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Enviroscan Ukrainian Institute of Speleology and Karstology


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Community news

Speleology in Kazakhstan

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

New publications on hypogene speleogenesis

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

The deepest terrestrial animal

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

Caves - landscapes without light

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

Did you know?

That calc-sinter is see sinter.?

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


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Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
See all featured articles
Featured articles from other Geoscience Journals
Karst environment, Culver D.C.
Mushroom Speleothems: Stromatolites That Formed in the Absence of Phototrophs, Bontognali, Tomaso R.R.; D’Angeli Ilenia M.; Tisato, Nicola; Vasconcelos, Crisogono; Bernasconi, Stefano M.; Gonzales, Esteban R. G.; De Waele, Jo
Calculating flux to predict future cave radon concentrations, Rowberry, Matt; Marti, Xavi; Frontera, Carlos; Van De Wiel, Marco; Briestensky, Milos
Microbial mediation of complex subterranean mineral structures, Tirato, Nicola; Torriano, Stefano F.F;, Monteux, Sylvain; Sauro, Francesco; De Waele, Jo; Lavagna, Maria Luisa; D’Angeli, Ilenia Maria; Chailloux, Daniel; Renda, Michel; Eglinton, Timothy I.; Bontognali, Tomaso Renzo Rezio
Evidence of a plate-wide tectonic pressure pulse provided by extensometric monitoring in the Balkan Mountains (Bulgaria), Briestensky, Milos; Rowberry, Matt; Stemberk, Josef; Stefanov, Petar; Vozar, Jozef; Sebela, Stanka; Petro, Lubomir; Bella, Pavel; Gaal, Ludovit; Ormukov, Cholponbek;
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Your search for equilibria (Keyword) returned 65 results for the whole karstbase:
Showing 16 to 30 of 65
Thermodynamic equilibrium, kinetics, activation barriers, and reaction mechanisms for chemical reactions in Karst Terrains, 1997,
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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

Sea water intrusion in coastal karst springs: Example of the Blaz spring (Croatia), 1997,
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Bonacci O, Rojebonacci T,
Brackish karst springs are common along every karstic sea shore consisting of limestone and dolomite. On the Croatian sea coast there are more than 300 permanent or temporary brackish karst springs. From the standpoint of water supply, the problem of karst spring water salinization is quite significant because large quantities of high quality fresh water are not available to be used either as drinking water or for industrial and agricultural purposes. The salinity of brackish karst springs situated along the Adriatic coast varies from 10 to more than 18 000 mg Cl 1(-1) with an unfavourable distribution during the year. In the wet winter period, when water quantities in the region are abundant, the salinity is exceedingly low. In the warm and dry summer period the chloride concentration is high. At that season, when a shortage of flesh water in the region occurs, especially due to tourism, karst spring water is so salty that it cannot be used at all. The mechanism of sea water intrusion is relatively well known but the problem of karst springs desalinization has not been solved in practice. The Ghyben-Herzberg relationship is formulated exclusively on the basis of hydrostatic equilibrium, and its use under dynamic conditions is limited. The dynamics of fresh water circulation towards karst spring exits are very specific for each individual spring. Using numerous hydrological, hydrometric, hydrogeological and speleological investigations of the brackish Blaz (Croatia) karst spring, this paper gives the plausible position and dimensions of the main karst conduits through which sea water penetrates into the spring exit

Estimating subsurface fissure apertures in karst aquifers from equilibrium activities, 1998,
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Field Ms, Mose Dg,
Rn-222 activities were determined for the karst aquifer underlying Walkersville, Maryland, in an area of ground-water discharge from a single geological unit during the summer and fall seasons, Radon-222 equilibrium activities in karst ground waters can be employed in mass-balance models to estimate microfissure, macrofissure, and conduit aperture dimensions, This approach defines Rn-222 generation and loss in karst aquifers as a function of fissure apertures and the U-238 content of the rock, High Rn-222 activities occur in tight fissures and low Rn-222 activities occur in conduits, In the vadose zone, Rn-222 activities are low as a result of degassing, especially if flow is turbulent and activities are decoupled from the phreatic zone, In the phreatic zone, if recharge to fissures causes a reduction of residence time below that required for equilibrium (approximate to 26 days), Rn-222 activities fall, At springs and in the vadose zone, after a rainfall event, Rn-222 activities increase as waters with long residence and with high Rn-222 activities are expelled from fissure and fracture storage, Field data and selected literature values were used to test the model, Models used to predict median microfissure apertures for this karst aquifer yield aperture estimates ranging from 2.8 mu m to 9.2 mu m. Median macrofissure apertures ranged from 5.53 cm to 5.88 cm, Median conduit apertures ranged from 1.16 m to 1.24 m, Comparison of the models results with published data on karst aquifers and observations at the field site suggest that the predicted apertures are reasonable

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

Contribution to knowledge of gypsum karstology, PhD thesis, 1998,
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Calaforra Chordi, J. M.

The objective of this study was not to establish a definitive judgement regarding a topic for which very little previous information was available, but rather to open new routes for research into karst by means of a particularized analysis of some of the factors involved in the speleogenesis of gypsiferous materials. The main obstacle to the attainment of this goal has been the scientific community's lack of interest in karst in gypsum, particularly in our country, until the nineteen eighties. To overcome this neglect it was decided, in my opinion quite correctly, to extend the bounds of the study as far as possible, so that the information obtained from the contrast found between the most important worldwide zones of karst in gypsum could be applied to the gypsiferous karst in our country, and in particular, to the most significant, the karst in gypsum of Sorbas.
This is the justification for the numerous references in the text to the gypsiferous karst and cavities in gypsum that are most relevant in Spain (Sorbas, Gobantes, Vallada, Archidona, Estremera, Baena, the Ebro Basin, Estella, Beuda, Borreda, etc.) and also to the best-known gypsiferous karsts worldwide (Podolia, Secchia, Venna del Gesso Romagnolo, Sicily and New Mexico). By means of these comparisons, the initial lack of information has been overcome.
The study is based on three central tenets, which are interrelated and make up the first three chapters of this report. The first consideration was to attempt to characterize the particular typology of gypsiferous karst from the geological (both stratigraphic and structural) point of view. This chapter also provides an introduction to each of the gypsiferous karsts examined. The second chapter is dedicated to the geomorphology of gypsiferous karst, under both superficial and subterranean aspects. It is important to note that the study of a gypsiferous karst from the speleological point of view is something that may seem somewhat unusual; however, this is one of the points of principle of this paper, the attempt to recover the true meaning of a word that has historically been unfairly condemned by a large part of the Spanish scientific community. Thirdly, a detailed study has been made of the hydrochemistry of the most important gypsiferous karsts in our region, together with the presentation of a specific analytical methodology for the treatment of the hydrochemical data applicable to the gypsiferous karst.
Geological characterization of gypsum karst
In the characterization of karst in gypsum, the intention was to cover virtually all the possibilities from the stratigraphic and structural standpoints. Thus, there is a description of widely varying gypsiferous karsts, made up of Triassic to Miocene materials, some with a complex tectonic configuration and others hardly affected by folding. The gypsiferous karsts described, and their most significant geological characteristics, are as follows:
Karst in gypsum at Sorbas (Almeria): composed of Miocene gypsiferous levels with the essential characteristic of very continuous marly interstrata between the layers of gypsum, which decisively affect the speleogenesis of the area. The gypsum layers have an average thickness of about 10 m and, together with the fracturing in the zone, determine the development of the gypsiferous cavities. These are mainly selenitic gypsum - occasionally with a crystal size of over 2 m - and their texture also has a geomorphologic and hydrogeologic influence. This area is little affected by folding and so the tectonic influence of speleogenesis is reduced to the configuration of the fracturing.
The Triassic of Antequera (Malaga): this is, fundamentally, the gypsiferous outcrop at Gobantes-Meliones, originating in the Triassic and located within the well-known "Trias" of Antequera. It is made up of very chaotic gypsiferous materials containing a large quantity of heterometric blocks of varied composition; the formation may be defined as a Miocene olitostromic gypsiferous breccia that is affected by important diapiric phenomena. The presence of hypersoluble salts at depth is significant in the modification of the hydrochemical characteristics of the water and in the speleogenetic development of the karst.
The Triassic of Vallada (Valencia): Triassic materials outcrop in the Vallada area; these mainly correspond to the K5 and K4 formations of the Valencia Group, massive gypsum and gypsiferous clays. The influence of dolomitic intercalations in the sequence is crucial to the speleogenesis of the area and this, together with intense tectonic activity, has led to the development in this sector of the deepest gypsiferous cavity in the world: the "Tunel dels Sumidors". As in the above case, the presence of hypersoluble salts at depth and the varied lithology influence the variations in the hydrodynamics and hydrochemistry of the gypsiferous aquifer.
Other Spanish gypsum karsts: this heading covers a group of gypsiferous areas and cavities of significant interest from the speleogenetic standpoint. They include the area of Estremera (Madrid), with Miocene gypsiferous clays and massive gypsum arranged along a large horizontal layer; this has produced the development of the only gypsiferous cavity in Spain with maze configuration, the Pedro Fernandez cave. The study of this cave has important hydrogeological implications with respect to speleogenesis in gypsum in phreatic conditions. The Baena (Cordoba) sector, in terms of its lithology, is comparable to the "Trias de Antequera". Here, the cavities developed in gypsiferous conglomerates, following structural discontinuities have enabled contact between carbonate and gypsiferous levels, and so we may speak of a mixed karstification: a karst in calcareous rocks and gypsum. The karst of Archidona (Malaga) is similar to that of the Gobantes-Meliones group and is significant because of the geomorphologic evolution of the karst, which is related to the diapiric ascent of the area and the formation of karstic ravines. The karst in the Miocene and Oligocene gypsum of the Ebro Basin (Zaragoza), has been taken as a characteristic example of a gypsiferous karst developed under an alluvial cover, with the corresponding geomorphological implications in the evolution of the surface landforms. In the gypsiferous area of Borreda (Barcelona), the presence of anhydritic levels in the sequence might have influenced the speleogenesis of its cavities. The cavity of La Mosquera, in Beuda (Girona), developed in massive Paleogene gypsum. This is the only Spanish example of a phreatic gypsiferous cavity developed in saccaroid gypsum, which is related to the particular subterranean morphology discovered. Finally, this group includes other Spanish gypsiferous outcrops visited during the preparation of this report, the references to which may be found in the relevant chapters.
Karst in gypsum in Europe and America: In order to complete the study of karst in gypsum, and with the idea of using all the available data on the karstology of gypsiferous materials for comparative studies of data for our country, a complementary activity was to define the most significant geological characteristics of the most important gypsiferous karsts in the world. An outstanding example is the gypsiferous karst at Podolia (Ukraine), developed in microcrystalline Miocene gypsum which has undergone block tectonics related to the collapse of the Precarpatic foredeep. This gypsum provides interesting data on speleogenesis in gypsiferous materials, as its evolution is related to the confining of the only gypsiferous stratum (of 10 to 20 m depth) producing interconnected labyrinthine galleries of over 100 km in length. Another well-known karst in gypsum is the one located at "Venna del Gesso Romagnolo" (Italy), in the Bologna region, with a lithology that is very similar to that which developed at Sorbas, but with the difference that it underwent more intense tectonics with folding and fracturing of the Tertiary sediments of the Po basin. In the same Italian province, in "L'alta Val di Sec-chia", there are outcrops of karstified Triassic materials which correspond to the formation of Burano, composed of gypsum and anhydrite with hypersoluble salts at depth and very notable diapiric phenomena. The study of this area has been used for a comparative analysis - geomorphology and hydrogeochemistry - with the Spanish gypsiferous karsts developed in Triassic levels. The third Italian gypsiferous karst to be considered is the one developed in Sicily, which has extensive Messinian outcrops of microcrystalline and selenitic gypsum as well as a great variety of lithologic types within the gypsiferous sequence, which we term the "gessoso solfifera" sequence. This gypsiferous karst is especially interesting from the geomorphologic standpoint due to the great quantity and variety of present superficial karstic forms. This has also served as a guide for the study of Spanish gypsiferous karsts. Finally, considering the relation between climatology and the development of karstic forms, we have also studied the karst in gypsum in New Mexico, where there is an extensive outcrop of Permian gypsum, both micro and macrocrystalline, situated on a large platform almost unaffected by deformation, and where the conditions of aridity are very similar to those found in the gypsiferous karst of Sorbas.
Geomorphological characterization of gypsum karst
From the geomorphological standpoint, the intention is to give an overview of the great variety of karstic forms developed in gypsum, traditionally considered less important than those developed in carbonate areas. This report shows this is not the case.
The theory of Convergence of Forms has been shown to be an efficient tool for the study of the morphology of karst in gypsum. Here, its principles have been used to provide genetic explanations for various gypsiferous forms derived from carbonate studies, and for the reverse case. In fact, studying a karst in gypsum is like having available a geomorphological laboratory where not only are the processes faster but they are also applicable to the karstology of carbonate rocks.
A large number of minor karstic forms (Karren) have been identified. The most important factors conditioning their formation are the texture of the rock, climatology and the presence of overlying deposits. The first, particularly, is largely responsible for determining the abundance of certain forms with respect to others. Thus, Rillenkarren, Trittkarren and small "kamenitzas" are more frequently found in microcrystalline and sandstone gypsum (for example, karst in gypsum in Sicily (Italy) and Va-llada (Valencia, Spain). Others seem to be more exclusive to selenitic gypsum, such as exfoliation microkarren, or are closely related to the climatology of the area (Spitzkarren develops from the alteration of gypsum in semiarid conditions). Others are related either to the presence of developed soil cover (Rundkarren, using Convergence of Forms), or to their specific situation (candelas and Wallkarren around dolines and sinkholes) or to the microtexture of the gypsum and the orientation of the 010 and 111 crystalline planes and twinning planes for the development of nanokarren.
The tumuli are the most peculiar forms of the Sorbas karst in gypsum, though they have also been identified in other gypsiferous karsts (Bolonia, New Mexico, Vallada, etc.). These are subcircular domes of the most superficial layer of the gypsum. Their formation has been related to processes of precipitation-solution and of capillary movement through the gypsiferous matrix. Their extensive development is largely determined by the climatology of the area and by the structural organization. It is therefore clear that the best examples are found in the karst of Sorbas due to the abrupt changes in temperature and humidity that occur in a semiarid climate, and because of the horizontality of the gypsiferous sequence.
Karst in gypsum and its larger exokarstic forms, apart from being climatically determined, also depend on the structural state and lithological determinants of the area. Thus, it is possible to differentiate between gypsiferous karsts where the lithology, together with erosive breakup, is more important (Sorbas and New Mexico) and others where confining hydraulic conditions persist (Estremera and Podolia). In other cases, tectonics has played a significant modelling role, and there is a clear possibility of an inversion of the relief (Bolonia or Sicily) or of the effect of diapiric processes (Secchia, Vallada, Antequera). The typological diversity of the dolines is obviously also related to these premisses. Another example is the relation existing between carbonate precipitation and gypsum solution, as evidenced in contrasting examples (Bolonia versus Sorbas).
Subterranean karstic forms have been examined from a double perspective: the morphology of the passages and the mineralization within the cavities. With respect to the former, a noteworthy example is the interstratification karst of Sorbas, where subterranean channels have developed during two well-differentiated phases, the phreatic and the vadose. The first was responsible for the formation of the small proto-galleries, currently relicts that are observable as false dome channels in the bottom of the gypsiferous strata. The second, with an erosive character, enabled the breakup of the marly interstrata and the formation of the large galleries found today. Other aspects considered include the speleogenetic influence of the presence of calcareous intercalations in the gypsiferous sequence (Vallada karst), gypsiferous agglomerates (Baena karst), anhydrite (Rotgers karst), suffusion processes (Sorbas karst) and the importance of condensation.
Spelothemes in gypsiferous cavities have been approached with special concern for gypsiferous speleothemes, in particular those which, due to their genetic peculiarity or to the lack of previous knowledge about them, are most significant. Among these are gypsum balls, with phenomena of solution, detritic filling, capillarity and evaporation; gypsum hole stalagmites, where the precipitation-solution of the gypsum controlling the formation of the central orifice is related to the previous deposit of carbonate speleothemes; gypsum trays that mark the levels of maximum evaporation; gypsum dust, determined by abrupt changes in temperature and humidity in areas near the exterior of gypsiferous cavities. All of these are characteristic of, and practically exclusive to, gypsiferous karsts in semiarid ztenes such as Sorbas and New Mexico.
Karst in gypsum has been morphologically classified with reference to the previously-mentioned criteria: the presence and typology of epigean karstic forms, both macro and microform; the typology of hypogean karstic forms (passages) and the type of speleothemes within the cavities (gypsiferous or carbonate). All these variables are clearly influenced by climatology, and so a study of the geomorphology of gypsiferous karst is seen to be an efficient tool for the analysis of the paleoclimatology of an area.
Hydrogeochemical characterization of gypsum karst
The hydrogeochemical characterization of karst in gypsum was approached in two stages. The first one was intended to establish themodels to be applied to the hydrochemistry approach, while the second provided various examples of hydrochemical studies carried out in gypsiferous karsts.
The theoretical framework which has been shown to be most accurate with respect to the formulation of chemical equilibria in water related to gypsiferous karst is the Virial Theory and the Pitzer equations.
For this study, we used a simplification of these equations as far as the second virial coefficient by means of a simple, polynomial variation to obtain the equilibrium state of the water with respect to the gypsum, for an ionic strength value greater than 0.1 m and temperatures of between 0.5 and 40 "C. This was the case of the gypsiferous karsts found to be related to hypersaline water at depth (Vallada, Gobantes-Meliones, Poiano). In the remaining situations, where the ionic strength was below 0.1 m, only the theory of ionic matching was used.
The hydrochemical study of the gypsiferous karst of Gobantes-Meliones (Malaga) led to the hypothesis of the possible influence of hypersaline water on karstification in gypsum. Using theoretical examples of the mixing of water derived both from hypersaline water and from water related only to the gypsiferous karst, it was shown that above a percentage content of 0.1:0.9 of saline and sulphated water, the mixture is subsaturated with respect to gypsum and other minerals. On reaching percentages greater than 0.5:0.5, values of oversaturation are again found. This could mean that the contact between sulphated and hypersaline water is a karstification zone in gypsum at depth.
In the gypsiferous karst at Salinas-Fuente Camacho (Granada), a study has been made of the hydrochemical influence of dolomitic levels in the sequence by means of the analysis of the hydrochemical routes between hydraulically-connected points. The generic case of mass transfer in this gypsiferous aquifer implies a precipitation of calcite which is in-congruent with dolomitic solution, proving that the process of dedolomitization in gypsiferous aquifers with an abundance of dolomitic rocks can be an effective process. In situations of high salinity, with contributions of hypersaline water, the process may be inverted, such as occurs in coastal carbonate aquifers influenced by the fresh-saltwater interface.
The gypsiferous aquifer of Sorbas-Tabernas (Almeria) provides the best case of karstification in gypsum in Spain; the hydrochemical study carried out has been used as an example of karstification in gypsum completely uninfluenced by sodium-chloride facies. It is shown, from the hydrochemical similarities between the different sectors, that the uniformity of the flow from the system main spring (Los Molinos) responds to the delayed hydraulic input through the overlying post-evaporitic materials and to the pelitic intercalations of the gypsiferous sequence. The aquifer is partially semiconfined, a situation which is comparable to the onset of the karstification stage, while the area of the Sorbas karst, strictly speaking, bears no hydriaulic relation to the rest of the system, behaving like a free aquifer intrinsically related to the epikarstic zone. This fact is demonstrated by the hydrochemical differences between the main spring and those related to gypsiferous cavities.
Apart from the general study of the Sorbas-Tabemas aquifer, a study was also made of the hydrochemical-time variations within cavities, and in particular within the Cueva del Agua, where it is possible to observe particular processes affecting karstification in gypsum, such as the precipitation of carbonates on the floor of the cavity which produce, in that area, a greater solution of gypsum (the phenomenon of hyperkarstification). Furthermore, the temporal evolution of the chemistry of the cavity, along 800 m of subterranean flow through its interior, shows the existence of inertial sectors where the variations were less abrupt. Only in the case of particular sectors, related to sporadic hydriaulic contributions or to the proximity to points of access., was a notable seasonal influence detected.
A similar hydrochemical study was carried out in the karst of Vallada (Valencia), along the cavity of the Tunel dels Sumidors. The chemistry here was compared with that of the springs of Brolladors (whose water rapidly infiltrates into the cavity) and Saraella (a saline resurgence of the whole system). Unexpected increases in the ionic content of certain salts (sulphates and chlorides) were detected during periods of increased flow; these were interpreted as the effect of the recharging of the Saraella spring arising from the immediate contribution of rapidly circulating sulfated water coming from the cavity and the subsequent mobilization of interstitial water with an ionic content higher than the characteristic level of the spring.
We present as a hypothesis the idea that, in addition to the hydrogeochemical processes described that can affect the evolution of a gypsiferous karst, the processes of sulphate reduction also influence karstification in gypsum, at least during the earliest stages. Some examples such as the presence of gypsum with abundant organic matter reprecipitated into phreatic channels (Sorbas) or veins of sulphur related to gypsiferous karsts (Podolia, Sicily) lend support to this idea.
Studies of the solution-erosion of gypsum have been performed by physical methods (tablets and M.E.M.) showing that the solution-erosion of gypsum within cavities is minimal (0.03 mm/ year) compared to that existing in the exterior (0.3 mm/year). The speleogenetic effect of condensation within the cavities has also been shown, with solution-erosion rates of 0.005 mm/year to be like the equivalent surface lowering. These data correspond to the karst in gypsum at Sorbas, where, additionally, a study about the time variation of the solution-erosion was carried out. It was found that the process is not continuous but clearly sporadic. During periods of torrential rain, the solution-erosion ranges from a weight loss of 400 mg/cm2/year on the surface of the karst to 75 mg/cm2/year inside the caves, while during the rest of the year the weight loss was barely 1 mg/cm2/year. The physical methods were compared with the results obtained from chemical methods, and it was found that, in general, higher values were obtained with the former (10-20% higher when weighted for the rainfall during the measuring periods). Thus it is reasonable to consider that the erosive process is more marked than was at first assumed.
In total, three cavity tracing experiments were carried out, all with fluoresceine, two of them in Cueva del Agua in Sorbas (during periods of high and low water levels) and the other in Tunel dels Sumidors in Vallada. At the first site, the comparison of the two tracing tests reveals a differential hydrodynamic behaviour of the cavity for the two contrasting situations; periods of high water input and periods of low rainfall. This behaviour is characteristic of well developed karstic aquifers, where the hydrodynamic effect of the circulation of water through small channels or, in this case, through the gypsiferous matrix and interbedded marly layers, seems to be more important under conditions of low hydraulic input than when rainfall is abundant. The two situations tested seem to confirm that the Cueva del Agua system, an epikarstic aquifer, which is representative of karstification in gypsum, has scarce retentive power and so large volumes of precipitation are totally discharged via the spring within a few days. However, the explanation of the small but continuous flow from the base of the cavity requires the inclusion of other factors in the interpretation. In this case, the flow seems to be fairly independent of rainfall and attributable to other processes, in addition to the previously described ones, such as the retentive power of the gypsiferous matrix and the marly interstrata. These might include the high degree of condensation measured over long periods, both on the surface of the karst in gypsum and within the cavities. In the case of the Tunel dels Sumidors, a highly irregular response was found, despite the fact that the coefficient of dispersivity was found to be 0.4. This value is similar to that obtained for the karst in gypsum at Sorbas in response to low water conditions, and so, here too, one might assume the influence of greater than expected flow-retaining processes, between the entry and exit points. Doubtless the karstic system of the Tunel dels Sumidors is more complex than was initially expected and in fact, the irregularity reflected by the fluoresceine concentration curve over time implies the existence of other factors to explain the diversity of the relative maxima obtained. Firstly, the presence of numerous Triassic clay intercalations might delay the flow, in addition to retaining a certain quantity of fluoresceine by ionic exchange. There is also a possibility that the flow is dispersed through a network of small conduits and pores, due to the permeability of the gypsiferous matrix. Finally, we cannot discount the possible existence of a deep-level input which, in this case, would be responsible for the variation in the flow and the chemical composition. This set of suppositions, as a whole, would explain the fact that the response of the spring to tracing is so irregular, even though we cannot achieve a definition of the qualitative influence of each one on the hydrodynamics of the system.
In order to verify some of the above hypotheses, particularly those referring to the process of condensation within cavities, an experiment was designed, consisting of a microtracing test at some points where condensation had been detected within the Cueva del Agua at Sorbas. The test produced a range of condensation flow speed values of 0.2 to 30 cm/hour and shows that, in those sections where the presence of condensation flow is visually apparent, there is a rapid dispersion of the colourant. However, it also shows that at points where there is no apparent condensation the process also occurs, but at a lower rate of efficiency. The importance of condensation within cavities has two aspects; firstly, speleogenetic, with the development of solution forms (cupolas) and deposit forms (capillarity boxwork); and secondly, hydrogeological, as this is the reason why certain processes (strong changes in temperature and humidity, multiple routes of airflow exchange with the exterior) may in themselves constitute a hydraulic contribution, of slight importance, but sufficient to explain a large part of the base flow (0.2 - 0.8 L/s) of a whole cavity system such as the Cueva del Agua in semiarid conditions.
With the intention of completing the analyses carried out in various karsts in gypsum, instruments were installed in the Cueva del Agua at Sorbas to measure, by continuous registration, some important physico-chemical parameters that might provide additional data on the hydro-geologic behaviour of this gypsiferous karst, especially at the level of the epikarstic zone. The parameters of temperature and water conductivity were considered most important, due to their singular behaviour patterns. During the experiment there were two periods of rainfall that modified the chemistry of the cavity, one of 30 mm in two days and another of 200 mm (almost the annual total) in four days. In the second case, which was much more extreme, a very significant increase in water temperature (up to 7 °C during the initial period of high water flow) was detected, while conductivity fell. But suddenly, when the minimum conductivity was reached, the temperature dropped sharply by 6-7 °C to return to the base temperature of the cavity. Subsequently, the temperature again stabilized at about 7 °C above the data recorded during the dry period. This behaviour pattern was not detected when the rainfall was slight. The explanation for this dual behaviour observed is fundamentally based on the quantity of rainfall and on the differences between the exterior air temperature, the temperature of interstitial water and the temperature recorded in the spring during high water flow. When water temperature in the cavity during high water flow is higher than the base temperature recorded in the period immediately before, it means that the interstitial water does not mobilize. However, when at any time the two temperatures coincide, one might suppose that there might have existed a process of mobilization of the water previously resident in the rock, by a piston effect, but in the unsaturated zone. On the other hand, the temporal variations of these parameters during the months following periods of high rainfall have enabled us to detect the existence of distinct periods during the return to normal cavity conditions. By carefully examining the decrease curve of water temperature inside the cavity while conductivity regained its maximum stable value, two periods may be differentiated. The first may be termed the "inertial influence period", when the rainfall occurring removes all signs of natural variation in the cavity. Thus, the daily external influences are not clearly detectable and the curve is downward-sloping and asymptotic with no significant oscillations. In the second period, which ends with the total stabilization of the parameter at the level of the initial conditions, the asymptotic descent is seen to be affected by daily temperature variations. This is termed the "inertial recovery period", during which external variations start to have an effect on the interior of the cavity such that there is a progressive increase in the amplitude of the daily variation in water temperature, air temperature and relative humidity. This behaviour pattern of variation of these parameters during periods of high rainfall, might be extended to all karstic systems, varying only in magnitude and temporal extent.


La conservation des grottes ornees: un probleme de stabilite d'un systeme naturel (l'exemple de la grotte prehistorique de Gargas, Pyrenees francaises), 1999,
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Mangin Alain, Bourges Francois, D'hulst Dominique,
Painted caves are karstic cavities here considered as stable physical systems in a state of dynamic equilibrium. From the example of the Gargas cave, we show that introduction of excess energy (visitors, lighting) causes a loss of stability and introduces a risk of degradation in the cavity. From different approaches, we identify the periods and the causes of instability and we determine the maximum level of introduced energy which would preserve the conservative properties of the cavity. These results allow cave equipment and visitor capacity compatible with satisfactory conservation conditions to be defined.ResumeLes grottes ornees sont des cavites karstiques considerees comme des systemes physiques stables en etat d'equilibre dynamique. Nous montrons, a partir de l'exemple de la grotte de Gargas, que l'introduction d'une energie excedentaire (visiteurs, eclairage) destabilise le systeme naturel, determinant ainsi un risque de degradation dans la cavite. Differentes approches permettent d'identifier les periodes et les causes de la destabilisation et de determiner le niveau maximum d'energie introduite permettant le maintien du pouvoir conservatoire de la cavite. Ces resultats permettent de definir des amenagements et un niveau de frequentation compatible avec des conditions de conservation satisfaisantes

The inhibiting action of intrinsic impurities in natural calcium carbonate minerals to their dissolution kinetics in aqueous H2O-CO2 solutions, 1999,
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Eisenlohr L, Meteva K, Gabrovsek F, Dreybrodt W,
We have measured the surface controlled dissolution rates of natural calcium carbonate minerals (limestone and marble) in H2O-CO2 solutions by using free drift batch experiments under closed system conditions with respect to CO2, at 10 degrees C with an initial partial pressure of carbon dioxide of 5.10(-2) atm. All experiments revealed reaction rates F, which can be described by the empirical relation: F-n1 = k(n1) . (1 - c/c(eq))(n1) for c < c(s), which switches to a higher order n(2) for calcium concentrations c greater than or equal to c(s) described by F-n2 = k(n2) . (1 - c/c(eq))(n2) . k(n1) and k(n2) are rate constants in mmole/(cm(2) . s), c(eq) is the equilibrium concentration with respect to calcite. The values of the constants n(1), n(2), k(n1), k(n2) and c(s) depend on the V/A ratio employed, where V is the volume of the solution and A is the surface area of the reacting mineral. Different calcium carbonate minerals exhibit different values of the kinetic constants. But generally with increasing V/A, there is a steep variation in the values of all kinetic constants, such that the rates are reduced with increasing V/A ratio. Finally with sufficiently large V/A these values become constant. These results are explained by assuming intrinsic inhibitors in the bulk of the mineral. During dissolution these are released from the calcite matrix and are adsorbed irreversibly at the reacting surface, where they act as inhibitors. The thickness d of the mineral layer removed by dissolution is proportional to the VIA ratio. The amount of inhibitors released per surface area is given by d c(int), where c(int) is their concentration id the bulk of the mineral. At low thicknesses up to approximate to 3 . 10(-4) cm in the investigated materials, the surface concentration of inhibitors increases until saturation is attained for thicknesses above this value. To analyze the surface concentration and the type of the inhibitors we have used Auger spectroscopy, which revealed the presence of aluminosilicate complexes at the surface of limestone, when a thickness of d approximate to 10(-3) cm had been removed by dissolution. In unreacted samples similar signals, weaker by one order of magnitude, were observed. Depth profiles of the reacted sample obtained by Ar-ion sputtering showed the concentration of these complexes to decrease to the concentration observed in the unreacted sample within a depth of about 10 nm. No change of the concentration with depth was observed in unreacted samples. These data suggest that complexes of aluminosilicates act as inhibitors, although other impurities cannot be excluded. Copyright (C) 1999 Elsevier Science Ltd

The use of alkalinity as a conservative tracer in a study of near-surface hydrologic change in tropical karst, 1999,
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Chandler Dg, Bisogni Jj,
Water shortages commonly increase in frequency following forest clearance on lauds overlying karst in the tropics. The mechanism underlying this hydrologic change is likely to depend on the land use which follows forest cover. To determine the flow paths which prevail for a progression of land uses common to the uplands of Leyte, Philippines, samples of interflow were collected during the rainy season and titrated to determine their alkalinities. The ratio of the measured alkalinity to the value predicted by equilibrium calculations for each sample was used as an indication of the contact time of the water with the limestone. The responses of the alkalinity saturation ratio and the runoff depth to increasing rainfall depth were used to substantiate the hypothesis that epikarst infilling and changing soil structure create throttles to percolation and infiltration. The forest site was found to generate interflow primarily as pipe how, with the infiltration and percolation throttles rarely exceeded. Similarly, infiltration was not: limiting for the slash/mulch Site, however, level of soil disturbance was adequate to initiate a throttle at the epikarst which increased the volume of interflow generated. The total percolation was similar for the plowed and slash/mulch sites; however, the interflow was decreased at the plowed site by reduced infiltration at the soil surface. The throttles to surface infiltration and epikarst percolation were even greater at the pasture sites, resulting in high runoff generation. However, comparatively greater infiltration was observed in the pasture having contour-hedgerows. (C) 1999 Elsevier Science B.V. All rights reserved

A model of early evolution of karst conduits affected by subterranean CO2 sources, 2000,
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Gabrovsek F, Menne B, Dreybrodt W,
In investigating early karstification of one-dimensional conduits by computer models, so far one has assumed that the CO2 content of the calcite aggressive water stems entirely from the surface. Subterranean sources of CO2, however, can rejuvenate the solutional power of water already close to equilibrium with respect to calcite, and boast dissolution rates. In a first scenario we have investigated the influence of a punctual source of CO2 as the most simple case of release of CO2 into a karstifiable fracture at some position KL from its entrance of the widening joint with length L, (K < 1). The results show that only a small increase of the p(CO2) in the solution to about 0.01 atm is sufficient to reduce the breakthrough times to about 0.3 with respect to the case, where no CO2 is delivered. Other sources of CO2 are due to the metabolic activity of microorganisms. The existence of such diverse subterraneous microbial life in karst systems demonstrated. Whether situated on the fissure surfaces or free floating in the karst water, one basic product of their metabolism is CO2. This contributes over the whole flow path to the p(CO2) of the karst water. Therefore in a second scenario we assumed a constant rate of CO2-input along parts of the fracture, as could be delivered by the activity of aerobic bacteria dwelling at its walls. Such a scenario also applies to an extended diffuse CO2 migration from volcanic activity deep underground. In this case drastic reductions of the breakthrough time by about one order of magnitude are observed. These reductions are enhanced when the fracture aperature width of the initial fracture decreases. The physicochemical mechanisms of enhancement of karstification are discussed in detail by considering the evolution of the fracture aperature width and of the dissolution rates in space and time

Depositional Facies and Aqueous-Solid Geochemistry of Travertine-Depositing Hot Springs (Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, U.S.A.), 2000,
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Fouke Bw, Farmer Jd, Des Marais Dj, Pratt L, Sturchio Nc, Burns Pc, Discipulo Mk,
Petrographic and geochemical analyses of travertine-depositing hot springs at Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, have been used to define five depositional facies along the spring drainage system. Spring waters are expelled in the vent facies at 71 to 73{degrees}C and precipitate mounded travertine composed of aragonite needle botryoids. The apron and channel facies (43-72{degrees}C) is floored by hollow tubes composed of aragonite needle botryoids that encrust sulfide-oxidizing Aquificales bacteria. The travertine of the pond facies (30-62{degrees}C) varies in composition from aragonite needle shrubs formed at higher temperatures to ridged networks of calcite and aragonite at lower temperatures. Calcite 'ice sheets', calcified bubbles, and aggregates of aragonite needles ('fuzzy dumbbells') precipitate at the air-water interface and settle to pond floors. The proximal-slope facies (28-54{degrees}C), which forms the margins of terracette pools, is composed of arcuate aragonite needle shrubs that create small microterracettes on the steep slope face. Finally, the distal-slope facies (28-30{degrees}C) is composed of calcite spherules and calcite 'feather' crystals. Despite the presence of abundant microbial mat communities and their observed role in providing substrates for mineralization, the compositions of spring-water and travertine predominantly reflect abiotic physical and chemical processes. Vigorous CO2 degassing causes a unit increase in spring water pH, as well as Rayleigh-type covariations between the concentration of dissolved inorganic carbon and corresponding {delta}13C. Travertine {delta}13C and {delta}18O are nearly equivalent to aragonite and calcite equilibrium values calculated from spring water in the higher-temperature ([~]50-73{degrees}C) depositional facies. Conversely, travertine precipitating in the lower-temperature (<[~]50{degrees}C) depositional facies exhibits {delta}13C and {delta}18O values that are as much as 4{per thousand} less than predicted equilibrium values. This isotopic shift may record microbial respiration as well as downstream transport of travertine crystals. Despite the production of H2S and the abundance of sulfide-oxidizing microbes, preliminary {delta}34S data do not uniquely define the microbial metabolic pathways present in the spring system. This suggests that the high extent of CO2 degassing and large open-system solute reservoir in these thermal systems overwhelm biological controls on travertine crystal chemistry

Equilibrium chemistry of karst water in limestone terranes, 2000,
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Dreybrodt W.
This chapter summarizes the equilibria of the chemical reactions occurring in CaCO3 - H2O - CO2 solutions, as they are typical for karst water. The evolution of the chemical composition of such solutions during their interaction with limestone depends on specific geological conditions, such as dissolution proceeding under the conditions of the open or closed system with respect to CO2. Since the CO2 concentration in karst water determines its further chemical evolution and the equilibrium concentration of Ca 2+ with respect to calcite in all cases of interest, equations are derived which describe the evolution of the chemical composition in the most general case, i.e. when a limited volume of gaseous CO2 is in contact with a solution dissolving limestone. This includes the cases of open and closed system with respect to CO2 as end members. Finally we discuss the influence of foreign ions common in karst, such as Mg 2+, SO4 2-, Na + and Cl - to the equilibrium concentration of dissolved Ca 2+ ions with respect to calcite.

Chemical and physical controls on waters discharged from abandoned underground coal mines, 2001,
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Lopez D. L. , Stoertz M. W. ,
Abandoned up-dip drift mines in high-sulphur coal are a major source of acid mine drainage (AMD) in Appalachia. Studies of mines in the Monday Creek watershed of southeastern Ohio show that mines are recharged by surface runoff into subsidence features that dilate the natural stress-relief fracture system. The direct connection between the ground surface and the mines leads to a rapid response in the hydrograph, with a one- to four-day lag between precipitation and corresponding peak mine discharge. Subsidence occurs in topographic depressions where overburden is presumably relatively thin. Subsidence features drain 20-36% of the surface area. Unsaturated storage appears to be volumetrically insignificant, so that far more recharge occurs than the 5% often assumed for this region. Mine storage can change rapidly due to subsidence recharge. Hydrologically, mines with subsidence features behave like karst systems, with meteoric quickflow' representing more than 50% of the total flow. Mine discharge concentrations are relatively uniform through time, suggesting either equilibrium controls on chemistry or drainage of a well-mixed pool, or both. Evidence of dilution by high flows is slight. The first high flows after a baseflow period show only a slight increase in concentrations, attributed to flushing of stored reaction products. Loadings (concentrations x flow) depend on volumetric discharge and as a consequence are highly variable. The Eh/pH environment in up-dip drift mines indicates that mine waters are in contact with the atmosphere at least part of the time, unlike a true groundwater. Iron buffering partly controls pH, which clusters around values of 3.6-5.0

Recent active faults in Belgian Ardenne revealed in Rochefort Karstic network (Namur Province, Belgium), 2001,
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Vandycke S. , Quinif Y. ,
This paper presents observations of recent faulting activity in the karstic network of the Rochefort Cave (Namur Province, Belgium, Europe). The principal recent tectonic features are bedding planes reactivated as normal faults, neo-formatted normal faults in calcite flowstone, fresh scaling, extensional features, fallen blocks and displacement of karstic tube. The seismotectonic aspect is expanded by the presence of fallen blocks where normally the cavity must be very stable and in equilibrium. Three main N 070degrees fault planes and a minor one affect, at a decimetre scale, the karst features and morphology. The faults are still active because recent fresh scaling and fallen blocks are observable. The breaking of Holocene soda straw stalactites and displacements of artificial features observed since the beginning of the tourist activity, in the last century, also suggest very recent reactivation of these faults. This recent faulting can be correlated to present-day tectonic activity, already evidenced by earthquakes in the neighbouring area. Therefore, karstic caves are favourable sites for the observation and the quantification of recent tectonic activity because they constitute a 3-D framework, protected from erosion. Fault planes with this recent faulting present slickensides. Thus a quantitative analysis in term of stress inversion, with the help of striated faults, has permitted to reconstruct the stress tensor responsible for the brittle deformation. The principal NW-SE extension (sigma(3) horizontal) is nearly perpendicular to that of the present regional stress as illustrated by the analysis of the last strong regional earthquake (Roermond, The Netherlands) in 1992. During the Meso-Cenozoic, the main stress tectonics recorded in this part of the European platform is similar to the present one with a NE-SW direction of extension. The discrepancy between the regional stress field and the local stress in the Rochefort cave can be the result of the inversion of the sigma(2) and sigma(3) axes of the stress ellipsoid due to its symmetry or of a local modification at the ground surface of the crustal stress field as it has been already observed in active zones

Origin of iron-rich Mississippi Valley-type deposits, 2001,
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Marie James St, Kesler Stephen E. , Allen Cameron R. ,
The abundance of iron in Mississippi Valley-type lead-zinc deposits and districts varies greatly; some deposits contain large amounts and others are almost free of iron. Iron in Mississippi Valley-type deposits is largely paragenetically early pyrite or marcasite that was replaced by sphalerite and galena, often in the central part of the deposit or district. Sedimentary exhalative and Irish-type base metal deposits, which also form from basinal brines, have similar variations in iron content. Calculated metal contents of brines in equilibrium with galena, sphalerite, and pyrite show that iron is significantly more abundant than lead and zinc in high-temperature (>200 {degrees}C), relatively acid brines with low sulfur contents, whereas zinc dominates under most other conditions, including brines with high temperatures and high sulfur contents. These results suggest that iron-rich Mississippi Valley-type deposits form from brines expelled from the deepest, hottest parts of sedimentary basins

Hydrochemistry of the Cesme geothermal area in western Turkey, 2001,
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Gemici U, Filiz S,
Hydrochemical characterization of thermal waters discharged from springs and wells in the Cesme geothermal area show that there are two groups. One is of thermal waters from a lower aquifer composed of Triassic karst limestones, which are the main potential reservoir of the area. They are of Na-Cl type and between 37 and 62degreesC and have total dissolved solids (TDS) with around 35 000 mg/l. The other group are thermal waters derived from an upper aquifer formed by Neogene terrestrial sediments. These have lower discharge temperatures (37-40degreesC) and lower TDS values due to their having mixed with local groundwater before emerging. The isotopic and chemical data shows that the initial aqueous solution is a mixture of modern seawater and meteoric water in various proportions. Enrichment in delta(18)O and deltaD values and tritium contents (8 1 TU) of thermal waters reflect a rapid circulation and the contribution of modern seawater. The thermal waters are undersaturated with respect to gypsum but oversaturated, or around equilibrium, with respect to dolomite and calcite. Several chemical geothermometry techniques applied to Cesme geothermal waters gave estimated reservoir temperatures of around 85-100degreesC. (C) 2001 Elsevier Science B.V. All rights reserved

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