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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 rejuvenation is a process that interrupts an active erosional or development cycle and initiates a new cycle. rejuvenation is most commonly achieved in the karst and speleogenesis context by erosional baselevel changes caused by relative uplift (or sea-level fall) or by local water-table changes caused by downcutting of surface valleys intercepting deeper drainage lines [9].?

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Your search for closed-system (Keyword) returned 8 results for the whole karstbase:
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

Oxidation of organic matter in a karstic hydrologic unit supplied through stream sinks (Loiret, France), 1998, Alberic P, Lepiller M,
The aim of this paper is to appraise the ability of the oxidation of riverine organic matter in the control of limestone dissolution, in a karst network. Biogeochemical processes during infiltration of river water into an alluvial aquifer have already been described for an average flow velocity of 4-5 m d(-1) (Jacobs, L. A., von Gunten, H. R., Keil, R, and Kuslys, M. (1988) Geochemical changes along a river-groundwater infiltration flow path: Glattfelden, Switzerland. Geochim. Cosmochim. Acta 52, 2693-2706; Von Gunten, H. R., Karametaxas, G., Krahenbuhl, U., Kuslys, M., Giovanoli R., Hoehn E. and Keil R. (1991) Seasonal biogeochemical cycles in riverborne groundwater. Geochim. Cosmochim. Acta 55, 3597-3609; Bourg, A. C. M. and Bertin, C. (1993) Quantitative appraisal of biogeochemical chemical processes during the infiltration of river water into an alluvial aquifer. Environ. Sci. Technol. 27, 661-666). Karstic drainage networks, such as in the River Loire-Val d'Orleans hydrologic system (Fig. 1), make possible flow velocities up to 200 m h(-1 a) and provide convenient access to different water samples several tens of km apart, at both extremities of the hydrologic unit (Chery, J.-L. (1983) Etude hydrochimique d'un aquifere karstique alimente par perte de cours d'eau (la Loire): Le systeme des calcaires de Beauce sous le val d'Orleans. These, Universite d'Orleans; Livrozet, E. (1984) Influence des apports de la Loire sur la qualite bacteriologique et chimique de l'aquifere karstique du val d'Orleans. These, Universite d'Orleans). Recharge of the karstic aquifer occurs principally from influent waters from stream sinks, either through coarse alluvial deposits or directly from outcrops of the regional limestone bedrock (Calcaires de Beauce). Recharge by seepage waters From the local catchment basin is small (Zunino, C., Bonnet, M. and Lelong, F. (1980) Le Val d'Orleans: un exemple d'aquifere a alimentation laterale. C. R. somm. Soc. Geol. Fr. 5, 195-199; Gonzalez R. (1992) Etude de l'organisation et evaluation des echanges entre la Loire moyenne et l'aquifere des calcaires de Beauce. These, Universite d'Orleans) and negligible in summer. This karstic hydrologic: system is the largest in France in terms of flow (tens to hundreds of m(3)/s) and provides the main water resource of the city of Orleans. Chemical compositions of influent waters (River Loire) and effluent waters (spring of the river Loiret) were compared, in particular during floods in summer 1992 and 1993 (Figs 2-4). Variation of chloride in the River Loire during the stream rise can be used as an environmental tracer of the underground flow (Fig. 2). Short transit times of about 3 days are detectable (Fig, 2) which are consistent with earlier estimations obtained with chemical tracers (Ref. in Chery, J.-L. (1983) These, Universite d'Orleans). Depending on the hydrological regime of the river, organic carbon discharge ranges between 3-7 and 2-13 mg/l for dissolved and particulate matter respectively (Fig. 3). Eutrophic characteristics and high algal biomasses are found in the River Loire during low water (Lair, N. and Sargos, D. (1993) A 10 year study at four sites of the middle course of the River Loire. I - Patterns of change in hydrological, physical and chemical variables in relation to algal biomass. Hudroecol. Appl. 5, 1-27) together with more organic carbon rich suspended particulate matter than during floods (30-40 C-org % dry weight versus 5-10%). Amounts of total organic carbon and dissolved oxygen (Fig. 3) dramatically decrease during the underground transport, whereas conversely, dissolved calcium, alkalinity and inorganic carbon increase (Fig. 4). Anoxia of outflows map start in April. Dissolution of calcium carbonates along the influent path outweighs closed system calcite equilibrium of inflow river waters (Table 3). The impact of organic matter oxidation on calcite dissolution may be traced by variations of alkalinity and total carbonates in water. Following, Jacobs, L. A., von Gunten, H. R., Keil, R. and Kuslys, M. (1988) Geochemical changes along a river-groundwater infiltration flow path: Glattfelden, Switzerland. Geochim. Cosmochim. Acta 52, 2693-2706), results are shown graphically (Fig. 5). Extent of reactions is controlled by the consumption of dissolved O-2 and nitrate for organic matter oxidation and by the release of Ca2 for calcite dissolution (Table 2). The karstic network is considered to behave like a biological reactor not exchanging with the atmosphere, with steady inhabitant microbial communities (Mariotti A., Landreau A, and Simon B. (1988) N-15 isotope biogeochemisrry and natural denitrification process in groundwater: Application to the chalk aquifer of northern France. Geochim. Cosmochim. Acta 52, 1869-1878; Gounot, A.-M. (1991) Ecologie microbienne des eaux ei des sediments souterrains. Hydrogeologie, 239-248). Thus, energy requirements only are considered, not carbon assimilation. Moreover, there is no necessity to invoke any delay for nitrification enhancement, as observed elsewhere, after waste water discharge into the river (Chesterikoff, A., Garban, B., Billen, G. and Poulin, M. (1992) Inorganic nitrogen dynamics in the River Seine downstream from Paris (France). Biogeochem. 17, 147-164). Main microbial processes are assumed to be aerobic respiration, nitrification and denitrification. Reactions with iron and manganese, real but not quantitatively important, were neglected. Sulphate reduction and methane formation, certainly not active, were not considered. Denitrification, which is suggested by low nitrate and ammonium concentrations and anoxia in the outflow, is known to be rapid enough to be achieved in a short time (Dupain, S. (1992) Denitrification biologique heterotrophe appliquee au traitement des eaux d'alimentation: Conditions de fonclionnement et mise au point d'un procede. These, Universite Claude Bernard, Lyon). Reaction are somewhat arbitrary but conform to general acceptance (Morel, M. M. and Hering, J. G. (1993) Principles and Applications of Aquatic Chemistry. Wiley, New York). Anaerobic ammonium oxidation (Mulder A., van de Graaf, A. A., Robertson, L: A. and Kuenen, J. G. (1995) Anaerobic ammonium oxidation discovered in a denitrifying fluidized bed reactor. FEMS Microbiol. Ecol. 16, 177-184). although possible, was not considered. In fact, C/N ratio of the reactive organic matter has only mild repercussions on the results; i.e. in the same range as the analytical errors for alkalinity and total carbonates. The objective was simply to roughly confront characteristics of outflowing waters and the calculation. Respective roles of aerobes and denitrifiers, for instance, are not certain. Several periods during low water or floods were selected with various ranges for calcium dissolution or nitrate and oxygen concentrations. The result is that in most cases simulation and data are in reasonable accordance (Fig. 5). Amounts of organic matter in River Loire are generally sufficient to sustain the process (Table 3. Particulate organic matter is probably the most reactive. The balance of oxidation of organic matter indicates that about 65 mu g C-org/l.h are oxidized during the transport without much variation with the river regime or organic discharge. It is concluded that limestone dissolution is directly dependent on organic matter oxidation, but variation occurs (7-29 mg CuCO3/l) with the level of bases that can be neutralized in the River Loire water. (C) 1998 Elsevier Science Ltd. All rights reserved

The inhibiting action of intrinsic impurities in natural calcium carbonate minerals to their dissolution kinetics in aqueous H2O-CO2 solutions, 1999, Eisenlohr L, Meteva K, Gabrovsek F, Dreybrodt W,
We have measured the surface controlled dissolution rates of natural calcium carbonate minerals (limestone and marble) in H2O-CO2 solutions by using free drift batch experiments under closed system conditions with respect to CO2, at 10 degrees C with an initial partial pressure of carbon dioxide of 5.10(-2) atm. All experiments revealed reaction rates F, which can be described by the empirical relation: F-n1 = k(n1) . (1 - c/c(eq))(n1) for c < c(s), which switches to a higher order n(2) for calcium concentrations c greater than or equal to c(s) described by F-n2 = k(n2) . (1 - c/c(eq))(n2) . k(n1) and k(n2) are rate constants in mmole/(cm(2) . s), c(eq) is the equilibrium concentration with respect to calcite. The values of the constants n(1), n(2), k(n1), k(n2) and c(s) depend on the V/A ratio employed, where V is the volume of the solution and A is the surface area of the reacting mineral. Different calcium carbonate minerals exhibit different values of the kinetic constants. But generally with increasing V/A, there is a steep variation in the values of all kinetic constants, such that the rates are reduced with increasing V/A ratio. Finally with sufficiently large V/A these values become constant. These results are explained by assuming intrinsic inhibitors in the bulk of the mineral. During dissolution these are released from the calcite matrix and are adsorbed irreversibly at the reacting surface, where they act as inhibitors. The thickness d of the mineral layer removed by dissolution is proportional to the VIA ratio. The amount of inhibitors released per surface area is given by d c(int), where c(int) is their concentration id the bulk of the mineral. At low thicknesses up to approximate to 3 . 10(-4) cm in the investigated materials, the surface concentration of inhibitors increases until saturation is attained for thicknesses above this value. To analyze the surface concentration and the type of the inhibitors we have used Auger spectroscopy, which revealed the presence of aluminosilicate complexes at the surface of limestone, when a thickness of d approximate to 10(-3) cm had been removed by dissolution. In unreacted samples similar signals, weaker by one order of magnitude, were observed. Depth profiles of the reacted sample obtained by Ar-ion sputtering showed the concentration of these complexes to decrease to the concentration observed in the unreacted sample within a depth of about 10 nm. No change of the concentration with depth was observed in unreacted samples. These data suggest that complexes of aluminosilicates act as inhibitors, although other impurities cannot be excluded. Copyright (C) 1999 Elsevier Science Ltd

Formation of dolomite mottling in Middle Triassic ramp carbonates (Southern Hungary), 2000, Torok A. ,
The Middle Triassic carbonates of the Villany Mountains were deposited on a homoclinal carbonate ramp. Many of the carbonates from the 700 m-thick sequence show partial or complete dolomitization. The present paper describes dolomites that occur in a limestone unit as irregular mottles and as pore- and fracture-filling cements. Replacement-type scattered dolomite rhombs in the mottles having inclusion-rich, very dull luminescent cores and limpid non-luminescent outer zones represent the initial phase of dolomitization. The isotopic composition of these dolomites (delta(13)C = .30 parts per thousand VPDB, delta(18)O = -3.60 parts per thousand VPDB) is similar to that of the calcitic micrite (delta(13)C = .6 parts per thousand VPDB, delta(18)O = -4.00 parts per thousand VPDB) indicating that no external fluids were introduced during dolomite formation. The elevated Sr content of the micrites implies that sediment was originally aragonite or high-Mg calcite. Dolomitization took place in the burial realm from a 'marine' pore-fluid in a partly closed system. Later fracture-related saddle dolomite reflects elevated formation temperatures and increasing burial. Five calcites were identified. Multiple generations of calcite-filled fractures were formed during burial diagenesis generally having dull or no luminescence (delta(13)C = .80 parts per thousand VPDB, delta(18)O = -6.40 parts per thousand VPDB). The latest phase calcites are related to karst formation, having a very negative isotopic composition (delta(13)C = -5.0 to -7.2 parts per thousand VPDB and delta(18)O approximate to -7.44 parts per thousand VPDB). The karst-related processes include dissolution, calcite precipitation and partial replacement of dolomites by complex zoned bright yellow calcite. The timing of dolomitization is uncertain, but the first phase took place in a partly closed system prior to stylolite formation. Late-stage saddle dolomites were precipitated during maximum burial in the Cretaceous. The dissolution of dolomites and karst-related calcite replacement was not earlier than Late Cretaceous. (C) 2000 Elsevier Science B.V. All rights reserved

Limestone dissolution rates in karst environments, 2000, Dreybrodt W. , Eisenlohr L.
The removal of limestone from the bedrock at the surface and below ground by CO2-containing aqueous solutions sculptures karst landscapes and complex karst aquifers. To understand the evolution of such karstic features requires the knowledge of dissolution rates under various hydrogeological conditions. These rates are controlled by several complex mechanisms: 1) The rate equations of Plummer et al. (1978), from which surface reaction rates can be obtained when the concentrations of reacting species at the surface are known. 2) The slow reaction of CO2 to H+ and HCO3, which provides the H+ ion for converting carbonate to bicarbonate ions. 3) Mass transport by diffusion, either in laminar or turbulent flow. 4) Inhibition of surface reaction rates by the presence of impurities in natural carbonate minerals. 5) Open- or closed-system conditions with respect to CO2, under which dissolutional removal of limestone is active. Depending on the actual conditions each of these processes can greatly effect dissolution rates. This paper addresses these problems and provides data, which can be used to obtain realistic dissolution rates, when solutions flow laminarly in narrow fractures, but also for turbulent flow in large conduits, and a variety of other different hydrogeological conditions. These data are also necessary as input for modeling the evolution of karst.

Isotopic and geochemical evolution of ground and surface waters in a karst dominated geological setting: A case study from Belize, Central America, 2004, Marfia A. M. , Krishnamurthy R. V. , Atekwana E. A. , Panton W. F. ,
Analysis of stable isotopes and major ions in groundwater and surface waters in Belize, Central America was carried out to identify processes that may affect drinking water quality. Belize has a subtropical rainforest/savannah climate with a varied landscape composed predominantly of carbonate rocks and clastic sediments. Stable oxygen (delta(18)O) and hydrogen (deltaD) isotope ratios for surface and groundwater have a similar range and show high d-excess (10-40.8parts per thousand). The high d-excess in water samples suggest secondary continental vapor flux mixing with incoming vapor from the Caribbean Sea. Model calculations indicate that moisture derived from continental evaporation contributes 13% to overhead vapor load. In surface and groundwater, concentrations of dissolved inorganic carbon (DIC) ranged from 5.4 to 112.9 mg C/l and delta(13)C(DIC) ranged from -7.4 to -17.4parts per thousand. SO42, Ca2 and Mg2 in the water samples ranged from 2-163, 2-6593 and 2-90 mg/l, respectively. The DIC and delta(13)C(DIC) indicate both open and closed system carbonate evolution. Combined delta(13)C(DIC) and Ca2, Mg2 SO42- suggest additional groundwater evolution by gypsum dissolution and calcite precipitation. The high SO42- content of some water samples indicates regional geologic control on water quality. Similarity in the range of delta(18)O, deltaD and delta(13)C(DIC) for surface waters and groundwater used for drinking water supply is probably due to high hydraulic conductivities of the karstic aquifers. The results of this study indicate rapid recharge of groundwater aquifers, groundwater influence on surface water chemistry and the potential of surface water to impact groundwater quality and vise versa. (C) 2003 Elsevier Ltd. All rights reserved

Hypogene and supergene alteration of the Late Palaeozoic Ratburi Limestone during the Mesozoic and Cenozoic (Thailand, Surat Thani Province). Implications for the concentration of mineral commodities, 2005, Dill H. G. , Botz R. , Luppold F. W. , Henjeskunst F.
An interdisciplinary study of the Upper Carboniferous to Middle Permian Ratburi Group, Peninsular Thailand, is presented. The investigation involved sedimentary petrography, inorganic geochemistry, Sr, C, O isotope analyses, micropalaeontology as well as radio-carbon age dating. Emphasis was placed on the post-depositional evolution of the Ratburi Limestone in the Surat Thani Province. The Holocene chemical residues and the various calcite and dolomite minerals which have formed since the Late Palaeozoic in the Ratburi Limestone are the product of a complex, multistage alteration which is called supergene and hypogene karstifications, respectively. Sedimentation took place in a shelf environment with some reefs evolving during the late Murgabian at the shelf margin. There was no pre-concentration of elements, except for Ca and F during sedimentation. Diagenetic neomorphism and cementation under marine and freshwater conditions caused the Ratburi Limestone to convert into a marble-like rock. Fabric-selective dolomitization is of local scale and has impacted only on part of the Ratburi Limestone during the Lower to Upper Permian. A significant enhancement of pore space and better conduits were generated during the Late Cretaceous epithermal alteration. The most favorable conditions for the accumulation of metals were provided during the high-temperature stage of epithermal alteration when a low-metal concentration with As, Zn, Sb, U, Co and Pb existed. Unlike the other elements, Sb was subject to a multiphase concentration, giving rise to a considerable Sb deposit in the region. The most recent stage of karstification produced numerous caves, dripstones, tufa terraces and encrustations around brine pools in the study area. This alteration originated from per descensum and per ascensum processes which may be traced back to 15,000 years before present. The alteration of the Ratburi Limestone may be subdivided into two parts. The prograde post-depositional alteration, beginning with diagenesis, reached its temperature climax during epithermal subsurface alteration I. The retrograde branch of alteration lasted until the most recent times. The initial stages deposition and diagenesis took place under more or less closed-system conditions relative to the succeeding stages of the prograde alteration which saw the strongest influx of metal-bearing brine during the epithermal stage I. The retrograde branch of alteration is element-conservative.

Sulfur isotopic composition and the source of dissolved sulfur species in thermo-mineral springs of the Cerna Valley, Romania, 2010, Wynn Jonathan G. , Sumrall Jonathan B. , Onac Bogdan P.

Documenting the source and processes controlling dissolved sulfur (S) mineralization in thermo-mineral waters of the Cerna Valley, Romania is important to understanding speleogenesis in this karst region, in addition to understanding hydrogeological controls, therapeutic qualities and sustainability of the region's historic spas. Stable S and carbon (C) isotopic results reported here elucidate controls on redox processes, the source of dissolved S mineralization, and sulfur-bearing mineral precipitation in this unique karst hydrothermal system. At reservoir temperatures that occur in the Cerna Valley aquifers, it is likely that thermochemical sulfate reduction (TSR) is the dominant S reduction pathway. However the apparent isotope enrichment that we observed between coexisting dissolved sulfate and sulfide is higher than normally associated with TSR—a fact that likely reflects rapid redox cycling at low grade hydrothermal temperatures. δ13C values of dissolved inorganic carbon (DIC) are consistent with TSR using methane as an electron donor. δ34S values of total dissolved S (sum of sulfide and sulfate) in all springs sampled and particularly in those for which closed-system conditions can be demonstrated, is greater than + 16‰, consistently pointing to dissolved S that derives from marine-derived sulfate mineral sources. To this combined S–C isotope data set, we apply a model of Rayleigh distillation which describes exponentially increasing δ34S values of a diminishing sulfate reservoir during TSR, and linearly decreasing δ13C values of DIC indicating mixing of C from the electron donor involved in TSR. Comparison of our results to this model shows two distinct stages of TSR during transport of fresh water from karst aquifers towards the local geothermal anomaly. In an up-gradient group of springs and wells, incomplete TSR progress that is limited by energy from electron donors is evident from: low concentrations of dissolved sulfide with low δ34S values (as low as − 21.9‰), a large balance of remaining as SO42− similar in isotopic composition to its source ( + 17.4‰), and δ13C values showing little methane-derived DIC. Conversely, in a downstream group of springs and wells, excess concentration of methane provides abundant energy for near-complete TSR, and this near complete reaction progress is evident from: high δ34S values of remaining SO42− (up to + 71.8‰), high dissolved sulfide concentrations (> 32 mg/L as S2−) with δ34S values that take on the approximate isotopic signature of the total dissolved S (mean + 17.4‰), and low δ13C values of additional DIC derived from methane (as low as − 30‰). Thus the unique hydrogeology of the Cerna Valley allows the observation of two end-members of TSR (energy- and sulfate-limited) demonstrating wide boundary conditions of stable isotopic composition of dissolved S and C produced by TSR in a single natural system.


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