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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. ...

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 lime is calcium oxide, cao; used loosely and incorrectly in referring to limestone [10].?

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Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
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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 vein (Keyword) returned 56 results for the whole karstbase:
Showing 1 to 15 of 56
The Coxco Deposit; a Proterozoic mississippi valley-type deposit in the McArthur River District, Northern Territory, Australia, 1983, Walker R. N. , Gulson B. , Smith J. ,
Strata-bound dolomite-hosted lead-zinc deposit. Crusts of colloform sphalerite, galena, pyrite, and marcasite (stage I mineralization) were deposited on the surfaces of the karst-produced solution cavities. Reduced sulfur was produced by sulfate-reducing bacteria within the karst system. A second stage of mineralization consisting of coarsely crystalline sphalerite, galena, pyrite, and marcasite occurs in veins and as the matrix for dolomite breccias.--Modified journal abstract

Sr isotope study of vein and cave calcites from southern Israel, 1990, Avigour A, Magaritz M, Issar A, Dodson Mh,
The strontium isotope compositions of secondary calcites from the Negev, southern Israel, were compared to those of the marine carbonate host rocks, which range in age from Triassic to Eocene, in order to understand fluid source and migration through fracture systems in dominantly carbonate strata. The Sr isotopes of these calcite clusters are divided into two groups: (1) calcites with 87Sr/86Sr values greater than those of the host carbonates; and (2) calcites with 87Sr/86Sr values close to the values of the host carbonate. 1. (1) These secondary calcites were found on the main tectonic lines of the Negev (faults and fold axes) and are enriched in 87Sr (87Sr/86Sr = 0.707709-0.709151) relative to the marine carbonate country rocks (87Sr/86Sr = 0.707251-0.70755, with one exception). These calcites are associated or crossed by thin veins filled by Fe- and Mn-oxides.2. (2) Secondary calcites with 87Sr/86Sr values close to those of the marine carbonate country rocks (0.7073-0.7077) are found in karstic caves and veins, and are located in sites which are not on the major faults and fold axes. These calcites are not crossed by Fe- and Mn-oxides.The isotopic results indicate that the solutions from which the secondary minerals of the first group precipitated were not in isotopic equilibrium with the marine host rocks. The possible source of the precipitating solutions can be either surface rain descending through the fault system or ascending groundwaters from the deep Nubian aquifer (Paleozoic to Early Cretaceous in age). In both cases there would be a limited interaction with the host sandstone rock which usually is depleted in Sr. The similarity of the 87Sr/86Sr values to those of the host rocks in the second group suggests that the main source of Sr in these calcite crystals was from the dissolution of the marine carbonate country rocks by rain- and flood waters

LATE TO POSTHERCYNIAN HYDROTHERMAL ACTIVITY AND MINERALIZATION IN SOUTHWEST SARDINIA (ITALY), 1992, Boni M, Iannace A, Koppel V, Fruhgreen G, Hansmann W,
Several kinds of base metal deposits occur in the lower Paleozoic of southwest Sardinia (Iglesiente-Sulcis mineral district). This paper deals with those deposits which are generally referred to as Permo-Triassic, because they accompany and postdate the Hercynian orogeny and are related to magmatic activity. A large number of previously published geochemical data, integrated with additional new data (Sr, Pb, O, C, and S isotopes), are reviewed and discussed in the frame of the late to post-Hercynian geologic evolution of southwest Sardinia. According to geological and mineralogical characteristics, three types of deposits can be distinguished: (1) skarn ores related to late Hercynian leucogranitic intrusions, (2) high-temperature veins, and (3) low-temperature veins and karst filling. Pervasive epigenetic dolomitization phenomena are geochemically related to the low-temperature deposits. Sr and Pb isotopes of the first and second types (0.7097-0.7140 Sr-87/Sr-86; 17.97-18.29 Pb-206/Pb-204; 38.11-38.45 Pb-208/Pb-204) are distinctly more radiogenic than those of the third type (0.7094-0.7115 Sr-87/Sr-86; 17.86-18.05 Pb-206/Pb-204; 37.95-38.19 Pb-208/Pb-204) which, in turn, are closer to Paleozoic ores and carbonates. Fluid inclusion data indicate that the fluids responsible for mineralization of the first and second types of deposits were hot and dilute (T(h)= 370-degrees-140-degrees-C; <5 wt % NaCl equiv). In contrast, relatively colder and very saline fluids (T(h)= 140-degrees-70-degrees-C; >20 wt % NaCl equiv) were responsible for the third type of mineralization, as well for epigenetic dolomitization of the Cambrian host rocks. O isotopes measured in minerals from the first two types (deltaO-18SMOW = 12.8-18.9 parts per thousand) are O-18 depleted with respect to the third type (deltaO-18SMOW = 15.9-22.1 parts per thousand). These data, coupled with fluid inclusion formation temperatures, indicate that the fluids responsible for the first two types of mineralization were O-18 enriched with respect to those of the third type and related hydrothermal phenomena. The deltaS-34CDT in sulfides of the first two types vary between 3.7 and 10.73 per mil, whereas the values of the third type range from 12.0 to 17.9 per mil. Late to post-Hercynian mineralization is thus explained as the result of three distinct, though partly superimposed, hydrothermal systems. System 1 developed closer to the late Hercynian leucogranitic intrusions and led to the formation of the first and subsequently the second type of mineralization. The relatively hot and diluted fluids had a heated meteoric, or even partly magmatic, origin. Metals were leached from an external, radiogenic source, represented either by Hercynian leucogranites or by Paleozoic metasediments. Sulfur had a partly magmatic signature. System 2 was characterized by very saline, colder fluids which promoted dolomitization, silicification, and vein and karst mineralization. These fluids share the typical characteristics of formation waters, even though their origins remain highly speculative. The hydrothermal system was mainly rock dominated, with only a minor participation of the external radiogenic source of metals. Sulfur was derived by recirculation of pre-Hercynian strata-bound ores. System 3 records the invasion of fresh and cold meteoric waters which precipitated only minor ore and calcite gangue. It may represent the further evolution of system 2, possibly spanning a time well after the Permo-Triassic. The timing of all these phenomena is still questionable, due to the poor geologic record of the Permo-Triassic in southwest Sardinia. Nevertheless, the hypothesized scenario bears many similarities with hydrothermal processes documented throughout the Hercynian in Europe and spanning the same time interval. A comparison with the latter mineralization and hydrothermal activities leads to the hypothesis that the first two types of mineralization are linked to late Hercynian magmatic activity, whereas the third type may be related to either strike-slip or tensional tectonics which, throughout Europe mark the transition from the Hercynian orogeny to the Alpine cycle

DISLOCATION OF THE EVAPORITIC FORMATIONS UNDER TECTONIC AND DISSOLUTION CONTROLS - THE MODEL OF THE DINANTIAN EVAPORITES FROM VARISCAN AREA (NORTHERN FRANCE AND BELGIUM), 1993, Rouchy J. M. , Groessens E. , Laumondais A. ,
Within the Franco-Belgian segment of the Hercynian orogen, two thick Dinantian anhydritic formations are known, respectively in the Saint-Ghislain (765 m) and Epinoy 1 (904 m) wells. Nevertheless, occurrences of widespread extended breccias and of numerous pseudomorphs of gypsum/anhydrite in stratigraphically equivalent carbonate deposits (boreholes and outcrops), suggest a larger extent of the evaporitic conditions (fig. 1, 2). The present distribution of evaporites is controlled by palaeogeographical differentiation and post-depositional parameters such as tectonics and dissolution. These latter have dissected the deposits formerly present in all the structural units. By using depositional, diagenetic and deformational characters of these formations, the article provides a model for the reconstruction of a dislocated evaporitic basin. This segment of the Hercynian chain is schematically composed of two main units (fig. 1, 3) : (1) the autochthonous or parautochthonous deposits of the Namur synclinorium, (2) the Dinant nappe thrusted northward over the synclinorium of Namur. The major thrust surface is underlined by a complex fault bundle (faille du Midi) seismically recognized over more than 100 km. A complex system of thrust slices occurs at the Hercynian front. Except for local Cretaceous deposits, most of the studied area has been submitted to a long period of denudation since the Permian. Sedimentary, faunistic and geochemical data argue for a marine origin of the brines which have generated the evaporites interbedded with marine limestones. Sedimentary structures. - The thick evaporitic formations are composed of calcium-sulfates without any clear evidence of the former presence of more soluble salts (with the exception of a possible carbonate-sulfate breccia in the upper part of the Saint-Ghislain formation). As in all the deeply buried evaporitic formations, the anhydrite is the main sulfate component which displays all the usual facies : pseudomorphs after gypsum (fig. 4A, B), nodular and mosaic (fig. 4C), laminated. The gypsum was probably an important component during the depositional phase despite the predominant nodular pattern of the anhydrite. Early diagenetic nodular anhydrite may have grown during temporary emersion of the carbonates (sabkha environments), but this mechanism cannot explain the formation of the whole anhydrite. So, most of the anhydrite structures result from burial-controlled gypsum --> anhydrite conversion and from mechanical deformations. Moreover, a complex set of diagenetic processes leads to various authigenic minerals (celestite, fluorite, albite, native sulfur, quartz and fibrous silica) and to multistaged carbonate <> sulfate replacements (calcite and dolomite after sulfate, replacive anhydrite as idiomorphic poeciloblasts, veinlets, domino-like or stairstep monocrystals...). These mineral transformations observed ill boreholes and in outcrops have diversely been controlled during the complex evolution of the series as : depositional and diagenetic pore-fluid composition, pressure and temperature changes with burial, bacterial and thermochemical sulfate reduction, deep circulations favored by mechanical brecciation, mechanical stresses, role of groundwater during exhumation of the series. Deformational structures. - A great variety of deformational structures as rotational elongation, stretching, lamination, isoclinal microfolding, augen-like and mylonitic structures are generated by compressive tectonic stresses (fig. 4D to J). The similarities between tectonic-generated structures and sedimentary (lamination) or diagenetic (pseudo-nodules) features could lead lo misinterpretations. The calcareous interbeds have undergone brittle deformation the style and the importance of which depend of their relative thickness. Stretching, boudins, microfolds and augen structures F, H. I) affect the thin layers while thicker beds may be broken as large fractured blocks dragged within flown anhydrite leading to a mylonitic-like structure (fig, 4G). In such an inhomogeneous formation made of interlayered ductile (anhydrite) and brittle (carbonate) beds, the style and the intensity of the deformation vary with respect to the relative thickness of each of these components. Such deformational features of anhydrite may have an ubiquitous significance and can result either from compressive constraints or geostatic movements (halokinesis). Nevertheless, some data evidence a relation with regional tangential stresses: (1) increase of the deformation toward the bottom of the Saint-Ghislain Formation which is marked by a deep karst suggesting the presence of a mechanical discontinuity used as a drain for dissolving solutions (fig. 3, 4); (2) structural setting (reversed series, internal slidings) of the Epinoy 1 formation under the Midi thrust. However, tectonic stresses also induce flowing deformations which have contributed to cause their present discontinuity. It can be assumed that the evaporites played an active role for the buckling of the regional structure as detachment or gliding layers and more specifically for the genesis of duplex structures. Breccia genesis. - Great breccia horizons are widely distributed in outcrops as well as in the subsurface throughout the greater part of the Dinant and Namur units (fig. 2). The wide distribution of pseudomorphosed sulfates in outcrops and the stratigraphical correlation between breccia and Saint-Ghislain evaporitic masses (fig. 2) suggest that some breccia (although not all) have been originated from collapse after evaporites solution. Although some breccia may result from synsedimentary dissolution, studied occurrences show that most of dissolution processes started after the Hercynian deformation and, in some cases, were active until recently : elements made of lithified and fractured limestones (Llandelies quarries) (fig. 5A), preservation of pseudomorphs of late replacive anhydrite (Yves-Gomezee) (fig. 5B, C), deep karst associated with breccia (Douvrain, Saint Ghislain, Ghlin boreholes) (fig. 3, 4, 5D)). Locally, the final brecciation may have been favored by a mechanical fragmentation which controlled water circulations (fig. 5E). As postulated by De Magnee et al. [19861, the dissolution started mostly after the Permian denudation and continued until now in relation with deep circulations and surface weathering (fig. 6). So, the above-mentioned occurrences of the breccia are logically explained by collapse after dissolution of calcium-sulfates interbeds of significant thickness (the presence of salt is not yet demonstrated), but other Visean breccia may have a different origin (fig. 5F). So, these data prove the extension of thick evaporitic beds in all the structural units including the Dinant nappe, before dissolution and deformation. Implications. - Distribution of Visean evaporites in northern France and Belgium is inherited from a complicated paleogeographic, tectonic and post-tectonic history which has strongly modified their former facies, thicknesses and limits (fig. IA, 6). Diversified environments of deposition controlled by both a palaeogeographical differentiation and water level fluctuations led to the deposition of subaqueous (gypsum) or interstitial (gypsum, anhydrite) crystallization. Nevertheless, most of the anhydrite structures can be interpreted as resulting from burial conversion of gypsum to anhydrite rather than a generalized early diagenesis in sabkha-like conditions. Deformation of anhydrite caused by Hercynian tangential stresses and subsequent flow mechanisms, have completed the destruction of depositional and diagenetic features. The tectonic deformations allow us to consider the role of the evaporites in the Hercynian deformations. The evaporites supplied detachment and gliding planes as suggested for the base of the Saint-Ghislain Formation and demonstrated by the structural setting of Epinoy 1 evaporites in reverse position and in a multi-system of thrust-slices below the Midi overthrust (fig. 7). So, although the area in which evaporation and precipitation took place cannot be exactly delineated in geographic extent, all the data evidence that the isolated thick anhydritic deposits represent relics of more widespread evaporites extending more or less throughout the different structural units of this Hercynian segment (fig. 1B). Their present discontinuity results from the combination of a depositional differentiation, mechanical deformations and/or dissolution

SEDIMENT-HOSTED GOLD MINERALIZATION IN THE RATATOTOK DISTRICT, NORTH SULAWESI, INDONESIA, 1994, Turner S. J. , Flindell P. A. , Hendri D. , Hardjana I. , Lauricella P. F. , Lindsay R. P. , Marpaung B. , White G. P. ,
The Ratatotok district in the Minahasa Regency of North Sulawesi, Indonesia is an area of significant gold mineralisation. Gold has been mined in the district since at least the 1850s, and intensively by the Dutch between 1900 and 1921 with a recorded production of 5,060 kg of gold. Newmont began exploring the district in 1986, and has delineated a major sediment-hosted replacement-style deposit at Mesel, and other smaller deposits in an 8 X 5 km area. A total drill-indicated resource of over 60 metric tonnes of gold ( 2 Moz) is reported for Mesel, and three of the smaller deposits. Approximately 80% of this resource is refractory. Silver grades are usually low (< 10 g/t). The Mesel deposit is similar to many Carlin-type deposits in carbonate hostrocks, alteration, geochemical signature and ore mineralogy, but is distinct in tectonic setting. The discovery of replacement-style mineralisation at Mesel, in an impure limestone within a Tertiary island arc environment, demonstrates that deposits with outward characteristics similar to Carlin-type mineralisation are not restricted to a continental setting. Carbonate sediments in the Ratatotok district were deposited in a Late Miocene restricted basin. Later compressional tectonics caused uplift that resulted in karst development in the limestone and erosion of the adjacent volcanic arc with deposition of a thick epiclastic unit. This was followed by intrusion of shallow level pre-mineral andesite into the sequence. Mineralisation at Mesel, and probably elsewhere in the district, is synchronous with the late-stage reactivation of strike-slip faults. Mineralising fluids at Mesel were focussed along steep structures sympathetic to these faults, and trapped below a relatively impermeable andesite cap rock. Hydrothermal fluids caused decalcification of the silty, more permeable carbonate units with the formation of secondary dolomite, deposition of fine arsenian pyrite, silica veinlets and gold. Volume loss due to decalcification and dolomite formation caused collapse brecciation which enhanced fluid flow and further mineralisation. This locally culminated in total decarbonation and deposition of massive silica. Late-stage stibnite occurs in structural zones within the ore deposit, whereas arsenic (as realgar and orpiment) and mercury (as cinnabar) are concentrated on the periphery. Elsewhere in the Ratatotok district, gold mineralisation is restricted to replacement-style mineralisation in permeable zones along limestone-andesite contacts, open-space-filling quartz-calcite veins and stockworks, and residual quartz-clay breccias. The residual breccias are developed in-situ, and are interpreted to form by dissolution of the wallrock limestone from around pre-existing mineralisation. This has resulted in widespread eluvial gold occurrences

Guab As, une grotte dans de la dolomie mgascristalline hydrothermale (Namibie occidentale), 1995, Marais E. , Martini J. , Irish J.
The authors describe a cave in the semi-desert area of the Hakos Mountains, 100km to the southwest of Windhoek, Namibia. The cave is significant due to the very unusual country rock, with which it is associated. It formed by dissolution of the dolomite core of a large quartz vein, which is 800 m long and 200 m wide, developed in mica-schist. The cave consists of a complex succession of large chambers, more or less overlapping each others, with walls generally consisting of quartz. In most instances the dolomite has been completely dissolved or occurs under the floor, concealed by dust and scree. Although the cave developed within a very small volume of carbonate, the total length reaches 695 m and the depth 85 m. The bottom is occu-pied by a pool which is only temporarily filled with water and probably marks the position of a perched water-table. The cave formed in a perched phreatic environment during an undetermined period

200-MILLION YEARS OF KARST HISTORY, DACHSTEIN LIMESTONE, HUNGARY, 1995, Juhasz E. , Korpas L. , Balog A. ,
Platform carbonates of the Upper Triassic Dachstein Limestone in Naszaly Hill have been karstified extensively over the past 200 million years. They provide an excellent example of polyphase karstic diagenesis that is probably typical of many subaerially exposed carbonate sequences. Seven karstic phases are recognized in the area, each of which include polyphase karstic events. The first karst phase was associated with the Lofer cycles. Meteoric waters caused dissolution; enlarged fractures and cavities were filled by marine and/or vadose silts and cement. The second karst phase was caused by local tectonic movements. Bedding-plane-controlled phreatic caves were formed, and filled by silts. The third karst phase lasted from the end of the Triassic to the Eocene. This was a regional, multiphase karstic event related to younger composite unconformities. Bauxitic fill is the most characteristic product of this phase. The karst terrain reached its mature or senile stage with very little porosity. Narrow veins and floating rafts of white calcite marks karst phase 4, which resulted from hydrothermal activity associated with Palaeogene magmatism. The early Rupelian phase of Alpine uplift caused large-scale rejuvenation of the former karst terrain (karst phase 5). Subsequently Naszaly Hill was buried as an area of juvenile karst with significant porosity. A second period of hydrothermal activity in the area (karst phase 6) was induced by Miocene volcanism, which resulted in wide, pale green calcite veins. Finally karst phase 7 was of tectonic origin. Following the most recent, Miocene uplift of the Naszaly Hill, the carbonates have again become the site of vadose karst development

Karst Geomorphology and Hydrology of Gunung Tempurung, Perak, Malaysia, 1995, Gilleson David , Holland Ernst , Davies Gareth

Gunung Tempurung is a 600-metre high limestone tower in the Kinta Valley located to the south of the city of Ipoh, Malaysia. The tower contains at least one extensive cave system, Gua Tempurung, which has a length of approximately 4800 metres and a vertical range of about 200 metres. The tower is an erosional remnant of a thick sequence of Silurian - Permian Limestones initially formed as a shelf deposit near an ancient coastline. The carbonate rocks lie adjacent to, and are laterally bounded by, Late Mesozoic granite plutoniic rocks emplaced by activity related to the Late Triassic uplift from plate boundary stresses along the western edge of the Malay Peninsular. The limestones have been folded and compressed between the granites and have been altered by contact metamorphism to marbles and skarn. Hydrothermal mineralisation of the limestone host rock has yeilded deposits of tin, with some tungsten minerals and other minor ores. In the central part of the karst tower a river-cave system, Gua Tempurung, developed from local damming of the north and south outlets of a small catchment derived from the granite upland area to the east. In several locations inside the dry upper chambers of the cave, vein deposits of tin (cassiterite) are evident in walls and ceilings. Additionally alluvial tin deposits derived from the Old Alluvium are present in the cave.


Dedolomitization as a driving mechanism for karst generation in Permian Blaine formation, southwestern Oklahoma, USA, 1997, Raines M. A. , Dewers T. A. ,
Cyclic deposits of Permian shales, dolomites, and halite and gypsum-bearing strata in the Blaine Formation of Southwestern Oklahoma contain abundant karst features. The present study shows that an important mechanism of karst development in these sequences is dedolomitization, wherein gypsum and dolomite in close spatial proximity dissolve and supersaturate groundwaters with respect to calcite. The net loss of mass accompanying this process (dolomite and gypsum dissolution minus calcite precipitation) can be manifest in secondary porosity development while the coupled nature of this set of reactions results in the retention of undersaturated conditions of groundwater with respect to gypsum. The continued disequilibrium generates karst voids in gypsum-bearing aquifers, a mineral-water system that would otherwise rapidly equilibrate. Geochemical modeling (using the code PHRQPITZ, Plummer et al 1988) of groundwater chemical data from Southwestern Oklahoma from the 1950's up to the present suggests that dedolomitization has occurred throughout this time period in evaporite sequences in Southwestern Oklahoma. Reports from groundwater well logs in the region of vein calcite suggest secondary precipitation, an observation in accord with dedolomite formation In terms of the amounts of void space produced by dissolution, dedolomitization can dominate gypsum dissolution alone, especially in periods of quiescent aquifer recharge when gypsum-water systems would have otherwise equilibrated and karst development ceased. Mass balance modeling plus molar volume considerations show that for every cubic cm of original rock (dolomite plus gypsum), there is 0.54 cm(3) of calcite and 0.47 cm(3) of void space produced Only slightly more pore space results if the dedolomitization reaction proceeds by psuedomorphic replacement of dolomite by calcite than in a reaction mechanism based on conservation of bicarbonate

Geology, geochemistry, and origin of the continental karst-hosted supergene manganese deposits in the western Rhodope massif, Macedonia, northern Greece, 1997, Nimfopoulos M. K. , Pattrick R. A. D. , Michailidis K. M. , Polya D. A. , Esson J. ,
Economic Mn-oxide ore deposits of commercial grade occur in the Rhodope massif near Kato Nevrokopi in the Drama region, Northern Greece. The Mn-oxide mineralization has developed by weathering of continental hypogene rhodochrosite-sulphide veins. The vein mineralization is confined by tectonic shear zones between marble and metapelites, extending laterally into the marble as tabular, pod or lenticular oreshoots (up to 50 m x 20 m x 5-10 m). Supergene oxidation of the hypogene mineralization led to the formation of in-situ residual Mn-oxide ore deposits, and secondary infills of Mn-oxide ore in embryonic and well developed karst cavities. Whole rock geochemical profiles across mineralized zones confirm the role of thrusts and faults as solution passageways and stress the importance of these structures in the development of hydrothermal and supergene mineralization at Kato Nevrokopi. Three zones an recognized in the insitu supergene veins: (A) a stable zone of oxidation, where immobile elements form (or substitute in) stable oxide mineral phases, and mobile elements are leached; (B) a transitional (active) zone in which element behavior is strongly influenced by seasonal fluctuations of the groundwater table and variations in pH-Eh conditions; and (C) a zone of permanent flooding, where variations in pH-Eh conditions are minimal. Zone (B) is considered as the source zone for the karst cavity mineralization. During weathering, meteoric waters, which were CO2-rich (P-CO2 similar to 10(-3.8) to 10(-1.4)) and oxygenated (fO(2) -10(-17) for malachite), percolated downward within the veins, causing breakdown and dissolution of sulfides and marble, and oxidation of rhodochrosite to Mn-oxides. Karat cavity formation was favored by the high permeability along thrust zones. Dissolved Mn2 was transported into karst cavities in reduced meteoric waters at the beginning of weathering (pH similar to 4-5), and as Mn(HCO3)(2) in slightly alkaline groundwaters during advanced weathering (pH similar to 6-8). Mn4? precipitation took place by fO(2) increase in ground waters, or pH increase by continuous hydrolysis and carbonate dissolution. In the well developed karst setting, some mobility of elements occurred during and after karst ore formation in the order Na>K>Mg>Sr>Mn>As>Zn>Ba>Al>Fe>Cu>Cd>Pb. (C) 1998 Canadian Institute of Mining, Metallurgy and Petrolem. Published by Elsevier Science Ltd. All rights reserved

Hydrothermal Calcite Veins and the Origin of Caves in the Lower Paleozoic of the Barrandian Basin, Czech Republic: Evidence of Extensive (Post?) Variscan Fluid Flow, 1997, Suchy V. , Zeman A. , Bosak P. , Dobes P. , Hladikova J. , Jackova I.

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.


The evolution of karst and caves in the Konûprusy region Bohemian Karst, Czech Republic), Part II: Hydrothermal paleokarst, 1998, Bosak, Pavel

The origin of hydrothermal karst cavities was connected with the Variscan hydrothermal process. The cavities were formed and filled by crystalline calcite. The process was accompanied by the intensive dolomitisation. Younger phase of hydrothermal karstification was not connected with vein-filling, but with the deep circulation of groundwater, probably associated with neovolcanic activity in the Bohemian Massif. This is supported by pollen grains and decomposed volcanic ash in speleothems which were formed after the major phases of speleogenesis. It is supposed that caves in the Konûprusy Devonian were formed in confined aquifer under phreatic and batyphreatic conditions. Thermal conditions appeared when paleogeothermic gradient was increased due to intensive neovolcanic activity. Hydrothermal karstification partly changed the morphology of caves. The maximum temperatures were stated to 60-700 C from large calcite crystals precipitated under phreatic and deeply phreatic conditions. The piezometric level was situated above limestones in Upper Cretaceous platform siliciclastics as indicated by numerous subvertical phreatic tubes („depressions") filled with sunkened Cretaceous and Tertiary sediments after the water buyoancy support decreased. Popcorn-like silicified Konûprusy Rosettes can be result of decrease of thermal water level and mixing with infiltrating meteoric waters. Outer zones of large calcite crystals with precipitation temperatures of about 400 C can indicate the gradual cooling of the whole system.


Dating of Speleothems in Kartchner Caverns, Arizona, 1999, Ford, D. C. , Hill, C. A.
Uranium-series dates on calcite travertine samples collected from Kartchner Caverns range from ~200- 40 Ka. These dates span from the Illinoian glacial to the Wisconsin glacial, but the majority cluster within the wetter Sangamon interglacial. Petromorphic vein quartz (>35 Ka from alpha spectrometry and >1 Ma from 234U/238U ratios) dates from an earlier thermal episode associated with Basin and Range faulting. All that can be surmised about the time of cave dissolution from these dates is that it happened >200 Ka

The Vazante zinc mine, Minas Gerais, Brazil; constraints in willemitic mineralization and fluid evolution, 1999, Lena Virginia Soares Monteiro, Jorge Silva Bettencourt, Baruch Spiro, Rodnei Graca, And Tolentino Flavio De Oliveira
The Vazante Mine is located in the Vazante District, the largest zinc district in Brazil. The Vazante deposit consists dominantly of an unusual willemitic ore. Small sulfide bodies are tectonically imbricated with the willemitic ore, within the Vazante shear zone. Structural styles of deformation and petrographic and isotopic evidence indicate that willemitic mineralization and deformation occurred synchronously during the Neo-Proterozoic. Various generations of hydrothermal veins and hydraulic breccias may pre-date, accompany and overprint the mineralization. Ore-formation temperatures are deduced from stable isotope geothermometry and mineral chemistry of both sulfide bodies and willemitic ore. Temperatures during the main stage of mineralization range from 206 degrees C to 294 degrees C (willemitic ore) and 317 degrees C (sulfides), and reflect the prevailing metamorphic conditions within the shear zone. The fluid from which the gangue minerals of the sulfide bodies precipitated (at 250 degrees C) had an oxygen isotopic average value of delta 18 O = +19.4 per mil. This value appears to reflect the interaction of metamorphic fluid with the carbonate rocks of the Vazante formation. At 250 degrees C, the fluid in equilibrium with the vein mineral phases and willemitic ore assemblage exhibits a uniform oxygen isotopic composition, with an average value of delta 18 O = +11.5 per mil. The positive linear covariance of delta 18 O and delta 13 C ratios of the carbonates is most likely due to the mixing of metamorphic and meteoric fluids. The delta 34 S values of sulfides indicate a direct crustal origin for the sulfur. It is suggested that the sulfur is largely derived from pre-existing sulfide bodies and has been transported by metamorphic fluids. The willemitic ore may have originated from the precipitation of metal in sulfur-poor fluids under oxidized conditions, within the Vazante shear zone.

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