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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 creek, brook is watercourse of lesser volume than a river.?

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.
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 anoxic (Keyword) returned 28 results for the whole karstbase:
Showing 1 to 15 of 28
Sulfate reducing bacteria in microbial mats: Changing paradigms, new discoveries, 0000,
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Baumgartner Lk, Reid Rp, Dupraz C, Decho Aw, Buckley Dh, Spear Jr, Przekop Km, Visscher Pt,
Sulfate reducing bacteria (SRB) have existed throughout much of Earth's history and remain major contributors to carbon cycling in modern systems. Despite their importance, misconceptions about SRB are prevalent. In particular, SRB are commonly thought to lack oxygen tolerance and to exist only in anoxic environments. Through the last two decades, researchers have discovered that SRB can, in fact, tolerate and even respire oxygen. Investigations of microbial mat systems have demonstrated that SRB are both abundant and active in the oxic zones of mats. Additionally, SRB have been found to be highly active in the lithified zones of microbial mats, suggesting a connection between sulfate reduction and mat lithification. In the present paper, we review recent research on SRB distribution and present new preliminary findings on both the diversity and distribution of [delta]-proteobacterial SRB in lithifying and non-lithifying microbial mat systems. These preliminary findings indicate the unexplored diversity of SRB in a microbial mat system and demonstrate the close microspatial association of SRB and cyanobacteria in the oxic zone of the mat. Possible mechanisms and further studies to elucidate mechanisms for carbonate precipitation via sulfate reduction are also discussed

Chronology of the Black Sea over the last 25,000 years, 1972,
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Degens Et, Ross Da,
Deep-water sediments of the Black Sea deposited during Late Pleistocene and Holocene time are distinguished by three sedimentary units: (1) a microlaminated coccolith ooze mainly consisting of Emiliania huxleyi; (2) a sapropel; and (3) a banded lutite. The base of the first unit lies at 3,000 years B.P., that of the second at 7,000 years B.P., and that of the third at least at about 25,000 years B.P. Fossils and geochemical criteria are used to decipher the environmental events of this time period. Beginning with the base of the section dated at about 25,000 years B.P. we witness the final stage of metamorphosis from anoxic marine to oxic freshwater conditions. By the time this stage ended, about 22,000 years B.P., the Black Sea had become a truly freshwater habitat. The lake phase lasted about 12,000 to 13,000 years. Sedimentation rates were in the order of 1 m/103 years, but began to decrease as sea level rose during the last 5,000 years of this phase (9,000-15,000 years B.P.). Starting at about 9,000 years B.P. and continuing to 7,000 years B.P., Mediterranean waters occasionally spilled over the Bosporus as a consequence of ice retreat and sea level rise. This marked the beginning of a gradual shift from freshwater to marine, and from well aerated to stagnant conditions. At about 7,000 years B.P. when deposition of unit 2 started, the H2S zone was well established. Sedimentation rates dropped to 10 cm/103 years. Environmental conditions similar to those of today finally became established around 3,000 years B.P., almost exactly the time when Jason and the Argonauts sailed through the Bosporus in search of the Golden Fleece

Evolution des karsts Ocaniens (Karsts, bauxite et phosphates), 1992,
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Bourrouilhlejan, Fr.
EVOLUTION OF THE PACIFIC OCEAN KARSTS - Karst phenomena constitute one of the main characteristics of the "high carbonate islands" of the Pacific Ocean. They are the key to the under-standing of the geological evolution, the stratigraphy, from Lower Miocene to Pleistocene and mid-Holocene, the diagenesis, mainly dolomitization and the current economic interest based on bauxite and phosphate. The eustatic variations have been numerous over the past 25 million years and can be added or substracted from the emersion and submersion movements of the plate supporting these carbonate platforms. Each island therefore has its own complex geological background with dolomitization, calcrete, bauxitic soils, fossil marine notches and karst surface either submerged or filled with phosphate, which can be mined for profit. Thanks to a thorough study of these platforms, it has been possible to establish an evolution of karst genesis in accordance with the evolution of the Pacific lithosphere and also to draw up a new model of phosphate genesis linked to phosphato-bauxitic soils and meromictic anoxic lakes.

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Eichem Ac, Dodds Wk, Tate Cm, Edler C,
Dry Chinquapin oak (Quercus macrocarpa) and American elm (Ulmus americana) leaves were placed in four microcosms fed by groundwater springs to monitor changes in dry mass, ash-free dry mass, and microbial activity over a 35-day period. Oxygen microelectrodes were used to measure microbial activity and to estimate millimeter-scale heterogeneity in that activity. Oak leaves lost mass more slowly than elm leaves. Generally, there was a decrease in total dry weight over the first 14 days, after which total dry weight began to increase. However, there were consistent decreases in ash-free dry mass over the entire incubation period, suggesting that the material remaining after initial leaf decomposition trapped inorganic particles. Microbial activity was higher on elm leaves than on oak leaves, with peak activity occurring at 6 and 27 days, respectively. The level of oxygen saturation on the bottom surface of an elm leaf ranged between 0 and 75% within a 30-mm2 area. This spatial heterogeneity in O2 saturation disappeared when the water velocity increased from 0 to 6 cm s-1. Our results suggest that as leaves enter the groundwater, they decompose and provide substrate for microorganisms. The rate of decomposition depends on leaf type, small-scale variations in microbial activity, water velocity, and the length of submersion time. During the initial stages of decomposition, anoxic microzones are formed that could potentially be important to the biogeochemistry of the otherwise oxic aquifer

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Stoessell R. K. , Moore Y. H. , Coke J. G. ,
Dissolution of carbonate minerals in the coastal halocline is taking place in the karst terrain along the northeastern coast of the Yucatan Peninsula. The dissolution is being accelerated in cenotes (sinkholes) where sulfate reduction and oxidation of the produced sulfide is occurring. Hydrogen-sulfide concentrations ranged from 0.06 to 4 mmolal within the halocline in two sinkholes. Relative to concentrations expected by conservative mixing, fluids with high hydrogen-sulfide concentrations were correlated with low sulfate concentrations, high alkalinities, low pH values, and heavy sulfur isotope values for sulfate. Hydrogen-sulfide concentrations were less than those predicted from sulfate reduction, calculated from deficiencies in measured sulfate concentrations, indicating mobility and loss of aqueous sulfide. Fluids with low hydrogen-sulfide concentrations were correlated with very high calcium concentrations, high strontium and sulfate concentrations, slightly elevated alkalinities, low pH values, and sea-water sulfur isotope values for sulfate. Gypsum dissolution is supported by the sulfur isotopes as the major process producing high sulfate concentrations. However, oxidation of aqueous sulfide to sulfuric acid, resulting in carbonate-mineral dissolution is needed to explain the calcium concentrations, low pH values, and only slightly elevated alkalinities. The halocline may trap hydrogen sulfide that has been stripped from the underlying anoxic salt water. The halocline can act as a stable, physical boundary, holding some of the hydrogen sulfide until it is oxidized back to sulfuric acid through interaction with the overlying, oxygenated fresh water or through the activity of sulfide-oxidizing bacteria

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Katz B. G. , Lee T. M. , Plummer L. N. , Busenberg E. ,
Leakage from sinkhole lakes significantly influences recharge to the Upper Floridan aquifer in poorly confined sediments in northern Florida. Environmental isotopes (oxygen 18, deuterium, and tritium), chlorofluorocarbons (CFCs: CFC-11, CCl3F; CFC-12, CCl2F2; and CFC-113, C2Cl3F3), and solute tracers were used to investigate groundwater flow patterns near Lake Barco, a seepage lake in a mantled karst setting in northern Florida. Stable isotope data indicated that the groundwater downgradient from the lake contained 11-67% lake water leakage, with a limit of detection of lake water in groundwater of 4.3%. The mixing fractions of lake water leakage, which passed through organic-rich sediments in the lake bottom, were directly proportional to the observed methane concentrations and increased with depth in the groundwater flow system. In aerobic groundwater upgradient from Lake Barco, CFC-modeled recharge dates ranged from 1987 near the water table to the mid 1970s for water collected at a depth of 30 m below the water table. CFC-modeled recharge dates (based on CFC-12) for anaerobic groundwater downgradient from the lake ranged from the late 1950s to the mid 1970s and were consistent with tritium data. CFC-modeled recharge dates based on CFC-11 indicated preferential microbial degradation in anoxic waters. Vertical hydraulic conductivities, calculated using CFC-12 modeled recharge dates and Darcy's law, were 0.17, 0.033, and 0.019 mid for the surficial aquifer, intermediate confining unit, and lake sediments, respectively. These conductivities agreed closely with those used in the calibration of a three-dimensional groundwater flow model for transient and steady state flow conditions

The combined use of Sr-87/Sr-86 and carbon and water isotopes to study the hydrochemical interaction between groundwater and lakewater in mantled karst, 1996,
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Katz B. G. , Bullen T. D. ,
The hydrochemical interaction between groundwater and lakewater influences the composition of water that percolates downward from the surficial aquifer system through the underlying intermediate confining unit and recharges the Upper Floridan aquifer along highlands in Florida. The Sr-87/Sr-86 ratio along with the stable isotopes, D, O-18, and C-13 were used as tracers to study the interaction between groundwater, lakewater, and aquifer minerals near Lake Barco, a seepage lake in the mantled karst terrane of northern Florida. Upgradient from the lake, the Sr-87/Sr-86 ratio of groundwater decreases with depth (mean values of 0.71004, 0.70890, and 0.70852 for water from the surficial aquifer system, intermediate confining unit, and Upper Floridan aquifer, respectively), resulting from the interaction of dilute oxygenated recharge water with aquifer minerals that are less radiogenic with depth. The concentrations of Sr2 generally increase with depth, and higher concentrations of Sr2 in water from the Upper Floridan aquifer (20-35 mu g/L), relative to water from the surficial aquifer system and the intermediate confining unit, result from the dissolution of Sr-bearing calcite and dolomite in the Eocene limestone. Dissolution of calcite [delta(13)C = -1.6 permil (parts per thousand)] is also indicated by an enriched delta(13)C(DIC) (-8.8 to -11.4 parts per thousand) in water from the Upper Floridan aquifer, relative to the overlying hydrogeologic units (delta(13)C(DIC) < -16 parts per thousand). Groundwater downgradient from Lake Barco was enriched in O-18 and D relative to groundwater upgradient from the lake, indicating mixing of lakewater leakage and groundwater. Downgradient from the lake, the Sr-87/Sr-86 ratio of groundwater and aquifer material become less radiogenic and the Sr2 concentrations generally increase with depth. However, Sr2 concentrations are substantially less than in upgradient groundwaters at similar depths. The lower Sr2 concentrations result from the influence of anoxic lakewater leakage on the mobility of Sr2 from clays. Based on results from mass-balance modeling, it is probable that cation exchange plays the dominant role in controlling the Sr-87/Sr-86 ratio of groundwater, both upgradient and downgradient from Lake Barco. Even though groundwater from the three distinct hydrogeologic units displays considerable variability in Sr concentration and isotopic composition, the dominant processes associated with the mixing of lakewater leakage with groundwater, as well as the effects of mineral-water interaction, can be ascertained by integrating the use of stable and radiogenic isotopic measurements of groundwater, lakewater, and aquifer minerals

Oxidation of organic matter in a karstic hydrologic unit supplied through stream sinks (Loiret, France), 1998,
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Alberic P, Lepiller M,
The aim of this paper is to appraise the ability of the oxidation of riverine organic matter in the control of limestone dissolution, in a karst network. Biogeochemical processes during infiltration of river water into an alluvial aquifer have already been described for an average flow velocity of 4-5 m d(-1) (Jacobs, L. A., von Gunten, H. R., Keil, R, and Kuslys, M. (1988) Geochemical changes along a river-groundwater infiltration flow path: Glattfelden, Switzerland. Geochim. Cosmochim. Acta 52, 2693-2706; Von Gunten, H. R., Karametaxas, G., Krahenbuhl, U., Kuslys, M., Giovanoli R., Hoehn E. and Keil R. (1991) Seasonal biogeochemical cycles in riverborne groundwater. Geochim. Cosmochim. Acta 55, 3597-3609; Bourg, A. C. M. and Bertin, C. (1993) Quantitative appraisal of biogeochemical chemical processes during the infiltration of river water into an alluvial aquifer. Environ. Sci. Technol. 27, 661-666). Karstic drainage networks, such as in the River Loire-Val d'Orleans hydrologic system (Fig. 1), make possible flow velocities up to 200 m h(-1 a) and provide convenient access to different water samples several tens of km apart, at both extremities of the hydrologic unit (Chery, J.-L. (1983) Etude hydrochimique d'un aquifere karstique alimente par perte de cours d'eau (la Loire): Le systeme des calcaires de Beauce sous le val d'Orleans. These, Universite d'Orleans; Livrozet, E. (1984) Influence des apports de la Loire sur la qualite bacteriologique et chimique de l'aquifere karstique du val d'Orleans. These, Universite d'Orleans). Recharge of the karstic aquifer occurs principally from influent waters from stream sinks, either through coarse alluvial deposits or directly from outcrops of the regional limestone bedrock (Calcaires de Beauce). Recharge by seepage waters From the local catchment basin is small (Zunino, C., Bonnet, M. and Lelong, F. (1980) Le Val d'Orleans: un exemple d'aquifere a alimentation laterale. C. R. somm. Soc. Geol. Fr. 5, 195-199; Gonzalez R. (1992) Etude de l'organisation et evaluation des echanges entre la Loire moyenne et l'aquifere des calcaires de Beauce. These, Universite d'Orleans) and negligible in summer. This karstic hydrologic: system is the largest in France in terms of flow (tens to hundreds of m(3)/s) and provides the main water resource of the city of Orleans. Chemical compositions of influent waters (River Loire) and effluent waters (spring of the river Loiret) were compared, in particular during floods in summer 1992 and 1993 (Figs 2-4). Variation of chloride in the River Loire during the stream rise can be used as an environmental tracer of the underground flow (Fig. 2). Short transit times of about 3 days are detectable (Fig, 2) which are consistent with earlier estimations obtained with chemical tracers (Ref. in Chery, J.-L. (1983) These, Universite d'Orleans). Depending on the hydrological regime of the river, organic carbon discharge ranges between 3-7 and 2-13 mg/l for dissolved and particulate matter respectively (Fig. 3). Eutrophic characteristics and high algal biomasses are found in the River Loire during low water (Lair, N. and Sargos, D. (1993) A 10 year study at four sites of the middle course of the River Loire. I - Patterns of change in hydrological, physical and chemical variables in relation to algal biomass. Hudroecol. Appl. 5, 1-27) together with more organic carbon rich suspended particulate matter than during floods (30-40 C-org % dry weight versus 5-10%). Amounts of total organic carbon and dissolved oxygen (Fig. 3) dramatically decrease during the underground transport, whereas conversely, dissolved calcium, alkalinity and inorganic carbon increase (Fig. 4). Anoxia of outflows map start in April. Dissolution of calcium carbonates along the influent path outweighs closed system calcite equilibrium of inflow river waters (Table 3). The impact of organic matter oxidation on calcite dissolution may be traced by variations of alkalinity and total carbonates in water. Following, Jacobs, L. A., von Gunten, H. R., Keil, R. and Kuslys, M. (1988) Geochemical changes along a river-groundwater infiltration flow path: Glattfelden, Switzerland. Geochim. Cosmochim. Acta 52, 2693-2706), results are shown graphically (Fig. 5). Extent of reactions is controlled by the consumption of dissolved O-2 and nitrate for organic matter oxidation and by the release of Ca2 for calcite dissolution (Table 2). The karstic network is considered to behave like a biological reactor not exchanging with the atmosphere, with steady inhabitant microbial communities (Mariotti A., Landreau A, and Simon B. (1988) N-15 isotope biogeochemisrry and natural denitrification process in groundwater: Application to the chalk aquifer of northern France. Geochim. Cosmochim. Acta 52, 1869-1878; Gounot, A.-M. (1991) Ecologie microbienne des eaux ei des sediments souterrains. Hydrogeologie, 239-248). Thus, energy requirements only are considered, not carbon assimilation. Moreover, there is no necessity to invoke any delay for nitrification enhancement, as observed elsewhere, after waste water discharge into the river (Chesterikoff, A., Garban, B., Billen, G. and Poulin, M. (1992) Inorganic nitrogen dynamics in the River Seine downstream from Paris (France). Biogeochem. 17, 147-164). Main microbial processes are assumed to be aerobic respiration, nitrification and denitrification. Reactions with iron and manganese, real but not quantitatively important, were neglected. Sulphate reduction and methane formation, certainly not active, were not considered. Denitrification, which is suggested by low nitrate and ammonium concentrations and anoxia in the outflow, is known to be rapid enough to be achieved in a short time (Dupain, S. (1992) Denitrification biologique heterotrophe appliquee au traitement des eaux d'alimentation: Conditions de fonclionnement et mise au point d'un procede. These, Universite Claude Bernard, Lyon). Reaction are somewhat arbitrary but conform to general acceptance (Morel, M. M. and Hering, J. G. (1993) Principles and Applications of Aquatic Chemistry. Wiley, New York). Anaerobic ammonium oxidation (Mulder A., van de Graaf, A. A., Robertson, L: A. and Kuenen, J. G. (1995) Anaerobic ammonium oxidation discovered in a denitrifying fluidized bed reactor. FEMS Microbiol. Ecol. 16, 177-184). although possible, was not considered. In fact, C/N ratio of the reactive organic matter has only mild repercussions on the results; i.e. in the same range as the analytical errors for alkalinity and total carbonates. The objective was simply to roughly confront characteristics of outflowing waters and the calculation. Respective roles of aerobes and denitrifiers, for instance, are not certain. Several periods during low water or floods were selected with various ranges for calcium dissolution or nitrate and oxygen concentrations. The result is that in most cases simulation and data are in reasonable accordance (Fig. 5). Amounts of organic matter in River Loire are generally sufficient to sustain the process (Table 3. Particulate organic matter is probably the most reactive. The balance of oxidation of organic matter indicates that about 65 mu g C-org/l.h are oxidized during the transport without much variation with the river regime or organic discharge. It is concluded that limestone dissolution is directly dependent on organic matter oxidation, but variation occurs (7-29 mg CuCO3/l) with the level of bases that can be neutralized in the River Loire water. (C) 1998 Elsevier Science Ltd. All rights reserved

Contribution ltude du karst et des grottes du Kaokoland (Namibie), 1999,
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Martini J. E. J. , Marais J. C. E. , Irish J.
The authors describe the dolomite karst of Kaokoland, an arid region of Namibia, which had been very poorly investigated speleologically. The geomorphology, the karst hydrology and the water chemistry are reviewed. Although the karst area is large, caves are scarce and usually reduced to single large chambers. Integrated networks of passages are appa_rently missing. Seven caves are described in detail, including their mineralogy which comprise rare species. The Kookoland karst is compa_red with other ones develo_ped in more humid areas of Southern Africa. A speleogenetic model is proposed, which involves mixing of near surface ground water with anoxic sulphide-rich water of deep origin and could explain the very localised forma_tion of large cavities.

Dolomitization of Holocene Shallow-Marine Deposits Mediated by Sulfate Reduction and Methanogenesis in Normal-Salinity Seawater, Northern Belize, 2000,
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Teal Chellie S. , Mazzullo S. J. , Bischoff William D. ,
Dolomite constitutes an average of 12% of the Holocene organic-rich sediments over a 15 km2 area of the Cangrejo Shoals mudbank in northern Belize. Although it defines a laterally persistent stratiform body that averages 3 m thick, it is present throughout the 7.6-m-thick sediment section. These transgressive sediments are less than [~]6400 years old and were deposited in shallow-marine environments of normal salinity. The dolomite is dominantly cement, and average crystal size is 7 m. There are no significant correlations among amount of dolomite vs. sediment texture, mineralogy, porosity, or mole % MgCO3 in associated particulate high-Mg calcite, depth, or location on the shoals. The dolomites are poorly ordered and calcic (39.5-44.5 mole % MgCO3), with low mean Mn (210 ppm) and relatively high mean Sr (1034 ppm) concentrations. There is no evidence of recrystallization or geochemical alteration of the dolomite. {delta}18O values of the dolomites range from 0.5 to 2.8{per thousand}PDB, and the mean value (2.1{per thousand}) suggests that the dolomite precipitated from normal-salinity pore water. Dolomite {delta}13C values range from -5.2{per thousand} to .6{per thousand}PDB (mean seawater {delta}13C = 0.5{per thousand}), which suggests dolomitization promoted by both bacterial sulfate reduction and methanogenesis in environments with anoxic pore water. Dolomitization attending these organodiagenetic reactions apparently was reversible over time, and episodic rather than continual precipitation is indicated. Requisite Mg and Ca were provided by seawater and by some dissolution of host sediments. The most rapid period of dolomitization may have been during early transgression, when relatively high sedimentation rates sustained high levels of organodiagenesis and pore-water alkalinities

Palaeo-mixing zone karst features from Palaeocene carbonates of north Spain: criteria for recognizing a potentially widespread but rarely documented diagenetic system, 2001,
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Bacetaa J. I. , Wrightb V. P. , Pujalte V.

Marine-meteoric mixing zone dissolution effects are a major feature of present day karst systems in carbonate platforms,yet are rarely reported in the geological record. An example is described from the upper Danian platform limestones of the Alava province,in  the western Pyrenees,north Spain. This consists of several narrow zones with sponge-like porosity analogous to the "Swiss-cheese" features found in present day mixing  zones. These zones are stained by Fe-oxides and overlie limestones which are irregularly  dolomitized  and contain disseminated pyrite. These high-porosity  zones are interpreted as having developed in marine mixing zones where mixing corrosion and microbially  mediated processes increased dissolution. If collapsed,ancient mixing zones could be misinterpreted as "terra-rossa" palaeosols. The main criteria to identify them as mixing zone products are their occurrence below a palaeo-meteoric phreatic zone,their association with stratified oxic and anoxic redox zones and petrographic evidence for highly variable calcite saturation states.

Palaeo-mixing zone karst features from Palaeocene carbonates of north Spain: criteria for recognizing a potentially widespread but rarely documented diagenetic system , 2001,
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Baceta J. I. , Wrightb V. P. , Pujaltec V.

Marine-meteoric mixing zone dissolution effects are a major feature of present day karst systems in carbonate platforms,yet are rarely reported in the geological record. An example is described from the upper Danian platform limestones of the Alava province,in the western Pyrenees,north Spain. This consists of several narrow zones with sponge-like porosity analogous to the "Swiss-cheese" features found in present day mixing zones. These zones are stained by Fe-oxides and overlie limestones which are irregularly dolomitized and contain disseminated pyrite. These high-porosity zones are interpreted as having developed in marine mixing zones where mixing corrosion and microbially mediated processes increased dissolution. If collapsed,ancient mixing zones could be misinterpreted as "terra-rossa" palaeosols. The main criteria to identify them as mixing zone products are their occurrence below a palaeo-meteoric phreatic zone,their association with stratified oxic and anoxic redox zones and petrographic evidence for highly variable calcite saturation states

The Barremian-Aptian Evolution of The Eastern Arabian Carbonate Platform Margin (Northern Oman), 2003,
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Hillgartner Heiko, Van Buchem Frans S. P. , Gaumet Fabrice, Razin Philippe, Pittet Bernard, Grotsch Jurgen, Droste Henk,
Carbonate platform margins are sensitive recorders of changes in sea level and climate and can reveal the relative importance of global and regional controls on platform evolution. This paper focuses on the Barremian to Aptian interval (mid Cretaceous), which is known for climatic and environmental changes towards more intensified greenhouse conditions. The study area in the northern Oman mountains offers one of the very few locations where the Cretaceous carbonate margin of the Arabian Plate can be studied along continuous outcrops. Our detailed sedimentological and sequence stratigraphic model of the platform margin demonstrates how major environmental and ecological changes controlled the stratigraphic architecture. The Early Cretaceous platform margin shows high rates of progradation in Berriasian to Hauterivian times followed by lower rates and some aggradation in the Late Hauterivian to Barremian. High-energy bioclastic and oolitic sands were the dominant deposits at the margin. Turbidites were deposited at the slope and in the basin. The Early Aptian platform margin shows a marked change to purely aggradational geometries and a welldeveloped platform barrier that was formed mainly by microbial buildups. The sudden dominance in microbial activity led to cementation and stabilization of the margin and slope and, therefore, a decrease of downslope sediment transport by turbidites. In the Late Aptian, large parts of the Arabian craton were subaerially exposed and a fringing carbonate platform formed. Seven Barremian to Early Albian large-scale depositional sequences reflecting relative sea-level changes are identified on the basis of time lines constrained by physical correlation and biostratigraphy. The reconstruction of the margin geometries suggests that tectonic activity played an important role in the Early Aptian. This was most likely related to global plate reorganization that was accompanied by increased volcanic activity in many parts of the world. Along the northeastern Arabian platform the associated global changes in atmospheric and oceanic circulation are recorded with a change in platform-margin ecology from an ooid-bioclast dominated to a microbial dominated margin. Time-equivalent argillaceous deposits suggest an increase in rainfall and elevated input of nutrients onto the platform. This process contributed to the strongly diminished carbonate production by other organisms and favored microbial activity. The platform margin may thus represent a shallow-marine response to the Early Aptian global changes, commonly associated with an oceanic anoxic event in basinal environments

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.

The transition of a freshwater karst aquifer to an anoxic marine system, 2005,
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Garman Km, Garey Jr,
Jewfish Sink is located in the shallow seagrass flats of the Gulf of Mexico in west central Florida. Jewfish Sink was a submarine spring until the drought of 1961-1962 when it ceased flowing. Today, the sink is an anaerobic marine basin and provides the opportunity to study the implications of saltwater intrusion in coastal karstic areas. The biogeochemistry of Jewfish Sink was studied from summer 2001 through spring 2004. A distinct feature of the sink is the uniform cold temperature (16-17 degrees C) of the deeper anoxic water that does not match groundwater found nearshore or onshore (22-24 degrees C). There are four zones within the sink: oxic zone, transition zone, upper anoxic zone, and anoxic bottom water. The anoxic bottom water does not mix with water from above but may be linked to deep Gulf shelf water through ancient aquifer conduits. The other three zones vary seasonally in oxygen, salinity, and temperature because of limited mixing in the winter due to cooling and sinking of surface water. The walls of the anoxic zones have characteristic microbial mats that are found in other sulfidic karstic features in the area. Bacterial activity appears to be carbon limited in the anoxic zones where sulfate reduction appears to be the major metabolic process. The reduction of sulfate to sulfide appears to be driven by irregular influxes of organic matter including macroalgae, horseshoe crabs, and stingrays that become entrapped within the sink. Bacterial activity in the oxic zones appears to be phosphate limited. Although the system is partially isolated from the overlying marine ecosystem, organic input from above drives the bacterial anaerobic ecosystem, resulting in a sulfide pump. In this model, sulfide percolates up through the karst and removes oxygen from the overlying sediment, which has likely caused changes in the shallow benthic ecosystem. Jewfish Sink appears to be part of an extensive anoxic subterranean estuary that extends under parts of at least three coastal counties in Florida and can serve as a model for the effects of rising sea levels or aquifer mining

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