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Speleology in Kazakhstan

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

New publications on hypogene speleogenesis

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

The deepest terrestrial animal

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

Caves - landscapes without light

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

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That curve fitting is the fitting of experimental data points to a theoretical type curve [16].?

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Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
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Featured articles from other Geoscience Journals
Karst environment, Culver D.C.
Mushroom Speleothems: Stromatolites That Formed in the Absence of Phototrophs, Bontognali, Tomaso R.R.; D’Angeli Ilenia M.; Tisato, Nicola; Vasconcelos, Crisogono; Bernasconi, Stefano M.; Gonzales, Esteban R. G.; De Waele, Jo
Calculating flux to predict future cave radon concentrations, Rowberry, Matt; Marti, Xavi; Frontera, Carlos; Van De Wiel, Marco; Briestensky, Milos
Microbial mediation of complex subterranean mineral structures, Tirato, Nicola; Torriano, Stefano F.F;, Monteux, Sylvain; Sauro, Francesco; De Waele, Jo; Lavagna, Maria Luisa; D’Angeli, Ilenia Maria; Chailloux, Daniel; Renda, Michel; Eglinton, Timothy I.; Bontognali, Tomaso Renzo Rezio
Evidence of a plate-wide tectonic pressure pulse provided by extensometric monitoring in the Balkan Mountains (Bulgaria), Briestensky, Milos; Rowberry, Matt; Stemberk, Josef; Stefanov, Petar; Vozar, Jozef; Sebela, Stanka; Petro, Lubomir; Bella, Pavel; Gaal, Ludovit; Ormukov, Cholponbek;
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Your search for thermodynamic (Keyword) returned 17 results for the whole karstbase:
Showing 1 to 15 of 17
Elments d'une approche nergtique du karst, application quelques exemples rels de karsts, 1983, Quinif, Y.
DATA FOR AN ENERGIZING APPROACH OF THE KARST. APPLICATIONS TO A FEW EXAMPLES OF KARST AREAS - One considers the karst like an open thermodynamic system where the located dissipation of hydrodynamical, chemical and mechanical energies gives to the karst a structurated heterogeneity. One discusses about the modalities of the energy dissipation into the karst. The study of some real examples of karstic networks allows understanding how these theoretical concepts explain their characteristics. One ends by a prospect of research: to consider the karstic system like a dissipative system in the meaning of Prigogine.

DISSOLUTION OF ARAGONITE-STRONTIANITE SOLID-SOLUTIONS IN NONSTOICHIOMETRIC SR(HCO3)2-CA(HCO3)2-CO2-H2O SOLUTIONS, 1992, Plummer L. N. , Busenberg E. , Glynn P. D. , Blum A. E. ,
Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated nonstoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25-degrees-C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer approximately 60 angstrom on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer approximately 25 angstrom (as much as 26 mol% SrCO3 on aragonite and 44 mol% CaCO3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO3)2) than in solutions spiked with the more soluble component (Ca(HCO3)2), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a nonstoichiometric surface reactive zone significantly decreases dissolution rates

HYDROGEOCHEMISTRY OF GRAND-CAYMAN, BRITISH-WEST-INDIES - IMPLICATIONS FOR CARBONATE DIAGENETIC STUDIES, 1995, Ng K. C. , Jones B. ,
Groundwater in the dolostone aquifers of the Bluff Group (Oligocene-Miocene) on Grand Cayman is divided into fresh, lightly and highly brackish, and saline (Type I and II) zones according to chemical characteristics that were determined during a 3 year (1985-1988) monitoring program. Brackish and Type I saline waters display the greatest variation in chemical properties whereas the Type II saline water has the most stable chemical characteristics. Most groundwaters from these dolostone aquifers are thermodynamically capable of precipitating calcite and/or dolomite. The saturation indices for these minerals, however, vary through time and space even in the context of small water lens. Simple mixing of fresh and sea water cannot explain the chemistry of the water found in the joint and karst controlled dolostone aquifers of Grand Cayman. Deviation from a simple mixing model is due to variations caused by tidal fluctuation, the rate of rain water recharge, influx of Ca-rich groundwater from the surrounding limestone aquifers, influx of CO2-rich surface water from sinkholes and swamps, and water-rock interactions (dissolution and precipitation of calcite and dolomite). Sustained groundwater abstraction from a lens can significantly alter the hydrochemistry of the water lens. This suggests that hydrochemical characterization of small fresh water lenses, like those on Grand Cayman, cannot be based on spot or short-term sampling. Interpretation of such fluids in terms of calcite-dolomite precipitation and/or dissolution must be treated with caution if the data base has not been derived from long-term monitoring

Thermodynamic equilibrium, kinetics, activation barriers, and reaction mechanisms for chemical reactions in Karst Terrains, 1997, White W. B. ,
Chemical reactions pertinent to karst systems divide broadly into (a) speciation reactions within aqueous solutions, (b) dissolution/precipitation and other acid/base reactions between aqueous solutions and solid minerals, and (c) redox reactions involving various carbon and sulfur-bearing species. As a backdrop against which other chemistry can be evaluated, selected phase diagrams and equilibrium speciation diagrams were calculated for the system Ca--Mg--O--H--C--S. The kinetics of reactions within this system span time scales from milliseconds for homogeneous reactions in solution through hundreds of hours for carbonate mineral dissolution reactions, to geologic time scales for reactions such as the aragonite/calcite inversion or the oxidation/reduction of native sulfur. In purely inorganic systems, kinetic barriers, typically on the order of tens of kJ/mole, are set by nucleation processes and by activated complex formation. Biological processes impact the purely inorganic chemistry by the following mechanisms: (a) Secretions and waste products from biological activity or consumption of CO2 by organisms changes the chemistry in the microenvironments of reaction surfaces. Oxidation potentials, pH, and ion activities may be modified, thus shifting equilibria. (b) Reaction rates may be increased due to modification of activated complexes and thus the activation barriers to reaction. (c) Organic compounds or microorganisms may act as substrates, thus lowering nucleation barriers. The preservation of microorganisms in cave deposits does not necessarily prove a cause and effect relationship

Dissipation dnergie et adaptabilit dans les systmes karstiques, 1998, Quinif, Yves
The phenomenon of karstification and even the term "karst" have been studied extensively but the concepts used explain only partially this complex problem. In this paper is proposed a global thermodynamic and geological approach to karstification. The universal thermodynamic concepts - energy dissipation and entropy variation - are first studied. In the second approach the karstic systems are studied in their geological and geomorphological environment.

Precipitation and alteration of late Cretaceous sedimentary apatites and siderites (Leonie Trough, Bavaria, Germany), 1998, Sattler C. D. , Halbach P. ,
Late Cretaceous sedimentary siderites and fluorapatites of the iron ore deposit 'Leonie' (Bavaria, Germany) have been investigated by geochemical and mineralogical methods to define their origin. The siderites consist to more than 90 mol% of FeCO3. This elemental composition relates to an early diagenetic fresh water depositional environment. The stable isotope geochemistry of carbon and oxygen (delta(18)O: parts per thousand SMOW; delta(13)C: -12 parts per thousand PDB) also supports a siderite genesis in meteoric waters, with carbon originating from oxidation of organic matter. The chemical composition of the fluorapatites is relatively pure and shows a very low elemental substitution for calcium and phosphate. This is the result of an intense epigenetic alteration of the primary carbonate fluorapatite and, thus, cannot be related to specific source aspects. Microscopic investigations and thermodynamic calculations reveal a precursory apatite precipitation before siderite was formed. This process is thought to have removed calcium from karst waters to a level which enables siderite to be precipitated. Because of the data and observations a siderite formation in a stagnant fresh water basin is postulated, while the apatite formation probably was initiated during a connection to the open ocean (Tethys) with temporary marine ingressions. The input of iron and partly of phosphorus and fluorine into the karst basins resulted from the draining of the uplifted easterly mountains of the igneous Bohemian Massif under the influence of a humid warm climate. During the postulated marine ingressions especially phosphorus and fluorine were brought into the system whereas most of the calcium and carbonate reached the karst troughs by dissolution of the Late Jurassic Maim limestones

Calibration of the speleothem delta function: an absolute temperature record for the Holocene in northern Norway, 1999, Lauritzen Stein Erik, Lundberg Joyce,
The speleothem delta function (SDF) provides a new transfer function between the d18O signal of speleothem calcite and surface ground temperature. The function is based on physical principles, relating d18O of the calcite to thermodynamic fractionation, and to the dripwater function, which in turn relates d18O of dripwaters to that of the local precipitation and thus to the modification of source water in relationship to the geographical position of the site. The SDF must be calibrated against at least two reliable and well-dated palaeotemperature points. The end product is a reconstruction of absolute cave and surface temperatures. The technique is tested using a Holocene speleothem from north Norway, SG93, dated by 12 TIMS U-Th dates. The reconstructed temperature curve is presented and compared with the GISP2 ice-core record and with the historic record. In both cases the correlation with SG93 is impressive, indicating the validity of the technique

LOW-TEMPERATURE ACID WEATHERING IN NEWHAVEN, SUSSEX, UNITED KINGDOM, AND ITS APPLICATION TO THEORETICAL MODELING IN RADIOACTIVE WASTE-DISPOSAL SITES, 2000, De Putter T, Bernard A, Perruchot A, Nicaise D, Dupuis C,
Tertiary weathered sediments located immediately to the west of the harbor at Newhaven, Sussex, UK, were investigated by examination of major and trace elements by scanning electron microscope (SEM), microprobe, and inductively coupled plasma mass spectrometer (ICP-MS), and the mineralogy was studied by optical petrography, X-ray diffraction (XRD), transmission electron microscope (TEM), selective leaching, and thermodynamic modeling. Studied outcrops experienced acid leaching by sulfuric acid percolating downward through Tertiary sediments overlying Cretaceous chalk. The progressive neutralization of the percolating acid fluids resulted in 'sequentially' layered neoformation of minerals: jarosite, iron oxides, aluminous minerals (sulfates, oxyhydroxides), gypsum, and Fe-Mn oxides. Substantial agreement was found between field observations and mineral assemblages obtained by modeling with the program CHILLER. These results suggest that the initial assumptions on the weathering process and mechanisms are correct. The relevance and implications of this study in the modeling of future denudation and weathering processes of radioactive waste-disposal sites (both deeply buried sites for high-level waste and surface sites for low-level waste) are discussed. Neoformed phases, such as jarosite, aluminous minerals, and silico-aluminous gels may play a significant role in the efficient trapping of mobilized pollutant radionuclides

Melting of the glacier base during a small-volume subglacial rhyolite eruption: evidence from Blahnukur, Iceland, 2002, Tuffen H. , Pinkerton H. , Mcgarvie D. W. , Gilbert J. S. ,
Although observations of recent volcanic eruptions beneath Vatnajokull, Iceland have improved the understanding of ice deformation and meltwater drainage, little is known about the processes that Occur at the glacier base. We present observations of the products of a small-volume, effusive subglacial rhyolite eruption at Blahnukur. Torfajokull, Iceland. Lava bodies, typically 7 m long, have unusual conical morphologies and columnar joint orientations that suggest emplacement within cavities melted into the base of a glacier. Cavities appear to have been steep-walled and randomly distributed. These features can be explained by a simple model of conductive heat loss during the ascent of a lava body to the glacier base. The released heat melts a cavity in the overlying ice. The development of vapour-escape pipes in the waterlogged, permeable breccias surrounding the lava allows rapid heat transfer between lava and ice. The formed meltwater percolates into the breccias, recharging the cooling system and leaving a steam-filled cavity. The slow ascent rates of intrusive rhyolitic magma bodies provide ample time for a cavity to be melted in the ice above, even during the final 10 m of ascent to the glacier base. An equilibrium Cavity Size is Calculated at which melting, is balanced by creep closure, This is dependent upon the heat input and the difference between glaciostatic and cavity pressure. The cavity sizes inferred from Blahnukur are consistent with a pressure differential of 2-4 MPa, suggesting that the ice was at least 200 m thick. This is consistent with the volcanic stratigraphy, which indicates that the ice exceeded 350 in in thickness, Although this is the first time that a subglacial cavity system of this type has been reconstructed from an ancient volcanic sequence. it shares many characteristics with the modem fim cave system formed by fumarolic melting within the summit crater of Mount Rainier. Washington, At both localities, it appears that localised heating at the glacier base has resulted in heterogeneous melting patterns. Despite the different theological properties of ice and fim, similar patterns of cavity roof deformation are inferred. The development of low-pressure subglacial cavities in regions of high heat nux may influence the trajectory of rising magma, with manifold implications for eruptive mechanisms and resultant subglacial volcanic landforms. (C) 2002 Elsevier Science B.V. All rights reserved

Quartzite dissolution: karst or pseudokarst?, 2003, Wray, R. A. L.

A wide range of landforms of great similarity to limestone karst is found on many of the world's quartz sandstones and quartzites. These landforms have often been dismissed as pseudokarst, but recent investigation shows that the dissolutional removal of silica, even quartz, under earth-surface conditions is a critical process in their formation. They must therefore be regarded as true karst features. Recognition of these genetically similar forms on quartzose rocks now demands the worldwide adoption of a less restrictive, process-based, karst definition. Direct evidence for this near-surface dissolutional weathering is not common. Examples of this process are reviewed here, along with further evidence for the dissolution of silica from within the quartz sandstones of the Sydney Basin in temperate south-eastern Australia. Some of the complex processes by which dissolution attacks the rock remain unclear. However the solubility, thermodynamics, fluid throughput and physical removal of detritus are all critical factors in the formation of what can only be termed karst on quartzites and quartz sandstone.


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

Geochemical simulation of the formation of brine and salt minerals based on Pitzer model in Caka Salt Lake, 2004, Liu X. Q. , Cai K. Q. , Yu S. S. ,
The geochemical simulation of the formation of brine and salt minerals based on Pitzer model was made in Caka Salt Lake. The evolution of the mixed surface-water and the mineral sequences were calculated and compared with the hydrochemical compositions of the brine and the salt minerals of the deposit in Caka Salt Lake. The results show that the formation temperature of the lake is between 0degreesC and 5degreesC, which is well identical with other studies. The mixing of salt-karst water with the surface waters, neglected by the former researchers, is very important to the formation of the lake, indicating that the initial waters resulting in the formation of the lake are multi-source. It is the first time to use Pitzer model in China for making geochemical simulation of the formation and evolution of inland salt lake and satisfactory results have been achieved

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

Calcite dissolution kinetics and solubility in Na-Ca-Mg-Cl brines of geologically relevant composition at 0.1 to 1 bar pCO2 and 25 to 80°C. Doctoral dissertation, Texas A&M University. , 2005, Gledhill, Dwight Kuehl

Sedimentary basins can contain close to 20% by volume pore fluids that are commonly classified as brines. These fluids can become undersaturated with respect to calcite as a result of processes such as migration, dispersive mixing, or anthropogenic injection of CO2. This study measured calcite solubility and dissolution rates in geologically relevant Na-Ca-Mg-Cl synthetic brines (35 to 200 g L-1 TDS). In brines < 50 g L-1 TDS, the EQPITZER calculated calcium carbonate ion activity product (IAP) at steady-state was in reasonable agreement (±10%) with the thermodynamic solubility constant for calcite (Kc). However, the IAP systematically exceeded Kc in more concentrated brines. The deviation was strongly correlated with calcium concentration and also was observed in magnesium-free solutions. This is interpreted as an uncertainty in the carbonate ion activity coefficient, and minor adjustment in stoichiometric association constants (K*M2+CO30) for the CaCO30 or MgCo30 ion pairs would correct for the error. The dissolution rate dependency on brine composition, pCO2 (0.1 to 1 bar), and temperature (25.0 to 82.5 °C) was modeled using the empirical rate equation ()nkRΩ−=1 where R is the rate, k and n are empirical fitting terms, and Ω the degree of disequilibrium with respect to calcite. When Ω was defined relative to an apparent kinetic solubility, n could be assumed first-order over the range of Ω investigated (Ω = 0.2 to 1.0). Rates increased with increasing pCO2 as did the sensitivity to brine concentration. At 0.1 bar, rates were nearly independent of concentration (k = 13.0 ±2.0 x 10-3 moles m-1 hr-1). However, at higher CO2 partial pressures rates became composition dependent and the rate constant, k, was shown to be a function of temperature, pCO2, ionic strength, and calcium and magnesium activity. The rate constant (k) can be estimated from a multiple regression (MR) model of the form k = B0 + B1(T) + B2(pCo2) + B4(aCa2+) + B5(aMg2+). A relatively high activation energy (Ea = 20 kJ mol-1) was measured, along with a stirring rate independence suggesting the dissolution is dominated by surface controlled processes at saturation states Ω > 0.2 in these calcium-rich brines. These findings offer important implications to reaction-transport models in carbonate-bearing saline reservoirs.


The role of geochemical transformations in karst geomorphogenesis, 2010, Vakhrushev B. A.

Geochemical transformations in the system «water - rock» constitute the genetic basis of karst morphogesis. The article demonstrates that corrosion and chemical sedimentation are largely responsible for the morphological look of cavities. The basic method used is thermodynamic calculations of geochemical equilibria, which determine an aggressiveness of natural solutions.

The change of isobar-isothermal potential (free energy of Gibbs) was used as a measure of chemical affinity of matters, i.e. their capabilities to enter into a reaction between them with formation of other matters.

Variety of hydrochemical situations taking place in carbonate , summarized in five typical conditions, which include considerable part of possible karst morphogenetic settings, while others can be obtained by combination of the examined ones. Every situation is described by hydrochemical calculations.

The second part of the paper is dedicated to practical application of the described methodology, i.e. to the calculations of thermodynamic equilibria observed in the underground streams of the Krasnaya (Red) Cave in Crimea. Close connection of morphological look of the cave with geochemical transformations is shown, which control corrosion and chemical accumulation along the whole length of the karst system.


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