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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 flow, uniform is a characteristic of a flow system where specific discharge has the same magnitude and direction at any point [22].?

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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 calcium (Keyword) returned 132 results for the whole karstbase:
Showing 16 to 30 of 132
Late Quaternary U-series speleothem growth record from southeastern Minnesota, 1983, Lively R. S. ,
Cyclic deposition of secondary calcium carbonate that coincides with cycles of late Pleistocene glaciation. Peak intervals of deposition occur from the present to 13,000 yr B.P., from 35,000 to 70,000 yr B.P., from 90,000 to 170,000 yr B.P., and an undivided interval from 170,000 to 350,000 yr B.P. Local climatic conditions seem to have had as much importance in determining when deposition occurred as did the major climatic cycles recorded in the marine record.--Modified journal abstract

Palaeogeographic environment during the desiccation of the Black Sea, 1983, Kojumdgieva Emilia,
During the latest Chersonian (about 10.3 m.y. ago) tectonic movements took place leading to an elevation of the Crimean-Caucasian chain and to an isolation of the Fore-Caucasian part of the Black Sea Basin. This part of the basin had been draining the rivers of the Russian Platform and after the isolation it became desalinized, while the main part of the Black Sea Basin was almost desiccated and evaporites, mainly dolomites, formed in it due to the predominant calcium---magnesium---carbonate composition of the Chersonian Sea waters. These dolomites are found in the drillings of DSDP Leg 42B and are confirmed geophysically.The tectonic movements during the latest Chersonian led to the formation of a series of grabens along which the Mediterranean Sea invaded the north Aegean area and a little later (during the Early Maeotian) the Black Sea

Deposition of Tufa on Ryans and Stockyard Creeks, Chillagoe Karst, North Queensland: The Role of Evaporation, 1987, Dunkerley, D. L.

A spring which feeds Ryans and Stockyard Creeks west of Cillagoe, was examined in order to understand the circumstances producing extensive deposits of tufa in the stream channels. The spring water was found to be of considerable hardness (300 ppm total carbonates) and to emerge only very slightly supersaturated with respect to calcium carbonate, but undersaturated with respect to dolomite. Both saturation levels rose very rapidly during the first 150 m of subaerial flow, as did pH and water temperature. In contrast to the reported behaviour of other limestone springs, carbonate hardness at this site does not decrease monotonically downstream, but rather locally undergoes significant increases. In particular, magnesium hardness at 1 km downstream is more than 4 times its value at the spring. These phenomena are explained in terms of evaporative concentration of the dissolved carbonates and in terms of possible chemical changes associated with the mixture of waters having contrasting characteristics at channel and pool sites along the streams.


An Investigation of the Mechanisms of Calcium Carbonate Precipitation on Straw Speleothems in Selected Karst Caves - Buchan, Victoria., 1988, Canning, E.

The relative significance of straw speleothem growth from evaporation and from CO2 degassing was determined in Lilli-Pilli and Moons Caves (Buchan, Victoria) from a seven-month study of cave climate and water chemistry. The relative importance of these two mechanisms was inferred from the calculation of the straw growth rates according to a degassing model and an evaporation model. The modelled straw growth rates from the carbon dioxide degassing model were on hundred to one thousand times those attributable to evaporation. A third model was used to calculate straw growth rates from the overall supersaturation of the water. Growth rates were found to be within the range of 0.01 to 0.07mm per annum.


Groundwater chemistry and cation budgets of tropical karst outcrops, Peninsular Malaysia, I. Calcium and magnesium, 1989, Crowther J,
The discharge and chemical properties of 217 autogenic groundwaters were monitored over a 1-yr period in the tower karsts of central Selangor and the Kinta Valley, and in the Setul Boundary Range. Because of differences in soil PCO2, calcium concentrations are significantly higher in the Boundary Range (mean, 82.5 mg l-1) than in the tower karst terrain (44.6 mg l-1). Local differences in both source area PCO2 and amounts of secondary deposition underground cause marked intersite variability, particularly in the tower karst. Dilution occurs during flood peaks in certain conduit and cave stream waters. Generally, however, calcium correlates positively with discharge, since the amount of secondary deposition per unit volume of water decreases at higher flows. Magnesium concentrations and Mg:Ca Mg ratios of groundwaters are strongly influenced by bedrock composition, though bedrock heterogeneity and the kinetics and equilibria of carbonate dissolution reactions preclude extremely low or high Mg:Ca Mg values. Net chemical denudation rates range from 56.6 to 70.9 m3km2yr-1.The results are considered in relation to cation fluxes in surface runoff, soil throughflow and nutrient cycling. Preliminary calcium and magnesium budgets show that (1) dissolutional activity is largely confined to the near-surface zone; and (2) the annual uptake of calcium and magnesium by tropical limestone forests is similar in magnitude to the net solute output in groundwaters

Biologie et concrtionnement : un exemple. Les baguettes de gours, 1991, Adolphe J. P. , Choppy J. , Choppy B. , Loubiere Jf. , Paradas J. , Soleilhavoup F.
Biology and speleothems: an example, the rimstone poolfingers - Previous studies had shown the influence of bacteria on marine and continental carbonate flowstone deposit, including in caves. On the occasion of a problem raised by new type of speleothem, " rimstone poolfingers" (baguette de gours) whose genesis seemed linked to a biological phenomenon, the same results were obtained for this cave deposit. The present of bacteria likely to contribute to the crystallisation of calcium carbonate has been demonstrated in the presence of blackish clay sediment, to be found above the sticks.

KINETIC ENRICHMENT OF STABLE ISOTOPES IN CRYOGENIC CALCITES, 1992, Clark Id, Lauriol B,
The C-13 and O-18 contents of cryogenic calcites formed by expulsion during the freezing of bicarbonate groundwaters are examined. Samples from karst caves within the permafrost region of northern Yukon, Canada, have deltaC-13-values as high as 17.0 parts per thousand, representing the most isotopically enriched freshwater carbonates yet reported. To account for such enrichments, calcium bicarbonate solutions were frozen and sublimated under controlled laboratory conditions. The rapid rate of reaction is shown to effectively preclude isotopic equilibration during bicarbonate dehydration, resulting in a kinetic partitioning of C-13 between CO2 and CaCO3. We find a value of 31.2 1.5 parts per thousand for 1000ln13alpha(KIE)(13alpha(KIE) = 1.032), which is considerably greater than the equilibrium fractionation factor (13epsilon(CaCO3-CO2)) of 10.3 parts per thousand at 0-degrees-C. This kinetic isotope effect (KIE) represents the ratio of the absolute reaction rate constants (13k(d)/12k(d)) for the two isotopic species during the dehydration of dissolved bicarbonate. Similar results for deltaO-18-values confirm that the reaction proceeds without isotope exchange. The KIE of O-18 is determined to be 1.006 for this reaction at 0-degrees-C. These data are compared with the KIE which occurs during the reverse reaction: CO2 hydroxylation by reaction with OH- in hyperalkaline waters

Carbonate chemistry of surface waters in a temperate karst region: the southern Yorkshire Dales, UK, 1992, Pentecost Allan,
A detailed study of surface water chemistry is described from an important limestone region in northern England. Major ions and pH were determined for 485 sites (springs, seeps, streams, rivers and lakes) during summertime. The saturation state of the waters with respect to calcite was determined as the calcite saturation ratio ([Omega]). An unexpectedly large number of samples were found to be supersaturated (65.5% of the 268 km of watercourses surveyed). As a consequence, several streams entering major cave systems were incapable of further limestone solution, at least during periods of low flow. Many waters were supersaturated from their source and some deposited travertine. A significant negative correlation was found between spring discharge and both ([Omega]) and pH. Supersaturation was caused primarily by atmospheric degassing, with some contribution from aquatic plant photosynthesis.The median total dissolved inorganic carbon and Ca concentrations were 2.49 and 1.35 millimoles 1-1 respectively. Calcium originated exclusively from limestone, and carbon dioxide mainly from the soil and dissolved limestone. South facing catchments provided springwaters with significantly higher levels of TDIC and Ca when compared with north facing catchments. The study suggests that acid rain made a measurable contribution to limestone dissolution.Carboniferous limestone denudation rates were estimated as 54 to 63 m3 km-2 a-1 (54 to 63 mm 1000 years-1). About 50% of the Mg came from limestone and the remainder, together with most K, Na, SO4 and Cl from precipitation.Concentrations of dissolved nutrients were low, medians for NO3, NH4, total PO4 and SiO3 were 24 [mu]mol, 1.4 [mu]mol, 0.64 [mu]mol and 15.5 [mu]mol 1-1 respectively. The concentration of a further 23 trace elements was determined

DISLOCATION OF THE EVAPORITIC FORMATIONS UNDER TECTONIC AND DISSOLUTION CONTROLS - THE MODEL OF THE DINANTIAN EVAPORITES FROM VARISCAN AREA (NORTHERN FRANCE AND BELGIUM), 1993, Rouchy J. M. , Groessens E. , Laumondais A. ,
Within the Franco-Belgian segment of the Hercynian orogen, two thick Dinantian anhydritic formations are known, respectively in the Saint-Ghislain (765 m) and Epinoy 1 (904 m) wells. Nevertheless, occurrences of widespread extended breccias and of numerous pseudomorphs of gypsum/anhydrite in stratigraphically equivalent carbonate deposits (boreholes and outcrops), suggest a larger extent of the evaporitic conditions (fig. 1, 2). The present distribution of evaporites is controlled by palaeogeographical differentiation and post-depositional parameters such as tectonics and dissolution. These latter have dissected the deposits formerly present in all the structural units. By using depositional, diagenetic and deformational characters of these formations, the article provides a model for the reconstruction of a dislocated evaporitic basin. This segment of the Hercynian chain is schematically composed of two main units (fig. 1, 3) : (1) the autochthonous or parautochthonous deposits of the Namur synclinorium, (2) the Dinant nappe thrusted northward over the synclinorium of Namur. The major thrust surface is underlined by a complex fault bundle (faille du Midi) seismically recognized over more than 100 km. A complex system of thrust slices occurs at the Hercynian front. Except for local Cretaceous deposits, most of the studied area has been submitted to a long period of denudation since the Permian. Sedimentary, faunistic and geochemical data argue for a marine origin of the brines which have generated the evaporites interbedded with marine limestones. Sedimentary structures. - The thick evaporitic formations are composed of calcium-sulfates without any clear evidence of the former presence of more soluble salts (with the exception of a possible carbonate-sulfate breccia in the upper part of the Saint-Ghislain formation). As in all the deeply buried evaporitic formations, the anhydrite is the main sulfate component which displays all the usual facies : pseudomorphs after gypsum (fig. 4A, B), nodular and mosaic (fig. 4C), laminated. The gypsum was probably an important component during the depositional phase despite the predominant nodular pattern of the anhydrite. Early diagenetic nodular anhydrite may have grown during temporary emersion of the carbonates (sabkha environments), but this mechanism cannot explain the formation of the whole anhydrite. So, most of the anhydrite structures result from burial-controlled gypsum --> anhydrite conversion and from mechanical deformations. Moreover, a complex set of diagenetic processes leads to various authigenic minerals (celestite, fluorite, albite, native sulfur, quartz and fibrous silica) and to multistaged carbonate <> sulfate replacements (calcite and dolomite after sulfate, replacive anhydrite as idiomorphic poeciloblasts, veinlets, domino-like or stairstep monocrystals...). These mineral transformations observed ill boreholes and in outcrops have diversely been controlled during the complex evolution of the series as : depositional and diagenetic pore-fluid composition, pressure and temperature changes with burial, bacterial and thermochemical sulfate reduction, deep circulations favored by mechanical brecciation, mechanical stresses, role of groundwater during exhumation of the series. Deformational structures. - A great variety of deformational structures as rotational elongation, stretching, lamination, isoclinal microfolding, augen-like and mylonitic structures are generated by compressive tectonic stresses (fig. 4D to J). The similarities between tectonic-generated structures and sedimentary (lamination) or diagenetic (pseudo-nodules) features could lead lo misinterpretations. The calcareous interbeds have undergone brittle deformation the style and the importance of which depend of their relative thickness. Stretching, boudins, microfolds and augen structures F, H. I) affect the thin layers while thicker beds may be broken as large fractured blocks dragged within flown anhydrite leading to a mylonitic-like structure (fig, 4G). In such an inhomogeneous formation made of interlayered ductile (anhydrite) and brittle (carbonate) beds, the style and the intensity of the deformation vary with respect to the relative thickness of each of these components. Such deformational features of anhydrite may have an ubiquitous significance and can result either from compressive constraints or geostatic movements (halokinesis). Nevertheless, some data evidence a relation with regional tangential stresses: (1) increase of the deformation toward the bottom of the Saint-Ghislain Formation which is marked by a deep karst suggesting the presence of a mechanical discontinuity used as a drain for dissolving solutions (fig. 3, 4); (2) structural setting (reversed series, internal slidings) of the Epinoy 1 formation under the Midi thrust. However, tectonic stresses also induce flowing deformations which have contributed to cause their present discontinuity. It can be assumed that the evaporites played an active role for the buckling of the regional structure as detachment or gliding layers and more specifically for the genesis of duplex structures. Breccia genesis. - Great breccia horizons are widely distributed in outcrops as well as in the subsurface throughout the greater part of the Dinant and Namur units (fig. 2). The wide distribution of pseudomorphosed sulfates in outcrops and the stratigraphical correlation between breccia and Saint-Ghislain evaporitic masses (fig. 2) suggest that some breccia (although not all) have been originated from collapse after evaporites solution. Although some breccia may result from synsedimentary dissolution, studied occurrences show that most of dissolution processes started after the Hercynian deformation and, in some cases, were active until recently : elements made of lithified and fractured limestones (Llandelies quarries) (fig. 5A), preservation of pseudomorphs of late replacive anhydrite (Yves-Gomezee) (fig. 5B, C), deep karst associated with breccia (Douvrain, Saint Ghislain, Ghlin boreholes) (fig. 3, 4, 5D)). Locally, the final brecciation may have been favored by a mechanical fragmentation which controlled water circulations (fig. 5E). As postulated by De Magnee et al. [19861, the dissolution started mostly after the Permian denudation and continued until now in relation with deep circulations and surface weathering (fig. 6). So, the above-mentioned occurrences of the breccia are logically explained by collapse after dissolution of calcium-sulfates interbeds of significant thickness (the presence of salt is not yet demonstrated), but other Visean breccia may have a different origin (fig. 5F). So, these data prove the extension of thick evaporitic beds in all the structural units including the Dinant nappe, before dissolution and deformation. Implications. - Distribution of Visean evaporites in northern France and Belgium is inherited from a complicated paleogeographic, tectonic and post-tectonic history which has strongly modified their former facies, thicknesses and limits (fig. IA, 6). Diversified environments of deposition controlled by both a palaeogeographical differentiation and water level fluctuations led to the deposition of subaqueous (gypsum) or interstitial (gypsum, anhydrite) crystallization. Nevertheless, most of the anhydrite structures can be interpreted as resulting from burial conversion of gypsum to anhydrite rather than a generalized early diagenesis in sabkha-like conditions. Deformation of anhydrite caused by Hercynian tangential stresses and subsequent flow mechanisms, have completed the destruction of depositional and diagenetic features. The tectonic deformations allow us to consider the role of the evaporites in the Hercynian deformations. The evaporites supplied detachment and gliding planes as suggested for the base of the Saint-Ghislain Formation and demonstrated by the structural setting of Epinoy 1 evaporites in reverse position and in a multi-system of thrust-slices below the Midi overthrust (fig. 7). So, although the area in which evaporation and precipitation took place cannot be exactly delineated in geographic extent, all the data evidence that the isolated thick anhydritic deposits represent relics of more widespread evaporites extending more or less throughout the different structural units of this Hercynian segment (fig. 1B). Their present discontinuity results from the combination of a depositional differentiation, mechanical deformations and/or dissolution

THE OCCURRENCE AND EFFECT OF SULFATE REDUCTION AND SULFIDE OXIDATION ON COASTAL LIMESTONE DISSOLUTION IN YUCATAN CENOTES, 1993, 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

The influence of bedding planes on the development of karst caves (in Slovenian and with an English summary and abstract), PhD thesis, 1996, Knez, M.

There have been much less researchers looking for the initial water ways in karst along the bedding-planes than those who deduced the origin of cave channels from tectonic structures. The aim of my research was to focus scientific attention on the sphere where the answers within the sedimentology might be expected. The study identified that the basic idea of bedding-plane importance at the initiation of cave channels was correct but also, that the interrelation is different from how it had been supposed. Single lithological, petrological or stratigraphical parameters of the inception are only partly known, or merely guessed. My research threw light on the problem of initial channels met in Velika dolina in Skocjanske jame. Cave passages, or their fragments and other traces of the underground karstification do not appear scattered at random on the walls but they are obviously gathered along a small number of so-called bedding-planes.
The basic working method was to locate the phreatic channels or their fragments, to sample and microscope those parts of the layers adjacent to a bedding-plane. Somewhere a whole layer was considered. Other methods were: regional distribution of caves, photographing, inventarisation and classification of speleogens and complexometry, the latter providing the purity of limestones.
The original channels are practically gathered along only three formative bedding-planes (out of 62 measured); their close vicinity differs from the others in several important properties: typically damaged rock, higher level of calcium carbonate, smaller porosity and others. Consequently the mentioned concordance cannot possibly be only apparent.
From the lithological point of view, I got neither substantial argument nor explanation for selective karstification. However, it was identified that at least in respect of a concrete example from Velika dolina, the inception started along interbedded slides that without doubt pushed the beds aside leaving an interval.


Hydrochemographs of Berghan Karst Spring as Indicators of Aquifer Characteristics, 1997, Raeisi, E. , Karami, G.
Berghan Spring is located in the southern part of Iran, northwest of Shiraz. The catchment area of the spring consists of the southern flank of the Gar Anticline, which is made up of the karstic calcareous Sarvak Formation. There are no sinkholes or other karst landforms in the catchment area. Because of the existence of several faults, the aquifer has been brecciated and may have caused karstification to occur in most of the pores and fissures. The specific conductance, pH and water temperature were measured once every twenty days for a period of 32 months and water samples were analyzed for major anions and cations. Flow rate was measured daily during the recession, and once every three weeks during the rest of the study period. Using the WATEQF computer model, the partial pressure of carbon dioxide and the saturation index of calcite and dolomite also were estimated. Three distinct periods, the first recession, the second recession, and precipitation, were observed in the hydrograph of Berghan Spring. No considerable differences were observed between the first and second recession coefficients. Base flow constitutes 71.5%, 100% and 66.2% of total flow in the first recession period, the second recession period and the precipitation period, respectively. The variation of specific conductance, calcium and bicarbonate concentrations and calcite saturation indices are not significant during the study period, implying that aquifer characteristics control the chemical behavior of the spring. The morphology and geology of the Berghan Spring catchment area, and data from hydrographs and chemographs, show that the hydrologic system is dominantly diffuse flow. Evidence for this is shown by autogenic recharge, a brecciated aquifer, and small values and slight differences in hydrograph recession coefficients. In addition, specific conductance, calcium and bicarbonate concentrations, and water temperature did not show significant variations during the study period suggesting a diffuse flow aquifer.

Elevated and variable values of 13C in speleothems in a British cave system, 1997, Baker A, Ito E, Smart Pl, Mcewan Rf,
[delta] 13C isotope variations in speleothems have been investigated for samples from the British Isles, where plants which use the Hatch-Slack or C4 photosynthetic pathway are not present. The range of [delta] 13C expected in speleothem carbonate formed in isotopic equilibrium with soil CO2 derived from the overlying C3 vegetation should thus fall in the range -12 to -6[per mille sign]. Forty-one actively growing speleothem samples from low-discharge sites were analysed from Stump Cross Caverns, Yorkshire, England. Ten percent have [delta] 13C greater than -6%. In addition, a large range of [delta] 13C was observed (-8.06 1.38[per mille sign], a 1 [sigma] variability of 17%), with adjacent samples having [delta] 13C differing by a maximum of 4.74[per mille sign]. Similar findings were obtained from a review of analyses of late Quaternary speleothem samples from the British Isles, with 75% of flowstone samples and 57% of high-flow stalagmite samples exhibiting elevated [delta] 13C. Three possible processes are proposed as possible causes of elevated [delta] 13C in speleothems. Firstly, fractionation may occur between the stalactite and stalagmite due to evaporation or degassing. Secondly, degassing of the groundwaters may have occurred within the aquifer before reaching the cave void, allowing release of some CO2 from the water whilst remaining saturated in calcium. Finally, the elevated [delta] 13C may be due to short water residence times in the soil, such that equilibrium between soil water and soil CO2 is not reached. Evidence presented here demonstrates that any one of these mechanisms may be important in the karst areas of the British Isles. Caution is needed before interpreting the [delta] 13C signal within speleothems in terms of palaeovegetation

Mixed transport reaction control of gypsum dissolution kinetics in aqueous solutions and initiation of gypsum karst, 1997, Raines M. A. , Dewers T. A. ,
Experiments with gypsum in aqueous solutions at 25 degrees C, low ionic strengths, and a range of saturation states indicate a mixed surface reaction and diffusional transport control of gypsum dissolution kinetics. Dissolution rates were determined in a mixed flow/rotating disc reactor operating under steady-state conditions, in which polished gypsum discs were rotated at constant speed and reactant solutions were continuously fed into the reactor. Rates increase with velocity of spin under laminar conditions (low rates of spin), but increase asymptotically to a constant rate as turbulent conditions develop with increasing spin velocity, experiencing a small jump in magnitude across the laminar-turbulent transition. A Linear dependence of rates on the square root of spin velocity in the laminar regime is consistent with rates being limited by transport through a hydrodynamic boundary layer. The increase in rate with onset of turbulence accompanies a near discontinuous drop in hydrodynamic boundary layer thickness across the transition. A relative independence of rates on spinning velocity in the turbulent regime plus a nonlinear dependence of rates on saturation state are factors consistent with surface reaction control. Together these behaviors implicate a 'mixed' transport and reaction control of gypsum dissolution kinetics. A rate law which combines both kinetic mechanisms and can reproduce experimental results under laminar flow conditions is proposed as follows: R = k(t) {1 - Omega(b)() zeta [1 - (1 2(1 - Omega(b)())(1/2)]} where k(t) is the rate coefficient for transport control, and Omega(b)() is the mean ionic saturation state of the bulk fluid. The dimensionless parameter zeta(=Dm(eq)()/2 delta k() where m(eq)() = mean ionic molal equilibrium concentration, D is the diffusion coefficient through the hydrodynamic boundary layer, delta equals the boundary layer thickness and k() is the rate constant for surface reaction control) indicates which process, transport or surface reaction, dominates, and is sensitive to the hydrodynamic conditions in the reactor. For the range of conditions used in our experiments, zeta varies from about 1.4 to 4.5. Rates of gypsum dissolution were also determined in situ in a cavern system in the Permian Blaine Formation, southwestern Oklahoma. Although the flow conditions in the caverns were not determinable, there is good agreement between lab- and field-determined rates in that field rate magnitudes lie within a range of rates determined experimentally under zero to low spin velocities A numerical model coupling fluid flow and gypsum reaction in an idealized circular conduit is used to estimate the distance which undersaturated solutions will travel into small incipient conduits before saturation is achieved. Simulations of conduit wall dissolution showed-member behaviors of conduit formation and surface denudation that depend on flow boundary conditions (constant discharge or constant hydraulic gradient and initial conduit radius. Surface-control of dissolution rates. which becomes more influential with higher fluid flow velocity, has the effect that rate decrease more slowly as saturation is approached than otherwise would occur if rates were controlled by transport alone. This has the effect that reactive solutions can penetrate much farther into gypsum-bearing karst conduits than heretofore thought possible, influencing timing and mechanism of karst development as well as stability of engineered structures above karst terrain

Dissolution kinetics of calcium carbonate minerals in H2O-CO2 solutions in turbulent flow: The role of the diffusion boundary layer and the slow reaction H2O? reversible arrow H?, 1997, Liu Z. H. , Dreybrodt W. ,

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