0.1 mu m and 20.3 0.7 mu m in diameter) resembling the calcareous rock-boring cyanobacterium Schizothrix and clusters (6 mu m in diameter) of sarcina-like cells morphologically resembling methanogenic bacteria. White mats were composed of attached filaments resembling Beggiatoa (19.3 0.5 mu m, 39.0 1.7 mu m, and 66.9 3.3 mu m in diameter) and Thiothrix (4.2 0.2 mu m in diameter). Flexibacteria (<1 mu m in diameter) were common to both mats. Beggiatoa-like filaments were morphologically similar to those attached to rocks and the byssal threads of mussels from Lucky Strike vent field on the Mid-Atlantic Ridge, Morphological comparisons were also made with typical gliding Beggiatoa from shallow seeps in Eckernforder Bucht, Baltic Sea. White mats displayed chemoautotrophic fixation of CO2 under relatively well-oxygenated laboratory conditions (maximum rate 50.2 nmol CO2/mg dry wt/h) using internal S-0 or possibly S2O32- as electron donor. Photosynthesis may be limited in the Grotta Azzurra by insufficient illumination (6.3 x 10(-7) mu einsteins/cm(2)/s), with the possibility of Schizothrix living (at least in part) as a chemoheterotroph on while mats. Chemoautotrophic fixation of CO2 by white mats is proposed as a significant source of nutrition for benthic fauna in these caves, and has been estimated as contributing 50-70 mu mol CO2/m(2) of mat/min, as measured under laboratory conditions

Microbiology and geochemistry in a hydrogen-sulphide-rich karst environment, 2000,
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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

Carbonate platform systems: components and interactions -- an introduction, 2000,
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Insalaco Enzo, Skelton Peter, Palmer Tim J. ,
Carbonate platforms are open systems with natural boundaries in space and time. Across their spatial boundaries there are fluxes of energy (e.g. light, chemical energy in compounds, and kinetic energy in currents and mass flows) and matter (e.g. nutrients, dissolved gases such as CO2, and sediment -- especially, of course, carbonates). Internally, these fluxes are regulated by myriads of interactions and feedbacks (Masse 1995), and the residue is consigned to the geological record. The most distinctive aspect of carbonate platforms is the predominant role of organisms in producing, processing and/or trapping carbonate sediment, even in Precambrian examples. Because of evolutionary changes in this strong biotic input, it is harder to generalize about carbonate platforms than about most other sedimentary systems. Evolution has altered both the constructive and destructive effects of platform-dwelling organisms on carbonate fabrics, with profound consequences for facies development. Moreover, changing patterns in the provision of accommodation space (e.g. between greenhouse and icehouse climatic regimes) have also left their stamp on facies geometries, in turn feeding back to the evolution of the platform biotas. Hence simplistic analogies between modern and ancient platforms may give rise to misleading interpretations of what the latter were like and how they formed. Although a number of carbonate platform and reef specialists have warned of the dangers of such misplaced uniformitarianism (e.g. Braithwaite 1973; Gili et al. 1995; Wood 1999), it remains depressingly commonplace in the literature on ancient carbonate platforms. The endless quest in the literature for an allpurpose definition of reefs' ... This 250-word extract was created in the absence of an abstract

Views on cave Formation before 1900, 2000,
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Shaw T.
Nearly all present-day explanations for the formation of caves in limestone had been suggested before 1900, and some had been developed in considerable detail. Speleogenesis by erosion and the role of carbon dioxide in the solution of cave passages were understood in the first half of the 19th century, and by the end of it there already existed schools of thought which supported solution by vadose water and by phreatic water. The most important names in all this are those of Catcott who in 1756 recognized that caves resulted from water action (though he did attribute the water to the biblical Flood), Lyell and Thirria who independently in 1830 appreciated the importance of carbon dioxide in enabling water to dissolve caves in limestone, Evans who understood in 1870 that some caves were formed by solution in groundwater, Martel who from 1890 emphasized the solutional activity of vadose water and made it well known among speleologists, Posepny who described the movement of groundwater and its speleogenetic effect in 1893, and Dupont who developed that idea. There were also some distinctly primitive explanations, mostly in earlier times, including the creation of cavities when beds were folded and mountains formed, erosion of rock by water before it had become hard, expansion in the soft rock of gases from decomposing animal bodies drowned in the Flood, and the solution of salt inclusions having the same shape as the resulting caves. These catastrophic theories were often inspired by the need to explain the formation of caves, as of all landforms, in the relatively short period since the creation of the world, which was commonly believed to have happened 4000 years BC.

Soil carbon dioxide in a summer-dry subalpine karst, Marble Mountains, California, USA, 2001,
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Davis J, Amato P, Kiefer R,
Studies of the seasonality, spatial variation and geomorphic effects of Soil CO2 concentrations in a summer-dry subalpine karst landscape in the Marble Mountains, Klamath National Forest, California, demonstrate the significance of soil moisture as a limiting factor. Modeled actual evapotranspiration (AET) in the four weeks prior to sampling explains 36% of the observed soil-CO2 concentrations, pointing to the importance of root respiration processes in these systems. Late snows are significant in controlling the timing of a snowmelt-initiated pulse of respiration and groundwater. CO2 concentrations were measured at multiple sites in two seasons - 1995 and 1997 - with contrasting patterns of snowmelt. Other than wet-meadow anomalies, where CO2 concentrations reached up to 3.8% in midsummer, alpine meadows on schist were the sites of the highest spring peak concentrations of approximately 1%. Forest sites and sites with thin soils on marble typically peaked at approximately 0.5%, also within a month of snowmelt exposure. Ongoing karstification in the upper bare karst is focused in soil-filled grikes where late-season snowmelt concentrates flow during high-respiration periods, but the lack of active speleothem development suggests that the carbonate solution system is greatly reduced from preglacial periods

Groundwater chemical composition changes in the Dubravsky Massif hydrogeological structure, induced by magnesite exploitation, 2004,
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Bajtos P,
Exploited magnesite bodies of the Dubravsky Massif create parts of karst-fissure aquifer confined by Carboniferous metamorphic rocks of low fissure permeability. Extensive mining progress caused considerable changes in both groundwater circulation and groundwater chemical composition of the aquifer. A model of groundwater chemical composition genesis in such complicated conditions is presented in this paper. Saturation indices (SI) for chosen minerals were computed based on speciation modelling, which indicate oversaturation of groundwater with magnesite, dolomite, calcite, and undersaturation with gypsum in all saturated zone of karst-fissure aquifer. Statistical interpretations of hydrochemical data suppose that anthropogenically unaffected groundwater, where mineralisation is slightly altered by pyrite oxidation in dolomitic environment, represents hydrogeochemical background within the aquifer. It is supposed, that azonic acid, generated by condensation of nitrogen-rich gases freeing by blast-firings in mine, accelerate magnesite and dolomite dissolution. Produced groundwater types are of higher content of NO3, Mg and TIC in comparison with background values. Estimated acceleration of karstification processes due to underground mining is about 1.5 times. In spite of detected contamination, threshold values of drinking water standard, given by the Edict of the Slovak Ministry of Health Care No. 29 / 2002 Z. z. are not markedly exceeded for tested parameters. Future possible exploitation of studied aquifer after mining termination is not excluded

Dolomites in SE Asia -- varied origins and implications for hydrocarbon exploration, 2004,
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Carnell Ajh, Wilson Mej,
Carbonates in SE Asia range in age from Palaeozoic to Recent, but are most important as reservoirs in the Neogene where they comprise a major target for hydrocarbon exploration (e.g. Batu Raja Formation, South Sumatra, Sunda and Northwest Java basins). Carbonates of pre-Tertiary, Palaeogene and Neogene age all show a strong diagenetic overprint in which dolomite occurs as both cementing and replacive phases associated with variable reservoir quality. This paper reviews published data on the occurrence and types of dolomites in SE Asian carbonates, and considers the models that have been used to explain the distribution and origin of dolomite within these rocks. Pre-Tertiary carbonates form part of the economic basement, and are little studied and poorly understood. Although some, such as in the Manusela Formation of Seram, may form possible hydrocarbon reservoirs, most are not considered to form economic prospects. They are best known from the platform carbonates of the Ratburi and Saraburi groups. in Thailand, and the oolitic grainstones of the Manusela Formation of Seram. The Ratburi Group shows extensive dolomitization with dolomite developed as an early replacive phase and as a late-stage cement. Palaeogene carbonates are widely developed in the region and are most commonly developed as extensive foraminifera-dominated carbonate shelfal systems around the margins of Sundaland (e.g. Tampur Formation, North Sumatra Basin and Tonasa Formation, Sulawesi) and the northern margins of Australia and the Birds Head microcontinent (e.g. Faumai Formation, Salawati Basin). Locally, carbonates of this age may form hydrocarbon reservoirs. Dolomite is variably recorded in these carbonates and the Tampur Formation, for example, contains extensive xenotopic dolomite. Neogene carbonates (e.g. Peutu Formation, North Sumatra) are commonly areally restricted, reef-dominated and developed in mixed carbonate-siliciclastic systems. They most typically show a strong diagenetic overprint with leaching, recrystallization, cementation and dolomitization all widespread. Hydrocarbon reservoirs are highly productive and common in carbonates of this age. Dolomite is variably distributed and its occurrence has been related to facies, karstification, proximity to carbonate margins and faults. The distribution and origin of the dolomite has been attributed to mixing-zone dolomitization (commonly in association with karstic processes), sulphate reduction via organic matter oxidation, and dewatering from the marine mudstones that commonly envelop the carbonate build-up. Dolomite has a variable association with reservoir quality in the region, and when developed as a replacive phase tends to be associated with improved porosity and permeability characteristics. This is particularly the case where it is developed as an early fabric-retentive phase. Cementing dolomite is detrimental to reservoir quality, although the extent of this degradation generally reflects the abundance and distribution of this dolomite. Dolomitization is also inferred to have influenced the distribution of non-hydrocarbon gases. This is best documented in North Sumatra where carbon dioxide occurs in quantities ranging from 0 to 85%. There are a number of possible mechanisms for generating this CO2 (e.g. mantle degassing), although the most likely source is considered to be the widely dolomitized Eocene Tampur Formation that forms effective basement for much of the basin. High heat flows are suggested to have resulted in the thermogenic decomposition of dolomite with CO2 produced as a by-product

Cavity-based secondary mineralization in volcanic tuffs of Yucca Mountain, Nevada: a new type of the polymineral vadose speleothem, or a hydrothermal deposit?, 2005,
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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,
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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

Using Multiple Chemical Indicators to Assess Sources of Nitrate and Age of Groundwater in a Karstic Spring Basin, 2005,
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Katz Brian, Copeland Rick, Greenhalgh Tom, Ceryak Ron, Zwanka Warren,
Human health and ecological concerns have arisen due to a steady increase in nitrate-N concentrations during the past 40 years in Fannin Springs (0.3-4.7 mg/L), a regional discharge point with an average flow of >2.8 m3/second (>100 ft3/second) for water from the karstic Upper Floridan aquifer (UFA). Multiple chemical indicators (major dissolved species, 15N and 18O of nitrate, dissolved gases, 78 pesticides and degradates, and 67 organic compounds typically found in domestic and industrial wastewater) and transient tracers (3H/3He, chlorofluorocarbons [CFCs], sulfur hexafluoride [SF6]) were analyzed in water samples from nine wells along three transects and in spring water to assess groundwater age and potential contaminant sources. Land use is predominantly agricultural (52 percent) and forest (31 percent) in the 320 km2 (124 mi2) spring basin, which was delineated from a potentiometric-surface map of the UFA using high-resolution water-level data. Nitrate-N concentrations were highly variable in the oxic UFA and ranged from <0.02 to 4.7 mg/L. {delta}15N-NO3 values (3.4-9.9 per mil) indicated that nitrate contamination originated from inorganic sources (synthetic fertilizer) and organic sources (manure spreading or waste disposal). Higher nitrate concentrations and the younger age of spring water relative to water from upgradient wells indicate better communication with N sources at the surface. Apparent ages of groundwater correlated positively with well depth (P < 0.05) and were younger in water from wells nearer to the spring (<8 years) compared with other wells (10-50 years). Most transient tracer concentrations were consistent with binary mixing curves representing mixtures of water recharged during the past 10 years and older water (recharged before 1940). Young water mixing fractions ranged from 0.07 to 0.90. Trace levels of herbicides found in groundwater and spring water were indicative of applications for vegetative control in agricultural and other land-use types

Sedimentary manganese metallogenesis in response to the evolution of the Earth system, 2006,
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Roy Supriya,
The concentration of manganese in solution and its precipitation in inorganic systems are primarily redox-controlled, guided by several Earth processes most of which were tectonically induced. The Early Archean atmosphere-hydrosphere system was extremely O2-deficient. Thus, the very high mantle heat flux producing superplumes, severe outgassing and high-temperature hydrothermal activity introduced substantial Mn2 in anoxic oceans but prevented its precipitation. During the Late Archean, centered at ca. 2.75[no-break space]Ga, the introduction of Photosystem II and decrease of the oxygen sinks led to a limited buildup of surface O2-content locally, initiating modest deposition of manganese in shallow basin-margin oxygenated niches (e.g., deposits in India and Brazil). Rapid burial of organic matter, decline of reduced gases from a progressively oxygenated mantle and a net increase in photosynthetic oxygen marked the Archean-Proterozoic transition. Concurrently, a massive drawdown of atmospheric CO2 owing to increased weathering rates on the tectonically expanded freeboard of the assembled supercontinents caused Paleoproterozoic glaciations (2.45-2.22[no-break space]Ga). The spectacular sedimentary manganese deposits (at ca. 2.4[no-break space]Ga) of Transvaal Supergroup, South Africa, were formed by oxidation of hydrothermally derived Mn2 transferred from a stratified ocean to the continental shelf by transgression. Episodes of increased burial rate of organic matter during ca. 2.4 and 2.06[no-break space]Ga are correlatable to ocean stratification and further rise of oxygen in the atmosphere. Black shale-hosted Mn carbonate deposits in the Birimian sequence (ca. 2.3-2.0[no-break space]Ga), West Africa, its equivalents in South America and those in the Francevillian sequence (ca. 2.2-2.1[no-break space]Ga), Gabon are correlatable to this period. Tectonically forced doming-up, attenuation and substantial increase in freeboard areas prompted increased silicate weathering and atmospheric CO2 drawdown causing glaciation on the Neoproterozoic Rodinia supercontinent. Tectonic rifting and mantle outgassing led to deglaciation. Dissolved Mn2 and Fe2 concentrated earlier in highly saline stagnant seawater below the ice cover were exported to shallow shelves by transgression during deglaciation. During the Sturtian glacial-interglacial event (ca. 750-700[no-break space]Ma), interstratified Mn oxide and BIF deposits of Damara sequence, Namibia, was formed. The Varangian ([identical to] Marinoan; ca. 600[no-break space]Ma) cryogenic event produced Mn oxide and BIF deposits at Urucum, Jacadigo Group, Brazil. The Datangpo interglacial sequence, South China (Liantuo-Nantuo [identical to] Varangian event) contains black shale-hosted Mn carbonate deposits. The Early Paleozoic witnessed several glacioeustatic sea level changes producing small Mn carbonate deposits of Tiantaishan (Early Cambrian) and Taojiang (Mid-Ordovician) in black shale sequences, China, and the major Mn oxide-carbonate deposits of Karadzhal-type, Central Kazakhstan (Late Devonian). The Mesozoic period of intense plate movements and volcanism produced greenhouse climate and stratified oceans. During the Early Jurassic OAE, organic-rich sediments host many Mn carbonate deposits in Europe (e.g., Urkut, Hungary) in black shale sequences. The Late Jurassic giant Mn Carbonate deposit at Molango, Mexico, was also genetically related to sea level change. Mn carbonates were always derived from Mn oxyhydroxides during early diagenesis. Large Mn oxide deposits of Cretaceous age at Groote Eylandt, Australia and Imini-Tasdremt, Morocco, were also formed during transgression-regression in greenhouse climate. The Early Oligocene giant Mn oxide-carbonate deposit of Chiatura (Georgia) and Nikopol (Ukraine) were developed in a similar situation. Thereafter, manganese sedimentation was entirely shifted to the deep seafloor and since ca. 15[no-break space]Ma B.P. was climatically controlled (glaciation-deglaciation) assisted by oxygenated polar bottom currents (AABW, NADW). The changes in climate and the sea level were mainly tectonically forced

Observations on the biodiversity of sulfidic karst habitats, 2007,
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Engel Annette Summers
Recognition of the metabolic process of chemosynthesis has recently overthrown the ecological dogma that all life on earth is dependent on sunlight. In complete darkness, complex ecosystems can be sustained by the energy and nutrients provided by chemosynthetic microorganisms. Many of these chemosynthetically-based ecosystems result from microbial manipulation of energy-rich sulfur compounds that can be found in high concentrations in groundwater. Subsurface environments in general can be highly stressful habitats (i.e., darkness, limited food, etc.), but in the case of sulfidic groundwater habitats, organisms must also tolerate and adapt to different stresses (e.g., toxic levels of gases or lethally low oxygen concentrations). Nevertheless, these habitats, and specifically cave and karst aquifers, have a richly diverse fauna. This review focuses on the biodiversity (as the number and types of species) of sulfur-based cave and karst aquifer systems. The relationships among ecosystem productivity, biodiversity, and habitat and ecosystem stresses are explored. The relatively high numbers of species and complex trophic levels could be attributed to the rich and plentiful, chemosyntheticallyproduced food source that has permitted organisms to survive in and to adapt to harsh habitat conditions. The geologic age and the hydrological and geochemical stability of the cave and karst aquifer systems may have also influenced the types of ecosystems observed. However, similar to non-sulfidic karst systems, more descriptions of the functional roles of karst aquifer microbes and macroscopic organisms are needed. As subterranean ecosystems are becoming increasingly more impacted by environmental and anthropogenic pressures, this review and the questions raised within it will lead to an improved understanding of the vulnerability, management, and sustainability challenges facing these unique ecosystems.

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