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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. ...

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. ...

Speleology in Kazakhstan

Shakalov on 11 Jul, 2012
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 raft is a thin sheet of crystalline calcite supported by surface tension on a cave pool or lake. the calcite is precipitated mainly in response to evaporation of the pool water and rafts are therefore found mainly in caves in arid regions or caves with powerful through draughts.?

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Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
Engineering challenges in Karst, Stevanović, Zoran; Milanović, Petar
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Featured articles from other Geoscience Journals
Geochemical and mineralogical fingerprints to distinguish the exploited ferruginous mineralisations of Grotta della Monaca (Calabria, Italy), Dimuccio, L.A.; Rodrigues, N.; Larocca, F.; Pratas, J.; Amado, A.M.; Batista de Carvalho, L.A.
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
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Your search for seawater (Keyword) returned 85 results for the whole karstbase:
Showing 1 to 15 of 85
Dissolution kinetics of calcium carbonate in seawater. Theory of calcite solution, 1974, Berner R. A. , Morse J. W.

Strontium geochemical evidence for the origin of the barite deposits from Sardinia, Italy, 1984, Barbieri M, Masi U, Tolomeo L,
Sr content of 137 samples of barite, 81 samples of fluorite, and 65 samples of calcite from 27 post-Cambrian karst and hydrothermal deposits. Karst calcites have an average Sr content of 26 ppm, quite similar to that of the hydrothermal calcites. Hydrothermal fluorites show an average content of 56 ppm. Forty-five percent of the karst barites have an Sr content over 6,000 ppm, while as much as 83.8 percent of the hydrothermal barites contain more than 6,000 ppm Sr. The Sr isotope composition of the Cambrian stratiform barites (0.70867 or - 3) is similar to that of Cambrian seawater, suggesting that the bulk of the Sr was provided by this source. The Sr isotope ratios of the karst barite (average 87 Sr/ 86 Sr = 0.70947 or - 1) indicate that Sr was not only derived by recycling of the stratiform barite but was also provided by the noncarbonate fraction of the Cambrian wall rocks. The Sr isotope composition of the hydrothermal barites ranges from 0.70990 or - 4 to 0.71837 or - 4, suggesting that the Sr derived mainly from a high 87 Sr/ 86 Sr ratio source.--Modified journal abstract

Shallow-marine carbonate facies and facies models, 1985, Tucker M. E. ,
Shallow-marine carbonate sediments occur in three settings: platforms, shelves and ramps. The facies patterns and sequences in these settings are distinctive. However, one type of setting can develop into another through sedimentational or tectonic processes and, in the geologic record, intermediate cases are common. Five major depositional mechanisms affect carbonate sediments, giving predictable facies sequences: (1) tidal flat progradation, (2) shelf-marginal reef progradation, (3) vertical accretion of subtidal carbonates, (4) migration of carbonate sand bodies and (5) resedimentation processes, especially shoreface sands to deeper subtidal environments by storms and off-shelf transport by slumps, debris flows and turbidity currents. Carbonate platforms are regionally extensive environments of shallow subtidal and intertidal sedimentation. Storms are the most important source of energy, moving sediment on to shoreline tidal flats, reworking shoreface sands and transporting them into areas of deeper water. Progradation of tidal flats, producing shallowing upward sequences is the dominant depositional process on platforms. Two basic types of tidal flat are distinguished: an active type, typical of shorelines of low sediment production rates and high meteorologic tidal range, characterized by tidal channels which rework the flats producing grainstone lenses and beds and shell lags, and prominent storm layers; and a passive type in areas of lower meteorologic tidal range and higher sediment production rates, characterized by an absence of channel deposits, much fenestral and cryptalgal peloidal micrite, few storm layers and possibly extensive mixing-zone dolomite. Fluctuations in sea-level strongly affect platform sedimentation. Shelves are relatively narrow depositional environments, characterized by a distinct break of slope at the shelf margin. Reefs and carbonate sand bodies typify the turbulent shelf margin and give way to a shelf lagoon, bordered by tidal flats and/or a beach-barrier system along the shoreline. Marginal reef complexes show a fore-reef--reef core--back reef facies arrangement, where there were organisms capable of producing a solid framework. There have been seven such phases through the Phanerozoic. Reef mounds, equivalent to modern patch reefs, are very variable in faunal composition, size and shape. They occur at shelf margins, but also within shelf lagoons and on platforms and ramps. Four stages of development can be distinguished, from little-solid reef with much skeletal debris through to an evolved reef-lagoon-debris halo system. Shelf-marginal carbonate sand bodies consist of skeletal and oolite grainstones. Windward, leeward and tide-dominated shelf margins have different types of carbonate sand body, giving distinctive facies models. Ramps slope gently from intertidal to basinal depths, with no major change in gradient. Nearshore, inner ramp carbonate sands of beach-barrier-tidal delta complexes and subtidal shoals give way to muddy sands and sandy muds of the outer ramp. The major depositional processes are seaward progradation of the inner sand belt and storm transport of shoreface sand out to the deep ramp. Most shallow-marine carbonate facies are represented throughout the geologic record. However, variations do occur and these are most clearly seen in shelf-margin facies, through the evolutionary pattern of frame-building organisms causing the erratic development of barrier reef complexes. There have been significant variations in the mineralogy of carbonate skeletons, ooids and syn-sedimentary cements through time, reflecting fluctuations in seawater chemistry, but the effect of these is largely in terms of diagenesis rather than facies

Continuous inflow of seawater and outflow of brackish water in the substratum of the karstic island of Cephalonia, Greece, 1989, Drogue N.

LATE-STAGE DOLOMITIZATION OF THE LOWER ORDOVICIAN ELLENBURGER GROUP, WEST TEXAS, 1991, Kupecz J. A. , Land L. S. ,
Petrography of the Lower Ordovician Ellenburger Group, both in deeply-buried subsurface cores and in outcrops which have never been deeply buried, documents five generations of dolomite, three generations of microquartz chert, and one generation of megaquartz. Regional periods of karstification serve to subdivide the dolomite into 'early-stage', which predates pre-Middle Ordovician karstification, and 'late-stage', which postdates pre-Middle Ordovician karstification and predates pre-Permian karstification. Approximately 10% of the dolomite in the Ellenburger Group is 'late-stage'. The earliest generation of late-stage dolomite, Dolomite-L1, is interpreted as a precursor to regional Dolomite-L2. L1 has been replaced by L2 and has similar trace element, O, C, and Sr isotopic signatures, and similar cathodoluminescence and backscattered electron images. It is possible to differentiate L1 from L2 only where cross-cutting relationships with chert are observed. Replacement Dolomite-L2 is associated with the grainstone, subarkose, and mixed carbonate-siliciclastic facies, and with karst breccias. The distribution of L2 is related to porosity and permeability which focused the flow of reactive fluids within the Ellenburger. Fluid inclusion data from megaquartz, interpreted to be cogenetic with Dolomite-L2, yield a mean temperature of homogenization of 85 6-degrees-C. On the basis of temperature/delta-O-18-water plots, temperatures of dolomitization ranged from approximately 60 to 110-degrees-C. Given estimates of maximum burial of the Ellenburger Group, these temperatures cannot be due to burial alone and are interpreted to be the result of migration of hot fluids into the area. A contour map of delta-O-18 from replacement Dolomite-L2 suggests a regional trend consistent with derivation of fluids from the Ouachita Orogenic Belt. The timing and direction of fluid migration associated with the Ouachita Orogeny are consistent with the timing and distribution of late-stage dolomite. Post-dating Dolomite-L2 are two generations of dolomite cement (C1 and C2) that are most abundant in karst breccias and are also associated with fractures, subarkoses and grainstones. Sr-87/Sr-86 data from L2, C1, and C2 suggest rock-buffering relative to Sr within Dolomite-L2 (and a retention of a Lower Ordovician seawater signature), while cements C1 and C2 became increasingly radiogenic. It is hypothesized that reactive fluids were Pennsylvanian pore fluids derived from basinal siliciclastics. The precipitating fluid evolved relative to Sr-87/Sr-86 from an initial Pennsylvanian seawater signature to radiogenic values; this evolution is due to increasing temperature and a concomitant evolution in pore-water geochemistry in the dominantly siliciclastic Pennsylvanian section. A possible source of Mg for late-stage dolomite is interpreted to be from the dissolution of early-stage dolomite by reactive basinal fluids

The sulfate speleothems of Thampanna cave, Nullarbor Plain, Australia, 1991, James, Julia M.

Examination of gypsum speleothems and chemical analysis of the cave drip waters (ions to chloride mole ratios, tot. dissolved solids, nitrate) confirm that the major source of the sulfate in Thampanna cave (Western Australia) is from seawater transported by rain.


HYDROGEOLOGY OF GRAND CAYMAN, BRITISH-WEST-INDIES - A KARSTIC DOLOSTONE AQUIFER, 1992, Ng K. C. , Jones B. , Beswick R. ,
On Grand Cayman, freshwater bodies present in the Bluff Formation are typically small and occur as thin lenses floating on top of dense saline water. Evaluation of the water resource potential of these freshwater lenses is difficult because of their variable hydrological conditions, complex paleohydrogeology and aquifer heterogeneity. Secondary porosity created by preferential dissolution of aragonitic fossil components is common. Open fissures and joints developed under tectonic stress and karst development associated with sea-level fluctuations are, however, the two most important causes of porosity and permeability in the aquifers on Grand Cayman. Fracture and karst porosity control the lens occurrence by: (1) acting as avenues for the intrusion of seawater or upward migration of saline water; (2) acting as recharge focal points; (3) enhancing hydrodynamic dispersion; (4) defining lens geometry; (5) facilitating carbonate dissolution along joints and fissures. A clear understanding of the hydrological and geological conditions is important in developing small lenses in a setting similar to that on Grand Cayman. This pragmatic approach can help identify the optimum location of the well field and avoid areas particularly susceptible to saline water intrusion

THE OCCURRENCE AND EFFECT OF SULFATE REDUCTION AND SULFIDE OXIDATION ON COASTAL LIMESTONE DISSOLUTION IN YUCATAN CENOTES, 1993, Stoessell R. K. , Moore Y. H. , Coke J. G. ,
Dissolution of carbonate minerals in the coastal halocline is taking place in the karst terrain along the northeastern coast of the Yucatan Peninsula. The dissolution is being accelerated in cenotes (sinkholes) where sulfate reduction and oxidation of the produced sulfide is occurring. Hydrogen-sulfide concentrations ranged from 0.06 to 4 mmolal within the halocline in two sinkholes. Relative to concentrations expected by conservative mixing, fluids with high hydrogen-sulfide concentrations were correlated with low sulfate concentrations, high alkalinities, low pH values, and heavy sulfur isotope values for sulfate. Hydrogen-sulfide concentrations were less than those predicted from sulfate reduction, calculated from deficiencies in measured sulfate concentrations, indicating mobility and loss of aqueous sulfide. Fluids with low hydrogen-sulfide concentrations were correlated with very high calcium concentrations, high strontium and sulfate concentrations, slightly elevated alkalinities, low pH values, and sea-water sulfur isotope values for sulfate. Gypsum dissolution is supported by the sulfur isotopes as the major process producing high sulfate concentrations. However, oxidation of aqueous sulfide to sulfuric acid, resulting in carbonate-mineral dissolution is needed to explain the calcium concentrations, low pH values, and only slightly elevated alkalinities. The halocline may trap hydrogen sulfide that has been stripped from the underlying anoxic salt water. The halocline can act as a stable, physical boundary, holding some of the hydrogen sulfide until it is oxidized back to sulfuric acid through interaction with the overlying, oxygenated fresh water or through the activity of sulfide-oxidizing bacteria

MICROBIOLOGICAL ACTIVITY IN THERMOGLACIAL KARST SPRINGS, SOUTH SPITSBERGEN, 1994, Lauritzen S. E. , Bottrell S. ,
Along the Hornsund fault zone, South Spitsbergen (76-degrees-60'N), thermokarstic springs smell of H2S and display either growth of, or eject fragments of, organic slime. The temperature in individual springs varies between 4 and 15-degrees-C. Their rate of discharge is approximately 1 L s-1 to 18 m3 s-1, corresponding to a minimum temperature of 30-degrees-C within the base of the aquifer. The water, which contains a few ppm SO4(2-), 0.5 ppm S2-, and several thousand ppm NaCl, appears to be a mixture of turbid glacial meltwater and hot brine. Water chemistry and stable isotopes indicate that the salinity is not the result of simple dilution of modern seawater from the brackish zone beneath the coastal karst aquifer, but rather originates from a deep thermal brine component where concentrations and isotopic composition of various species are controlled by water-rock interaction in the source area of the brine. A value of DELTAdeltaS-34 of up to about 30 parts per thousand indicates that sulfide is a bioreduction product of sulfate. Scanning electron microscope (SEM) studies revealed bacteria and fungal hypha in the organic slime, and larger spherical particles (approximately 3.8 mum diameter) that display high concentrations of Fe and S. These findings demonstrate the presence of sulfate-reducing bacteria within the subpermafrost aquifer

DEBATE ABOUT IRONSTONE - HAS SOLUTE SUPPLY BEEN SURFICIAL WEATHERING, HYDROTHERMAL CONVECTION, OR EXHALATION OF DEEP FLUIDS, 1994, 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

CHEMICAL EVOLUTION OF GROUNDWATER NEAR A SINKHOLE LAKE, NORTHERN FLORIDA .1. FLOW PATTERNS, AGE OF GROUNDWATER, AND INFLUENCE OF LAKE WATER LEAKAGE, 1995, Katz B. G. , Lee T. M. , Plummer L. N. , Busenberg E. ,
Leakage from sinkhole lakes significantly influences recharge to the Upper Floridan aquifer in poorly confined sediments in northern Florida. Environmental isotopes (oxygen 18, deuterium, and tritium), chlorofluorocarbons (CFCs: CFC-11, CCl3F; CFC-12, CCl2F2; and CFC-113, C2Cl3F3), and solute tracers were used to investigate groundwater flow patterns near Lake Barco, a seepage lake in a mantled karst setting in northern Florida. Stable isotope data indicated that the groundwater downgradient from the lake contained 11-67% lake water leakage, with a limit of detection of lake water in groundwater of 4.3%. The mixing fractions of lake water leakage, which passed through organic-rich sediments in the lake bottom, were directly proportional to the observed methane concentrations and increased with depth in the groundwater flow system. In aerobic groundwater upgradient from Lake Barco, CFC-modeled recharge dates ranged from 1987 near the water table to the mid 1970s for water collected at a depth of 30 m below the water table. CFC-modeled recharge dates (based on CFC-12) for anaerobic groundwater downgradient from the lake ranged from the late 1950s to the mid 1970s and were consistent with tritium data. CFC-modeled recharge dates based on CFC-11 indicated preferential microbial degradation in anoxic waters. Vertical hydraulic conductivities, calculated using CFC-12 modeled recharge dates and Darcy's law, were 0.17, 0.033, and 0.019 mid for the surficial aquifer, intermediate confining unit, and lake sediments, respectively. These conductivities agreed closely with those used in the calibration of a three-dimensional groundwater flow model for transient and steady state flow conditions

Evaporites, brines and base metals: What is an evaporite? Defining the rock matrix, 1996, Warren J. K. ,
This paper, the first of three reviews on the evaporite-base-metal association, defines the characteristic features of evaporites in surface and subsurface settings. An evaporite is a rock that was originally precipitated from a saturated surface or near-surface brine in hydrological systems driven by solar evaporation. Evaporite minerals, especially the sulfates such as anhydrite and gypsum, are commonly found near base-metal deposits. Primary evaporites are defined as those salts formed directly via solar evaporation of hypersaline waters at the earth's surface. They include beds of evaporitic carbonates (laminites, pisolites, tepees, stromatolites and other organic rich sediment), bottom nucleated salts (e.g. chevron halite and swallow-tail gypsum crusts), and mechanically reworked salts (such as rafts, cumulates, cross-bedded gypsarenites, turbidites, gypsolites and halolites). Secondary evaporites encompass the diagenetically altered evaporite salts, such as sabkha anhydrites, syndepositional halite and gypsum karst, anhydritic gypsum ghosts, and more enigmatic burial associations such as mosaic halite and limpid dolomite, and nodular anhydrite formed during deep burial. The latter group, the burial salts, were precipitated under the higher temperatures of burial and form subsurface cements and replacements often in a non-evaporite matrix. Typically they formed from subsurface brines derived by dissolution of an adjacent evaporitic bed. Because of their proximity to 'true' evaporite beds, most authors consider them a form of 'true' evaporite. Under the classification of this paper they are a burial form of secondary evaporites. Tertiary evaporites form in the subsurface from saturated brines created by partial bed dissolution during re-entry into the zone of active phreatic circulation. The process is often driven by basin uplift and erosion. They include fibrous halite and gypsum often in shale hosts, as well as alabastrine gypsum and porphyroblastic gypsum crystals in an anhydritic host. In addition to these 'true' evaporites, there is another group of salts composed of CaSO4 or halite. These are the hydrothermal salts. Hydrothermal salts, especially hydrothermal anhydrite, form by the subsurface cooling or mixing of CaSO4- saturated hydrothermal waters or by the ejection of hot hydrothermal water into a standing body of seawater or brine. Hydrothermal salts are poorly studied but often intimately intermixed with sulfides in areas of base-metal accumulations such as the Kuroko ores in Japan or the exhalative brine deeps in the Red Sea. In ancient sediments and metasediments, especially in hydrothermally influenced active rifts and compressional belts, the distinction of this group of salts from 'true' evaporites is difficult and at times impossible. After a discussion of hydrologies and 'the evaporite that was' in the second review, modes and associations of the hydrothermal salts will be discussed more fully in the third review

Geochemistry of submarine warm springs in the limestone cavern of Grotta Azzurra, Capo Palinuro, Italy: evidence for mixing-zone dolomitisation, 1996, 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

Geochemistry and water dynamics: Application to short time-scale flood phenomena in a small Mediterranean catchment .1. Alkalis, alkali-earths and Sr isotopes, 1997, Benothman D, Luck Jm, Tournoud Mg,
We report major, trace elements and Sr isotope data for water samples taken regularly during a four-day-long September flood of a Mediterranean river, the Vene (Herault, S. France). The objective is to combine all these data into a dynamic model that describes the origin(s) and movements of waters and their loads. This river drains the runoff from a small, mainly carbonate, partly karstified watershed with Miocene and Jurassic lithologies. The watershed is also impacted by both agricultural and urban activities. Both the dissolved and the particulate loads were analyzed. Concentrations of the dissolved components show major remobilization of almost all elements during the first few hours of the flood (water treatment plants and aerosol scavenging), followed by a sharp concentration decrease. Some major species return to their previous summer values (Ca, HCO3) while others reach low 'background' levels (Na, K, Cl, SO4). Some trace elements (Rb, Sr, Cs) show similar behaviour but (Ba) appears somewhat unaffected. Trace element concentrations and ratios define two main periods (three in the suspended particulate matter). Ratios do not allow distinguishing between the three main sources for the dissolved load in the first period (Miocene, Jurassic, water treatment plants), but clearly show the Jurassic karst influence later on. The Sr-87/Sr-86 Of the suspended particulate matter is more variable and more radiogenic than in the dissolved phase. Variations in concentration ratios and Sr isotope composition in particulates indicate the large and variable contribution of Miocene silicates with some carbonate. However, there is a need for another component with [Rb]/[Sr] higher than bedrocks, internal or external to the watershed, possibly due to differential erosion. Dissolved Ca and Mg fluxes during the flood were calculated at 0.26 ton and 0.029 ton/km(2), respectively. Even though the carbonate nature of the watershed restricts variability in Sr isotope composition in the dissolved load, we distinguish several endmembers: seawater(approximate to marine rain), Miocene marls, Jurassic limestones, water treatment plants (and possibly another attributable to fertilizers). Combined with major and trace element variational Sr isotope fluctuations indicate time-varying proportions of different water endmembers at the outflow and suggest a general dynamic model. Based on PCA (principal component analysis), a 3D representation allows to visualize the geochemical evolution of the Vene waters. In particular, Sr isotopes clearly indicate that the inflow of karstic waters during the flood was not continuous but occurred as a series of marked oscillations between flowing waters with chemical signature of Miocene lithologies and increasing flushes of deeper waters that interacted with Jurassic lithologies. (C) 1997 Elsevier Science B.V

Precipitation kinetics of calcite in the system CaCO3-H2O-CO2: The conversion to CO2 by the slow process H?->CO2? as a rate limiting step, 1997, Dreybrodt W, Eisenlohr L, Madry B, Ringer S,
Precipitation rates of CaCO3 from supersaturated solutions in the H2O - CO2 - CaCO3 system are controlled by three rate-determining processes: the kinetics of precipitation at the mineral surface, mass transport of the reaction species involved to and from the mineral surface, and the slow kinetics of the overall reaction HCO3- H --> CO2 H2O. A theoretical model by Buhmann and Dreybrodt (1985a,b) taking these processes into account predicts that, due to the slow kinetics of this reaction, precipitation rates to the surface of CaCO3 minerals depend critically on the ratio V/A of the volume V of the solution to the surface area A of the mineral in contact with it, for both laminar and turbulent flow. We have performed measurements of precipitation rates in a porous medium of sized particles of marble, limestone, and synthetic calcite, with V/A ratios ranging from 3.10(-4) to 1.2-10(-2) cm at 10 degrees C. Calcite was precipitated from supersaturated solutions with [Ca2] approximate to 4 mmol/L and an initial P-CO2 of 5.10(-3) or 1.10(-3) atm, respectively, using experimental conditions which prevented exchange of CO2 with the atmosphere, i.e., closed system. The results are in qualitative agreement with the theoretical predictions. Agreement with the observed data, however, is obtained by modifying the rate law of Plummer et al. (1978) to take into account surface-controlled inhibition effects. Experiments with supersaturated solutions containing carbonic anhydrase, an enzyme which enhances the conversion of HCO3- into CO2, yield rates increased by a factor of up to 15. This provides for the first time unambiguous experimental evidence that this reaction is rate limiting. We have also measured precipitation rates in batch experiments, stirring sized mineral particles in a solution with V/A ranging from 0.03 to 0.75 cm. These experiments also give clear evidence on the importance of the conversion of HCO3- into CO2 as rate limiting step. Taken together our experiments provide evidence that the theoretical model of Buhmann and Dreybrodt (1985a,b) can be used to predict reliable rates from the composition of CaHCO3- solutions with low ionic strength in many geologically relevant situations. Copyright (C) 1997 Elsevier Science Ltd

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