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Enviroscan Ukrainian Institute of Speleology and Karstology


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Community news

Speleology in Kazakhstan

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

New publications on hypogene speleogenesis

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

The deepest terrestrial animal

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

Caves - landscapes without light

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

Did you know?

That mantled karst is karst topography that is wholly or partly covered by a relatively thin veneer of post-karst rock or sediment and is part of the contemporary landscape [17]. see also buried karst; covered karst.?

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.
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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 brines (Keyword) returned 34 results for the whole karstbase:
Showing 16 to 30 of 34
Carbonate-Hosted Zn-Pb Deposits in Upper Silesia, Poland: Origin and Evolution of Mineralizing Fluids and Constraints on Genetic Models, 2003,
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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,
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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

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

Hydrothermal mixing, carbonate dissolution and sulfide precipitation in Mississippi Valley-type deposits, 2004,
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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

Magmatic and Hydrothermal Chronology of the Giant Rio Blanco Porphyry Copper Deposit, Central Chile: Implications of an Integrated U-Pb and 40Ar/39Ar Database, 2005,
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Deckart K, Clark Ah, Celso Aa, Ricardo Vr, Bertens An, Mortensen Jk, Fanning M,
The history of hypabyssal intrusion and hydrothermal activity in the northeastern and central parts of the be-hemothian (sensu Clark, 1993) Rio Blanco-Los Bronces porphyry copper-molybdenum deposit is clarified on the basis of integrated U-Pb and 40Ar/39Ar geochronology. Isotope dilution thermal ion mass spectrometry (ID-TIMS) U-Pb dates for zircon separates and ID-TIMS and sensitive high resolution ion microprobe (SHRIMP) dates for single zircon grains in pre-, syn- and late-mineralization volcanic and intrusive host rocks in the Rio Blanco, Don Luis, and Sur-Sur mining sectors provide a temporal framework for interpretation of incremental-heating and spot-fusion 40Ar/39Ar dates for, respectively, magmatic biotite and hydrothermal biotite, muscovite, and orthoclase. The ore deposit is hosted in part by 16.77 {} 0.25 to 17.20 {} 0.05 (2{sigma}) Ma andesitic volcanic strata of the Farellones Formation, but the major host rocks are units of the San Francisco batholith, including the 11.96 {} 0.40 Ma Rio Blanco granodiorite (mine terminology), the 8.40 {} 0.23 Ma Cascada granodiorite, and the 8.16 {} 0.45 Ma diorite. Hypabyssal dacitic intrusions (late porphyries) emplaced into the batholith yield 206Pb/238U ID-TIMS dates ranging from 6.32 {} 0.09 Ma (quartz monzonite porphyry), through 5.84 {} 0.03 Ma (feldspar porphyry) to 5.23 {} 0.07 Ma (Don Luis porphyry). The late-mineralization Rio Blanco dacite plug yields a SHRIMP zircon age of 4.92 {} 0.09 Ma. The 40Ar/39Ar plateau ages for phenocrystic biotites in quartz monzonite porphyry, feldspar porphyry, and Don Luis porphyry, as well as the preore diorite, range only from 5.12 {} 0.07 to 4.57 {} 0.06 Ma. All are significantly younger than the corresponding zircons and exhibit no correlation with intrusive sequence. The 40Ar/39Ar ages for hydrothermal biotite and orthoclase veins within the San Francisco batholith units fall in a narrow interval from 5.32 {} 0.27 to 4.59 {} 0.11 Ma. Hydrothermal sericites (muscovite), one associated with chalcopyrite, yielded spot-fusion ages of 4.40 {} 0.15 Ma (Rio Blanco granodiorite hosted) and 4.37 {} 0.06 Ma (Don Luis porphyry hosted). Comparison with the ID-TIMS and SHRIMP zircon ages indicates that most of the 40Ar/39Ar ages, even 95 percent plateaus, do not record initial magmatic cooling or hydrothermal alteration-mineralization events, evidence for quasipervasive reheating to at least 300{degrees}C by successive intrusions. Published Re-Os ages for two molybdenite samples range from 5.4 to 6.3 Ma and overlap extensively with the zircon U-Pb ages for the late porphyries. They imply that Cu-Mo mineralization overlapped temporally with the emplacement of, at least, quartz monzonite porphyry and feldspar porphyry units of the late porphyry suite and was, therefore, contemporaneous with the rise of dacitic melts to subvolcanic levels. Hydrothermal activity is inferred to have continued until 4.37 {} 0.06 Ma, following intrusion of the Don Luis porphyry and the early stages of emplacement of the Rio Blanco dacite plug complex. Hypogene Cu-Mo mineralization therefore probably persisted for 2 m.y. The geochronologic data do not resolve whether ore formation was continuous or episodic, but the observed crosscutting relationships between intensely altered and mineralized country rocks and less altered and mineralized late porphyry bodies support a model in which the ascent of metal-rich brines from an unexposed zone of the parental magma chamber was periodically stimulated by magma perturbation and hypabyssal intrusion

Calcite dissolution kinetics and solubility in Na-Ca-Mg-Cl brines of geologically relevant composition at 0.1 to 1 bar pCO2 and 25 to 80°C. Doctoral dissertation, Texas A&M University. , 2005,
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Gledhill, Dwight Kuehl

Sedimentary basins can contain close to 20% by volume pore fluids that are commonly classified as brines. These fluids can become undersaturated with respect to calcite as a result of processes such as migration, dispersive mixing, or anthropogenic injection of CO2. This study measured calcite solubility and dissolution rates in geologically relevant Na-Ca-Mg-Cl synthetic brines (35 to 200 g L-1 TDS). In brines < 50 g L-1 TDS, the EQPITZER calculated calcium carbonate ion activity product (IAP) at steady-state was in reasonable agreement (±10%) with the thermodynamic solubility constant for calcite (Kc). However, the IAP systematically exceeded Kc in more concentrated brines. The deviation was strongly correlated with calcium concentration and also was observed in magnesium-free solutions. This is interpreted as an uncertainty in the carbonate ion activity coefficient, and minor adjustment in stoichiometric association constants (K*M2+CO30) for the CaCO30 or MgCo30 ion pairs would correct for the error. The dissolution rate dependency on brine composition, pCO2 (0.1 to 1 bar), and temperature (25.0 to 82.5 °C) was modeled using the empirical rate equation ()nkRΩ−=1 where R is the rate, k and n are empirical fitting terms, and Ω the degree of disequilibrium with respect to calcite. When Ω was defined relative to an apparent kinetic solubility, n could be assumed first-order over the range of Ω investigated (Ω = 0.2 to 1.0). Rates increased with increasing pCO2 as did the sensitivity to brine concentration. At 0.1 bar, rates were nearly independent of concentration (k = 13.0 ±2.0 x 10-3 moles m-1 hr-1). However, at higher CO2 partial pressures rates became composition dependent and the rate constant, k, was shown to be a function of temperature, pCO2, ionic strength, and calcium and magnesium activity. The rate constant (k) can be estimated from a multiple regression (MR) model of the form k = B0 + B1(T) + B2(pCo2) + B4(aCa2+) + B5(aMg2+). A relatively high activation energy (Ea = 20 kJ mol-1) was measured, along with a stirring rate independence suggesting the dissolution is dominated by surface controlled processes at saturation states Ω > 0.2 in these calcium-rich brines. These findings offer important implications to reaction-transport models in carbonate-bearing saline reservoirs.


Australian Zn-Pb-Ag Ore-Forming Systems: A Review and Analysis, 2006,
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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

Mineralogy of stalactites formed by subaerial weathering of natrocarbonatite hornitos at Oldoinyo Lengai, Tanzania, 2006,
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Mitchell R. H. ,
Stalactites formed by the chemical weathering of natrocarbonatite lava decorate the roofs of hollow inactive hornitos at Oldoinyo Lengai, Tanzania. The stalactites are composed principally of trona with lesser and very variable amounts of nahcolite, (NaHCO3), thermonatrite (Na2CO3.H2O), aphthitalite [(K,Na)3Na(SO4)2], kogarkoite [Na3(SO4)F], schairerite [Na21(SO4)7F6Cl], halite and sylvite. Stalactites are considered to form by the evaporation of Ca-free highly alkaline brines seeping from the altered lavas which form the roofs of the hornitos. The principal subaerial weathering products of natrocarbonatite, i.e. pirsonnite, gaylussite, shortite and calcite are not found in the stalactites and are retained in the altered lavas of the homito roof. Fluorine required for the formation of kogarkoite and schairerite is derived from the decomposition of fluorite at high pH (>10). Sulphur is derived from the decomposition of gregoryite

Exhumation of Messinian evaporites in the deep-sea and creation of deep anoxic brine-filled collapsed basins, 2006,
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Cita Mb,
The first part of the paper summarizes some basic concepts concerning (a) the distribution of Messinian evaporites in the deepest parts of the Mediterranean Sea and (b) the Mediterranean Ridge accretionary wedge and its peculiar characteristics deriving from the presence of a substantial evaporitic body in the deforming sedimentary prism.Then five brine-filled anoxic collapsed basins (Tyro, Bannock, Urania, Atalante and Discovery), discovered from 1983 to 1994, are presented and discussed in their physiographic, geologic, hydrologic and geochemical characters. High density brines deriving from submarine dissolution of outcropping or subcropping evaporites accumulate at the bottom of collapsed basins, if they are not swept away by submarine currents. The interface separating normal sea-water from high density brines is sharp with a density contrast of about 20% and lies at 3200-3500[no-break space]m below sea level. Strong bacterial activity is developing at the interface and living bacteria have been recovered from the anoxic salty brines. Thickness of the brines may be up to 500[no-break space]m. Thermal stratification has been observed in three brine lakes. Exhumation and dissolution of Messinian evaporites in the Mediterranean Ridge occur in different tectonic settings: pull-apart basin (Tyro), subducting seamount close to the outer deformation front (Bannock Basin), top of a backstop (Urania, Atalante and Discovery Basins).Chemistry of the brines is strongly variable and suggests dissolution of different layers or levels of the Messinian suite. Discovery brines are the saltiest ever recorded in natural environment. Their saturation in Mg chloride (bischofite), the end product of sea-water evaporation, suggests that the deepest parts of the eastern Mediterranean were close to dryness at the end of the salinity crisis, strongly supporting the deep basin desiccation model

The beginning, development and termination of the Middle Miocene Badenian salinity crisis in Central Paratethys, 2006,
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Peryt Tadeusz Marek,
Middle Miocene Badenian evaporites of the Carpathian region are underlain and overlain by deep-water deposits, the onset of evaporite deposition was sudden but not synchronous in all facies zones and the deposition of evaporites was controlled by the evolution of Carpathian orogen. In the Carpathian Foredeep (and most probably in other basins) the Badenian evaporites represent the lower part of the NN6 zone. Halite and associated deposits in the central part of the Badenian evaporite basin show the same facies successions and marker beds can be traced across and between individual basins. Characteristic marker beds made it possible to correlate various facies zones of the marginal Ca-sulfate platform. These marker beds seem to reflect events that may be related to sudden and widespread changes in water chemistry, which in turn imply major changes in basin hydrology. The onset of the evaporitic deposition in the Carpathian Foredeep was clearly diachronous and the evaporites deposited in the basin centre preceded the beginning of evaporite sedimentation in the marginal basin, however, depositional history in the marginal basin and the basin centre was the same. A general transgressive sequence of evaporites found in the Carpathian Foredeep resulted from the migration of facies zones induced by the nappe movement.Isotopic studies of Badenian foraminifers occurring below evaporites suggest that the interrupted communication of the Paratethys with the ocean was a consequence of eustatic sea-level fall, possibly related to climatic cooling, and it was coupled with a tectonic closure of connection with the Tethys. Thus both tectonics and eustacy have contributed to the origin of salinity crisis. Sedimentological and geochemical data indicate recycling of evaporites throughout most of the evaporite deposition. The recycling at the end of gypsum deposition in the marginal sulfate platform was accompanied by a change in the hydrology of the Central Paratethys that was tectonically-driven, and possibly related to the block tectonic phase manifested in the marginal part of the Carpathian Foredeep Basin. The change in hydrology implied the dilution of brines by inflowing marine water and this terminated the Middle Miocene Badenian salinity crisis. The onset of the Badenian salinity crisis shows great similarities to the onset of the Messinian salinity crisis and the terminations of both crises were different

Evidence against the Dorag (mixing-zone) model for dolomitization along the Wisconsin arch - A case for hydrothermal diagenesis , 2006,
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Luczaj, J. A.

Ordovician carbonates near the Wisconsin arch represent the type locality in ancient rocks for the Dorag, or mixing-zone, model for dolomitization. Field, petrographic, and geochemical evidence suggests a genetic link between the pervasive dolomite, trace Mississippi Valley–type (MVT) minerals, and potassium (K)-silicate minerals in these rocks, which preserve a regional hydrothermal signature. Constraints were placed on the conditions of water-rock interaction using fluid-inclusion methods, cathodoluminescence and plane-light petrography, stable isotopic analyses, and organic maturity data. Homogenization temperatures of two-phase aqueous fluid inclusions in dolomite, sphalerite, and quartz range between 65 and 120°C. Freezing data suggest a Na-Ca-Mg-Cl-H2O fluid with salinities between 13 and 28 wt.% NaCl equivalent. The pervasive dolomitization of Paleozoic rocks on and adjacent to the Wisconsin arch was the result of water-rock interaction with dense brines at elevated temperatures, and it was coeval with regional trace MVT mineralization and K-silicate diagenesis. A reevaluation of the Dorag (mixing-zone) model for dolomitization, in conjunction with convincing new petrographic and geochemical evidence, has ruled out the Dorag model as the process responsible for pervasive dolomitization along the Wisconsin arch and adds to the abundant body of literature that casts serious doubt about the viability of the Dorag model in general.

John Luczaj is an assistant professor of earth science in the Department of Natural and Applied Sciences at the University of Wisconsin–Green Bay. He earned his B. S. degree in geology from the University of Wisconsin–Oshkosh. This was followed by an M.S. degree in geology from the University of Kansas. He holds a Ph.D. in geology from Johns Hopkins University in Baltimore, Maryland. His recent interests include the investigation of water-rock interaction in Paleozoic sedimentary rocks in the Michigan Basin and eastern Wisconsin. Previous research activities involve mapping subsurface uranium distributions, reflux dolomitization, and U-Pb dating of Permian Chase Group carbonates in southwestern Kansas.


Pervasive dolomitization with subsequent hydrothermal alteration in the Clarke Lake gas field, Middle Devonian Slave Point Formation, British Columbia, Canada , 2006,
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Lonnee J. , Machel H. G.

The Clarke Lake gas field in British Columbia, Canada, is hosted in pervasively dolomitized Middle Devonian carbonates of the Slave Point Formation. The Clarke Lake field consists mostly of pervasive matrix dolomite and some saddle dolomite, the latter varying in volume from about zero in limestones to normally 20–40% (locally up to 80%) in dolostones over any given 10-m (33-ft) core interval. Some of the saddle dolomite is replacive, some is cement, and both varieties are associated with dissolution porosity and recrystallized matrix dolomite. The major objective of this study is to identify the causes and timing of matrix and saddle dolomite formation, specifically, whether these dolomites are hydrothermal. A comprehensive petrographic and geochemical examination indicates that pervasive matrix dolomitization was accomplished by long-distance migration of halite-saturated brines during the Late Devonian toMississippian. Fluid-inclusion homogenization temperatures suggest about 150 (uncorrected) to 190jC (corrected) at the time of matrix dolomitization. These temperatures differ markedly from most published work on the dolomitized Devonian reefs in the Alberta Basin south of the Peace River arch, where pervasive matrix dolomitization was accomplished by advection of slightly modified seawater at temperatures of about 60–80jC, and where no hydrothermal influence was ever present. The saddle dolomites at Clarke Lake are not cogenetic with matrix dolomite and are not the product of hydrothermal dolomitization (sensu stricto). Instead, they formed through the hydrothermal alteration of matrix dolomite by way of invasion of a gypsum-saturated brine during periods of extremely high heat flow and regional plate-margin tectonics in the Late Devonian to Mississippian. Fluidinclusion homogenization temperatures suggest that hydrothermal alteration occurred between 230 (uncorrected) and 267jC (corrected), which is significantly higher than the maximumtemperature of about 190jC attained by the Slave Point Formation during burial. The sources of the halite- and gypsum-saturated brines are Middle Devonian evaporite depositional environments roughly 200 km (124 mi) south and/or east of Clarke Lake, near the Peace River arch


Fractured hydrothermal dolomite reservoirs in the Devonian Dundee Formation of the central Michigan Basin, 2006,
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Luczaj J. A. , Harrison Iii. W. B. , Williams N. S.

The Middle Devonian Dundee Formation is the most prolific oilproducing unit in the Michigan Basin, with more than 375 million bbl of oil produced to date. Reservoir types in the Dundee Formation can be fracture controlled or facies controlled, and each type may have been diagenetically modified. Although fracture-controlled reservoirs produce more oil than facies-controlled reservoirs, little is known about the process by which they were formed and diagenetically modified. In parts of the Dundee, preexisting sedimentary fabrics have been strongly overprinted by medium- to coarse-grained dolomite. Dolomitized intervals contain planar and saddle dolomite, with minor calcite, anhydrite, pyrite, and uncommon fluorite. Fluid inclusion analyses of two-phase aqueous inclusions in dolomite and calcite suggest that some water-rock interaction in these rocks occurred at temperatures as high as 120–150jC in the presence of dense Na-Ca-Mg-Cl brines. These data, in conjunction with published organic maturity data and burial reconstructions, are not easily explained by a long-term burial model and have important implications for the thermal history of the Michigan Basin. The data are best explained by a model involving short-duration transport of fluids and heat from deeper parts of the basin along major fault and fracture zones connected to structures in the Precambrian basement. These data give new insight into the hydrothermal processes responsible for the formation of these reservoirs. 


Tectonic-hydrothermal brecciation associated with calcite precipitation and permeability destruction in Mississippian carbonate reservoirs, Montana and Wyoming , 2006,
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Katz D. A. , Eberli G. P. , Swart P. K. , Smith Jr. L. B.

The Mississippian Madison Formation contains abundant fracture zones and breccias that are hydrothermal in origin based on their morphology, distribution, and geochemical signature. The hydrothermal activity is related to crustal shortening during the Laramide orogeny. Brecciation is accompanied by dedolomitization, late-stage calcite precipitation, and porosity occlusion, especially in outcrop dolomites. The tectonic-hydrothermal late-stage calcite reduces permeability in outcrops and, potentially, high-quality subsurface reservoir rocks of the subsurface Madison Formation, Bighorn Basin. The reduction of permeability and porosity is increased along the margins of the Bighorn Basin but not predictable at outcrop scale. The destruction of porosity and permeability by hydrothermal activity in the Madison Formation is unique in comparison to studies that document enhanced porosity and permeability and invoke hydrothermal dolomitization models. Hydrothermal breccias from the Owl Creek thrust sheet are classified into four categories based on fracture density, calcite volume, and clast orientation. Shattered breccias dominate the leading edge of the tip of the Owl Creek thrust sheet in the eastern Owl Creek Mountains, where tectonic deformation is greatest, whereas fracture, mosaic, and chaotic breccias occur throughout the Bighorn Basin. The breccias are healed by calcite cements with d18O values ranging between _26.5 and _15.1xPeedee belemnite (PDB), indicating that the cements were derived from isotopically depleted fluids with elevated temperatures. In the chaotic and mosaic breccia types, large rotated and angular clasts of the host rock float in the matrix of coarse and nonzoned late-stage calcite. This appearance, combined with similar d18O values across even large calcite veins, indicates that the calcite precipitated rapidly after brecciation. Values for d13C(_5–12xPDB) from the frontal part of the Owl Creek thrust sheet indicate equilibrium between methane and CO2-bearing fluids at about 180jC. Fluid inclusions from the eastern basin margin show that these cements are in equilibrium with fluids having minimum temperatures between 120 and 140jC and formed from relatively low-salinity fluids, less than 5 wt.% NaCl. Strontium isotope ratios of these hydrothermal fluids are more radiogenic than proposed values for Mississippian seawater, suggesting that the fluids mixed with felsic-rich basement before migrating vertically into the Madison Formation. We envisage that the tectonic-hydrothermal late-stage calcitecemented breccias and fractures originated from undersaturated meteoric ground waters that migrated into the burial environment while dissolving and incorporating Ca2+ and CO3 2_ and radiogenic Sr from the dissolution of the surrounding carbonates and the felsic basement, respectively. In the burial environment, these fluids were heated and mixed with hypersaline brines from deeply buried parts of the basement. Expulsion of these fluids along basementrooted thrust faults into the overlying strata, including the Madison Formation, occurred most likely during shortening episodes of the Laramide orogeny by earthquake-induced rupturing of the host rock. The fluids were injected forcefully and in an explosive manner into the Madison Formation, causing brecciation and fracturing of the host rock, whereas the subsequent and sudden decrease in the partial pressure of CO2 caused the rapid precipitation of calcite cements. The explosive nature of hydrothermal fluid migration ultimately produces heterogeneities in reservoir-quality carbonates. In general, flow units in the Madison Formation are related to sequence boundaries, which create vertical subdivisions in the porous dolomite. The late-stage calcite cement surrounds hydrothermal breccia clasts and invades the dolomite, reducing porosity and permeability of the reservoir-quality rock. As a consequence, horizontal flow barriers and compartments are established that are locally unpredictable in their location and extent and regionally predictable along the margins of the Bighorn Basin. 


Nonsulfide and sulfide-rich zinc mineralizations in the Vazante, Ambrsia and Fagundes deposits, Minas Gerais, Brazil: Mass balance and stable isotope characteristics of the hydrothermal alterati, 2007,
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Soares Monteiro Lena Virgí, Nia, Bettencourt Jorge Silva, Juliani Caetano, De Oliveira Tolentino Flvio
The Vazante Group hosts the Vazante nonsulfide zinc deposit, which comprises high-grade zinc silicate ore (ZnSiO4), and late-diagenetic to epigenetic carbonate-hosted sulfide-rich zinc deposits (e.g. Morro Agudo, Fagundes, and Ambrósia). In the sulfide-rich deposits, hydrothermal alteration involving silicification and dolomitization was related with ground preparation of favorable zones for fluid migration (e.g. Fagundes) or with direct interaction with the metalliferous fluid (e.g. Ambrósia). At Vazante, hydrothermal alteration resulted in silicification and dolomite, siderite, jasper, hematite, and chlorite formation. These processes were accompanied by strong relative gains of SiO2, Fe2O3(T), Rb, Sb, V, U, and La, which are typically associated with the nonsulfide zinc mineralization. All sulfide-rich zinc ores in the district display a similar geochemical signature suggesting a common metal source from the underlying sedimentary sequences. Oxygen and carbon isotope compositions of hydrothermally altered rocks reveal a remarkable alteration halo at the Vazante deposit, which is not a notable feature in the sulfide-rich deposits. This pattern could be attributed to fluid mixing processes involving the metalliferous fluid and channelized meteoric water, which may control the precipitation of the Vazante nonsulfide ore. Sulfide deposition resulted from fluid?rock interaction processes and mixing between the ascending metalliferous fluids and sulfur-rich tectonic brines derived from reduced shale units.

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