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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. ...

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. ...

Speleology in Kazakhstan

Shakalov on 11 Jul, 2012
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 bogaz is 1. (slavic.) an elongated depression in limestone or karst terrain; thus it embraces a defile, a blind valley or a ravine leading to a ponor. it can be considered as a giant grike. this meaning is based on the serbian use [20]. 2. a variable-discharge artesian spring in which hydrostatic pressure is great enough to cause a turbulent or even fountain-like discharge. 3. a long narrow chasm enlarged by solution of the limestone [10]. 4. large linear fissure or box valley through a karst block. effectively a giant grike, perhaps 50 m deep and 1 km long, formed by dissolution on a fault or joint in very massive limestone [9]. synonyms: (french.) defile, bogaz; (german.) doline, karstgabe, blindtal, zangon; (greek.) faragothis doline; (spanish.) zanjon; (turkish.) bogaz; (yugoslavia.) bogaz. see also canyon; gorge; grike; corridor; struga; zanjon.?

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Your search for calcite dissolution (Keyword) returned 39 results for the whole karstbase:
Showing 1 to 15 of 39
Critical review of the kinetics of calcite dissolution and precipitation, 1979, Plummer L. N. , Parkhurst D. C. , Wigley T. M. L.

Mixing corrosion in CaCO3/1bCO2/1bH2O systems and its role in the karstification of limestone areas, 1981, Dreybrodt W,
Mixtures of two saturated H2O/1bCO2/1bCaCO3 solutions of different chemical composition gain renewed capability of dissolving calcite. This is an important mechanism in the solution processes of limestone during karstification. Using recent data on the kinetics of calcite dissolution, dissolution rates in mixture corrosion are calculated. In the region of the chemical composition of natural karst waters the solution rate is approximated by:R=-[alpha]([Ca2] - [Ca2]s where [Ca2], [Ca2]s are the concentrations of the Ca2 ion in the solution and at saturation, respectively. [alpha] ranges from 10-4 to 3[middle dot]10-4 cm s-1.This result is applied to the solution of limestone in karst water mixtures flowing in cylindrical conduits. The saturation length, i.e. the length xs which the solution has to travel to drop to 37% of its renewed dissolving capability, is calculated in the region of turbulent flow. This region starts at conduit radii R of several millimeters. At the onset of turbulent flow the saturation length is 260 m, increasing with R1.665. The increase of conduit radii is calculated from the dissolution rates of calcite solution to be on the order of 10-3 cm yr.-1.The results are discussed for a comprehensive model of karstification and cave development, which for the first time gives a realistic theoretical time region for cave development, in agreement to experience


Kinetics of Calcite Dissolution and its Consequences to Karst Evolution from the Initial to the Mature State, 1987, Drybrodt, Wolfgang

Limestone caves form along ground-water paths of greatest discharge and solutional aggressiveness. Flow routes that acquire increasing discharge accelerate in growth, while others languish with negligible growth. As discharge increases, a maximum rate of wall retreat is approached, typically about 0.01-0.1 cm/yr, determined by chemical kinetics but nearly unaffected by further increase in discharge. The time required to reach the maximum rate is nearly independent of kinetics and varies directly with flow distance and temperature and inversely with initial fracture width, discharge, gradient, and P(CO2). Most caves require 10(4) - 10(5) yr to reach traversable size. Their patterns depend on the mode of ground-water recharge. Sinkhole recharge forms branching caves with tributaries that join downstream as higher-order passages. Maze caves form where (1) steep gradients and great undersaturation allow many alternate paths to enlarge at similar rates or (2) discharge or renewal of undersaturation is uniform along many alternate routes. Flood water can form angular networks in fractured rock, anastomotic mazes along low-angle partings, or spongework where intergranular pores are dominant. Diffuse recharge also forms networks and spongework, often aided by mixing of chemically different waters. Ramiform caves, with sequential outward branches, are formed mainly by rising thermal or H2S-rich water. Dissolution rates in cooling water increase with discharge, CO2 content, temperature, and thermal gradient, but only at thermal gradients of more than 0.01-degrees-C/m can normal ground-water CO2 form caves without the aid of hypogenic acids or mixing. Artesian flow has no inherent tendency to form maze caves. Geologic structure and stratigraphy influence cave orientation and extent, but alone they do not determine branch-work versus maze character

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

Modeling of flow and solutional processes within networks of interconnected conduits in limestone aquifers indicates that enlargement occurs very selectively during the early stages of karst aquifer development under laminar flow. If initial flow paths are uniform in size, almost all enlargement occurs along a single set of connected conduits that lie along a direct path between recharge and discharge locations and are aligned along the hydraulic gradient. With a sufficiently large variation in initial aperture widths, enlargement occurs along the flow path offering the least resistance to flow, but since flow rates in laminar flow are proportional to the fourth power of diameter but only linearly proportional to hydraulic gradient, the preferentially enlarged set of fractures may follow an indirect path. Results disfavor earlier suggestions that nonselective cave patterns result from artesian flows (at least under laminar flow conditions) and that all passages should be competitive until the onset of turbulent flow

Recent flowstone growth rates: field measurements and comparison to theoretical results, 1995, Baker A. , Smart Pl. ,
The model of calcite precipitation kinetics of D. Buhmann and W. Dreybrodt, based on the rate laws of L.N. Plummer et al., is used to predict cave flowstone growth rates. These theoretically modelled growth rates are compared to actual growth rates of recent samples found in cave and mine sites in southwest England. A good agreement is found between modelled and actual growth rates within the 95% confidence level of the determinations, although in general modelled growth rates overestimate actual growth rate by between 2.4 and 4.7 times. Several reasons for this overestimation are discussed, including uncertainties arising from the experimental data of L.N. Plummer et al., seasonal shut-off of water flow onto the flowstones and significant variations in the growth rate determining parameters during the period of flowstone growth. For one flowstone an underestimation of growth rate is observed and is explained by the presence of rimstone pools which pond water on the sample surface

Principles of early development of karst conduits under natural and man-made conditions revealed by mathematical analysis of numerical models, 1996, Dreybrodt W,
Numerical models of the enlargement of primary fissures in limestone by calcite aggressive water show a complex behavior. If the lengths of the fractures are large and hydraulic heads are low, as is the case in nature, dissolution rates at the exit of the channel determine its development by causing a slow increase of water flow, which after a long gestation time by positive feedback accelerates dramatically within a short time span. Mathematical analysis of simplified approximations yields an analytical expression for the breakthrough time, when this happens, in excellent agreement with the results of a numerical model. This expression quantifies the geometrical, hydraulic, and chemical parameters determining such karat processes. If the lengths of the enlarging channels are small, but hydraulic heads are high, as is the case for artificial hydraulic structures such as darns, it is the widening at the entrance of the flow path which determines the enlargement of the conduit. Within the lifetime of the dam this can cause serious water losses, This can also be explained by mathematical analysis of simplified approximations which yield an analytical threshold condition from which the safety of a dam can be judged. Thus in both cases the dynamic processes of karstification are revealed to gain a deeper understanding of the early development of karst systems. As a further important result, one finds that minimum conditions, below which karstification cannot develop, do not exist

The effect of metal cations on the kinetics of limestone neutralisation of acid waters, 1997, Vantonder G. J. , Schutte C. F. ,
Limestone (CaCO3), is a lower cost alternative to lime (CaO) for the neutralisation of acid water, but the limestone neutralisation reaction is impaired by iron(II), iron(III) and aluminium in solution. This paper describes the kinetics of limestone neutralisation in the presence of these metals. The reaction rate is affected by the type of metal cation, by the concentration of the cation and by pH. At pH levels below 2.0 the limestone dissolution reaction rate decreases sharply with increasing pH. In the pH range 4.0 to 5.5 the reaction rate decreases linearly with increasing pH. The pH range 2.0 to 4.0 is a transition range, from the non-linear to linear dissolution rate characteristics. Metal concentrations below 80 mg l(-1): At pH levels less than 4, iron(II) had the strongest suppressing effect followed by aluminium, while the presence of iron(III) increased the reaction rate. In the pH range 4.0 to 5.5 aluminium had the strongest suppressing effect followed by iron(III) and iron(II). Metal concentrations above 80 mg l(-1): Iron(II) and aluminium suppress the reaction rate at all pH levels. At pH levels less than 4 iron(II) had the strongest suppressing effect, followed by aluminium. In the pH range 4.0 to 5.5 aluminium had the strongest suppressing effect followed by iron(II). With iron(III) the rate is suppressed at pH levels below 2, however the rate is speeded up in the pH range 25 to 3.5. At higher pH levels, the iron(III) concentration is limited to less than 80 mg l(-1) because of precipitation of iron(III) at pH levels higher than 2.5. The extent to which the overall neutralisation reaction proceeds was modelled to assist in reactor design. The overall reaction is impaired most by aluminium, followed by iron(II) and iron(III)

Ground-water silicifications in the calcareous facies of the Tertiary piedmont deposits of the Atlas Mountain (Hamada du Guir, Morocco), 1997, Thiry M. , Benbrahim M. ,
The Tertiary piedmont deposits (Hamada Formations), on the southern edge of the Haut-Atlas mountains, form extensive tablelands in the Boudenib area. They consist of two main sedimentary sequences, the Hamada de Boudenib and the Hamada du Guir, of Eocene and Miocene age. Both sequences show elastic facies at their base (conglomerates, calcareous sandstones, silty clays) and end with thick lacustrine limestones and pedogenic calcretes are characterised by rather confined facies, palygorskite-rich, with some gypsum in the second sequence. The recent evolution of the region is marked by the dissection of the tableland that is lined with high cliffs. The water flaw is mainly through wide karst features as there is no major river on the tableland. Silicifications which affect the different facies, form pods of various shape and size, and show an erratic spatial distribution. In the calcareous sandstones, there are irregularly shaped tubules of about 5 cm in diameter, more planar bodies from 5 to 50 cm thick, which frequently display voids lined with translucent silica concretions. The conglomerates display relatively few silicifications, the more characteristic ones consist of a silica cortex on some Limestone pebble and silica plates fitting closely the base of the pebbles. The lacustrine limestones and the calcretes from the upper part of the formation show frequently well developed silicifications. These show very variable shapes; horizontally stretching layers, interconnected or isolated amoeba-like bodies, thin slabs, karst micro-breccia, with frequent concretionnary structures, and quartz crystallisations. Limestone nodules remain often included in these silicifications. The more argillaceous facies display either small tubules or thin plates formed of translucent concretionnary silica. As a rule, the importance of the voids and related structures (concretions, drusy crystals) has to be noticed in all these silicifications, sometimes they are also linked with fractures or karst pipes. Petrography of the silica minerals, their relation with the primary structures. their distribution and their succession, give invaluable information on the silicification processes. Microcrystalline and fibrous quartz are the most common silica minerals, including minor amounts of opal and euhedral quartz. But micrographic arrangements show clearly that primary opal deposits have been more extensive and have recrystallized into chalcedony, microcrystalline quartz, or even ''flame-like'' quartz. Silica deposits in voids make up an important part of the silica pods. The tubules and thin plates of translucent silica of the argillaceous facies are formed of laminar chalcedony deposited around voids. Silica deposits in voids are also particularly obvious in the sandstones. The pores between the quartz grains are then cemented by fibrous quartz and little opal. Some samples show very large cemented voids that cannot be related to the primary porosity of the sandstone. These large voids correspond to the dissolution of the primary calcareous cement, which even led to the collapse of the sandstone fabric. In the limestones, there are silicified micro-karst breccia with a very high primary porosity cemented by quartz crystals, and even in the large microcrystalline quartz zones there are numerous void fillings, the primary porosity often exceeding 50%. There is obviously the alternation of silica deposits and calcite dissolution. Beside the void filling, silicifications comprise also matrix epigenesis, that is replacement of the carbonate by silica with preservation of most of the limestone structures, without development of voids. Nevertheless, the epigenesis of the limestone matrix is restricted to the vicinity of the voids. The silicifications relate to diagenetic processes. The main part of the silica is formed of void deposits and matrix replacement (epigenesis) on the edge of the voids. These void deposits give evidence of the feeding solutions. The regularity of the deposits all around the voids point out to a hydrologic regime characterised by a ground-water our now. Silica originates most probably from alteration of the magnesian clay minerals along the ground-water path. Regarding the low solubility of silica in surficial waters, high flows are needed in order to renew continuously the silica precipitated from solution. This points to a relatively humid climate at time of silicification, and to relief and incised landscapes to bring about these high flows

An experimental study of calcite and limestone dissolution rates as a function of pH from -1 to 3 and temperature from 25 to 80 degrees C, 1998, Alkattan M, Oelkers Eh, Dandurand Jl, Schott J,
Dissolution rates of single calcite crystals, limestones, and compressed calcite powders were determined from sample weight loss using free-drift rotating disk techniques. Experiments were performed in aqueous HCl solutions over the bulk solution pH range -1 to 3, and at temperatures of 25 degrees, 50 degrees, and 80 degrees C. Corresponding rates of the three different sample types are identical within experimental uncertainty. Interpretation of these data using equations reported by Gregory and Riddiford [Gregory, D.P., Riddiford, A.C., 1956. Transport to the surface of a rotating disc. J. Chem. Sec. London 3, 3756-3764] yields apparent rate constants and H diffusion coefficients. The logarithms of overall calcite dissolution rates (r) obtained at constant disk rotation speed are inversely proportional to the bulk solution pH, consistent with r = k(2') a(H,b), where k(2)' stands for an apparent rate constant and a(H,b) designates the hydrogen ion activity in the bulk solution, This variation of dissolution rates with pH is consistent with corresponding rates reported in the literature and the calcite dissolution mechanism reported by Wollast [Wollast, R., 1990. Rate and mechanism of dissolution of carbonates in the system CaCO3-MgCO3. In: Stumm, W. (Ed.), Aquatic Chemical Kinetics. Wiley, pp. 431-445]. Apparent rate constants for a disk rotation speed of 340 rpm increase from 0.07 0.02 to 0.25 0.02 mol m(-2) s(-1) in response to increasing temperature from 25 degrees to 80 degrees C. H diffusion coefficients increase from (2.9 to 9.2) x 10(-9) m(2) s(-1) over this temperature range with an apparent activation energy of 19 kJ mol(-1). (C) 1998 Elsevier Science B.V. All rights reserved

Influence of aperture variability on dissolutional growth of fissures in karst formations, 1998, Hanna R. B. , Rajaram H. ,
The influence of aperture variability on dissolutional growth of fissures is investigated on the basis of two-dimensional numerical simulations. The logarithm of the fissure aperture before dissolution begins is modeled as a Gaussian stationary isotropic random field. The initial phase of dissolutional growth is studied up to the time when turbulent flow first occurs at a point within the fissure (the breakthrough time). The breakthrough time in variable aperture fissures is smaller than that in uniform fissures and decreases as the coefficient of variation of the aperture field (sigma/mu) increases. In comparing uniform and variable aperture fissures in limestone, the breakthrough time with sigma/mu = 0.1 is about a factor of 2 smaller than that in a uniform fissure. The breakthrough time is reduced by about an order of magnitude with sigma/mu = 2.0. The mechanism leading to reduced breakthrough times is the focusing of flow into preferential flow channels which are enlarged at a faster rate than the surrounding regions of slower flow. Dissolution channels are narrower and more tortuous as sigma/mu. increases. Investigations of the influence of reaction rate reveal that the influence of aperture variability is more pronounced in rapidly dissolving rock. In uniform fissures in rapidly dissolving minerals, breakthrough times are very long since water becomes saturated with respect to the mineral within a short distance of the entrance to the flow path. However, in variable aperture fissures, breakthrough occurs rapidly because of selective growth along preferential flow channels, which progressively capture larger fractions of the total flow. These results partly explain why conduits develop rapidly in gypsum, although previous one-dimensional studies suggest that conduit growth will not occur

Oxidation of organic matter in a karstic hydrologic unit supplied through stream sinks (Loiret, France), 1998, 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

The initiation of hypogene caves in fractured limestone by rising thermal water: investigation of a parallel series of competing fractures, 1999, Dumont K. A. , Rajaram H. , Budd D. A.
Integrated cave systems can either form at or near the surface of the earth (epigenic) or at some depth below the earth's surface (hypogenic)For caves that form in fractured limestone, the two most common types of cave-system morphologies are branchwork and mazeworkBranchwork caves are composed of tributaries that coalesce in the downstream direction, similar to surface streamsMazework caves exhibit two or more sets of parallel passages intersecting in a grid-like patternThe majority of epigenic caves exhibit branchwork morphologies, which represent the dominance of individual flow pathsIn contrast, mazework caves develop when dissolution occurs along numerous flow pathsWhereas most epigenic caves are related to surficial meteoric flow systems, some mazework caves are thought to have formed in hypogene environments where rising thermal water cools in response to the geothermal gradientOur objective is to examine the fundamental cause for the difference in morphology between epigenic and thermal hypogenic cave systems using numerical modelsIn particular, we are examining the competition between different flow paths in fractured limestone undergoing dissolutional enlargementAs noted in previous numerical studies, epigenic systems are characterized by the dominance of a single flow path, which is consistent with the structure of epigenic cavesSo, in order to explain the structure of maze caves, one has to explain why no single flow path attains dominanceThe retrograde solubility of calcite coupled with heat transfer from the fluid to the rock is hypothesized to provide the mechanism by which dissolutional power is distributed among all competing flow pathsNumerical models of fluid flow, heat transfer, and calcite dissolution chemistry are integrated to develop a model of hypogene cave initiation in fractured limestoneFlow is assumed to occur in the presence of a spatially variable rock temperature field that is constant through timePreliminary numerical modeling results for a system of parallel fractures demonstrate the differences in the nature of competition between flow paths in epigenic (constant temperature) and hypogenic systems (flow in the presence of a negative thermal gradient)Differences in results using various kinetic models for calcite dissolution are also presentedThe role of aperture variation and distribution in a parallel set of fractures is also examined

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