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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 dating of cave sediments is determination of the age of development of caves is normally impossible. only the sediments they contain can be dated, and these must necessarily be younger than the containing passage. geomorphological correlations may allow more accurate dating of the cave erosion. the most useful dating method in current use is based upon a knowledge of the rates of decay of radioactive isotopes of uranium to thorium in stalagmites. this technique allows measurement of ages in material up to 350,000 years old. dating of stalagmites has confirmed that many cave ages lie beyond this range. electron spin resonance (esr) measures the cumulative effects of radiation that are partly a function of time and can give stalagmite ages back to about 900,000 years. palaeomagnetism may recognize events up to 2 million years old, but a sequence of palaeomagnetically dated sediments is required to allow identification of the actual ages [9].?

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Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
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Geochemical and mineralogical fingerprints to distinguish the exploited ferruginous mineralisations of Grotta della Monaca (Calabria, Italy), Dimuccio, L.A.; Rodrigues, N.; Larocca, F.; Pratas, J.; Amado, A.M.; Batista de Carvalho, L.A.
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
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Your search for chloride (Keyword) returned 58 results for the whole karstbase:
Showing 1 to 15 of 58
The role of tributary mixing in chemical variations at a karst spring, Milandre, Switzerland, , Perrin J. , Jeannin P. Y. , Cornaton F. ,
SummarySolute concentration variations during flood events were investigated in a karst aquifer of the Swiss Jura. Observations were made at the spring, and at the three main subterraneous tributaries feeding the spring. A simple transient flow and transport numerical model was able to reproduce chemographs and hydrographs observed at the spring, as a result of a mixing of the concentration and discharge of the respective tributaries. Sensitivity analysis carried out with the model showed that it is possible to produce chemical variations at the spring even if all tributaries have constant (but different for each of them) solute concentrations. This process is called tributary mixing. The good match between observed and modelled curves indicate that, in the phreatic zone, tributary mixing is probably an important process that shapes spring chemographs. Chemical reactions and other mixing components (e.g. from low permeability volumes) have a limited influence.Dissolution-related (calcium, bicarbonate, specific conductance) and pollution-related parameters (nitrate, chloride, potassium) displayed slightly different behaviours: during moderate flood events, the former showed limited variations compared to the latter. During large flood events, both presented chemographs with significant changes. No significant event water participates in moderate flood events and tributary mixing will be the major process shaping chemographs. Variations are greater for parameters with higher spatial variability (e.g. pollution-related). Whereas for large flood events, the contribution of event water becomes significant and influences the chemographs of all the parameters. As a result, spring water vulnerability to an accidental pollution is low during moderate flood events and under base flow conditions. It strongly increases during large flood events, because event water contributes to the spring discharge

The Use of Titanium Tetrachloride In The Visualisation Of Air Movement In Caves, 1971, Halbert E. J. , Michie N. A.

The problems concerned with the visualisation of low-velocity air flow in caves are discussed. The behaviour of several chemical tracers in the Mammoth Cave, Jenolan, New South Wales, is described, in particular that of the compound titanium tetrachloride. A suitable method for the transport and use of this compound has been developed.


Hydrogeological investigations into discharge of salt-containing water from a stream into an aquifer., 1976, Neuss Matthias
An aquifer in a horseshoe bend of the Weser river was investigated regarding the processes of the river water infiltration. The geology and geometry of the aquifer was ascertained by means of numerous borings. The hydraulic situation before and after infiltration was determined by water table maps. The intrusion of a salt-freshwater lens could be reconstructed from the beginning of infiltration until ten years later by means of previous results of chemical analysis. By new chemical analysis it was proved that river water infiltrates into the aquifer. Additionally it was established that the relatively high concentration of chloride is reduced during the passage of the groundwater both by mixing with recharged groundwater and by adsorption of the ground. Furthermore temperature measurements in the groundwater at selected stations confirm qualitatively the river water infiltration into the polder.

The sulfate speleothems of Thampanna cave, Nullarbor Plain, Australia, 1991, James, Julia M.

Examination of gypsum speleothems and chemical analysis of the cave drip waters (ions to chloride mole ratios, tot. dissolved solids, nitrate) confirm that the major source of the sulfate in Thampanna cave (Western Australia) is from seawater transported by rain.


WATER-BUDGET, FUNCTIONING AND PROTECTION OF THE FONTAINE-DE-VAUCLUSE KARST SYSTEM (SOUTHEASTERN FRANCE), 1992, Blavoux B, Mudry J, Puig Jm,
The karst aquifer of the well-known Fontaine de Vaucluse has been recently studied, results have been got about delimitation of the system and its working. Geological data (lithology and structure) have allowed to delimit an 1115 Km2 intake area including Ventoux-Lure north facing range (1,909-1,826 m) and the Plateau which is prolonging it southwards (Fig. 1 and 2). The average altitude of the whole area, obtained by balancing elevation belt surfaces, is about 870 m. This elevation squares with results of tracing tests (Fig. 3), environmental physical, chemical and isotopic tracings, that allow to value a 850 m average altitude for the intake area (Fig. 4). The moisture balance has been computed from an altitude belts climatic model, using local rain an temperature gradients (Fig. 5 and Table II), because the weather network is not representative. So, rainfalls rise of about 55 mm per 100 m elevation and temperature decreases of about 0.5-degrees-C per 100 m. The consequence of these two antagonist phenomena is the quasi constant value of actual evapotranspiration on each altitude belt. With the Fig. 7 organigram, curves of effective rainfalls and infiltration coefficient versus elevation can be plotted (Fig. 6). This computation shows that 3/4 of the total and the whole of dry season effective rainfalls are provided by the part of the intake area situated above the average altitude: on the lowest belt, effective rainfalls are only 120 mm per year and increase to 1380 mm on the upper section (Fig. 8 and Table 1). The weighted effective rainfalls are about 570 mm per year for the whole intake area. Hydrodynamical and physico-chemical studies show, despite its large size, the weak inertia of the system, so proves its good karstification, that confirms for the whole system the pin-point speleological observations. The discharge of the spring, which average value is 21 m3.s-1 (only 18 for the last ten years), can exceed 100 m3.s-1 and the minimum has never been lower than 3.7 m3.s-1 (Fig. 9). When it rains on the intake area, the increase of the discharge is very sudden in a rainy period : one to four days. This short delay is due to seepage through epikarst and unsaturated zone. During dry periods, the spring reaction is deadened, due to storage in the unsaturated zone. The silica content distribution was plotted during several hydrokinematical phases (Fig. 10). It shows: an almost unimodal distribution for the 8 km2 fissured limestone aquifer of Groseau; a multimodal one for the 1115 km2 karst aquifer of Fontaine de Vaucluse. This proves that karstification is more important than size in the response of the system. Weak summer rainfalls do not influence the discharge, nevertheless they influence chemistry of the spring water, and so interrupts the water depletion phasis. Then, the decrease of discharge can continue after the end of the chemical depletion phasis, water which is overflowing after summer rainfalls (in a dry period) is influenced hy the chemistry of seepage water : on the graph of a principal components analysis, done on chemical variables. an hysteresis phenomenon can be seen (Fig. 11). A discriminant analysis (Fig. 12) confirms that these autumn waters, with high ratio seepage tracers, are not reserve waters from the saturated zone. The ratio of reserve water in the total discharge, is preponderant: 3/4 and 2/3 respectively of the yearly runoff volumes for 1981 and 1982 (Fig. 13), but an important part of these reserves can be stored in the unsaturated zone. This storage capacity can be valued by different means: transposing to Vaucluse (1115 km2) the volume measured on another karst system in the Pyrenees (13 km2); it gives about 100 million m2; using setting parameters of Bezes model (1976) on the same aquifer: it gives 113 million m3; using depletion curves, that show, for instance during the 1989 summer and autumn dry period, a 80 million m3 volume. In all cases, we get a value of about one hundred million m3 for the storage capacity of the unsaturated zone. With a 20 m range of fluctuation for the water table and with a 10(-2) specific yield, on a 500 to 1,000 km2 saturated zone, the zone of fluctuation can release about 10 to 20 million m3. Then, the volume of water stored in the whole saturated zone, with a 300 m minimum thickness (depth of the waterlogged pit of the Fontaine), a 500 km2 minimum surface and a 10(-3) specific yield, is about 150 million m3, including 27 million m3 stored in the channels. So, the unsaturated zone represents a significant part of the whole storage capacity and most of the yearly renewable reserves. Paradoxically, the biggest french spring is not tapped at all; as its intake area is neither a regional nor a national park, no general protection covers it : because of its good karstification, the vulnerability of the system is important. Good quality of water is attributable to the low population and human activities density on the intake area (4 inh.km-2). A great part of the intake area is uncultivated (large forest and ''garrigues'' areas). Due to the lack of surface water and scantness of soils, agriculture is not intensive (lavender, thyme, sage and bulk wheat fields. meadowlands). On the mountainous zone, roads are salted in winter and snowmelt water can reach a significantly high chloride ratio than in a natural climatic functioning (for instance 25 mg.l-1 in Font d'Angiou where the ratio would have been 3 mg.l-1). As tourism is developing both on the mountain and on the plateau, the management of the highest intake area must be carefully held: its part is preponderant in the feeding of the system

Convolution a debit variable a partir des reponses de tracages artificiels; application a un systeme karstique (Causse de Gramat, Lot, France): Convolution in time-dependent system from artificial tra, 1995, Dzikowski M, Delay F, Sauty Jp, Crampon N, De Marsily G,
ResumeLa realisation de tracages artificiels dans des conditions hydrodynamiques differentes sur le systeme karstique de I'Ouysse (Causse de Gamat, France) ainsi que de mesures physicochimiques portant entre autres sur les chlorures, nitrates et matieres en suspension ont permis d'exploiter les possibilites de l'analyse des systemes-tracages dependant du temps. Pour des tracages artificiels realises a des periodes hydrologiques differentes (basses-eaux et hauteseaux), les relations entre les reponses impulsionnelles a l'injection instantanee de traceur et les debits d'ecoulement variables associes sont mises en evidence sur un systeme a deux entrees (pertes de Themines et Theminettes) et une sortie (gouffre de Besaces). Ces relations etablissent une independance entre l'espace occupe par le traceur au cours de son transfert et les conditions hydrodynamiques dans la gamme de debits interessant chaque tracage. Des operations de convolutions d'entrees en chlorures, nitrates et matieres en suspension, basses sur l'hypothese d'un systeme a volume constant dependant du temps ont donc pu etre realisees. Les resultats sont compares au mesures experimentales au point de sortie (Besaces).AbstractArtificial tracer tests conducted under different hydrodynamic conditions on the karst system of Ouysse (Causse de Gramat, France) and chemical measurements have permitted the use of the time-dependent tracer test analysis. For artificial tracer experiments in different hydrologic periods (water rise and high flow), the relationships between the responses to an instantaneous injection are improved in a system defined by two inputs (losses of Themines and Theminettes). They show that the space occupied by the mass of tracer during its transfer can be considered as independent of the discharge according to the range of flow rate in which the tracer experiments have been conducted. Therefore, convolutions on chlorides, nitrates and suspended sediments are simulated under the hypothesis of a constant-volume and time-dependent system. The computed results are compared with the experimental data at the output (cave of Besaces)

Sulphate rocks as an arena for karst development., 1996, Andrejchuk Vjacheslav, Klimchouk Alexander
The rocks in which karst systems develop are most commonly composed of carbonate sulphate and chloride minerals. The sulphate minerals are quite numerous, but only gypsum and anhydrite form extensive masses in sedimentary sequences. Other minerals, which represent sulphates of K, Mg and Na, normally occur as minor beds (0.1-5.0 m), or as inclusions associated with chloride rocks. However some minerals precipitated in salt-generating basins, such as mirabilite and glauberite (typically formed in the Kara-Bogaz-Gol Gulf, salt lakes of Siberia and in China), form sequences up to 5-10 m thick where karst may develop. Due to the very high solubility of Na -sulphates, karst processes and features occurring in these rocks resemble salt karst. Thus, the term sulphate karst, although not strictly correct, is used mainly to indicate karst developed in gypsum and anhydrite.

Sea water intrusion in coastal karst springs: Example of the Blaz spring (Croatia), 1997, 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

Spatial differentiation of the chloride ion concentration in seepage water from the Zakrzwek quarry (Cracow region, S Poland). [in French], 1998, Motyka Jacek, Postawa Adam

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

Contribution to knowledge of gypsum karstology, PhD thesis, 1998, 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.


Basic phyisico-chemical Karst water properties on Notranjsko, 1998, Kogovš, Ek Janja

In 1986 and 1987 seven series of samples were taken at 36 to 47 sampling points on Babno, Loško and Cerkniško Polje and on Bloke and at Loški potok in order to find out their physico-chemical properties and their quality. Rainwater flows from the limestone and dolomite landscape around Babno, Loško and Cerkniško polje into springs feeding the sinking streams. The nitrate level at most of the springs was below 4 mg NO3-/l and chloride below 5 mg Cl-/l; the o-phosphate level varied around the value of 0.05 mg PO43-/l. The bacteriological analyses of the spring waters showed that they are not of drinking quality and only few springs were seasonally of good quality. Poorer quality was found in springs with populated catchments, such as are Pudobski Izvir, Podgorski and Mežnarjev Studenec and, obviously in all the sinking waters at swallow-holes where the nitrate and chloride level was up to 20 mg/l and phosphate up to 5 mg/l. Flowing over karst poljes this water receives pollution due to habitations and industry. As the water of these sinking streams reappears downstream in several lower-lying karst poljes this results in the transport and accumulation of pollution downstream even in springs that are captured for water supply.


Agricultural use and water quality at karstic Cuban western plain, 1999, Castillo Juan Reynerio Fagundo, Hernandez Patricia Gonzlez
In the paper some results of studies on the karstic aquifers of the western plain of Cuba are presented and discussed. The intensive exploitation of these aquifers for agriculture use and drinking water supply induces an increase of marine water intrusion, water salinisation and a progressive increase of chemical corrosion with a greater dissolution of carbonates. During the period of study (1983-1998) a trend in the deterioration of water quality was observed by means of a chronological series of hydrochloride content.

Hydrochemical evidence for mixing of river water and groundwater during high-flow conditions, lower Suwannee River basin, Florida, USA, 1999, Crandall Ca, Katz Bg, Hirten Jj,
Karstic aquifers are highly susceptible to rapid infiltration of river water, particularly during periods of high flow. Following a period of sustained rainfall in the Suwannee River basin, Florida, USA, the stage of the Suwannee River rose from 3.0 to 5.88 m above mean sea level in April 1996 and discharge peaked at 360 m(3)/s. During these high-now conditions, water from the Suwannee River migrated directly into the karstic Upper Floridan aquifer, the main source of water supply for the area. Changes in the chemical composition of groundwater were quantified using naturally occurring geochemical tracers and mass-balance modeling techniques. Mixing of river water with groundwater was indicated by a decrease in the concentrations of calcium, silica, and Rn-222; and by an increase in dissolved organic carbon (DOC), tannic acid, and chloride, compared to low-flow conditions in water from a nearby monitoring well, Wingate Sink, and Little River Springs. The proportion (fraction) of river water in groundwater ranged from 0.13 to 0.65 at Wingate Sink and from 0.5 to 0.99 at well W-17258, based on binary mixing models using various tracers. The effectiveness of a natural tracer in quantifying mixing of river water and groundwater was related to differences in tracer concentration of the two end members and how conservatively the tracer reacted in the mixed water. Solutes with similar concentrations in the two end-member waters (Na, Mg, K, Cl, SO4, SiO2) were not as effective tracers for quantifying mixing of river water and groundwater as those with larger differences in end-member concentrations (Ca, tannic acid, DOC, Rn-222, HCO3)

Geochemistry of Carlsbad Cavern Pool Waters, Guadalupe Mountains, New Mexico, 2000, Forbes, J. R.
Water samples collected from 13 pools in Carlsbad Cavern were analyzed to determine the concentrations of major ions. Air temperature, relative humidity, and carbon dioxide concentration of the cave atmosphere were also measured. Large differences in water quality exist among different cave pools, with some pools containing very fresh water, while others are brackish, with total dissolved solids concentrations up to 5000 mg/L. Brackish water pools appear to be associated with those portions of the cave where evaporation rates are high and/or soluble minerals are present. Geochemical speciation modeling showed that some pools are close to saturation with respect to the common cave minerals aragonite, calcite, gypsum, and hydromagnesite. A tracer test was performed using a non-toxic bromide salt to estimate the leakage rates of selected pools. Pool volumes calculated based on dilution of the bromide tracer were up to 550 m. The tracer test results were used to calculate mean residence times for the water in each pool. Calculated mean residence times based on bromide tracer loss rates ranged from less than a year for Rookery Pool and Devils Spring to 16 years for Lake of the Clouds. Calculated pool leakage rates ranged from 2 L/day to over 100 L/day. The pools with the highest leakage rates appear to be Rookery Pool, Green Lake, and Lake of the Clouds. The long residence times indicated by the tracer tests suggest that the pools evaporate more water than they leak. However, evaporation should result in an accumulation of dissolved chloride and other solutes in the pools, which for most pools does not appear to be the case. Taken together, these observations suggest that the pools are recharged primarily by infrequent precipitation events, separated by long periods of slow evaporation and minimal leakage.

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