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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 well is 1. a shaft or hole sunk into the earth to obtain water, oil, gas, or minerals [10]. 2. a deep vertical rounded hole or shaft in the floor of a cave or at the bottom of a closed depression [10]. 3. a bored, drilled or driven shaft, or a dug hole, whose depth is greater than the largest surface dimension [22].?

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Karst environment, Culver D.C.
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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 sulphate reduction (Keyword) returned 9 results for the whole karstbase:
Spheroidal dolomites in a Visean karst system - Bacterial induced origin?, 1997, Nielsen P. , Swennen R. , Dickson J. A. D. , Fallick A. E. , Keppens E. ,
Spheroidal dolomite crystals occur in the karstified top of a Dinantian dolomite sequence in eastern Belgium. The spheroidal dolomite crystals are best developed at the base of the karst system. The dolomite crystals are characterized by a spherulitic or dumb-bell inclusion pattern, and are overgrown by dolomite cements with a rhombohedral outline. They are considered to be bacterially related precipitates based on, (1) textural similarities with documented bacteriogenic precipitates, (2) the presence of 'bacterial' microspheres and framboidal pyrite embedded within the dolomite, and (3) their general geological setting. The geochemical characteristics of the dolomites and associated minerals support a bacterial origin. The ubiquity of framboidal pyrite, depleted in S-34 (delta(34)S = - 22.4 to - 25.5 parts per thousand CDT), testifies to a period of bacterial sulphate reduction. The isotopic composition of the spheroidal dolomites (delta(13)C = - 2.4 to - 3.2 parts per thousand PDB and delta(18)O = - 3.8 to - 3.4 parts per thousand PDB) suggest a contribution from oxidized organic carbon produced during bacterial sulphate reduction. Sulphate reduction may also result in a concomitant O-18 depletion if the system is nearly closed. It is however, evident from the sulphur isotopic composition of associated framboidal pyrite that the system was fairly open. The O-18 depletion of the spheroidal dolomite crystals (delta(18)O = - 3.8 to - 3.4 parts per thousand PDB) and their occurrence adjacent to, and within karst cavities suggests a mixing zone origin, with a significant proportion of freshwater in it. The rhombohedral cement-overgrowths have calculated delta(18)O values in the range of 0 to 5.3 parts per thousand PDB, which reflect precipitation from normal to slightly evaporated contemporaneous seawater

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.


Controls on bacterial sulphate reduction in a dual porosity aquifer system: the Lincolnshire Limestone aquifer, England, 2000, Bottrell Sh, Moncaster Sj, Tellam Jh, Lloyd Jw, Fisher Qj, Newton Rj,
Chemical and sulphur isotopic analyses are presented of fissure-waters and pore-waters in the deep confined zone of a dual porosity carbonate aquifer. Some of the fissure-waters show good evidence for bacterial sulphate reduction, with low concentrations of sulphide present which is strongly to moderately depleted in 34S relative to sulphate. The sulphur geochemistry is best interpreted as mixing between: (i) a reduced water with sulphide ~60[per mille sign] depleted in 34S relative to sulphate; and (ii) a sulphate-rich water from up-dip in the aquifer. In addition, sulphide oxidation occurs where sufficiently oxidizing water is drawn in by abstractions. The large isotope fractionation factor associated with the sulphidic waters is probably the result of redox cycling of sulphur with little net reduction, rather than a true kinetic fractionation factor. By contrast, pore-waters in the 'sulphate reducing zone' show little or no evidence for the effects of sulphate reduction, despite the fact that the pore-waters represent a significant reservoir of sulphate for reduction. Some pore-waters have been modified recognizably by diffusional exchange with the fissure-waters, but the aquifer matrix has not been colonized by sulphate reducing bacteria, probably because porethroats in the limestone are too small for bacteria to pass. Physical exclusion of bacteria from the aquifer matrix and limited diffusional exchange are likely to exert fundamental controls on bacterial redox processes in dual porosity aquifer systems and other systems with low permeability due to small pore interconnections

The geochemistry of sulphur in a mixed allogenic-autogenic karst catchment, Castleton, Derbyshire, UK, 2000, Bottrell Sh, Webber N, Gunn J, Worthington Srh,
Analyses are presented of anion chemistry and sulphur isotopic compositions of sulphate in sinking streams and groundwaters in a mixed allogenic-autogenic karst catchment. Using the sulphur isotopic data, sources of sulphate from agriculture and the effects of sulphate reduction arising from slurry application can be distinguished from natural rock weathering sources. Within the aquifer, sulphate in known autogenic waters has isotopic compositions distinct from allogenic waters, the autogenic waters being dominated by sulphate from rainfall and rock weathering in these low agricultural intensity catchments. On this basis, water rising at low flow from Whirlpool Rising, Speedwell Cavern, has been identified as dominantly autogenic. Groundwater flow between the sinks and risings in Speedwell Cavern is believed to be along conduits following mineralized faults (rakes). During transit SO42-/Cl- in the water increases. Isotopic mass balance shows that this must be due to addition of sulphate from the oxidation of ore minerals by groundwater. Mass balance considerations show that the present rate of sulphide oxidation must be the result of enhancement by lead mining operations on the rakes. Copyright (C) 2000 John Wiley & Sons, Ltd

Dolomites in SE Asia -- varied origins and implications for hydrocarbon exploration, 2004, Carnell Ajh, Wilson Mej,
Carbonates in SE Asia range in age from Palaeozoic to Recent, but are most important as reservoirs in the Neogene where they comprise a major target for hydrocarbon exploration (e.g. Batu Raja Formation, South Sumatra, Sunda and Northwest Java basins). Carbonates of pre-Tertiary, Palaeogene and Neogene age all show a strong diagenetic overprint in which dolomite occurs as both cementing and replacive phases associated with variable reservoir quality. This paper reviews published data on the occurrence and types of dolomites in SE Asian carbonates, and considers the models that have been used to explain the distribution and origin of dolomite within these rocks. Pre-Tertiary carbonates form part of the economic basement, and are little studied and poorly understood. Although some, such as in the Manusela Formation of Seram, may form possible hydrocarbon reservoirs, most are not considered to form economic prospects. They are best known from the platform carbonates of the Ratburi and Saraburi groups. in Thailand, and the oolitic grainstones of the Manusela Formation of Seram. The Ratburi Group shows extensive dolomitization with dolomite developed as an early replacive phase and as a late-stage cement. Palaeogene carbonates are widely developed in the region and are most commonly developed as extensive foraminifera-dominated carbonate shelfal systems around the margins of Sundaland (e.g. Tampur Formation, North Sumatra Basin and Tonasa Formation, Sulawesi) and the northern margins of Australia and the Birds Head microcontinent (e.g. Faumai Formation, Salawati Basin). Locally, carbonates of this age may form hydrocarbon reservoirs. Dolomite is variably recorded in these carbonates and the Tampur Formation, for example, contains extensive xenotopic dolomite. Neogene carbonates (e.g. Peutu Formation, North Sumatra) are commonly areally restricted, reef-dominated and developed in mixed carbonate-siliciclastic systems. They most typically show a strong diagenetic overprint with leaching, recrystallization, cementation and dolomitization all widespread. Hydrocarbon reservoirs are highly productive and common in carbonates of this age. Dolomite is variably distributed and its occurrence has been related to facies, karstification, proximity to carbonate margins and faults. The distribution and origin of the dolomite has been attributed to mixing-zone dolomitization (commonly in association with karstic processes), sulphate reduction via organic matter oxidation, and dewatering from the marine mudstones that commonly envelop the carbonate build-up. Dolomite has a variable association with reservoir quality in the region, and when developed as a replacive phase tends to be associated with improved porosity and permeability characteristics. This is particularly the case where it is developed as an early fabric-retentive phase. Cementing dolomite is detrimental to reservoir quality, although the extent of this degradation generally reflects the abundance and distribution of this dolomite. Dolomitization is also inferred to have influenced the distribution of non-hydrocarbon gases. This is best documented in North Sumatra where carbon dioxide occurs in quantities ranging from 0 to 85%. There are a number of possible mechanisms for generating this CO2 (e.g. mantle degassing), although the most likely source is considered to be the widely dolomitized Eocene Tampur Formation that forms effective basement for much of the basin. High heat flows are suggested to have resulted in the thermogenic decomposition of dolomite with CO2 produced as a by-product

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

Carbon and oxygen isotopic composition of the Middle Miocene Badenian gypsum-associated limestones of West Ukraine, 2012, Peryt T. M. , Durakiewicz T. , Peryt D. , Poberezhskyy A.

The middle Miocene Badenian basin of the Carpathian Foredeep is characterized by complex sedimentary and diagenetic carbonate-evaporite transitions. Six locations have been selected to evaluate the controls on the carbonand oxygen isotopic composition of the Badenian gypsum-associated limestones of the Tyras Formation in WestUkraine. At three locations marine limestones overlie the gypsum, at one location (Anadoly) the gypsum-associatedlimestones are polygenic, and at two localities (Pyshchatyntsi and Lozyna) gypsum deposits are lacking. Thestudied limestones have originated as primary, mostly peloidal carbonates as well as secondary carbonates formed by hypogene sulphate calcitisation. They show a wide range of δ13C (from from -0.9‰ to -39.8‰) and δ18O values(from 0.9‰ to -12.2‰). The Badenian limestones formed in marine environments (either as deposits accumulatedat the bottom of the sea or forming the infillings of solution cavities within gypsum) have less negative δ18O values compared to predominantly diagenetic formations. Wide ranges and usually very negative δ13C values andlow δ18O values of those limestones indicate that they suffered important meteoric diagenesis as supported bycommon sparitic fabrics. In addition, a large range of δ13C values even in the group of samples characterized byless-negative δ18O values shows that bacterial sulphate reduction and methane oxidation were active processes inthe pore fluids of the Tyras Formation. Very low carbon isotopic compositions (δ13C values from -22 to -40‰) of some sparitic limestones in the studied sections indicate the occurrence of oxidized methane within the diagenetic environment. Accordingly, the isotopic signatures of the studied limestones are a combination of both primary and secondary processes, the latter having a primordial importance. The common occurrence of similar negative δ13Cand δ18O values in evaporite-related carbonates in other Miocene evaporite basins suggest that extensive dissolution-reprecipitation in diagenetic or vadose-phreatic environments were common in evaporite-related carbonates.


Carbon and oxygen isotopic composition of the Middle Miocene Badenian gypsum-associated limestones of West Ukraine, 2012, Peryt T. M. , Durakiewicz T. , Peryt D. , Poberezhskyy A.

The middle Miocene Badenian basin of the Carpathian Foredeep is characterized by complex sedimentary and diagenetic carbonate-evaporite transitions. Six locations have been selected to evaluate the controls on the carbonand oxygen isotopic composition of the Badenian gypsum-associated limestones of the Tyras Formation in WestUkraine. At three locations marine limestones overlie the gypsum, at one location (Anadoly) the gypsum-associatedlimestones are polygenic, and at two localities (Pyshchatyntsi and Lozyna) gypsum deposits are lacking. Thestudied limestones have originated as primary, mostly peloidal carbonates as well as secondary carbonates formed by hypogene sulphate calcitisation. They show a wide range of δ13C (from from -0.9‰ to -39.8‰) and δ18O values(from 0.9‰ to -12.2‰). The Badenian limestones formed in marine environments (either as deposits accumulatedat the bottom of the sea or forming the infillings of solution cavities within gypsum) have less negative δ18O values compared to predominantly diagenetic formations. Wide ranges and usually very negative δ13C values andlow δ18O values of those limestones indicate that they suffered important meteoric diagenesis as supported bycommon sparitic fabrics. In addition, a large range of δ13C values even in the group of samples characterized byless-negative δ18O values shows that bacterial sulphate reduction and methane oxidation were active processes inthe pore fluids of the Tyras Formation. Very low carbon isotopic compositions (δ13C values from -22 to -40‰) of some sparitic limestones in the studied sections indicate the occurrence of oxidized methane within the diagenetic environment. Accordingly, the isotopic signatures of the studied limestones are a combination of both primary and secondary processes, the latter having a primordial importance. The common occurrence of similar negative δ13Cand δ18O values in 


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