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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 outwash plain is plain in front of a glacier that is composed of outwash material [16]. a broad, gently sloping sheet of outwash [6].?

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 fluid (Keyword) returned 298 results for the whole karstbase:
Showing 31 to 45 of 298
CHEMICAL-REACTION PATH MODELING OF ORE DEPOSITION IN MISSISSIPPI VALLEY-TYPE PB-ZN DEPOSITS OF THE OZARK REGION UNITED-STATES MIDCONTINENT, 1994,
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Plumlee G. S. , Leach D. L. , Hofstra A. H. , Landis G. P. , Rowan E. L. , Viets J. G. ,
The Ozark region of the U.S. midcontinent is host to a number of Mississippi Valley-type districts, including the world-class Viburnum Trend, Old Lead Belt, and Tri-State districts and the smaller Southeast Missouri barite, Northern Arkansas, and Central Missouri districts. There is increasing evidence that the Ozark Mississippi Valley-type districts formed locally within a large, interconnected hydrothermal system that also produced broad fringing areas of trace mineralization, extensive subtle hydrothermal alteration, broad thermal anomalies, and regional deposition of hydrothermal dolomite cement. The fluid drive was provided by gravity flow accompanying uplift of foreland thrust belts during the Late Pennsylvanian to Early Permian Ouachita orogeny. In this study, we use chemical speciation and reaction path calculations, based on quantitative chemical analyses of fluid inclusions, to constrain likely hydrothermal brine compositions and to determine which precipitation mechanisms are consistent with the hydrothermal mineral assemblages observed regionally and locally within each Mississippi Valley-type district in the Ozark region. Deposition of the regional hydrothermal dolomite cement with trace sulfides likely occurred in response to near-isothermal effervescence of CO2 from basinal brines as they migrated to shallower crustal levels and lower confining pressures. In contrast, our calculations indicate that no one depositional process can reproduce the mineral assemblages and proportions of minerals observed in each Ozark ore district; rather, individual districts require specific depositional mechanisms that reflect the local host-rock composition, structural setting, and hydrology. Both the Northern Arkansas and Tri-State districts are localized by normal faults that likely allowed brines to rise from deeper Cambrian-Ordovician dolostone aquifers into shallower carbonate sequences dominated by limestones. In the Northern Arkansas district, jasperoid preferentially replaced limestones in the mixed dolostone-limestone sedimentary packages. Modeling results indicate that the ore and alteration assemblages in the Tri-State and Northern Arkansas districts resulted from the flow of initially dolomite-saturated brines into cooler limestones. Adjacent to fluid conduits where water/rock ratios were the highest, the limestone was replaced by dolomite. As the fluids moved outward into cooler limestone, jasperoid and sulfide replaced limestone. Isothermal boiling of the ore fluids may have produced open-space filling of hydrothermal dolomite with minor sulfides in breccia and fault zones. Local mixing of the regional brine with locally derived sulfur undoubtedly played a role in the development of sulfide-rich ore runs. Sulfide ores of the Central Missouri district are largely open-space filling of sphalerite plus minor galena in dolostone karst features localized along a broad anticline. Hydrothermal solution collapse during ore deposition was a minor process, indicating dolomite was slightly undersaturated during ore deposition. No silicification and only minor hydrothermal dolomite is present in the ore deposits. The reaction path that best explains the features of the Central Missouri sulfide deposits is the near-isothermal mixing of two dolomite-saturated fluids with different H2S and metal contents. Paleokarst features may have allowed the regional brine to rise stratigraphically and mix with locally derived, H2S-rich fluids

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

ASSOCIATION OF TEPEES AND PALEOKARST IN THE LADINIAN CALCARE-ROSSO (SOUTHERN ALPS, ITALY), 1994,
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Mutti M. ,
The Ladinian Calcare Rosso of the Southern Alps provides a rare opportunity to examine the temporal relationships between tepees and palaeokarst. This unit comprises peritidal strata pervasively deformed into tepees, repeatedly capped by palaeokarst surfaces mantled by terra rossa. Palaeokarsts, characterized by a regional distribution across the Southern Alps, occur at the base and at the top of the unit. Local palaeokarsts, confined to this part of the platform, occur within the Calcare Rosso and strongly affected depositional facies. Tepee deformation ranges from simple antiformal structures (peritidal tepecs) to composite breccias floating in synsedimentary cements and internal sediments (senile tepees). Peritidal tepees commonly occur at the top of one peritidal cycle, in association with subaerial exposure at the cycle top, while senile tepees affect several peritidal cycles, and are always capped by a palaeokarst surface. Cements and internal sediments form up to 80% of the total rock volume of senile tepees. The paragenesis of senile tepees is extremely complex and records several, superimposed episodes of dissolution, cement precipitation (fibrous cements, laminated crusts, mega-rays) and deposition of internal sediments (marine sediment and terra rossa). Petrographical observations and stable isotope geochemistry indicate that cements associated with senile tepees precipitated in a coastal karstic environment under frequently changing conditions, ranging from marine to meteoric, and were altered soon after precipitation in the presence of either meteoric or mixed marine/meteoric waters. Stable isotope data for the cements and the host rock show the influence of meteoric water (average deltaO-18 = - 5.8 parts per thousand), while strontium isotopes (average Sr-87/Sr-86 = 0.707891) indicate that cements were precipitated and altered in the presence of marine Triassic waters. Field relationships, sedimentological associations and paragenetic sequences document that formation of senile tepees was coeval with karsting. Senile tepees formed in a karst-dominated environment in the presence of extensive meteoric water circulation, in contrast to previous interpretations that tepees formed in arid environments, under the influence of vadose diagenesis. Tepees initiated in a peritidal setting when subaerial exposure led to the formation of sheet cracks and up-buckling of strata. This porosity acted as a later conduit for either meteoric or mixed marine/meteoric fluids, when a karst system developed in association with prolonged subaerial exposure. Relative sea level variations, inducing changes in the water table, played a key role in exposing the peritidal cycles to marine, mixed marine/meteoric and meteoric diagenetic environments leading to the formation of senile tepees. The formation and preservation in the stratigraphic record of vertically stacked senile tepees implies that they formed during an overall period of transgression, punctuated by different orders of sea level variations, which allowed formation and later freezing of the cave infills

DIAGENESIS OF AN UPPER TRIASSIC REEF COMPLEX, WILDE-KIRCHE, NORTHERN CALCAREOUS ALPS, AUSTRIA, 1994,
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Satterley A. K. , Marshall J. D. , Fairchild I. J. ,
The Wilde Kirche reef complex (Early-Late Rhaetian) grew as an isolated carbonate structure within the shallow Kossen Basin. At the Triassic/Jurassic boundary a single brief(c. 10-50 ka) period of subaerial exposure occurred. The preserved karst profile (70 m thick) displays a vadose zone, enhanced dissolution at a possible palaeo-watertable (5-15m below the exposure surface), and a freshwater phreatic zone. Karst porosity was predominantly biomouldic. primary cavities and biomoulds were enlarged and interconnected in the freshwater phreatic zone; cavity networks developed preferentially in patch reef facies. Resubmegence of the reef complex allowed minor modification of the palaeokarst surface by sea floor dissolution and Fe-Mn crust deposition on a sediment-starved passive margin. Fibrous calcite (FC), radiaxial fibrous calcite (RFC) and fascicular optic calcite (FOC) cements preserved as low Mg calcite (LMC) are abundant in primary and karst dissolution cavities. FC cement is restricted to primary porosity, particularly as a synsedimentary cement at the windward reef margin. FC, RFC and FOC contain microdolomite inclusions and show patchy non-/bright cathodoluminescence. delta(18)O values ofnon-luminescent portions (interpreted as near original) are -1.16 to -1.82 parts per thousand (close to the inferred delta(18)O of calcite precipitated from Late Triassic sea water). delta(13)C values are constant ( to .2 parts per thousand). These observations suggest FC, RFC and FOC were originally marine high Mg calcite (HMC) precipitates, and that the bulk of porosity occlusion occurred not in the karst environment but in the marine environment during and after marine transgression. The HMC to LMC transition may have occurred in contact with meteoric water only in the case of FC cement. The most altered (brightly luminescent) portions of RFC/FOC cements yield delta(18)O = -2.44 to -5.8 parts per thousand, suggesting HMC to LMC alteration at up to 34 degrees C, in the shallow burial environment at depths of 180-250 m. Abundant equant cements with delta(18)O = -4.1 to -7.1 parts per thousand show crisp, uniform or zoned dull luminescence. They are interpreted as unaltered cements precipitated at 33-36 degrees C at 200-290 m burial depth, from marine-derived fluids under a slightly enhanced geothermal gradient. Fluids carrying the equant cements may have induced the HMC to LMC transition in the fibrous cements

DEBATE ABOUT IRONSTONE - HAS SOLUTE SUPPLY BEEN SURFICIAL WEATHERING, HYDROTHERMAL CONVECTION, OR EXHALATION OF DEEP FLUIDS, 1994,
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Kimberley M. M. ,
Ironstone is any chemical sedimentary rock with > 15% Fe. An iron formation is a stratigraphic unit which is composed largely of ironstone. The solutes which have precipitated to become ironstone have dissolved from the Earth's surface, from the upper crust, e.g. the basaltic layer of oceanic crust, or from deeper within the Earth. Genetic modellers generally choose between surficial weathering, e.g. soil formation, and hydrothermal fluids which have convected through the upper kilometre of oceanic crust. Most genetic modellers attribute cherty laminated iron formations to hydrothermal convection and noncherty oolitic iron formations to surficial weathering. However, both types of iron formations are attributable to the exhalation of fluids from a source region too deep for convection of seawater. Evidence for a deep source of ferriferous fluids comes from a comparison of ancient ironstone with modern ferriferous sediment in coastal Venezuela. A deep-source origin for ironstone has wide-ranging implications for the origins of other chemical sedimentary ores, e.g. phosphorite, manganostone, bedded magnesite, sedimentary uranium ore, various karst-filling ores, and even petroleum. Preliminary study of a modern oolitic iron deposit described herein suggests that the source of iron and silica to iron formations may have been even deeper than envisioned within most hydrothermal convection models

DAMPENING OF TRANSVERSE DISPERSION IN THE HALOCLINE IN KARST LIMESTONE IN THE NORTHEASTERN YUCATAN PENINSULA, 1995,
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Stoessell R. K. ,
A range of hydrodynamic dispersion coefficients was estimated for fracture-fluid and combined fracture and pore-fluid now within the halocline of the limestone aquifer forming the surface of the northern Yucatan Peninsula. The coefficients are fit parameters in a model reproducing observed halocline profiles in a sinkhole and in a borehole near the northeastern coast. Fitted coefficients range from 10(-7) to 10(-4) cm(2)/sec, of which molecular diffusion, without transverse (vertical) dispersion, can account for 10(-7) to 10(-5) cm(2)/sec. The mechanical stability of the vertical density gradient in the halocline dampens transverse dispersion in pore fluids and in fracture fluids that are transitional between laminar and turbulent flow. The dampening is proportional to the ratio of the energy needed for the fluid to rise and displace a less dense fluid to the vertical component of the kinetic energy of the fluid. The ratio of these two energies is at a maximum during the initial stage of development of a halocline and decreases as the halocline widens

HYDROGEOCHEMISTRY OF GRAND-CAYMAN, BRITISH-WEST-INDIES - IMPLICATIONS FOR CARBONATE DIAGENETIC STUDIES, 1995,
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Ng K. C. , Jones B. ,
Groundwater in the dolostone aquifers of the Bluff Group (Oligocene-Miocene) on Grand Cayman is divided into fresh, lightly and highly brackish, and saline (Type I and II) zones according to chemical characteristics that were determined during a 3 year (1985-1988) monitoring program. Brackish and Type I saline waters display the greatest variation in chemical properties whereas the Type II saline water has the most stable chemical characteristics. Most groundwaters from these dolostone aquifers are thermodynamically capable of precipitating calcite and/or dolomite. The saturation indices for these minerals, however, vary through time and space even in the context of small water lens. Simple mixing of fresh and sea water cannot explain the chemistry of the water found in the joint and karst controlled dolostone aquifers of Grand Cayman. Deviation from a simple mixing model is due to variations caused by tidal fluctuation, the rate of rain water recharge, influx of Ca-rich groundwater from the surrounding limestone aquifers, influx of CO2-rich surface water from sinkholes and swamps, and water-rock interactions (dissolution and precipitation of calcite and dolomite). Sustained groundwater abstraction from a lens can significantly alter the hydrochemistry of the water lens. This suggests that hydrochemical characterization of small fresh water lenses, like those on Grand Cayman, cannot be based on spot or short-term sampling. Interpretation of such fluids in terms of calcite-dolomite precipitation and/or dissolution must be treated with caution if the data base has not been derived from long-term monitoring

Grottes hydrothermales dans le nord-ouest de la Namibie : splogense et implications dans le dveloppement des karsts en climat aride, 1996,
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Martini J. E. J. , Marais J. C. E.
The authors investigated ten caves in Western Namibia, which is characterised by a semi- to hyper-arid climate. They seem to have formed in the past under hydrothermal conditions, which are evidenced by circular embayments, ceiling alveoles, avens, deposits of dog-tooth calcite and barite. The latter has been observed in one cave only. Fluid inclusions in calcite and barite indicate very low salinity and temperatures generally below + 70? C. It is proposed that the caves formed by mixing of hydrothermal solutions of deep origin with more surficial ground water in the vicinity of karst springs. Such ground water circulation patterns, close to the water-table, are suggested in several cases by the horizontal extension in caves, forming definite levels of passage networks cutting across the country rock stratigraphy. The alveolar avens developed upwards from these horizontal passages and seem to have formed subaerally by water evaporation from warm pools at the bottom, with condensation and corrosion above, against cooler rock. The suggested genetic processes are in agreement with models proposed by other authors. It is suggested that in arid climates, conditions are more favourable for development of this type of deep karst water circulation than under wetter conditions. It could possibly even be the predominant process of speleogenesis in very arid conditions. By extension, this concept - mixing of water of deep origin, not necessarily significantly hydrothermal with surficial ground water - could explain the peculiar nature of most of the Namibian caves. The latter are typically characterised by the development of very large chambers and phreatic networks, but with restricted extension and not forming well integrated systems.

Occurrence and significance of stalactites within the epithermal deposits at Creede, Colorado, 1996,
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Campbell Wr, Barton Pb,
In addition to the common and abundant features in karst terranes, stalactites involving a wide variety of minerals have also been found in other settings, including epigenetic mineral deposits, bur these are almost always associated with supergene stages. Here we describe a different mode of occurrence from the Creede epithermal ore deposits, in Colorado, wherein stalactites of silica, sphalerite, galena, or pyrite formed in a vapor-dominated setting, below the paleo-water table, and except possibly for pyrite, as part of the hypogene mineralization. Axial cavities may, or may not, be present. No stalagmites have been recognized. The stalactites are small, from a few millimeters to a few centimeters long and a few millimeters in outer diameter. They represent only a small fraction of one percent of the total mineralization, and are covered by later crystals. Their growth orientation usually is unobservable; however, the parallel arrangement of all stalactites in a given specimen, consistency with indicators of gravitational settling, and the common presence of axial structures make the stalactitic interpretation almost unavoidable. In contrast with common carbonate stalactites, the growth mechanism for th sulfide and silica stalactites requires extensive evaporation. Stalactitic forms have also been reported from other deposits, mostly epithermal or Mississippi Valley-type occurrences, but we caution that stalactite-like features can form by alternative processes

Geochemistry of submarine warm springs in the limestone cavern of Grotta Azzurra, Capo Palinuro, Italy: evidence for mixing-zone dolomitisation, 1996,
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Stuben Doris, Sedwick Peter, Colantoni Paolo,
Subtidal springs in and around the submarine limestone cavern of Grotta Azzurra, at Capo Palinuro, Italy, discharge fluids which are warm (-, Na and Mg2, and enriched in Si, alkalinity, Ca2, Sr2, Mn, NH4, PO43- and H2S, relative to surrounding seawater. The compositions of the warm fluid samples collected in and around the cave define mixing lines which suggest dilution of a single thermal fluid (T >= 23[deg]C) by cool overlying seawater (T= 17-17.6[deg]C). The chemical data suggest that the proposed thermal fluid contains two components, one derived from seawater ( 10%). Excess Si, alkalinity, Ca2, Sr2 and Mn relative to seawater are likely derived from the groundwater component or dissolution/hydrothermal alteration of the host rocks. Magnesium has been removed from the seawater component in exchange for Ca2, due to dolomitisation of the limestone and/or hydrothermal alteration reactions. Saturation-state calculations suggest that the vented fluids are near saturation with respect to calcite and supersaturated with respect to dolomite. This and the presence of dolomite in the host rocks and cave-floor sediments suggest that 'mixing-zone' dolomitisation of the limestones is occurring, perhaps kinetically assisted by elevated temperature and/or bacterial mediation in the reducing subseafloor zone. One possible 'end-member' condition is considered for the thermal fluid -- zero-Mg -- which suggests an end-member temperature of 50.5[deg]C and a fluid composition derived from ~ 38% seawater and ~ 62% groundwater. The heat source for the circulating fluids is uncertain, but may involve warm underlying igneous rocks or heating via the geothermal gradient. A continuous in-situ record of vent-fluid temperature, salinity, pH and O2 concentration collected within the cavern is consistent with our interpretation of the fluid origin, and suggests that tidal forcing affects circulation and venting of the warm fluids

Rock Fractures and Fluid Flow: Contemporary Understanding and Applications, 1996,
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The applicability of numerical models to adequately characterize ground-water flow in karstic and other triple-porosity aquifers, 1996,
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Quinlan J. F. , Davies G. J. , Jones S. W. , Huntoon P. W.

Evaporite karst of northern lower Michigan, 1997,
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Black Tj,
Michigan has three main zones of evaporite karst: collapse breccia in Late Silurian deposits of the Mackinac Straits region; breccia, collapse sinks, and mega-block collapse in Middle Devonian deposits of Northern Lower Michigan, which overlaps the preceding area; and areas of soil swallows in sinks of Mississippian deposits between Turner and Alabaster in Arenac and Iosco counties, and near Grand Rapids in Kent County. The author has focused his study on evaporite karst of the Middle Devonian deposits. The Middle Devonian deposits are the Detroit River Group: a series consisting of limestone, dolomite, shale, salt, gypsum and anhydrite. The group occurs from subcrop, near the surface, to nearly 1400 feet deep from the northern tip of the Southern Peninsula to the south edge of the ''solution front'' Glacial drift is from zero to 350 feet thick. Oil and gas exploration has encountered some significant lost-circulation zones throughout the area. Drilling without fluid returns, casing seal failures, and lost holes are strong risks in some parts of the region. Lost fluid returns near the top of the group in nearby areas indicate some karst development shortly after deposition. Large and irregular lost-circulation zones, linear and patch trends of large sink holes, and 0.25 mile wide blocks of down-dropped land in the northern Lower Peninsula of Michigan were caused by surface- and ground-water movement along faults into the Detroit River Group. Glaciation has removed some evidence of the karst area at the surface. Sinkhole development, collapse valleys, and swallows developed since retreat of the glacier reveal an active solution front in the Detroit River Group

Mixed transport reaction control of gypsum dissolution kinetics in aqueous solutions and initiation of gypsum karst, 1997,
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Raines M. A. , Dewers T. A. ,
Experiments with gypsum in aqueous solutions at 25 degrees C, low ionic strengths, and a range of saturation states indicate a mixed surface reaction and diffusional transport control of gypsum dissolution kinetics. Dissolution rates were determined in a mixed flow/rotating disc reactor operating under steady-state conditions, in which polished gypsum discs were rotated at constant speed and reactant solutions were continuously fed into the reactor. Rates increase with velocity of spin under laminar conditions (low rates of spin), but increase asymptotically to a constant rate as turbulent conditions develop with increasing spin velocity, experiencing a small jump in magnitude across the laminar-turbulent transition. A Linear dependence of rates on the square root of spin velocity in the laminar regime is consistent with rates being limited by transport through a hydrodynamic boundary layer. The increase in rate with onset of turbulence accompanies a near discontinuous drop in hydrodynamic boundary layer thickness across the transition. A relative independence of rates on spinning velocity in the turbulent regime plus a nonlinear dependence of rates on saturation state are factors consistent with surface reaction control. Together these behaviors implicate a 'mixed' transport and reaction control of gypsum dissolution kinetics. A rate law which combines both kinetic mechanisms and can reproduce experimental results under laminar flow conditions is proposed as follows: R = k(t) {1 - Omega(b)() zeta [1 - (1 2(1 - Omega(b)())(1/2)]} where k(t) is the rate coefficient for transport control, and Omega(b)() is the mean ionic saturation state of the bulk fluid. The dimensionless parameter zeta(=Dm(eq)()/2 delta k() where m(eq)() = mean ionic molal equilibrium concentration, D is the diffusion coefficient through the hydrodynamic boundary layer, delta equals the boundary layer thickness and k() is the rate constant for surface reaction control) indicates which process, transport or surface reaction, dominates, and is sensitive to the hydrodynamic conditions in the reactor. For the range of conditions used in our experiments, zeta varies from about 1.4 to 4.5. Rates of gypsum dissolution were also determined in situ in a cavern system in the Permian Blaine Formation, southwestern Oklahoma. Although the flow conditions in the caverns were not determinable, there is good agreement between lab- and field-determined rates in that field rate magnitudes lie within a range of rates determined experimentally under zero to low spin velocities A numerical model coupling fluid flow and gypsum reaction in an idealized circular conduit is used to estimate the distance which undersaturated solutions will travel into small incipient conduits before saturation is achieved. Simulations of conduit wall dissolution showed-member behaviors of conduit formation and surface denudation that depend on flow boundary conditions (constant discharge or constant hydraulic gradient and initial conduit radius. Surface-control of dissolution rates. which becomes more influential with higher fluid flow velocity, has the effect that rate decrease more slowly as saturation is approached than otherwise would occur if rates were controlled by transport alone. This has the effect that reactive solutions can penetrate much farther into gypsum-bearing karst conduits than heretofore thought possible, influencing timing and mechanism of karst development as well as stability of engineered structures above karst terrain

A governing equation for fluid flow in rough fractures., 1997,
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Ge S.

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