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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 active cave is 1. cave containing a running stream. 2. cave in which speleothems are growing. (less common and less desirable usage.) compare live cave [10].?

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;
See all featured articles from other geoscience journals

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Your search for h2s (Keyword) returned 81 results for the whole karstbase:
Showing 31 to 45 of 81
Al-Daher Cave (Bergish), Jordan, the first extensive Jordanian limestone cave: a convective Carlsbad-type cave?, 2006, Kempe S. , Almalabeh A. , Alshreideh A. , Henschel Hv.
In spite of the vast limestone area present in Jordan, no karstic caves to speak of were known there until 1995 when Al-Daher Cave was discovered. The cave is situated east of Bergish Reserve for Ecotourism in the mountains of Bergish at about 830 m above sea level. The cave formed in the Wadi As Sir Limestone Formation of Upper Cretaceous age. It is a maze developed along NW-SE and NE-SW striking joints which owe their existence to the Dead Sea Transform Fault situated a few kilometers to the west of the cave. Rooms, with a total area of 1750 m2, were formed within a square of 70 70 m. The cave is constrained to certain limestone strata, laminated and non-laminated, divided by four chert layers that form distinctive markers throughout the cave. Chert nodules occur also within the limestone layers. The cave formed phreatically exclusively by dissolution within a small body of rising and convecting water. It is suggested that the very localized solution capacity derived from the oxidation of either H2S, or possibly even CH4, by oxygen present near the former water table. Thus, Al-Daher Cave may have formed by a process similar to that which formed the Guadalupe Mountain caves, New Mexico, among them Carlsbad Cavern. The altitude of the cave suggests that it may be as old as upper Miocene. The cave contains several relict generations of speleothems but also active forms. The local government is hoping to develop the cave into a show cave; it would be the first in Jordan.

Australian Zn-Pb-Ag Ore-Forming Systems: A Review and Analysis, 2006, Huston David L. , Stevens Barney, Southgate Peter N. , Muhling Peter, Wyborn Lesley,
Zn-Pb-Ag mineral deposits are the products of hydrothermal ore-forming systems, which are restricted in time and space. In Australia, these deposits formed during three main periods at ~2.95, 1.69 to 1.58, and 0.50 to 0.35 Ga. The 1.69 to 1.58 Ga event, which accounts for over 65 percent of Australia's Zn, was triggered by accretion and rifting along the southern margin of Rodinia. Over 93 percent of Australia's Zn-Pb-Ag resources were produced by four ore-forming system types: Mount Isa (56% of Zn), Broken Hill (19%), volcanic-hosted massive sulfide (VHMS; 12%), and Mississippi Valley (8%). Moreover, just 4 percent of Australia's land mass produced over 80 percent of its Zn. The four main types of ore-forming systems can be divided into two 'clans,' based on fluid composition, temperature, and redox state. The Broken Hill- and VHMS-type deposits formed from high-temperature (>200{degrees}C) reduced fluids, whereas the Mount Isa- and Mississippi Valley-type deposits formed from low-temperature (<200{degrees}C), H2S-poor, and/or oxidized fluids. The tectonic setting and composition of the basins that host the ore-forming systems determine these fluid compositions and, therefore, the mineralization style. Basins that produce higher temperature fluids form in active tectonic environments, generally rifts, where high heat flow produced by magmatism drives convective fluid circulation. These basins are dominated by immature siliciclastic and volcanic rocks with a high overall abundance of Fe2. The high temperature of the convective fluids combined with the abundance of Fe2 in the basin allow inorganic sulfate reduction and leaching of sulfide from the country rock, producing reduced, H2S-rich fluids. Basins that produce low-temperature fluids are tectonically less active, generally intracratonic, extensional basins dominated by carbonate and variably mature siliciclastic facies with a relatively low Fe2 abundance. In these basins, sediment maturity depends on the paleogeography and stratigraphic position in an accommodation cycle. Volcanic units, if present, occur in the basal parts of the basins. Because these basins have relatively low heat flow, convective fluid flow is less important, and fluid migration is dominated by expulsion of basinal brines in response to local and/or regional tectonic events. Low temperatures and the lack of Fe2 prevent in-organic sulfate reduction during regional fluid flow, producing H2S-poor fluids that are commonly oxidized (i.e., {sum}SO4 > {sum}H2S). Fluid flow in the two basin types produces contrasting regional alteration systems. High-temperature fluid-rock reactions in siliciclastic-volcanic-dominated basins produce semiconformable albite-hematite-epidote assemblages, but low-temperature reactions in carbonate-siliciclastic-dominated basins produce regional K-feldspar-hematite assemblages. The difference in feldspar mineralogy is mostly a function of temperature. In both basin types, regional alteration zones have lost, and probably were the source of, Zn and Pb. The contrasting fluid types require different depositional mechanisms and traps to accumulate metals. The higher temperature, reduced VHMS- and Broken Hill-type fluids deposit metals as a consequence of mixing with cold seawater. Mineralization occurs at or near the sea floor, with trapping efficiencies enhanced by sub-surface replacement or deposition in a brine pool. In contrast, the low-temperature, oxidized Mount Isa- and Mississippi Valley-type fluids precipitate metals through thermochemical sulfate reduction facilitated by hydrocarbons or organic matter. This process can occur at depth in the rock pile, for instance in failed petroleum traps, or just below the sea floor in pyritic, organic-rich muds

Hydrocarbon Biomarkers in the Topla-Mezica Zinc-Lead Deposits, Northern Karavanke/Drau Range, Slovenia: Paleoenvironment at the Site of Ore Formation, 2006, Spangenberg Jorge E. , Herlec Ursos,
The Mississippi Valley-type zinc and lead deposits at Topla (250,150 metric tons (t) of ore grading 10 wt % Zn and 3.3 wt % Pb) and Me[z]ica (19 million metric tons (Mt) of ore grading 5.3 wt % Pb and 2.7 wt % Zn) occur within the Middle to Upper Triassic platform carbonate rocks of the northern Karavanke/Drau Range geotectonic units of the Eastern Alps, Slovenia. The ore and host rocks of these deposits have been investigated by a combination of inorganic and organic geochemical methods to determine major, trace, and rare earth element (REE) concentrations, hydrocarbon distribution, and stable isotope ratios of carbonates, kerogen, extractable organic matter, and individual hydrocarbons. These data combined with sedimentological evidence provide insight into the paleoenvironmental conditions at the site of ore formation. The carbonate isotope composition, the REE patterns, and the distribution of hydrocarbon biomarkers (normal alkanes and steranes) suggest a marine depositional environment. At Topla, a relatively high concentration of redox sensitive trace elements (V, Mo, U) in the host dolostones and REE patterns parallel to that of the North American shale composite suggest that sediments were deposited in a reducing environment. Anoxic conditions enhanced the preservation of organic matter and resulted in relatively higher total organic carbon contents (up to 0.4 wt %). The isotopic composition of the kerogen ({delta}13Ckerogen = -29.4 to -25.0{per thousand}, {delta}15Nkerogen = -13.6 to 6.8{per thousand}) suggests that marine algae and/or bacteria were the main source of organic carbon with a very minor contribution from detrital continental plants and a varying degree of alteration. Extractable organic matter from Topla ore is generally depleted in 13C compared to the associated kerogen, which is consistent with an indigenous source of the bitumens. The mineralization correlates with {delta}15Nkerogen values around 0 per mil, 13C depleted kerogen, 13C enriched n-heptadecane, and relatively high concentrations of bacterial hydrocarbon biomarkers, indicating a high cyanobacterial biomass at the site of ore formation. Abundant dissimilatory sulfate-reducing bacteria, feeding on the cyanobacterial remains, led to accumulation of biogenic H2S in the pore water of the sediments. This biogenic H2S was mainly incorporated into sedimentary organic matter and diagenetic pyrite. Higher bacterial activity at the ore site also is indicated by specific concentration ratios of hydrocarbons, which are roughly correlated with total Pb plus Zn contents. This correlation is consistent with mixing of hydrothermal metal-rich fluids and local bacteriogenic sulfide sulfur. The new geochemical data provide supporting evidence that Topla is a low-temperature Mississippi Valley-type deposit formed in an anoxic supratidal saline to hypersaline environment. A laminated cyanobacterial mat, with abundant sulfate-reducing bacteria was the main site of sulfate reduction

Cross-formational rising groundwater at an artesian karstic basin: the Ayalon Saline Anomaly, Israel, 2006, Frumkin A, Gvirtzman H,
It is proposed that a geothermal artesian karstic system at the central part of the Yarkon-Taninim aquifer creates the 'Ayalon Saline Anomaly' (ASA), whose mechanism has been under debate for several decades. A 4-year-long detailed groundwater monitoring was carried out at 68 new shallow boreholes in the Ayalon region, accompanied by a comprehensive survey of karstic voids. Results indicate the rising of warm-brackish groundwater through highly permeable swarms of karstic shafts, serving as an outflow of the artesian geothermal system. The ASA area contains 'hot spots', where groundwater contrasts with,normal' water hundreds of meters away. The ASA temperature reaches 30 degrees C ( similar to 5 degrees C warmer than its surroundings), chloride concentration reaches 528 mg/l (50-100 mg/l in the surrounding), H2S concentration reaches 5.6 mg/l (zero all around) and pH value is 7.0 (compared with 7.8 around). Subsequently, the hydrothermal water flows laterally of at the watertable horizon through horizontal conduits, mixing with 'normal' fresh water which had circulated at shallow depth. Following rainy seasons, maximal watertable rise is observed in the ASA compared to its surroundings. Regional hydrogeology considerations suggest that the replenishment area for the ASA water is at the Samaria Mountains, east of the ASA. The water circulates to a great depth while flowing westward, and a cross-formational upward flow is then favored close the upper sub-aquifer's confinement border. (c) 2005 Elsevier Ltd All rights reserved

Textural, Elemental, and Isotopic Characteristics of Pleistocene Phreatic Cave Deposits (Jabal Madar, Oman), 2007, Immenhauser Adrian, Dublyansky Yuri V. , Verwer Klaas, Fleitman Dominik, Pashenko Serguei E. ,
Two main types of karst formation are commonly known: the surficial meteoric one and the subsurface (hypogenic) karst, which can be related to both carbonic (H2CO3) and sulfuric (H2S) acids. This paper documents evidence for a third, CO2-regime related, type of karst that is less commonly described. Petrographic and geochemical properties of exhumed Pleistocene phreatic cave deposits from the diapiric Jabal Madar dome in northern Oman are documented and discussed in a process-oriented context. These calcites form at the interface between two fundamentally different diagenetic and hydrogeological domains: the deep-seated, hydrothermal and the near-surficial, meteoric-vadose one. Four calcite phases are recognized: (i) acicular, (ii) blocky to stubby elongated, (iii) proto-palisade, and (iv) macro-columnar calcites. The macro-columnar calcites, forming the last stage of precipitation, are conspicuous due to their cyclical red zonation, and they form the main (geochemical) focus of this study. Fluid inclusion data point to fluid temperatures of between 30 to 50{degrees}C (monophase liquid inclusions) and elevated salinities (1.6 to 7.3 wt.% NaCl equivalent). Low carbon-isotope data (-8 to -9{per thousand}) are in agreement with the influx of soil-zone CO2 whereas decreasing {delta}18O (-15{per thousand}) values might point to mixing of saline hydrothermal and 18O depleted, meteoric freshwater, i.e., two fluid sources. Trace-element and stable-isotope data shift between the different cement phases and vary cyclically across the red zoning in macro-columnar calcites. With respect to the intra-crystal variability, these patterns are perhaps best explained in the context of redox potential. Two interpretations are presented; the one favored here suggests that the cyclical red zoning in macro-columnar calcites is controlled by Pleistocene monsoonal climate patterns

Hypogene Speleogenesis: Hydrogeological and Morphogenetic Perspective., 2007, Klimchouk A. B.

This book provides an overview of the principal environments, main processes and manifestations of hypogenic speleogenesis, and refines the relevant conceptual framework. It consolidates the notion of hypogenic karst as one of the two major types of karst systems (the other being epigenetic karst). Karst is viewed in the context of regional groundwater flow systems, which provide the systematic transport and distribution mechanisms needed to produce and maintain the disequilibrium conditions necessary for speleogenesis. Hypogenic and epigenic karst systems are regularly associated with different types, patterns and segments of flow systems, characterized by distinct hydrokinetic, chemical and thermal conditions. Epigenic karst systems are predominantly local systems, and/or parts of recharge segments of intermediate and regional systems. Hypogenic karst is associated with discharge regimes of regional or intermediate flow systems.

Various styles of hypogenic caves that were previously considered unrelated, specific either to certain lithologies or chemical mechanisms are shown to share common hydrogeologic genetic backgrounds. In contrast to the currently predominant view of hypogenic speleogenesis as a specific geochemical phenomenon, the broad hydrogeological approach is adopted in this book. Hypogenic speleogenesis is defined with reference to the source of fluid recharge to the cave-forming zone, and type of flow system. It is shown that confined settings are the principal hydrogeologic environment for hypogenic speleogenesis. However, there is a general evolutionary trend for hypogenic karst systems to lose their confinement due to uplift and denudation and due to their own expansion. Confined hypogenic caves may experience substantial modification or be partially or largely overprinted under subsequent unconfined (vadose) stages, either by epigenic processes or continuing unconfined hypogenic processes, especially when H2S dissolution mechanisms are involved.

Hypogenic confined systems evolve to facilitate cross-formational hydraulic communication between common aquifers, or between laterally transmissive beds in heterogeneous soluble formations, across cave-forming zones. The latter originally represented low-permeability, separating units supporting vertical rather than lateral flow. Layered heterogeneity in permeability and breaches in connectivity between different fracture porosity structures across soluble formations are important controls over the spatial organization of evolving ascending hypogenic cave systems. Transverse hydraulic communication across lithological and porosity system boundaries, which commonly coincide with major contrasts in water chemistry, gas composition and temperature, is potent enough to drive various disequilibrium and reaction dissolution mechanisms. Hypogenic speleogenesis may operate in both carbonates and evaporites, but also in some clastic rocks with soluble cement. Its main characteristic is the lack of genetic relationship with groundwater recharge from the overlying or immediately adjacent surface. It may not be manifest at the surface at all, receiving some expression only during later stages of uplift and denudation. In many instances, hypogenic speleogenesis is largely climate- independent.

There is a specific hydrogeologic mechanism inherent in hypogenic transverse speleogenesis (restricted input/output) that suppresses the positive flow-dissolution feedback and speleogenetic competition in an initial flowpath network. This accounts for the development of more pervasive channeling and maze patterns in confined settings where appropriate structural prerequisites exist. As forced-flow regimes in confined settings are commonly sluggish, buoyancy dissolution driven by either solute or thermal density differences is important in hypogenic speleogenesis.

In identifying hypogenic caves, the primary criteria are morphological (patterns and meso-morphology) and hydrogeological (hydrostratigraphic position and recharge/flow pattern viewed from the perspective of the evolution of a regional groundwater flow system). Elementary patterns typical for hypogenic caves are network mazes, spongework mazes, irregular chambers and isolated passages or crude passage clusters. They often combine to form composite patterns and complex 3- D structures. Hypogenic caves are identified in various geological and tectonic settings, and in various lithologies. Despite these variations, resultant caves demonstrate a remarkable similarity in cave patterns and meso-morphology, which strongly suggests that the hydrogeologic settings were broadly identical in their formation. Presence of the characteristic morphologic suites of rising flow with buoyancy components is one of the most decisive criteria for identifying hypogenic speleogenesis, which is much more widespread than was previously presumed. Hypogenic caves include many of the largest, by integrated length and by volume, documented caves in the world.

The refined conceptual framework of hypogenic speleogenesis has broad implications in applied fields and promises to create a greater demand for karst and cave expertise by practicing hydrogeology, geological engineering, economic geology, and mineral resource industries. Any generalization of the hydrogeology of karst aquifers, as well as approaches to practical issues and resource prospecting in karst regions, should take into account the different nature and characteristics of hypogenic and epigenic karst systems. Hydraulic properties of karst aquifers, evolved in response to hypogenic speleogenesis, are characteristically different from epigenic karst aquifers. In hypogenic systems, cave porosity is roughly an order of magnitude greater, and areal coverage of caves is five times greater than in epigenic karst systems. Hypogenic speleogenesis commonly results in more isotropic conduit permeability pervasively distributed within highly karstified areas measuring up to several square kilometers. Although being vertically and laterally integrated throughout conduit clusters, hypogenic systems, however, do not transmit flow laterally for considerable distances. Hypogenic speleogenesis can affect regional subsurface fluid flow by greatly enhancing initially available cross- formational permeability structures, providing higher local vertical hydraulic connections between lateral stratiform pathways for groundwater flow, and creating discharge segments of flow systems, the areas of low- fluid potential recognizable at the regional scale. Discharge of artesian karst springs, which are modern outlets of hypogenic karst systems, is often very large and steady, being moderated by the high karstic storage developed in the karstified zones and by the hydraulic capacity of an entire artesian system. Hypogenic speleogenesis plays an important role in conditioning related processes such as hydrothermal mineralization, diagenesis, and hydrocarbon transport and entrapment.

An appreciation of the wide occurrence of hypogenic karst systems, marked specifics in their origin, development and characteristics, and their scientific and practical importance, calls for revisiting and expanding the current predominantly epigenic paradigm of karst and cave science.


Modelling of calcium sulphate solubility in concentrated multi-component sulphate solutions, 2007, Azimi G. , Papangelakis V. G. , Dutrizac J. E.

The chemistry of several calcium sulphate systems was successfully modelled in multi-component acid-containing sulphate solutions using the mixed solvent electrolyte (MSE) model for calculating the mean activity coefficients of the electrolyte species. The modelling involved the fitting of binary mean activity, heat capacity and solubility data, as well as ternary solubility data. The developed model was shown to accurately predict the solubility of calcium sulphate from 25 to 95 °C in simulated zinc sulphate processing solutions containing MgSO4, MnSO4, Fe2(SO4)3, Na2SO4, (NH4)2SO4 and H2SO4. The addition of H2SO4 results in a significant increase in the calcium sulphate solubility compared to that in water. By increasing the acid concentration, gypsum, which is a metastable phase above 40 °C, dehydrates to anhydrite, and the conversion results in a decrease in the solubility of calcium sulphate. In ZnSO4–H2SO4 solutions, it was found that increasing MgSO4, Na2SO4, Fe2(SO4)3 and (NH4)2SO4 concentrations do not have a pronounced effect on the solubility of calcium sulphate. From a practical perspective, the model is valuable tool for assessing calcium sulphate solubilities over abroad temperature range and for dilute to concentrated multi-component solutions.


Sulfidic ground-water chemistry in the Frasassi Caves, Italy, 2008, Galdenzi S. , Cocchioni M. , Moricheui L. , Amici V. , And Scud S.
A year-long study of the sulfidic aquifer in the Frasassi caves (central Ita ly) employed chemical analysis of the water and measurements of its level, as well as assessments of the concentration of H2S, CO2, and O2 in the cave air. Bica rbonate water seepage derives from diffuse infiltration of meteoric water into the karst surface, and contributes to sulfidic ground-water dilution, with a percentage that varies between 30% and 60% during the year. Even less diluted sulfidic ground water was found in a localized area of the cave between Lago Verde and nearby springs . This water rises from a deeper phreatic zone , and its chemistry changes only slightly with the seasons with a contribution of seepage water that does not exceed 20'10 . In order to understand how the H2S oxidation, which is considered the main cave forming process, is influenced by the seasonal changes in the cave hydrology, the sulfide/total sulfur ratio was related to ground-water dilution and air composition. The data suggest that in the upper phreatic zone, limestone corrosion due to H2S oxidation is prominent in the wet season because of the high recharge of Oj-rich seepage water, while in the dry season, the H2S content increases, but the extent of oxidation is lower. In the cave atmosphere, the low H2S content in ground water during the wet season inhibits the release of this gas, but the H2S concentration increases in the dry season, favoring its oxidation in the air and the replacement of limestone with gypsum on the cave walls.

THE RELATIONSHIP BETWEEN CAVE MINERALS AND H2S RICH THERMAL WATERS ALONG THE CERNA VALLEY (SW ROMANIA), 2009, Onac Bogdan P. , Sumrall Jonathan, Tamas Tudor, Povara Ioan, Kearns Joe, Drmiceanu Veronica, Veres Daniel & Lascu Cristian
Within the Cerna Valley in southwestern Romania, over a 100 caves were formed in the Jurassic and Cretaceous limestone that outcrops on the valley walls. Three aspects are prominent when entering most of the caves in this region: the presence of considerable gypsum deposits, the amount of guano, and the cave temperature. High temperature anomalies are uncommon in the cave environment. In certain caves in the lower part of Cerna Valley, however, one can measure air temperatures as high as 40C. This situation is due to the presence of thermal water pooling or =owing through the caves or to the hot steam that rises along fractures from deeper thermal water pools. As a result, these caves provide a unique set of conditions that allowed for the deposition of a suite of unusual minerals. This study presents the results of fiftyy-seven mineral samples that were investigated by means of X-ray diffraction, geochemical, Fourier-transformed infrared spectroscopy, and scanning electron microscope analyses with the scope of linking the cave minerals with likely hypo- gene speleogenetic processes. Here we document the occurrence of twenty-two secondary cave minerals, among which, apjonite and tamarugite are the first recorded occurrences in a limestone cave environment. The minerals fall into three distinct associations: sulfate-dominated (Diana Cave), phosphate-dominated (Adam Shaft), and sulfate-phosphate-nitrate-rich assemblage (Great Salitrari Cave). Additional isotopic measurements performed on sulfate speleothems contribute valuable information on both minerals and cave origins.

NEW INSIGHTS INTO KARST AND CAVES OF NORTHWESTERN ZAGROS (NORTHERN IRAQ), 2009, Stevanovi? Zoran, Iurkiewicz Adrian & Maran Aleksandra
During 2002, several reconnaissance speleological explorations were undertaken by the authors and local enthusiasts in the karst of Northwestern Zagros in Northern Iraq. Some of the caves were visited for the first time and explored to a great depth by the scientists, while the Shanidar cave is a world-famous site representing one of the oldest discovered and investigated human settlements. The explored caves are located in well-karstified limestones of the Cretaceous age as well as in younger Eocene limestones. This paper contains the data from the nine largest caves. Their total explored lengths range from a few tens of meters up to several hundred meters. Four caves are fossil, containing only percolated water, while %ve represent still hydrogeologically active features. Two of them have resulted from the dissolution of carbonate or evaporate rocks stimulated by water oversaturated in H2S which migrated from deeper oil-bearing structures.

The relationship between cave minerals and H2S rich thermal waters along the Cerna Valley (SW Romania), 2009, Onac Bogdan P. , Sumbrall Jonathan, Tamas Tudor, Povara Ioan, Kearns Joe, Darmiceanu Veronica, Veres Daniel, Lascu Cristian

Within the Cerna Valley in southwestern Romania, over a 100 caves were formed in the Jurassic and Cretaceous limestone that outcrops on the valley walls. Three aspects are prominent when entering most of the caves in this region: the presence of considerable gypsum deposits, the amount of guano, and the cave temperature. High temperature anomalies are uncommon in the cave environment. In certain caves in the lower part of Cerna Valley, however, one can measure air temperatures as high as 40°C. This situation is due to the presence of thermal water pooling or =owing through the caves or to the hot steam that rises along fractures from deeper thermal water pools. As a result, these caves provide a unique set of conditions that allowed for the deposition of a suite of unusual minerals. This study presents the results of fiftyy-seven mineral samples that were investigated by means of X-ray diffraction, geochemical, Fourier-transformed infrared spectroscopy, and scanning electron microscope analyses with the scope of linking the cave minerals with likely hypo- gene speleogenetic processes. Here we document the occurrence of twenty-two secondary cave minerals, among which, apjonite and tamarugite are the first recorded occurrences in a limestone cave environment. The minerals fall into three distinct associations: sulfate-dominated (Diana Cave), phosphate-dominated (Adam Shaft), and sulfate-phosphate-nitrate-rich assemblage (Great Salitrari Cave). Additional isotopic measurements performed on sulfate speleothems contribute valuable information on both minerals and cave origins.


EVIDENCE FROM CERNA VALLEY CAVES (SW ROMANIA) FOR SULFURIC ACID SPELEOGENESIS: A MINERALOGICAL AND STABLE ISOTOPE STUDY, 2009, Onac B. , Sumrall J. , Wynn J. , Tamas T. , Dormiceanu V. , Cizma? C.

Over 30 caves are known to develop in the Jurassic and Cretaceous limestone that outcrops along the lower part of the Cerna Valley and its tributaries in southwestern Romania. There are three features that strike observers when entering most of these caves: a variety of sulfate speleothems, large amounts of bat guano (both fossil and fresh), and unusually high cave temperatures. Such thermal anomalies are rather uncommon in the ordinary cave environment. Along Cerna Valley, however, one can measure temperatures (in some cavities) as high as 40ºC. This situation is due to (i) presence of thermal water pools, (ii) hot water flowing along cave passages, (iii) hot steam rising up fractures from depth.
Seventy-four mineral samples were collected from eight caves in the Cerna Valley. These were investigated by means of X-ray diffraction, scanning electron microscope, and electron microprobe analyses. The minerals identified so far in Sălitrari, Ion Barzoni, Sălitrari 2, Diana, Adam, Despicătura, and Grota cu Aburi caves, are: calcite [CaCO3], aragonite [CaCO3], gypsum [CaSO4•2H2O], anhydrite [CaSO4], pickeringite [MgAl2(SO4)4•22H2O], halotrichite [Fe2+Al2(SO4)4•22H2O], kalinite [KAl(SO4)2•11H2O], melanterite [FeSO4•7H2O], apatite- (Ca(OH) [Ca5(PO4)3(OH)], brushite [CaHPO4•2H2O], darapskite [Na3(SO4)(NO3)•H2O], and nitratine [NaNO3]. The phosphates and nitrates (except for darapskite) were precipitated in a typical vadose environment from reactions between phosphoric solutions supplied by bat guano and limestone bedrock. Most of the sulfates and darapskite are the result of sulfuric acid speleogenesis.
In addition, sulfur isotope measurements (δ34S) on sulfate speleothems and spring waters were undertaken to determine the origin of cave sulfates (i.e., vadose, hypogene, bacteriogenic, etc.). The isotope measurements in the springs show sulfide δ34S ranges from -21.9‰ to 24.0‰ with a mean value of 6.6‰ (n=9), whereas the sulfate δ34S ranges from 16.6‰ to 71.3‰ with a mean value of 30.1‰ (n=10).
Three populations of sulfur isotope values (negative, near zero, and positive) were found in the caves. Samples from Barzoni Cave (the most distant cave from any modern thermal spring) are extremely depleted (-23 to -28‰). Sulfide values of the nearest springs are approximately -20‰. In Sălitrari Cave, the range of values was from -19.8 to +6.5‰. It is more than likely a reflection of the increase in completeness of the reduction of sulfate. The δ34S value of gypsum in Grota cu Aburi (active H2S hot steam cave) was 6.5‰. This value is similar to the sulfur isotopic composition measured in darapskite from Sălitrari Cave; thus, probably documenting earlier sulfuric acid activity in the latter cave.
The final population of caves, especially Despicătura and Diana caves, has enriched sulfur isotope values, which correspond well to the sulfide values of nearby springs. Diana Cave from which Diana 3 spring originates has a sulfide isotopic composition of +19‰, which is approximately the value of the mean of the cave sulfates from Diana Cave. This shows that the cave sulfate isotopic value is controlled by the sulfide, which (after being oxidized) reacts with limestone/marls to produce gypsum or other sulfate minerals.


The sulfidic thermal caves of Acquasanta Terme (central Italy), 2010, Galdenzi S. , Cocchioni F. , Filipponi G. , Morichetti L. , Scuri S. , Selvaggio R. , And Cocchioni M.

The caves of Acquasanta Terme (central Italy) open at the core of a wide anticline, in the valley of the Tronto River. Cave development is due to the rise of sulfidic thermal water flowing through a thick marine limestone sequence, overlain by thick, low- permeability formations. Some minor caves are developed in the terraced travertines deposited by the thermal water, but the major caves are developed in marine limestone in the small gorge of the Rio Garrafo stream, a tributary of the Tronto River. These caves have a rising pattern, due to the past flow of thermal water toward the surface. The deepening of the Tronto River Valley lowered the regional water table, perching the Rio Garrafo stream ,50 m above the thermal groundwater. At present, surface water sinks through the pre-existing karst passages to reach the thermal water flowing in the lower parts of the caves. Where these waters mix, rapid corrosion of the walls through sulfuric acid speleogenesis occurs. Annual temperature and chemistrymonitoring of the cave water showed that freshwater contributes up to 45% of the volume at the water table. Dilution events are associated with falling water temperature, which ranges between 44uC and 32uC. At the main spring, 2 km downstream, groundwater dilution was higher resulting in lower temperatures (32uC–21uC) and salinity. The periods of high freshwater dilution correspond with a lowering of pHin the phreatic water and with the release ofH2S and CO2 to the cave atmosphere. In the thermal zones, the concentration of H2S increased from 40 to over 240 ppm, while CO2 increased from 0.44% to 2.7%. These data evidence the influence of sinking surface water on the cave environment and speleogenesis.


Hypogenic caves in France. Speleogenesis and morphology of the cave systems, 2010, Audra Ph. , D'antoninebecourt J. C. , Bigot J. Y.

Hypogenic caves develop by recharge from below, not directly influenced by seepage from the overlying land surface. Several processes of speleogenesis are combined, involving CO2 or H2S produced at depth. If the recharge from depth remains uniform, the growth of selected fissures is prevented, giving rise to maze cave systems with an upward development trend, which is defined as “transverse speleogenesis” [Klimchouk, 2003]. Hypogenic caves are much fewer than epigenic caves (i.e. developed downwards by meteoric water with aggressivity derived from soil). In France, as in the rest of the world, hypogenic caves were poorly recognized until recently because of their lower frequency, subsequent epigenic imprint often hiding the true origin, and the absence of a global conceptual model. However, about a hundred of hypogenic caves have been identified recently in France. The extreme diversity of hypogenic cave patterns and features is due to the variety of geological and topographic settings and types of flow. Thermal caves are a sub-set of hypogenic caves. Active thermal caves are few and small (Mas d’En Caraman, Vallon du Salut). Often, thermal in fluences only occur as point thermal in feeders into epigenic caves (Mescla, Estramar). In addition to the higher temperature, they may be characterized by CO2 (Madeleine) or H2S degassing, by warm water flowing in ceiling channels, or by manganese deposits. The Giant Phreatic Shafts locate along regional active fault lines. They combine all characteristics (thermal, CO2, H2S), due to the fast rising of deep water. The Salins Spring has been explored by scuba diving down to –70 m. Such a hyperkarstification is responsible for the development of the deepest phreatic shafts of the world: pozzo del Merro, Italy (-392 m). Inactive hypogenic caves may be recognized by their specific mineralization or by the presence of large calcite spar. Metallic deposits are due to the rising of deep waters that are warm, aggressive, and low in oxidation potential. Mixing with meteoric water generates Mississippi Valley Type (MVT) sulfidic ores. Iron deposits as massive bodies (Lagnes) or onto microbial media (Iboussires, Malacoste) making specific facies, such as “black tubes”, iron flakes, and iron pool fingers. Other frequent minerals are Mn oxides and Pb sulfur. In such low thermal conditions, calcite deposits occur as large spar in geodes or as passage linings. Other inactive hypogenic caves may also be recognized by characteristic patterns, such as mazes. The relatively constant recharge into confined karst aquifers suppresses fissure competition, so they enlarge at similar rates, producing a maze pattern. In horizontal beds, mazes extend centrifugally around the upwelling feeder. The juxtaposition of multiple discrete vertical feeders produces extended horizontal mazes. In gently tilted structures, 2D mazes extend below aquitards, or along bedding or more porous beds (Saint-Sbastien). In thick folded limestone the rising hypogenic flow alternatively follows joints and bedding planes, producing a 3D maze cave in a stair case pattern (Pigette). Isolated chambers are large cupola-like chambers fed by thermal slots. Thermal convection of air in a CO2-rich atmosphere causes condensation-corrosion that quickly produces voids above the water table (Champignons Cave). Sulfuric acid caves with replacement gypsum are produced by H2S degassing in the cave atmosphere. H2S oxidizes to H2SO4, which corrodes the carbonate rock and replaces it with gypsum. The strongest corrosion occurs above the water table, where sulfide degassing and thermal convection produce strong condensation-corrosion. Caves develop head ward from springs and from thermo-sulfuric slots upward (Chevalley-Serpents System). The low-gradient main drains record base level positions and even the slightest stages of water-table lowering (Chat Cave). Hypogenic speleogenesis provides better understanding of the distribution of karst voids responsible for subsidence hazards and the emplacement of minerals and hydrocarbons.


Reconnaissance study of active sulfide springs and cave systems in the southern part of the Sulaimani Governorate (NE Iraq), 2010, Iurkiewicz Adrian A. , Stevanovic Zoran P.

A fairly important number of springs with H2S degassing were identified in all three structural compartments of northeastern Iraq, namely the thrust, high and Low Folded Zones. The speleogenesis process is active for some of these systems and the sulfuric acid dissolution is partly documented for the initiation and actual progress of the process. Apart from carbonic acid dissolution of carbonate rocks, the speleogenesis process can also be activated and sustained by sulfuric acid dissolution. Caves genetically based on the oxidation of H2S have been described in a continuously increasing number of sites distributed worldwide. Presence of sulfide springs in the northeastern part of Iraq is normal rather than exceptional. It is assumed that H2S from deeper oil/gas structures, or only resulting from hydrocarbons existent in caprocks or in
carbonate layers, is entrapped within the anticline plunge. Groundwater monitoring and intensive mapping activities exploiting UN-FAO program research data (2001–2003) support the preliminary hypothesis concerning the understanding and analysis of the most relevant sulfide spring. Specific to these karst systems is the combination of chemical/dissolution processes leading to mixed karst morphology features heaving as starting point occurrences of gypsum layers and possible hydrocarbon solutions inflows.


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