Formation of Willemite in Hydrothermal Environments, 2003, Brugger J, Mcphail Dc, Wallace M, Waters J,

Willemite (zinc silicate) is the main zinc mineral in some carbonate-hosted ore deposits (e.g., Franklin, New Jersey; Vazante, Brazil; Beltana, South Australia; Kabwe, Zambia). Recent interest in these unconventional zinc deposits has increased because of high zinc grades that exceed 40 wt percent, relatively low environmental impact of ore processing owing to the lack of acid-generating sulfides in the waste, and advances in ore processing technologies. In the past, most metallogenic studies proposed formation of willemite deposits by supergene or hypogene alteration of preexisting sulfide deposits. However, recent data on the Vazante, Beltana, and Kabwe deposits indicate willemite crystallization at temperatures in excess of 150{degrees}C, raising the possibility of primary precipitation from hydrothermal fluids. We use numerical geochemical modeling to examine the formation of willemite under hydrothermal conditions. Activity-activity diagrams reveal that, in the presence of dissolved sulfur and quartz, willemite instead of sphalerite will precipitate under oxidizing (e.g., hematite-stable, sulfate-predominant) and alkaline (pH higher than K feldspar-muscovite-quartz) conditions. Willemite also becomes more stable, relative to sphalerite, at high temperature, and willemite can coexist with magnetite at 300{degrees}C. The stabilities and solubilities of sphalerite, willemite, smithsonite, hydrozincite, and zincite were calculated for wide ranges of temperature (25{degrees}-300{degrees}C), chloride concentration, dissolved sulfur and carbon concentrations, pH, quartz saturation, and oxidation potential. Plots of the solubility of the different minerals as a function of two variables (e.g., temperature and redox state; pH and redox state) allow us to predict the effects of changing chemical conditions, which in turn permits an estimate of the efficiency of particular precipitation processes. Cooling is an effective process for precipitating sphalerite but not willemite, whereas pH increase (e.g., by acidic fluids reacting with carbonates) is effective for precipitating willemite but not sphalerite. Dynamic geochemical models that simulate physicochemical processes are used to understand the formation of the Beltana willemite deposit in the Adelaide geosyncline of South Australia. This small, high grade deposit (850,000 t at 36% Zn) is hosted in dolomite of the Cambrian Ajax Limestone, next to a tectonic contact with the diapiric, halite-bearing clastic sediments of the Callanna Group. The orebody is associated with hematite alteration and is characterized by the total absence of sulfides; willemite is the only zinc ore mineral, and the arsenate hedyphane (Ca2Pb3[AsO4]3Cl) is the main lead mineral. The model results show that willemite will precipitate in response to water-rock interaction and fluid mixing processes at temperatures above 120{degrees}C. The presence of arsenate in the hydrothermal fluid is likely to have been important at Beltana; in arsenate-absent models sulfate is reduced to sulfide by the precipitation of ferrous iron as hematite, resulting in the precipitation of sphalerite and galena. In contrast, in models including arsenate the reduction of sulfate to sulfide is inhibited and willemite is predicted to precipitate

Origin and Significance of Postore Dissolution Collapse Breccias Cemented with Calcite and Barite at the Meikle Gold Deposit, Northern Carlin Trend, Nevada, 2003, Emsbo P, Hofstra Ah,

The final event in a complicated hydrothermal history at the Meikle gold deposit was gold deficient but caused extensive postore dissolution of carbonate, collapse brecciation, and precipitation of calcite and barite crystals in the resulting cavities. Although previously interpreted to be part of the Carlin-type hydrothermal system, crosscutting relationships and U-Th-Pb geochronology constrain this hydrothermal event to late Pliocene time (ca. 2 Ma), nearly 36 Ma after ore formation. Mineralogic, fluid inclusion, and stable isotope data indicate that postore hydrothermal fluids were reduced, H2S-rich, unevolved meteoric waters ({delta}18O = -17{per thousand}) of low temperature (ca. 65{degrees}C). The{delta} 18O values of barite and calcite indicate that these minerals were in isotopic equilibrium, requiring that barite SO4 was derived from the oxidation of reduced sulfur; however, preexisting sulfides in breccia cavities were not oxidized. The{delta} 34S (15{per thousand}) values of barite are higher than those of local bulk sulfide and supergene alunite indicating that SO4 was not derived from supergene oxidation of local sulfide minerals. The 15 per mil {delta}34S value suggests that the H2S in the fluids may have been leached from sulfur-rich organic matter in the local carbonaceous sedimentary rocks. A reduced H2S-rich fluid is also supported by the bright cathodoluminescence of calcite which indicates that it is Mn rich and Fe poor. Calcite has a narrow range of {delta}13C values (0.3-1.8{per thousand}) that are indistinguishable from those of the host Bootstrap limestone, indicating that CO2 in the fluid was from dissolution of the local limestone. These data suggest that dissolution and brecciation of the Bootstrap limestone occurred where H2S-rich fluids encountered more oxidizing fluids and formed sulfuric acid (H2SO4). Intense fracturing in the mine area by previous structural and hydrothermal events probably provided conduits for the descent of oxidized surface water which mixed with the underlying H2S-rich waters to form the dissolving acid. The surface-derived fluid apparently contained sufficient oxygen to produce H2SO4 from H2S but not enough to alter pyrite to Fe oxide. Although H2S is an important gold-transporting ligand, the temperature was too low to transport a significant amount of gold. The presence of analogous calcite- and barite-lined cavities in other Carlin-type deposits suggests that the generation (and oxidation) of H2S-rich meteoric waters was a common phenomenon in north-central Nevada. Previous sulfur isotope studies have also shown that the Paleozoic sedimentary rocks were the principal source of H2S in Devonian sedimentary exhalative-type, Jurassic intrusion-related, Eocene Carlin-type, and Miocene low-sulfidation gold deposits in the region. The similar sulfur source in all of these systems suggests that basin brines, magmatic fluids, and meteoric waters all evolved to be H2S-rich ore fluids by circulation through Paleozoic sedimentary rocks. Thus, although not directly related to gold mineralization, the recent hydrologic history of the deposit provides important clues to earlier ore-forming processes that were responsible for gold mineralization

Carbonate-Hosted Zn-Pb Deposits in Upper Silesia, Poland: Origin and Evolution of Mineralizing Fluids and Constraints on Genetic Models, 2003, Heijlen Wouter, Muchez Philippe, Banks David A. , Schneider Jens, Kucha Henryk, Keppens Eddy,

Microthermometric and crush-leach analyses of fluid inclusions in ore and gangue minerals of the Upper Silesian Zn-Pb deposits, Poland, along with first results of Rb-Sr geochronology on sulfides, provide important constraints on the paleohydrogeologic and metallogenetic models for the origin of these ores. The analyzed samples comprise two generations of dolomite, two generations of sphalerite, galena, and late calcite. The two dolomite generations and the late calcite were also analyzed for their oxygen and carbon isotope compositions, allowing a characterization of the mineralizing fluids. The ore-forming fluids represent highly saline (20-23 wt % CaCl2 equiv) Na-Ca-Cl brines, episodically introduced into the Triassic host carbonates. They had an oxygen isotope composition of ~0 per mil V-SMOW. Their Na-Cl-Br content (molar Na/Br and Cl/Br ratios between 99 and 337 and between 248 and 560, respectively) suggests that they originated by evaporation of seawater, which most likely occurred in the Permian-Triassic. The relative concentrations of potassium (molar K/Cl between 0.0147 and 0.0746) and lithium (molar Li/Cl between 0.0004 and 0.0031) further indicate that the fluids significantly interacted with siliciclastic rocks. The ionic and calculated oxygen isotope compositions of the fluids indicate that they were more evolved than present-day brines in the Upper Silesian coal basin, and the present-day brines show more extensive mixing with low-salinity fluids. The first results of direct Rb-Sr dating of ore-stage sulfides yield an isochron model age of 135 {} 4 Ma for the mineralizing event. This is consistent with hydrothermal activity and ore formation in Upper Silesia occurring in response to Early Cretaceous crustal extension preceding the opening of the northern Atlantic Ocean. The data presented support a model in which bittern brines migrated down into the deep subsurface and evolved into mineralizing fluids owing to extensive water-rock interaction. They were episodically expelled along deeply penetrating faults during the Early Cretaceous to form Zn-Pb deposits in the overlying Mesozoic carbonate rocks

Geology and Geochemistry of the Reocin Zinc-Lead Deposit, Basque-Cantabrian Basin, Northern Spain, 2003, Velasco Francisco, Herrero Jose Miguel, Yusta Inaki, Alonso Jose Antonio, Seebold Ignacio, Leach David,

The Reocin Zn-Pb deposit, 30 km southwest of Santander, Spain, occurs within Lower Cretaceous dolomitized Urgonian limestones on the southern flank of the Santillana syncline. The Reocin deposit is one of the largest known strata-bound, carbonate-hosted, zinc-lead deposits in Europe. The total metal endowment of the deposit, including past production and remaining reserves, is 62 Mt of ore grading 8.7 percent Zn and 1.0 percent Pb. The epigenetic mineralization consists of sphalerite and galena, with lesser marcasite and trace pyrite with dolomite as gangue. Microprobe analyses of different generations of dolomite revealed nonstoichiometric compositions with various amounts of iron (up to 14 mol % of FeCO3). Replacement of host dolomite, open-space filling of fractures, and cementation of breccias derived from dissolution collapse are the principal types of ore occurrence. Detailed cross-section mapping indicates a stratigraphic and structural control on the deposit. A stratiform morphology is present in the western part of the orebody (Capa Sur), whereas mineralization in the eastern part is highly discordant but strata bound (Barrendera). Stratigraphic studies demonstrate that synsedimentary tectonic activity, related to the rifting of the North Atlantic (Bay of Biscay), was responsible for variation in sedimentation, presence of unconformities (including paleokarsts), local platform emergence and dolomitization along the N60 fault trend. In the Reocin area, two stages of dolomitization are recognized. The first stage is a pervasive dolomitization of the limestone country rocks that was controlled by faulting and locally affected the upper part of the Aptian and the complete Albian sequence. The second dolomitization event occurred after erosion and was controlled by karstic cavities. This later dolomitization was accompanied by ore deposition and, locally, filling of dolomite sands and clastic sediments in karstic cavities. The circulation of hydrothermal fluids responsible for sulfide deposition and the infilling of karst cavities were broadly contemporaneous, indicating a post-Albian age. Vitrinite reflectance data are consistent with previously measured fluid inclusion temperatures and indicate temperatures of ore deposition that were less than 100{degrees}C. Carbon and oxygen isotopic data from samples of regional limestone, host-rock dolostone and ore-stage dolomite suggest an early hydrothermal alteration of limestone to dolostone. This initial dolomitization was followed by a second period of dolomite formation produced by the mixing of basinal metal-rich fluids with local modified seawater. Both dolomitization events occurred under similar conditions from fluids exhibiting characteristics of basinal brines. The{delta} 34S values of sulfides are between -1.8 and .5 per mil, which is consistent with thermochemical sulfate reduction involving organic matter as the main source of reduced sulfur. Galena lead isotope compositions are among the most radiogenic values reported for Zn-Pb occurrences in Europe, and they are distinct from values reported for galena from other Basque-Cantabrian deposits. This suggests that a significant part of the lead was scavenged from the local underlying Asturian sediments. The stratigraphic and structural setting, timing of epigenetic mineralization, mineralogy, and isotopic geochemistry of sulfide and gangue minerals of the Reocin deposit are consistent with the features of most of Mississippi Valley-type ore deposits

Hydrothermal mixing, carbonate dissolution and sulfide precipitation in Mississippi Valley-type deposits, 2004, Corbella M, Ayora C, Cardellach E,

A large number of Mississippi Valley-Type (MVT) deposits are located within dissolution zones in carbonate host rocks. Some genetic models propose the existence of cavities generated by an earlier event such as a shallow karstification, that were subsequently filled with hydrothermal minerals. Alternative models propose carbonate dissolution caused by the simultaneous precipitation of sulfides. These models fail to explain either the deep geological setting of the cavities, or the observational features which suggest that the dissolution of carbonates and the precipitation of minerals filling the cavities are not strictly coeval. We present a genetic model inspired by the textural characteristics of MVT deposits that accounts for both the dissolution of carbonate and precipitation of sulfides and later carbonates in variable volumes. The model is based on the mixing of two hydrothermal fluids with a different chemistry. Depending on the proportion of the end members, the mixture dissolves and precipitates carbonates even though the two mixing solutions are both independently saturated in carbonates. We perform reactive transport simulations of mixing of a regional groundwater and brine ascending through a fracture, both saturated in calcite, but with different overall chemistries (Ca and carbonate concentrations, pH, etc). As a result of the intrinsic effects of chemical mixing, a carbonate dissolution zone, which is enhanced by acid brines, appears above the fracture, and another zone of calcite precipitation builds up between the cavity and the surrounding rock. Sulfide forms near the fracture and occupies a volume smaller than the cavity. A decline of the fluid flux in the fracture would cause the precipitation of calcite within the previously formed cavities. Therefore, dissolution of carbonate host rock, sulfide precipitation within the forming cavity, and later filling by carbonates may be part of the same overall process of mixing of fluids in the carbonate host rock

'Sour gas' hydrothermal jarosite: ancient to modem acid-sulfate mineralization in the southern Rio Grande Rift, 2005, Lueth V. W. , Rye R. O. , Peters L. ,

As many as 29 mining districts along the Rio Grande Rift in southern New Mexico contain Rio Grande Rift-type (RGR) deposits consisting of fluorite-barite sulfide-jarosite, and additional RGR deposits occur to the south in the Basin and Range province near Chihuahua, Mexico. Jarosite occurs in many of these deposits as a late-stage hydrothermal mineral coprecipitated with fluorite, or in veinlets that crosscut barite. In these deposits, many of which are limestone-hosted, jarosite is followed by natrojarosite and is nested within silicified or argillized wallrock and a sequence of fluorite-barite sulfide and late hematite-gypsum. These deposits range in age from similar to 10 to 0.4 Ma on the basis of Ar-40/Ar-39 dating of jarosite. There is a crude north-south distribution of ages, with older deposits concentrated toward the south. Recent deposits also occur in the south, but are confined to the central axis of the rift and are associated with modem geothermal systems. The duration of hydrothermal jarosite mineralization in one of the deposits was approximately 1.0 my. Most Delta(18)O(SO4)-OH values indicate that jarosite precipitated between 80 and 240 degrees C, which is consistent with the range of filling temperatures of fluid inclusions in late fluorite throughout the rift, and in jarosite (180 degrees C) from Pena Blanca, Chihuahua, Mexico. These temperatures, along with mineral occurrence, require that the jarosite have had a hydrothermal origin in a shallow steam-heated environment wherein the low pH necessary for the precipitation of jarosite was achieved by the oxidation of H2S derived from deeper hydrothermal fluids. The jarosite also has high trace-element contents (notably As and F), and the jarosite parental fluids have calculated isotopic signatures similar to those of modem geothermal waters along the southern rift; isotopic values range from those typical of meteoric water to those of deep brine that has been shown to form from the dissolution of Permian evaporite by deeply circulating meteoric water. Jarosite delta(34)S values range from -24 parts per thousand to 5 parts per thousand, overlapping the values for barite and gypsum at the high end of the range and for sulfides at the low end. Most delta(34)S values for barite are 10.6 parts per thousand to 13.1 parts per thousand and many delta(34)S values for gypsum range from 13.1 parts per thousand to 13.9 parts per thousand indicating that a component of aqueous sulfate was derived from Permian evaporites (delta(34)S = 12 2 parts per thousand). The requisite H2SO4 for jarosite formation was derived from oxidation of H2S which was likely largely sour gas derived from the thermochemical reduction of Permian sulfate. The low delta(34)S values for the precursor H2S probably resulted from exchange deeper in the basin with the more abundant Permian SO42-- at similar to 150 to 200 degrees C. Jarosite formed at shallow levels after the PH buffering capacity of the host rock (typically limestone) was neutralized by precipitation of earlier minerals. Some limestone-hosted deposits contain caves that may have been caused by the low pH of the deep basin fluids due to the addition of deep-seated HF and other magmatic gases during periods of renewed rifting. Caves in other deposits may be due to sulfuric acid speleogenesis as a result of H2S incursion into oxygenated groundwaters. The isotopic data in these 'sour gas' jarosite occurrences encode a recod of episodic tectonic or hydrologic processes that have operated in the rift over the last 10 my. (c) 2004 Elsevier B.V. All rights reserved

The Geomicrobiology of Ore Deposits, 2005, Southam G. , Saunders James A. ,

Bacterial metabolism, involving redox reactions with carbon, sulfur, and metals, appears to have been important since the dawn of life on Earth. In the Archean, anaerobic bacteria thrived before the Proterozoic oxidation of the atmosphere and the oceans, and these organisms continue to prosper in niches removed from molecular oxygen. Both aerobes and anaerobes have profound effects on the geochemistry of dissolved metals and metal-bearing minerals. Aerobes can oxidize dissolved metals and reduced sulfur, as well as sulfur and metals in sulfide minerals can contribute to the supergene enrichment of sulfide ores, and can catalyze the formation of acid mine drainage. Heterotrophic anaerobes, which require organic carbon for their metabolism, catalyze a number of thermodynamically favorable reactions such as Fe-Mn oxyhydroxide reductive dissolution (and the release of sorbed metals to solution) and sulfate reduction. Bacterial sulfate reduction to H2S can be very rapid if reactive organic carbon is present and can lead to precipitation of metal sulfides and perhaps increase the solubility of elements such as silver, gold, and arsenic that form stable Me-H2S aqueous complexes. Similarly, the bacterial degradation of complex organic compounds such as cellulose and hemicellulose to simpler molecules, such as acetate, oxalate, and citrate, can enhance metal solubility by forming Me organic complexes and cause dissolution of silicate minerals. Bacterially induced mineralization is being used for the bioremediation of metal-contaminated environments. Through similar processes, bacteria may have been important contributors in some sedimentary ore-forming environments and could be important along the low-temperature edges of high-temperature systems such as those that form volcanogenic massive sulfides

Discrimination of meteoric karst breccias from tectono-thermobaric breccias, 2005, Smith Langhorne B. , Palmer Arthur

Tectono-thermobaric breccias and associated hydrothermal dolomite reservoirs, such as those in the Trenton-Black River play, represent a major remaining resource in North America. Tectono-thermobaric breccias must be differentiated from paleokarst breccias for sound exploration and development decisions. Paleokarst breccias and collapsed meteoric caves are genetically related to sequence boundaries. Many have non-carbonate detrital matrix with vestiges of calcite speleothems. Perching on low-permeability strata is common. Modern meteoric caves are far more common in limestone than dolomite, typically <10 meters wide, and limited to areas of local topographic relief and discharge into a surface drainage system. Cavernous porosity is irregularly distributed and rarely more than 5% of the total rock volume. Ancient collapsed caves should show evidence for these characteristics. Tectono-thermobaric breccias form where space is created in active fault zones. Thermobaric (high-pressure, high-temperature) fluids flow up the active faults, enlarge fractures and precipitate minerals such as saddle dolomite, calcite and sulfides between clasts. Breccias follow fault trends, can be up to hundreds of meters wide, and are commonly concentrated beneath sealing shales or argillaceous limestones. These breccias can occur in limestone or dolomite but are commonly associated with hydrothermal matrix dolomitization. High permeability and porosity can be preserved between partially cemented clasts and in linked vugs, fractures and matrix. Tectono-thermobaric breccias form mainly in previously unbrecciated strata, but they may serendipitously intersect earlier meteoric karst. Tectono-thermobaric brecciated reservoirs commonly occur around wrench faults identifiable on seismic data. These reservoirs commonly do not require structural closure, so many potential targets remain undrilled. Tectono-thermobaric carbonate breccias also host many of the world's sulfide ore deposits. Many brecciated reservoirs and ore deposits that have been previously interpreted as meteoric karst may in fact be tectono-thermobaric in origin.

Hypogene Speleogenesis and Karst Hydrogeology of Artesian Basins, 2009,

The volume contains papers presented during the International Conference held May 13 through 17, 2009 in Chernivtsi, Ukraine.

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CONTENTS

PRINCIPAL FEATURES OF HYPOGENE SPELEOGENESIS
Alexander Klimchouk

HYPOGENE CAVE PATTERNS
Philippe Audra, Ludovic Mocochain, Jean-Yves Bigot, and Jean-Claude Nobécourt

MORPHOLOGICAL INDICATORS OF SPELEOGENESIS: HYPOGENIC SPELEOGENS
Philippe Audra, Ludovic Mocochain, Jean-Yves Bigot, and Jean-Claude Nobécourt

HYPOGENE CAVES IN DEFORMED (FOLD BELT) STRATA: OBSERVATIONS FROM EASTERN AUSTRALIA AND CENTRAL EUROPE
R.A.L. Osborne

IDENTIFYING PALEO WATER-ROCK INTERACTION DURING HYDROTHERMAL KARSTIFICATION: A STABLE ISOTOPE APPROACH
Yuri Dublyansky and Christoph Spötl

MICROORGANISMS AS SPELEOGENETIC AGENTS: GEOCHEMICAL DIVERSITY BUT GEOMICROBIAL UNITY
P.J.Boston, M.N. Spilde, D.E. Northup, M.D. Curry, L.A. Melim, and L. Rosales-Lagarde

SIDERITE WEATHERING AS A REACTION CAUSING HYPOGENE SPELEOGENESIS: THE EXAMPLE OF THE IBERG/HARZ/GERMANY Stephan Kempe

SIMULATING THE DEVELOPMENT OF SOLUTION CONDUITS IN HYPOGENE SETTINGS
C. Rehrl, S. Birk, and A.B. Klimchouk

EVOLUTION OF CAVES IN POROUS LIMESTONE BY MIXING CORROSION: A MODEL APPROACH
Wolfgang Dreybrodt, Douchko Romanov, and Georg Kaufmann

SPELEOGENESIS OF MEDITERRANEAN KARSTS: A MODELLING APPROACH BASED ON REALISTIC FRACTURE NETWORKS
Antoine Lafare, Hervé Jourde, Véronique Leonardi, Séverin Pistre, and Nathalie Dörfliger

GIANT COLLAPSE STRUCTURES FORMED BY HYPOGENIC KARSTIFICATION: THE OBRUKS OF THE CENTRAL ANATOLIA, TURKEY
C. Serdar Bayari, N. Nur Ozyurt, and Emrah Pekkans

ON THE ROLE OF HYPOGENE SPELEOGENESIS IN SHAPING THE COASTAL ENDOKARST OF SOUTHERN MALLORCA (WESTERN MEDITERRANEAN)
Joaquín Ginés, Angel Ginés, Joan J. Fornós, Antoni Merino and Francesc Gràcia

HYPOGENE CAVES IN THE APENNINES (ITALY)
Sandro Galdenzi

STEGBACHGRABEN, A MINERALIZED HYPOGENE CAVE IN THE GROSSARL VALLEY, AUSTRIA
Yuri Dublyansky, Christoph Spötl, and Christoph Steinbauer

HYPOGENE CAVES IN AUSTRIA
Lukas Plan, Christoph Spötl, Rudolf Pavuza, Yuri Dublyansky

KRAUSHÖHLE: THE FIRST SULPHURIC ACID CAVE IN THE EASTERN ALPS (STYRIA, AUSTRIA) (Abstract only)
Lukas Plan, Jo De Waele, Philippe Audra, Antonio Rossi, and Christoph Spötl

HYDROTHERMAL ORIGIN OF ZADLAŠKA JAMA, AN ANCIENT ALPINE CAVE IN THE JULIAN ALPS, SLOVENIA
Martin Knez and Tadej Slabe

ACTIVE HYPOGENE SPELEOGENESIS AND THE GROUNDWATER SYSTEMS AROUND THE EDGES OF ANTICLINAL RIDGES
Amos Frumkin

SEISMIC-SAG STRUCTURAL SYSTEMS IN TERTIARY CARBONATE ROCKS BENEATH SOUTHEASTERN FLORIDA, USA: EVIDENCE FOR HYPOGENIC SPELEOGENESIS?
Kevin J. Cunningham and Cameron Walker

HYPOGENE SPELEOGENESIS IN THE PIEDMONT CRIMEA RANGE
A.B. Klimchouk, E.I. Tymokhina and G.N. Amelichev

STYLES OF HYPOGENE CAVE DEVELOPMENT IN ANCIENT CARBONATE AREAS OVERLYING NON-PERMEABLE ROCKS IN BRAZIL AND THE INFLUENCE OF COMPETING MECHANISMS AND LATER MODIFYING PROCESSES
Augusto S. Auler

MORPHOLOGY AND GENESIS OF THE MAIN ORE BODY AT NANISIVIK ZINC/LEAD MINE, BAFFIN ISLAND, CANADA: AN OUTSTANDING EXAMPLE OF PARAGENETIC DISSOLUTION OF CARBONATE BEDROCKS WITH PENE-CONTEMPORANEOUS PRECIPITATION OF SULFIDES AND GANGUE MINERALS IN A HYPOGENE SETTING
Derek Ford

THE INFLUENCE OF HYPOGENE AND EPIGENE SPELEOGENESIS IN THE EVOLUTION OF THE VAZANTE KARST MINAS GERAIS STATE, BRAZIL
Cristian Bittencourt, Augusto Sarreiro Auler, José Manoel dos Reis Neto, Vanio de Bessa and Marcus Vinícios Andrade Silva

HYPOGENIC ASCENDING SPELEOGENESIS IN THE KRAKÓW-CZĘSTOCHOWA UPLAND (POLAND) ? EVIDENCE IN CAVE MORPHOLOGY AND SURFACE RELIEF
Andrzej Tyc

EVIDENCE FROM CERNA VALLEY CAVES (SW ROMANIA) FOR SULFURIC ACID SPELEOGENESIS: A MINERALOGICAL AND STABLE ISOTOPE STUDY
Bogdan P. Onac, Jonathan Sumrall, Jonathan Wynn, Tudor Tamas, Veronica Dărmiceanu and Cristina Cizmaş

THE POSSIBILITY OF REVERSE FLOW PIRACY IN CAVES OF THE APPALACHIAN MOUNTAIN BELT (Abstract only)
Ira D. Sasowsky

KARSTOGENESIS AT THE PRUT RIVER VALLEY (WESTERN UKRAINE, PRUT AREA)
Viacheslav Andreychouk and Bogdan Ridush

ZOLOUSHKA CAVE: HYPOGENE SPELEOGENESIS OR REVERSE WATER THROUGHFLOW?
V. Eirzhyk (Abstract only)

EPIGENE AND HYPOGENE CAVES IN THE NEOGENE GYPSUM OF THE PONIDZIE AREA (NIECKA NIDZIAŃSKA REGION), POLAND
Jan Urban, Viacheslav Andreychouk, and Andrzej Kasza

PETRALONA CAVE: MORPHOLOGICAL ANALYSIS AND A NEW PERSPECTIVE ON ITS SPELEOGENESIS
Georgios Lazaridis

HYPOGENE SPELEOGENESIS IN MAINLAND NORWAY AND SVALBARD?
Stein-Erik Lauritzen

VILLA LUZ PARK CAVES: SPELEOGENESIS BASED ON CURRENT STRATIGRAPHIC AND MORPHOLOGIC EVIDENCE (Abstract only)
Laura Rosales-Lagarde, Penelope J. Boston, Andrew Campbell, and Mike Pullin

HYPOGENE KARSTIFICATION IN SAUDI ARABIA (LAYLA LAKE SINKHOLES, AIN HEETH CAVE)
Stephan Kempe, Heiko Dirks, and Ingo Bauer

HYPOGENE KARSTIFICATION IN JORDAN (BERGISH/AL-DAHER CAVE, UWAIYED CAVE, BEER AL-MALABEH SINKHOLE)
Stephan Kempe, Ahmad Al-Malabeh, and Horst-Volker Henschel

ASSESSING THE RELIABILITY OF 2D RESISTIVITY IMAGING TO MAP A DEEP AQUIFER IN CARBONATE ROCKS IN THE IRAQI KURDISTAN REGION
Bakhtiar K. Aziz and Ezzaden N. Baban

FEATURES OF GEOLOGICAL CONDITIONS OF THE ORDINSKAYA UNDERWATER CAVE, FORE-URALS, RUSSIA
Pavel Sivinskih

INIAAIIINOE AEIIAAIIIAI NIAEAIAAIACA AI?II-NEEAA?AOIE IAEANOE CAIAAIIAI EAAEACA
A.A.Aao?ooaa

AEOAEIIIA NO?IAIEA AEA?IAAINOA?U: IIAAEU AA?OEEAEUIIE CIIAEUIINOE
A.I. Eaoaaa

?IEU EA?NOA A OI?IE?IAAIEE NIEAIUO AIA E ?ANNIEIA IEAI?ENEIAI AANNAEIA
Aeaenaia? Eiiiiia, Na?aae Aeaenaaa, e Na?aae Nooia

MORPHOLOGY AND GENESIS OF THE MAIN ORE BODY AT NANISIVIKZINC/LEAD MINE, BAFFIN ISLAND, CANADA: AN OUTSTANDING EXAMPLEOF PARAGENETIC DISSOLUTION OF CARBONATE BEDROCKS WITHPENE-CONTEMPORANEOUS PRECIPITATION OF SULFIDES AND GANGUEMINERALS, 2009, Ford D.

Nanisivik (Inuit – “the place where they find things’) zinc/lead mine is located at Lat. 73o N in northwestern Baf?n Island. The host rock is a Proterozoic platform carbonate 260-800 m thick, medium to massively bedded and pervasively dolomitized. It rests on mixed shales and shaly dolomites, and is overlain by 150+ m of further shales functioning as an aquitard. These formations were buried by later Proterozoic strata, uplifted, eroded and buried again in a Cambrian sedimentary basin. The ore-grade deposits are contained within a horst block of the dolomites dipping NW at 15o across it. Graben to the north and south are roofed in the overlying shales. The principal deposit, the Main Ore, is of zinc, lead and iron sul?de precipitates plus gangue minerals, chie?y secondary dolomite. It extends for three km E-W along the horst. It is horizontal, at ~300 m above sea level and terminated at both ends by modern valley entrenchments. The Main Ore body is consistently ~100 m in width and ?ve-seven m in depth. This wide ceiling is a nearly planar, horizontal corrosion bevel. The sulfdes scarcely extend above it anywhere. Within the Main Ore two or more generations of tapered ?ns of dolomite in situ extend from both south (updip) and north (downdip) walls into the cavity. Fin surfaces truncate the bedding. Edges of ?ns are sinuous, some meandering with a wavelength of ~50 m. Very sharp, horizontal corrosion notches 20-30 cm high extend into the dolomite walls for at least 20 m (the limit of deep crosscuts in the mine). They are ?lled with layered pyrites which continue out into the ore body as regular sheets truncating earlier, dipping mineral layers until they themselves are truncated by later fillings. One exceptional notch, one meter deep, is at least 350 m in breadth. The ore displays four sedimentary modes: (i) regular layers settled or precipitated onto the cavity floor; (ii) chaotic polymict breccias suggestive of channel cut-and-?ll episodes; (iii) the horizontal pyrite sheets in corrosion notches; (iv) minor metasomatic replacements of dolomite. The ore cavity was created by paragenesis in a channel ?ow mode, with ore and gangue deposition on the floor taking place in tandem with dissolutional cavity creation upwards,. Principal deposition took place when a fluid interface could be rigorously maintained. Fluid inclusions indicate derivation of the metals from exchange reactions with metalliferous sediments (the underlying shales), indicating low water/rock ratios and moderate temperatures. The ore fluids were similar to oil field brines. Sulfur isotope fractionations indicate temperatures of 90-150 +/-40o C, suggesting that the Main Ore formed along a gas/brine interface at a depth of at least 1600 m as a consequence of ?uid expulsion in the subsiding Cambrian sedimentary basin.

Speleothems in the dry Cave Parts of the Gamslöcher-Kolowrat Cave, Untersberg near Salzburg (Austria), 2011, Bieniok Anna, Zagler Georg, Brendel Uwe, Neubauer Franz

New, remarkably dry parts of the Gamslöcher-Kolowrat Cave at 728 to 853 m depth have been explored in the Untersberg near Salzburg in Austria. This region is called the Desert, its greatest cavity is called the White Hall. The new cave part is characterized by various white speleothems. The predominant ones are snow-like calcite powder with an extremely low density, and fine gypsum needles. Gypsum also occurs in the form of balls stuck to vertical walls. In addition, fluorescent hydromagnesite crusts, Mg5(CO3)4(OH)2·4H2O, as well as the sodium sulfate mineral mirabilite were identified in this part of the cave. Mirabilite and gypsum needles differ from the gypsum balls in their isotopic sulfur signature (δ34S of -16.9‰ and -18.4‰ vs. +2.9‰). The unusually low sulfur isotopic compositional values are tentatively explained by a source of bacteriogenetic sulfur from sulfides.

Black Mn-Fe Crusts as Markers of Abrupt Palaeoenvironmental Changes in El Soplao Cave (Cantabria, Spain), 2011, Gázquez Fernando, Calaforra Jose Maria, Forti Paolo

Peculiar iron and manganese deposits coating walls, floors and ceilings of many galleries are one of the special features of the El Soplao Cave (Cantabria, Spain). These speleothems appear to have been deposited over wall clay deposits, as well as forming part of flowstones. Structure of crusts is essentially amorphous but several manganese and iron oxides were identified like goethite and birnessite, though all occur with a low degree of crystallinity. In the outer layer of the crusts, alteration iron minerals appear that derive from previous minerals in a process probably mediated by microorganisms. EDX microanalyses report fairly high values of Fe and Mn in the crusts, though the Mn/Fe ratio varies considerably as a function of distance from the substrate/bedrock. The present study proposes a genetic model for crust speleothems in El Soplao, based on oscillations of the phreatic level. The origin of these deposits is related to mobilization, under phreatic conditions, of polymetallic sulfides in the host rock. Metal ions (including Fe²⁺ and Mn²⁺) released into the cave under reducing conditions, are oxidized and fixed in a process mediated by bacteria, giving rise to oxides and hydroxides of low crystallinity. The presence of various black intercalated layers in aragonite flowstones indicate periods when cave conditions suddenly changed from vadose, when aragonite is precipitated, to phreatic and epiphreatic conditions, when the Mn-Fe deposits are precipitated. Subsequently, vadose conditions were re-established, leading to the final stages of precipitation of aragonite recorded in the flowstone and recent aragonite helictites on the surface of the Mn-Fe crusts.

Sulfuric Acid Caves, 2012, Palmer A, Hill C.

Most caves owe their origin to carbonic acid generated in the soil. In contrast, sulfuric acid caves are produced by the oxidation of sulfides beneath the surface. Although sulfuric acid caves are relatively few, they include some large and well-known examples, such as Carlsbad Cavern, New Mexico. They also provide evidence for a variety of deep-seated processes that are important to petroleum geology, ore geology, tectonic history, and the nascent field of karst geomicrobiology.

Sulfuric acid caves: Morphology and evolution, 2013, Palmer, A. N.

Many hypogene caves are formed by sulfuric acid produced by the oxidation of sulfides, particularly hydrogen sulfide. This cave development can take place below, at, or above the water table. Most cave enlargement is subaerial, in water films and droplets that absorb gaseous hydrogen sulfide and oxygen. Sulfuric acid caves have irregular patterns with large variations in cross section and elevation, with relatively few subhorizontal passages formed along the water table. Cave origin is scattered, localized, and sporadic. Sulfuric acid caves provide evidence for regional geomorphic and tectonic history, groundwater flow patterns, and redox geochemistry.

DEEP TIME ORIGINS OF SINKHOLE COLLAPSE FAILURES IN SEWAGE LAGOONS IN SOUTHEAST MINNESOTA, 2013, Alexander Jr. E. C. , Runkel A. C. , Tipping R. G.

Three of the approximately twenty-three municipal wastewater treatment lagoons constructed in the 1970s and 1980s in southeastern Minnesota’s karst region have failed through sinkhole collapse. Those collapses occurred between 1974 and 1992. All three failures occurred at almost exactly the same stratigraphic position. That stratigraphic interval, just above the unconformable contact between the Shakopee and Oneota Formations of the Ordovician Prairie du Chien Group is now recognized as one of the most ubiquitous, regional-scale, karst hydraulic high-transmissivity zones in the Paleozoic hydrostratigraphy of southeastern Minnesota. These karst aquifers have been developing multi-porosity conduit flow systems since the initial deposition of the carbonates about 480 million years ago. The existence of syndepositional interstratal karst unconformities between the Oneota and Shakopee Formations and between the Shakopee and St. Peter Formations, were recognized in the 1800s. About 270 million years ago galena, sphalerite and iron sulfides were deposited in pre-existing solution enlarged joints, bedding planes and caves. The region has been above sea level since the Cretaceous and huge volumes of fresh water have flowed through these rocks. The regional flow systems have changed from east-to-west in the Cenozoic, to north-to-south in or before the Pleistocene. The incision of the Mississippi River and its tributaries has and is profoundly rearranging the ground water flow systems as it varies the regional base levels during glacial cycles. The Pleistocene glacial cycles have removed many of the surficial karst features and buried even more of them under glacial sediments. High erosion rates from row crop agriculture between the us1850s and 1930s filled many of the conduit systems with soil. Over eighty years of soil conservation efforts have significantly reduced the flux of mobilized soil into the conduits. Those conduits are currently flushing much of those stored soils out of their spring outlets. Finally, the increased frequency and intensity of major storm events is reactivating conduit segments that have been clogged and inactive for millions of years.The karst solution voids into which the lagoons collapsed have formed over 480 million years. The recognition and mapping of this major karst zone will allow much more accurate karst hazard maps to be constructed and used in sustainable resource management decisions.