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Community news

Speleology in Kazakhstan

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

New publications on hypogene speleogenesis

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

The deepest terrestrial animal

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

Caves - landscapes without light

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

Did you know?

That fracture spring is see spring, fracture.?

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


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Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
See all featured articles
Featured articles from other Geoscience Journals
Karst environment, Culver D.C.
Mushroom Speleothems: Stromatolites That Formed in the Absence of Phototrophs, Bontognali, Tomaso R.R.; D’Angeli Ilenia M.; Tisato, Nicola; Vasconcelos, Crisogono; Bernasconi, Stefano M.; Gonzales, Esteban R. G.; De Waele, Jo
Calculating flux to predict future cave radon concentrations, Rowberry, Matt; Marti, Xavi; Frontera, Carlos; Van De Wiel, Marco; Briestensky, Milos
Microbial mediation of complex subterranean mineral structures, Tirato, Nicola; Torriano, Stefano F.F;, Monteux, Sylvain; Sauro, Francesco; De Waele, Jo; Lavagna, Maria Luisa; D’Angeli, Ilenia Maria; Chailloux, Daniel; Renda, Michel; Eglinton, Timothy I.; Bontognali, Tomaso Renzo Rezio
Evidence of a plate-wide tectonic pressure pulse provided by extensometric monitoring in the Balkan Mountains (Bulgaria), Briestensky, Milos; Rowberry, Matt; Stemberk, Josef; Stefanov, Petar; Vozar, Jozef; Sebela, Stanka; Petro, Lubomir; Bella, Pavel; Gaal, Ludovit; Ormukov, Cholponbek;
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Your search for matrix (Keyword) returned 175 results for the whole karstbase:
Showing 16 to 30 of 175
Modeling of soil cover genesis and evolution, 1996,
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Goryachkin S. V. ,
In order to develop agenetic approach to soil cover studies, the algorithm of qualitative modeling of soil cover genesis and evolution is suggested. During a modeling process of this kind, a system of models is created, including sequentially: (1) a spatial model-soil cover structure, presented on a detailed map; (2) an ecological-genetic model-factor-ecological matrix, demonstrating the relations between the soil and the factors of soil formation; (3) a process-genetic model, reflecting processes and mechanisms that form soil cover, in the same way as the concept of elementary soil-forming processes describes the origin of soil profiles; (4) a spatial-genetic model-a soil map with differentiated demonstration of soil boundaries connected to soil genesis and stability; (5) evolutionary and/or prognostic models of the soil cover, describing its change in time. The algorithm was applied to soil cover of the karst denudation plain of the European North

Analysis of well hydrographs in a karst aquifer: Estimates of specific yields and continuum transmissivities, 1996,
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Shevenell L. ,
Hydrograph analysis techniques have been well developed for hydrographs obtained from streams and springs, where data are cast in terms of total discharge. The data obtained from well hydrographs provide water level versus time; hence, a method of hydrograph analysis is required for situations in which only water level data are available. It is assumed here that three segments on a recession curve from wells in a karst aquifer represent drainage from three types of storage: conduit (C), fracture (F) and matrix (M). Hydrographs from several wells in a karst aquifer are used to estimate the specific yields (S-y) associated with each portion of the aquifer (C, F, M), as well as continuum transmissivities (T). Data from three short injection tests at one well indicate continuum rat this well bore is approximately 5 m(2) day(-1), and tests at numerous other wells in the aquifer yield results between 1 and 7 m(2) day(-1). The T estimated with well hydrographs from two storms indicates a T of 9.8 m(2) day(-1). Well-developed conduit systems in which water levels in wells show a flashy response typically show S(y)s of 1 x 10(-4), 1 x 10(-3), and 3 x 10(-3) for C, F, and M, respectively. Less well-developed conduit areas show more nearly equal S(y)s (8.6 x 10(-4), 1.3 x 10(-3), 3 x 10(-3)). Areas with no evidence for the presence of conduits have only one, or in some cases two, slopes on the recession curve. In these cases, water-level responses are slow. Recession curves with a single slope represent drainage from only the lower T matrix. Those with two slopes have an additional, more rapid response segment on the recession curve which represents drainage from the higher T, lower S-y, fractures in the system

Structure et comportement hydraulique des aquifers karstiques, DSc thesis, 1996,
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Jeannin, P. Y.

This thesis aims to provide a better knowledge of karst flow systems, from a functional point of view (behaviour with time), as well as from a structural one (behaviour in space). The first part of the thesis deals with the hydrodynamic behaviour of karst systems, and the second part with the geometry of karstic networks, which is a strong conditioning factor for the hydrodynamic behaviour.
Many models have been developed in the past for describing the hydrodynamic behaviour of karst hydrogeological systems. They usually aim to provide a tool to extrapolate, in time and/or space, some characteristics of the flow fields, which can only be measured at a few points. Such models often provide a new understanding of the systems, beyond what can be observed directly in the field. Only special field measurements can verify such hypotheses based on numerical models. This is an significant part of this work. For this purpose, two experimental sites have been equipped and measured: Bure site or Milandrine, Ajoie, Switzerland, and Holloch site, Muotathal, Schwyz, Switzerland. These sites gave us this opportunity of simultaneously observe hydrodynamic parameters within the conduit network and, in drillholes, the "low permeability volumes" (LPV) surrounding the conduits.
These observations clearly show the existence of a flow circulation across the low permeability volumes. This flow may represent about 50% of the infiltrated water in the Bure test-field. The epikarst appears to play an important role into the allotment of the infiltrated waters: Part of the infiltrated water is stored at the bottom of the epikarst and slowly flows through the low permeability volumes (LPV) contributing to base flow. When infiltration is significant enough the other part of the water exceeds the storage capacity and flows quickly into the conduit network (quick flow).
For the phreatic zone, observations and models show that the following scheme is adequate to describe the flow behaviour: a network of high permeability conduits, of tow volume, leading to the spring, is surrounded by a large volume of low permeability fissured rock (LPV), which is hydraulically connected to the conduits. Due to the strong difference in hydraulic conductivity between conduits and LPV, hydraulic heads and their variations in time and space are strongly heterogeneous. This makes the use of piezometric maps in karst very questionable.
Flow in LPV can be considered as similar to flow in fractured rocks (laminar flow within joints and joints intersections). At a catchment scale, they can be effectively considered as an equivalent porous media with a hydraulic conductivity of about 10-6 to 10-7 m/s.
Flow in conduits is turbulent and loss of head has to be calculated with appropriate formulas, if wanting any quantitative results. Our observations permitted us to determine the turbulent hydraulic conductivity of some simple karst conduits (k', turbulent flow), which ranges from 0.2 to 11 m/s. Examples also show that the structure of the conduit network plays a significant role on the spatial distribution of hydraulic heads. Particularity hydraulic transmissivity of the aquifer varies with respect to hydrological conditions, because of the presence of overflow conduits located within the epiphreatic zone. This makes the relation between head and discharge not quadratic as would be expected from a (too) simple model (with only one single conduit). The model applied to the downstream part of Holloch is a good illustration of this phenomena.
The flow velocity strongly varies along the length of karst conduits, as shown by tracer experiments. Also, changes in the conduit cross-section produce changes in the (tow velocity profile. Such heterogeneous flow-field plays a significant role in the shape of the breakthrough curves of tracer experiments. It is empirically demonstrated that conduit enlargements induce retardation of the breakthrough curve. If there are several enlargements one after the other, an increase of the apparent dispersivity will result, although no diffusion with the rock matrix or immobile water is present. This produces a scale effect (increase of the apparent dispersivity with observation scale). Such observations can easily be simulated by deterministic and/or black box models.
The structure of karst conduit networks, especially within the phreatic zone, plays an important role not only on the spatial distribution of the hydraulic heads in the conduits themselves, but in the LPV as well. Study of the network geometry is therefore useful for assessing the shape of the flow systems. We further suggest that any hydrogeological study aiming to assess the major characteristics of a flow system should start with a preliminary estimation of the conduit network geometry. Theories and examples presented show that the geometry of karst conduits mainly depends on boundary conditions and the permeability field at the initial stage of the karst genesis. The most significant boundary conditions are: the geometry of the impervious boundaries, infiltration and exfiltration conditions (spring). The initial permeability field is mainly determined by discontinuities (fractures and bedding planes). Today's knowledge allows us to approximate the geometry of a karst network by studying these parameters (impervious boundaries, infiltration, exfiltration, discontinuity field). Analogs and recently developed numerical models help to qualitatively evaluate the sensitivity of the geometry to these parameters. Within the near future, new numerical tools will be developed and will help more closely to address this difficult problem. This development will only be possible if speleological networks can be sufficiently explored and used to calibrate models. Images provided by speleologists to date are and will for a long time be the only data which can adequately portray the conduit networks in karst systems. This is helpful to hydrogeologists. The reason that we present the example of the Lake Thun karst system is that it illustrates the geometry of such conduits networks. Unfortunately, these networks are three-dimensional and their visualisation on paper (2 dimensions) is very restrictive, when compared to more effective 3-D views we can create with computers. As an alternative to deterministic models of speleogenesis, fractal and/or random walk models could be employed.


Ce-anomalies in the textural components of upper Cretaceous karst bauxites from the Apulian carbonate platform (southern Italy), 1997,
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Mongelli G. ,
The chemical and mineralogical composition of Upper Cretaceous Apulian karat bauxites (southern Italy) and their textural components, i.e. ooids and matrix, has been studied. The bulk samples are composed of boehmite, hematite, anatase and kaolinite. The samples collected along a vertical profile show a downward enrichment for the elements Rb, Sr, Ba, Ni and Cr. A similar distribution is observed in deposits bauxitized in situ at the expense of matrix-like material collected in the karst zone. The ooids consist mainly of hematite with minor boehmite and anatase, whereas in the matrix boehmite prevails on hematite, kaolinite and anatase. In the void fillings in the matrix there is a Ca-fluorocarbonate having a Ce/Ce* of 5.8. The ooids, with the exception of Ce, are enriched in REE and show a higher (La/Yb)(ch) ratio relative to the matrix. The matrix exhibits a large positive Ce-anomaly whereas the ooids have negative Ce-anomaly. The Ce fractionation between the textural components can be explained assuming: (1) Ce oxidation and cerianite precipitation in the uppermost part of the deposits; (2) scavenging of REE from Ce-depleted percolating solutions by the iron oxide, inducing both REE-enrichment and Ce-negative anomalies in ooids; (3) remobilization of cerium as fluoride complex, as a consequence of more acidic conditions in the uppermost part of the deposit, and precipitation of Ce3 as fluorocarbonate mineral toward the carbonate bedrock barrier, at alkaline pH. Alternatively, the cerium remobilization, possibly as a carbonate-fluoride complex, could be due to an Eh decrease, favoured by a rise of the groundwater level. (C) 1997 Elsevier Science B.V

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

High-resolution records of soil humification and paleoclimate change from variations in speleothem luminescence excitation and emission wavelengths, 1998,
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Baker A, Genty D, Smart Pl,
Recent advances in the precision and accuracy of the optical techniques required to measure luminescence permit the nondestructive analysis of solid geologic samples such as speleothems (secondary carbonate deposits in caves). In this paper we show that measurement of speleothem luminescence demonstrates a strong relationship between the excitation and emission wavelengths and both the extent of soil humification and mean annual rainfall. Raw peat with blanket bog vegetation has the highest humification and highest luminescence excitation and emission matrix wavelengths, because of the higher proportion of high-molecular-weight organic acids in these soils. Brown ranker and rendzina soils with dry grassland and woodland cover have the lowest wavelengths. Detailed analysis of one site where an annually laminated stalagmite has been deposited over the past 70 yr during a period with instrumental climate records and no vegetation change suggests that more subtle variations in luminescence emission wavelength correlate best with mean annual rainfall, although there is a lag of approximately 10 yr. These results are used to interpret soil humification and climate change from a 130 ka speleothem at an upland site in Yorkshire, England. These data provide a new continuous terrestrial record of climate and environmental change for northwestern Europe and suggest the presence of significant variations in wetness and vegetation within interglacial and interstadial periods

Physical response of a karst drainage basin to flood pulses: Example of the Devil's Icebox cave system (Missouri, USA), 1998,
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Halihan T. , Wicks C. M. , Engeln J. F. ,
In karst aquifers, water moves from the recharge area (sinkhole plains and swallets) to the discharge area (springs), traveling kilometers through the groundwater system in a period of hems to days. Transit rimes through karst aquifers are a function of the conduit geometry and connectedness, intensity and duration of the recharge event, and antecedent soil moisture. Often many of these factors are unknown or difficult to quantify. Therefore, predicting the response of a karst basin to recharge is difficult. Numerous researchers have attempted to understand the response of a karst basin, but a good understanding of whether the response is dependent on local features or regional effects is currently lacking. From April 1994 to May 1995, flood pulse hydrographs from a karst aquifer with well-developed and well-documented conduits (Devil's Icebox cave system) were obtained from a gaging station near the spring of the karst basin. Data were also collected from within the conduit system in an attempt to determine whether flow was locally controlled by constrictions in the conduits. Based on an application of Bernoulli's equation, analyses of the changes in kinetic head and potential head over time indicated local control during storm events. The observed sediment patterns and water level variations also support localized flow control during storm events. A numerical model of the constrictions was rested and reproduced the responses observed at the spring during initial periods of storm events. The model illustrated that the constricted flow was very sensitive to recharge. It also illustrated the transition from local control due to constriction to regional controls due to the aquifer matrix. (C) 1998 Elsevier Science B.V

Structure et comportement hydraulique des aquifers karstiques, DSc. Thesis, faculte des Sciences de l'Universite de Neuchatel., 1998,
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Jeannin Py.
This thesis aims to provide a better knowledge of karst flow systems, from a functional point of view (behaviour with time), as well as from a structural one (behaviour in space). The first part of the thesis deals with the hydrodynamic behaviour of karst systems, and the second part with the geometry of karstic networks, which is a strong conditioning factor for the hydrodynamic behaviour. Many models have been developed in the past for describing the hydrodynamic behaviour of karst hydrogeological systems. They usually aim to provide a tool to extrapolate, in time and/or space, some characteristics of the flow fields, which can only be measured at a few points. Such models often provide a new understanding of the systems, beyond what can be observed directly in the field. Only special field measurements can verify such hypotheses based on numerical models. This is an significant part of this work. For this purpose, two experimental sites have been equipped and measured: Bure site or Milandrine, Ajoie, Switzerland, and Holloch site, Muotathal, Schwyz, Switzerland. These sites gave us this opportunity of simultaneously observe hydrodynamic parameters within the conduit network and, in drillholes, the "low permeability volumes" (LPV) surrounding the conduits. These observations clearly show the existence of a flow circulation across the low permeability volumes. This flow may represent about 50% of the infiltrated water in the Bure test-field. The epikarst appears to play an important role into the allotment of the infiltrated waters: Part of the infiltrated water is stored at the bottom of the epikarst and slowly flows through the low permeability volumes (LPV) contributing to base flow. When infiltration is significant enough the other part of the water exceeds the storage capacity and flows quickly into the conduit network (quick flow). For the phreatic zone, observations and models show that the following scheme is adequate to describe the flow behaviour: a network of high permeability conduits, of tow volume, leading to the spring, is surrounded by a large volume of low permeability fissured rock (LPV), which is hydraulically connected to the conduits. Due to the strong difference in hydraulic conductivity between conduits and LPV, hydraulic heads and their variations in time and space are strongly heterogeneous. This makes the use of piezometric maps in karst very questionable. Flow in LPV can be considered as similar to flow in fractured rocks (laminar flow within joints and joints intersections). At a catchment scale, they can be effectively considered as an equivalent porous media with a hydraulic conductivity of about 10-6 to 10-7 m/s. Flow in conduits is turbulent and loss of head has to be calculated with appropriate formulas, if wanting any quantitative results. Our observations permitted us to determine the turbulent hydraulic conductivity of some simple karst conduits (k',turbulent flow), which ranges from 0.2 to 11 m/s. Examples also show that the structure of the conduit network plays a significant role on the spatial distribution of hydraulic heads. Particularity hydraulic transmissivity of the aquifer varies with respect to hydrological conditions, because of the presence of overflow conduits located within the epiphreatic zone. This makes the relation between head and discharge not quadratic as would be expected from a (too) simple model (with only one single conduit). The model applied to the downstream part of Holloch is a good illustration of this phenomena. The flow velocity strongly varies along the length of karst conduits, as shown by tracer experiments. Also, changes in the conduit cross-section produce changes in the (tow velocity profile. Such heterogeneous flow-field plays a significant role in the shape of the breakthrough curves of tracer experiments. It is empirically demonstrated that conduit enlargements induce retardation of the breakthrough curve. If there are several enlargements one after the other, an increase of the apparent dispersivity will result, although no diffusion with the rock matrix or immobile water is present. This produces a scale effect (increase of the apparent dispersivity with observation scale). Such observations can easily be simulated by deterministic and/or black box models. The structure of karst conduit networks, especially within the phreatic zone, plays an important role not only on the spatial distribution of the hydraulic heads in the conduits themselves, but in the LPV as well. Study of the network geometry is therefore useful for assessing the shape of the flow systems. We further suggest that any hydrogeological study aiming to assess the major characteristics of a flow system should start with a preliminary estimation of the conduit network geometry. Theories and examples presented show that the geometry of karst conduits mainly depends on boundary conditions and the permeability field at the initial stage of the karst genesis. The most significant boundary conditions are: the geometry of the impervious boundaries, infiltration and exfiltration conditions (spring). The initial permeability field is mainly determined by discontinuities (fractures and bedding planes). Today's knowledge allows us to approximate the geometry of a karst network by studying these parameters (impervious boundaries, infiltration, exfiltration, discontinuity field). Analogs and recently developed numerical models help to qualitatively evaluate the sensitivity of the geometry to these parameters. Within the near future, new numerical tools will be developed and will help more closely to address this difficult problem. This development will only be possible if speleological networks can be sufficiently explored and used to calibrate models. Images provided by speleologists to date are and will for a long time be the only data which can adequately portray the conduit networks in karst systems. This is helpful to hydrogeologists. The reason that we present the example of the Lake Thun karst system is that it illustrates the geometry of such conduits networks. Unfortunately, these networks are three-dimensional and their visualisation on paper (2 dimensions) is very restrictive, when compared to more effective 3-D views we can create with computers. As an alternative to deterministic models of speleogenesis, fractal and/or random walk models could be employed.

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

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


Relation entre ecoulements et fractures ouvertes dans un systeme aquifere compartimente par des failles et mise en evidence d'une double porosite de fractures, 1999,
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Bruel T, Petit Jp, Massonnat G, Guerin R, Nolf Jl,
Hydrodynamic characterisation of real fracture systems is necessary to improve modelling of fracture reservoirs as well as nuclear waste disposal sites. This characterisation is usually considered globally and theoretically but very few studies have aimed to identify the real physical environment of flow (matrix, faults, joints etc.) before establishing hydrodynamical models. We present a case study in a fractured reservoir aiming to give an example of how and why fluids actually flow within a given fracture at the various scales of fracturation of a fracture network. This study demonstrates that the determination of type and orientation of fractures actually supporting flow is necessary for accurate interpretation of the pumping tests within a fractured reservoir. It also shows that there is no simple relationship between the fault offset and the importance of flow, probably due to the influence of in situ stress. It is shown that the combination of various methods can be used to determine the fracture-flow relationship and behaviour at subseismic scale in subsurface conditions

Growth and demise of an Archean carbonate platform, Steep Rock Lake, Ontario, Canada, 1999,
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Kusky T. P. , Hudleston P. J. ,
The Steep Rock Group of northwest Ontario's Wabigoon subprovince is one of the world's thickest Archean carbonate platform successions. It was deposited unconformably over a 3001-2928 Ma gneissic terrane, and contains a remarkable group of biogenic and oolitic limestones, dolostones, micrites, and karat breccias capped by a thick paleosol developed between and over karst towers. The presence of aragonite fans, herringbone calcite, and rare gypsum molds suggests that the carbonate platform experienced at least local anaerobic and hypersaline depositional conditions. This sequence shows that a combination of chemical and biological processes was able to build a carbonate platform 500 m thick by 3 billion years ago. The carbonate platform is structurally overlain by a mixture of complexly deformed rocks of the Dismal Ashrock forming a melange with blocks of ultramafic volcaniclastic rocks, mafic volcanics, carbonate, tonalite, lenses of Fe-ore rock, and metasedimentary rocks, in a shaly, serpentinitic, and fragmental ultramafic volcaniclastic matrix. The melange shows evidence of polyphase deformation, with early high-strain fabrics formed at amphibolite facies, and later superimposed brittle fabrics related to the final emplacement of the melange over the carbonate platform. An amphibolite- through greenschist-grade shear zone marks the upper contact of the melange with overlying mafic volcanic and tuffaceous rocks of the ca. 2932 Ma Witch Bay allochthon, interpreted as a primitive island are sequence. We suggest an evolutionary model for the area that begins with rifting of an are sequence (Marmion Complex of the Wabigoon are) that initiated subsidence and sedimentation on the Steep Rock platform and its correlatives that extend for a restored strike length exceeding 1000 km. Shallow water carbonate sedimentation continued until the platform was uplifted on the flanks of a flexural bulge related to the approach of the Witch Bay allochthon, representing collision of the rifted are margin of the Wabigoon subprovince with the Witch Bay are. Melange of the Dismal Ashrock was formed as off-axis volcanic rocks were accreted to the base of the Witch Bay allochthon prior to its collision with the Steep Rock platform

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

The Makapansgat Australopithecine site from a speleological perspective, 1999,
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Latham Alf G. , Herries Andrew, Quinney Patrick, Sinclair Anthony, Kuykendall Kevin,
Remains of Australopithecus africanus from the Limeworks Cave, Makapansgat, South Africa, are believed to belong mainly to a metre-thick, bone-rich, speleothem layer. The flowstone is one stratum among a sequence of speleothems, muds, silts, sands and fine and coarse breccias, the study of which has evoked some disagreement. The limeworkers' excavations revealed some stratigraphic relationships but they have obscured others. Partly because of this, controversy surrounds the supposition about whether there are separated depositional basins within the overall site and, if so, whether strata can be securely correlated. This is important because a reconstruction of an overall stratigraphic sequence was used as a basis for a magnetostratigraphic reversal record and by which the site has been tentatively dated. There is qualification and disagreement about the origin of the various flowstones and the actual depositional environment of the muds and silts. Evidence is presented which rules out some previous interpretations. From the point of view of the Australopithecine fossils themselves, it can be said that the calcite matrix in which they were provenanced was a low-energy environment and that the dense bone accumulation of this layer almost certainly did not arise by the action of floods, as previously supposed. The most likely main cause of the dense accumulation was hyena denning activity. It is clear that further work is needed to see how a reliable overall sequence can be established and that closer sampling is required for magnetostratigraphy

Quantification of matrix, fracture and channel contributions to storage and flow in a Paleozoic carbonate, 1999,
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Worthington S. R. H. , Davies G. J. , Ford D. C.

Controls on bacterial sulphate reduction in a dual porosity aquifer system: the Lincolnshire Limestone aquifer, England, 2000,
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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

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