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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 chalcanthite is a cave mineral - cuso4 5h2o [11].?

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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 pco2 (Keyword) returned 44 results for the whole karstbase:
Showing 1 to 15 of 44
A Chemical Investigation of some Groundwater of the Northern Limestone at Jenolan Caves, 1977, James Julia M. , Handel M. L.

A brief description of the geology and drainage of the Northern limestone at Jenolan Caves is introduced. Approaches to karst geochemistry are given. The reasons are given for the choice of complete chemical analyses followed by calculations of the thermochemical parameters (saturation indices with respect to calcite and dolomite, SIc and SId, and the partial pressure of carbon dioxide PCO2) for the Jenolan groundwaters. The methods of chemical analysis and thermochemical calculations are reported. The results of the groundwater survey are presented both as the raw chemical data and the derived thermochemical data. The raw data give more useful information than the calculated parameters. The results obtained by this survey are consistent with observations and the previous knowledge of the underground drainage of the Northern limestone. The water chemistry reflected the rock type and the residence time of the water in bedrock and gravels. It is concluded that the Jenolan underground River and Central River have different types of source and that Central River is not a braid of the Jenolan Underground River.


Groundwater chemistry and cation budgets of tropical karst outcrops, Peninsular Malaysia, I. Calcium and magnesium, 1989, Crowther J,
The discharge and chemical properties of 217 autogenic groundwaters were monitored over a 1-yr period in the tower karsts of central Selangor and the Kinta Valley, and in the Setul Boundary Range. Because of differences in soil PCO2, calcium concentrations are significantly higher in the Boundary Range (mean, 82.5 mg l-1) than in the tower karst terrain (44.6 mg l-1). Local differences in both source area PCO2 and amounts of secondary deposition underground cause marked intersite variability, particularly in the tower karst. Dilution occurs during flood peaks in certain conduit and cave stream waters. Generally, however, calcium correlates positively with discharge, since the amount of secondary deposition per unit volume of water decreases at higher flows. Magnesium concentrations and Mg:Ca Mg ratios of groundwaters are strongly influenced by bedrock composition, though bedrock heterogeneity and the kinetics and equilibria of carbonate dissolution reactions preclude extremely low or high Mg:Ca Mg values. Net chemical denudation rates range from 56.6 to 70.9 m3km2yr-1.The results are considered in relation to cation fluxes in surface runoff, soil throughflow and nutrient cycling. Preliminary calcium and magnesium budgets show that (1) dissolutional activity is largely confined to the near-surface zone; and (2) the annual uptake of calcium and magnesium by tropical limestone forests is similar in magnitude to the net solute output in groundwaters

TEMPORAL CYCLES OF KARST DENUDATION IN NORTHWEST GEORGIA, USA, 1994, Kiefer R. H. ,
Time patterns of karst denudation in northwest Georgia (U.S.A.) were investigated at three spring sites for 12 months and at five stream sites for 10 years. Rainfall was evenly distributed and showed no significant seasonality. At the springs, as well as the streams, water hardness was largely controlled by discharge. At the springs, Soil PCO2 and water pH were strongly correlated (r = -0.69 to -0.83). Solute transport in spring waters was highly seasonal, with two conduit flow springs removing more limestone in the winter, and the diffuse flow spring removing more during the growing season. At the stream sites, most denudation occurred during the winter and spring seasons, and least during the summer. Fourier analysis showed that variations in denudation occur on deterministic (long-wave) as well as stochastic (short-wave) time scales. As contributing variables, discharge varied in short-wave and long-wave cycles, whereas soil PCO2 showed only a long-wave cycle. The 12 month deterministic cycles were the most important, with changes in discharge taking precedence over Soil PCO2. Time series regression explains up to 69 per cent of changes in denudation through rain and soil pCO2. Time cycles in available water are the key controlling factor of denudation, and amounts of available Soil CO2 may not be as important in the temporal patterns of karst downwearing as has been believed previously

HYDRODYNAMIC CONTROL OF INORGANIC CALCITE PRECIPITATION IN HUANGLONG RAVINE, CHINA - FIELD-MEASUREMENTS AND THEORETICAL PREDICTION OF DEPOSITION RATES, 1995, Liu Z. H. , Svensson U. , Dreybrodt W. , Yuan D. X. , Buhmann D. ,
Hydrochemical and hydrodynamical investigations are presented to explain tufa deposition rates along the flow path of the Huanglong Ravine, located in northwestern Sichuan province, China, on an altitude of about 3400 m asl. Due to outgassing of CO2 the mainly spring-fed stream exhibits, along a valley of 3.5 km, calcite precipitation rates up to a few mm/year. We have carried out in situ experiments to measure calcite deposition rates at rimstone dams, inside of pools and in the stream-bed. Simultaneously, the downstream evolution of water chemistry was investigated at nine locations with respect to Ca2 Mg2, Na, Cl-, SO42-, and alkalinity. Temperature, pH, and conductivity were measured in situ, while total hardness, Ca-T, and alkalinity have been determined immediately after sampling, performing standard titration methods. The water turned out to be of an almost pure Ca-Mg-HCO3 type. The degassing of CO2 causes high supersaturation with respect to calcite and due to calcite precipitation the Ca2 concentration decreases from 6 . 10(-3) mole/l upstream down to 2.5 . 10(-3) mole/l at the lower course. Small rectangular shaped tablets of pure marble were mounted under different flow regimes, i.e., at the dam sites with fast water flow as well as inside pools with still water. After the substrate samples had stayed in the water for a period of a few days, the deposition rates were measured by weight increase, up to several tens of milligrams. Although there were no differences in hydrochemistry, deposition rates in fast flowing water were higher by as much as a factor of four compared to still water, indicating a strong influence of hydrodynamics. While upstream rates amounted up to 5 mm/year, lower rates of about 1 mm/year were observed downstream. Inspection of the marble substrate surfaces by EDAX and SEM (scanning electron microscope) revealed authigeneously grown calcite crystals of about 10 mu m. Their shape and habit are indicative of a chemically controlled inorganic origin. By applying a mass transfer model for calcite precipitation taking into account the reaction rates at the surface given by Plummer et al. (1978), slow conversion of CO2 into H and HCO3-, and diffusional mass transport across a diffusion boundary layer, we have calculated the deposition rates from the hydrochemistry of the corresponding locations. The calculated rates agree within a factor of two with the experimental results. Our findings confirm former conclusions with respect to fast flow conditions: reasonable rates of calcite precipitation can be estimated in reducing the PWP-rate calculated from the chemical composition of the water by a factor of about ten, thus correcting for the influence of the diffusion boundary layer

Combined use of environmental isotopic and hydrochemical data in differentiation of groundwater flow patterns through the Aladağ karstic aquifer-Turkey, Application of Tracers in Arid zone Hydro, 1995, Bayari C. S. , Gunay G.
Distinction between the different groundwater flow systems in karstic areas constitutes one of the major objetives of the basin-wide hydrogeologic research. Use of environmental isotopic and hydrochemical investigation techniques provide a great deal of information for the identification of regional groundwater flow systems. The Lower Zamantı Basin, located in the eastern Taurids, presents an accountable water resource potential that can be used for hydroelectric power production. The basin, with the elevation range between 400 m and 350 m, occupies a catchment area of 2000 km2. Humid and semi-arid climatic regimes prevail in the southern and northern parts of the basin. The carbonate rocks and the overlaying impervious ophiolite nappe constitute the major geologic units in the area. Systematic hydrochemical and environmental isotopic surveys have been carried out to discriminate between the different groundwater flow systems existing in the basin. Hydrochemical studies have been conducted by insitu measurements, sampling and analyses of water samples from about 80 points. Based on the results of hydrochemical evaluations, 23 sampling points, including streams and karstic springs, have been selected for environmental isotopic survey. The integrated evaluation of the available data indicates clearly that two different groundwater flow patterns exist in the basin; namely a shallow flow and a deep regional flow. The characteristic values of temperature, electrical conductivity, carbonate alkalinity and log PCO2 of the shallow-flow in the karstic effluents fed by shallow groundwater circulation springs are 8C, 80 S/cm, 1.5 meq/l and 10-2 atm, respectively. On the other hand, higher values, such as 15C, 455 S/cm, 5.0 meq/l and 10-1 atm are observed in the springs fed by deep-regional groundwater flow. The tritium data indicate that the springs fed by the deep-regional groundwater have longer residence times. Moreover, the recharge area elevations, as envisaged from the oxygen-18 data, also provide supporting evidence for the distinction of different groundwater flow patterns. Additionally, comparison of groundwater temperature with oxygen-18 content presents reliable information to understand the possible interaction among the different karstic effluents.

Geology, geochemistry, and origin of the continental karst-hosted supergene manganese deposits in the western Rhodope massif, Macedonia, northern Greece, 1997, Nimfopoulos M. K. , Pattrick R. A. D. , Michailidis K. M. , Polya D. A. , Esson J. ,
Economic Mn-oxide ore deposits of commercial grade occur in the Rhodope massif near Kato Nevrokopi in the Drama region, Northern Greece. The Mn-oxide mineralization has developed by weathering of continental hypogene rhodochrosite-sulphide veins. The vein mineralization is confined by tectonic shear zones between marble and metapelites, extending laterally into the marble as tabular, pod or lenticular oreshoots (up to 50 m x 20 m x 5-10 m). Supergene oxidation of the hypogene mineralization led to the formation of in-situ residual Mn-oxide ore deposits, and secondary infills of Mn-oxide ore in embryonic and well developed karst cavities. Whole rock geochemical profiles across mineralized zones confirm the role of thrusts and faults as solution passageways and stress the importance of these structures in the development of hydrothermal and supergene mineralization at Kato Nevrokopi. Three zones an recognized in the insitu supergene veins: (A) a stable zone of oxidation, where immobile elements form (or substitute in) stable oxide mineral phases, and mobile elements are leached; (B) a transitional (active) zone in which element behavior is strongly influenced by seasonal fluctuations of the groundwater table and variations in pH-Eh conditions; and (C) a zone of permanent flooding, where variations in pH-Eh conditions are minimal. Zone (B) is considered as the source zone for the karst cavity mineralization. During weathering, meteoric waters, which were CO2-rich (P-CO2 similar to 10(-3.8) to 10(-1.4)) and oxygenated (fO(2) -10(-17) for malachite), percolated downward within the veins, causing breakdown and dissolution of sulfides and marble, and oxidation of rhodochrosite to Mn-oxides. Karat cavity formation was favored by the high permeability along thrust zones. Dissolved Mn2 was transported into karst cavities in reduced meteoric waters at the beginning of weathering (pH similar to 4-5), and as Mn(HCO3)(2) in slightly alkaline groundwaters during advanced weathering (pH similar to 6-8). Mn4? precipitation took place by fO(2) increase in ground waters, or pH increase by continuous hydrolysis and carbonate dissolution. In the well developed karst setting, some mobility of elements occurred during and after karst ore formation in the order Na>K>Mg>Sr>Mn>As>Zn>Ba>Al>Fe>Cu>Cd>Pb. (C) 1998 Canadian Institute of Mining, Metallurgy and Petrolem. Published by Elsevier Science Ltd. All rights reserved

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

Kinetics and mechanisms of precipitation of calcite as affected by P-CO2 and organic ligands at 25 degrees C, 1998, Lebron I. , Suarez D. L. ,
This study was conducted to develop a model for the precipitation rate of calcite under varying CO2 partial pressures and concentrations of dissolved organic carbon (DOG). Precipitation rates of calcite were measured in solutions with supersaturation values (Omega) between 1 and 20 and in the presence of 2 m(2)L(-1) of calcite. Experiments were run at partial pressures of CO2 (P-CO2) in the range of 0.035-10 kPa and DOC concentrations in the range of 0.02-3.50 mM. The effects of these two variables were quantified separately for the precipitation mechanisms of crystal growth and heterogeneous nucleation. We found an increase in precipitation rate (at constant Omega) when P-CO2 increased. For constant Omega, we also found a linear relationship between calcite precipitation rate and activity of CaHCO3, indicating that CaHCO3 species have an active role in the mechanism of calcite precipitation. These findings suggest that the increase in the precipitation rate with higher P-CO2 levels is likely caused by the increase in the negative charge on the calcite surface together with an increase in the activity of CaHCO3 species in solution. The mechanism of inhibition of calcite crystal growth by organic ligands has been shown to be surface coating of the crystals by DOG. The amount of DOC adsorbed on the surface of the calcite crystals follows a Langmuir isotherm for all the P-CO2 levels studied; however, the amount of DOC necessary to inhibit calcite precipitation increased. With increasing P-CO2, the negative charge on the crystal increases, which affects crystal growth, but also these increases in P-CO2 cause a decrease in the solution pH and increase in the ionic strength for constant Omega. Solution pH and ionic strength affect the structure and degree of dissociation of the organic functional groups, which in turn affects the and DOC concentration on the inhibition of crystal growth and heterogeneous nucleation. The effect of P-CO2 and DOC concentration on the precipitation rate of calcite is expressed in a precipitation rate model which reflects the contributions of crystal growth and heterogeneous nucleation. Copyright (C) 1998 Elsevier Science Ltd

Seasonal Effects on the Geochemical Evolution of the Logsdon River, Mammoth Cave, Kentucky., 1998, Anthony, Darlene M. , Ms

The following research describes the collection and evaluation of geochemical data from the Logsdon River, an open-flow conduit that drains a portion of the Turnhole Spring drainage basin within the Mammoth Cave karst aquifer of south-central Kentucky. This spatial survey of nearly 10 km of continuous base-level conduit included seasonal sampling of carbon dioxide partial pressures (PCO2), dissolved ions, and saturation indices for calcite (SIcal). The highest PCO2 are found at the upstream site closest to the Sinkhole Plain recharge area, which creates undersaturated conditions. Rapid outgassing of CO2 into the cave atmosphere creates oversaturated conditions for several thousand meters. This change in chemistry results in the accumulation of travertine in these areas. A boost in PCO2 roughly half-way through the flow path returns the water to slightly undersaturated conditions. The most likely source for additional CO2 is in-cave organic decay, as the boost also occurs during winter months when microbial activity in the soil is at a minimum. A general decline in Ca2+, Mg2+, and HCO3- concentrations occurred over the distance through the Logsdon River conduit. This decline may reflect a diluting of water by localized inputs from the Mammoth Cave Plateau and precipitation of travertine along the flow path. Although values for all parameters are greater in summer than winter, the trend in evolution is similar for both seasonal extremes.
The nature of the transition from summer to winter conditions in the aquifer was investigated by way of an intensive study of the geochemistry at the Logsdon River monitoring well. The relationship between conductivity (spC) and pH was evaluated during both seasons in an attempt to predict the activity of hydrogen for any given water sample, based on continuous spC measurements at the well. Data collected during the 1997-98 seasonal transitions supported a single, nonlinear regression equation that may represent two distinct seasonal regimes.


Quelques mcanismes chimiques du creusement des cavernes (plus _particulirement pour ltude de la zone noye), 1999, Lismonde, Baudouin
The classical influences of physical parameters and mixing corrosion are presented to study the equilibrium of the water-air-limestone chemical system. The frequent observation of cave levels in the mountain karstic systems is often associated with the greater facility of dissolution, near the water table. Some chemical mechanisms are analysed to show the greater karst corrosion on this level. Increased air pressure induces an increase in the saturation pCO2 of the water. Two confinement coefficients are used to analyse the role of a limited quantity of air in contact with water. The first (k) is the water mass/water + air mass ratio, the second (kn) is the mass of CO2 in water/ mass of CO2 in water and air ratio. These two ratios show that the latter coefficient varies with air pressure, but is proportional to the varying pCO2.

Corrosion des coupoles de plafond par les fluctuations de pression de lair emprisonn, 2000, Lismonde, Baudouin
CORROSION OF CEILING POCKETS ASSOCIATED WITH PRESSURE OF CONFINE AIR neighbourhood of the water table is proposed. It is applied to the genesis of ceiling pockets. The rising of water confines the air of ceiling pockets. The CO2 pressure increases. The air compres_sion is almost isothermic and induces a mist. The drops of the mist capture the CO2 by a diffusion process. The mass transfer of CO2 from air to drops, then to water, induces a vigorous corrosion of the limestone. For example, 1 m3 of air (at pCO2 = 3.10-3) with a compression of 1 bar (10 m) produces a maximum calcite dissolution of 1 g. A rough computing model for the ceiling pockets' growth is presented also.

Controls on trace element (Sr-Mg) compositions of carbonate cave waters: implications for speleothem climatic records, 2000, Fairchild Ij, Borsato A, Tooth Af, Frisia S, Hawkesworth Cj, Huang Ym, Mcdermott F, Spiro B,
At two caves (Clamouse, S France and Ernesto, NE Italy), cave drip and pool waters were collected and sampled at intervals over a 2-3 year period. Mg/Ca and Sr/Ca concentration ratios, corrected for marine aerosols, are compared with those of bedrocks and, in some cases, aqueous leachates of soils and weathered bedrocks. Cave waters do not lie along mixing lines between calcite and dolomite of bedrock carbonate, but typically show enhanced and covarying Mg/Ca and Sr/Ca. Four factors are considered as controlling processes. (1) The much faster dissolution rate of calcite than dolomite allows for the possibility of increase of Mg/Ca if water-rock contact times are increased during drier conditions. A theoretical model is shown to be comparable to experimental leachates. (2) Prior calcite precipitation along a flow path is a powerful mechanism for generating enhanced and covarying Mg/Ca and Sr/Ca ratios. This mechanism requires the solution to lose CO, into pores or caverns. (3) Incongruent dolomite dissolution has only limited potential and is best regarded as two separate processes of dolomite dissolution and calcite precipitation. (4) selective leaching of Mg and Sr with respect to Ca is shown to be important in leachates from Ernesto where it appears to be a phenomenon of calcite dissolution. In general selective leaching can occur whenever Ca is sequestered into precipitates due to freezing or drying of soils, or if there is derivation of excess Sr and Mg from non-carbonate species. The Ernesto cave has abundant water supply which in the main chamber is derived from a reservoir with year-round constant P-CO2 of around 10(-2.4) and no evidence of calcite precipitation in the karst above the cave. Two distinct, bur overlying trends of enhanced and covarying Mg/Ca and Sr/Ca away from the locus of bedrock compositions are due to calcite precipitation within the cave and, at a variable drip site, due to enhanced selective leaching at slow drip rates. Mg-enhancement in the first chamber is due to a more dolomitic bedrock and longer residence times. The Clamouse site has a less abundant water supply and presents geochemical evidence of prior calcite precipitation. both in the cave and in overlying porous dolomite/dedolomitized limestone bedrock. Initial P-CO2 values as high as 10(-1) are inferred. Experimental incubations of Clamouse soils which generated enhanced P-CO2 and precipitated CaCO3 had compositions similar to the karst waters. Calcite precipitation is inferred to he enhanced in drier conditions. Hydrological controls on cave water chemistry imply that the trace element chemistry of speleothems may be interpretable in palaeohydrological terms. Drier conditions tends to promote not only longer mean residence times (enhancing dolomite dissolution and hence Mg/Ca), but also enhances degassing and calcite precipitation leading to increased Mg/Ca and Sr/Ca. (C) 2000 Elsevier Science B.V. All rights reserved

Microbiology and geochemistry in a hydrogen-sulphide-rich karst environment, 2000, Hose Louise D. , Palmer Arthur N. , Palmer Margaret V. , Northup Diana E. , Boston Penelope J. , Duchene Harvey R. ,
Cueva de Villa Luz, a hypogenic cave in Tabasco, Mexico, offers a remarkable opportunity to observe chemotrophic microbial interactions within a karst environment. The cave water and atmosphere are both rich in hydrogen sulphide. Measured H2S levels in the cave atmosphere reach 210 ppm, and SO2 commonly exceeds 35 ppm. These gases, plus oxygen from the cave air, are absorbed by freshwater that accumulates on cave walls from infiltration and condensation. Oxidation of sulphur and hydrogen sulphide forms concentrated sulphuric acid. Drip waters contain mean pH values of 1.4, with minimum values as low as 0.1.The cave is fed by at least 26 groundwater inlets with a combined flow of 200-300 l/s. Inlet waters fall into two categories: those with high H2S content (300-500 mg/l), mean PCO2=0.03-0.1 atm, and no measurable O2; and those with less than 0.1 mg/l H2S, mean PCO2=0.02 atm, and modest O2 content (up to 4.3 mg/l). Both water types have a similar source, as shown by their dissolved solid content. However, the oxygenated water has been exposed to aerated conditions upstream from the inlets so that original H2S has been largely lost due to outgassing and oxidation to sulphate, increasing the sulphate concentration by about 4%. Chemical modelling of the water shows that it can be produced by the dissolution of common sulphate, carbonate, and chloride minerals.Redox reactions in the cave appear to be microbially mediated. Sequence analysis of small subunit (16S) ribosomal RNA genes of 19 bacterial clones from microbial colonies associated with water drips revealed that 18 were most similar to three Thiobacilli spp., a genus that often obtains its energy from the oxidation of sulphur compounds. The other clone was most similar to Acidimicrobium ferrooxidans, a moderately thermophilic, mineral-sulphide-oxidizing bacterium. Oxidation of hydrogen sulphide to sulphuric acid, and hence the cave enlargement, is probably enhanced by these bacteria.Two cave-enlarging processes were identified. (1) Sulphuric acid derived from oxidation of the hydrogen sulphide converts subaerial limestone surfaces to gypsum. The gypsum falls into the cave stream and is dissolved. (2) Strongly acidic droplets form on the gypsum and on microbial filaments, dissolving limestone where they drip onto the cave floors.The source of the H2S in the spring waters has not been positively identified. The Villahermosa petroleum basin within 50 km to the northwest, or the El Chichon volcano [small tilde]50 km to the west, may serve as source areas for the rising water. Depletion of 34S values (-11.7[per mille sign] for sulphur stabilized from H2S in the cave atmosphere), along with the hydrochemistry of the spring waters, favour a basinal source

Seasonal variations in Sr, Mg and P in modern speleothems (Grotta di Ernesto, Italy), 2001, Huang Yiming, Fairchild Ian J. , Borsato Andrea, Frisia Silvia, Cassidy Nigel J. , Mcdermott Frank, Hawkesworth Chris J. ,
Sub-annual variations in trace element chemistry and luminescence have recently been demonstrated from speleothems and offer the potential of high-resolution palaeoclimatic proxies. However, no studies have yet examined microscopic trace element variations in relation to modern cave conditions. In this study, the spatial variations in trace element (Sr, Mg and P) concentrations in speleothems (a stalagmite and a soda straw stalactite) from the alpine Ernesto cave (temperature 6.60.1[deg]C) in a forested catchment in NE Italy have been studied using secondary ion mass spectrometry (SIMS) and compared with environmental parameters and waters in the modern cave. An annual lamination exists in the stalagmite and soda straw stalactite in the form of clear calcite with narrow visible layers, which are UV-fluorescent and interpreted to contain soil-derived humic/fulvic acids washed into the cave during autumn rains. Microanalyses were undertaken of seven annual laminae, probably deposited during the 1960s in the stalagmite, and seven laminae in the 1990s for the stalactite.The analysis results show that Sr consistently has a trough and P, a peak centred on the inclusion-rich layer. Mg shows mainly a negative covariation with Sr in laminae formed in the 1990s, but a positive covariation in the stalagmite formed in 1960s. The spatial scale of the main geochemical variations is the same as that of annual laminae of inclusion-poor and inclusion-rich couplets. Mass balance arguments are used to show that the P is inorganic in form and presumably occurs as individual phosphate ions within the calcite.Most drip waters show limited chemical variations, but a summer peak in trace elements in 1995 and a decrease in Mg/Ca in the following winter are notable. More pronounced covariations in Mg/Ca and Sr/Ca are shown by a site with highly variable drip rates where ratios increase at slow drip rates. The strongest seasonal variations are found in pool waters, where ratios increase reflecting significant Ca removal from the water into the calcite during the winter in response to seasonal PCO2 variations in cave air. Thus, the cave waters' compositions tend to reflect climate conditions, such that Mg/Ca and Sr/Ca are tentatively interpreted to be higher when climate conditions are dry.Combining results from the speleothems and cave water along with the behaviour of each trace species, Mg/Ca variations in the speleothems are considered to reflect their variation in the cave waters, whereas, Sr incorporation is also dependent on precipitation rate, in this case, mainly controlled by temporal variations in PCO2 in the cave (and conceivably, also by inhibitors such as phosphate). P adsorption (a fraction of which is subsequently incorporated within calcite) depends on aqueous phosphate concentration and water flux, both of which should increase during the autumn. Therefore, multiple trace element profiles in speleothems reflect multiple aspects of environment seasonality and conditions, and hence, a calibration against weather records is desirable to establish their palaeoclimatological meaning. The strong annual variation of trace elements, and particularly P, can provide chronological markers for high-resolution studies of other climate proxies, such as stable isotopes

Partitioning of Sr2 and Mg2 into calcite under karst-analogue experimental conditions, 2001, Huang Yiming, Fairchild Ian J. ,
There is a paucity of experimental data on calcite precipitation from waters at low ionic strength and low ratios of Mg/Ca and Sr/Ca, using controlled and constant precipitation rates. Such data are particularly needed for studies of speleothem geochemistry in relation to palaeoclimates.We carried out a series of experiments using a karst-analogue set-up in a chamber of constant temperature and 100% humidity. A steady flow of NaHCO3 and CaCl2 solutions at PCO2 around 10-3.2 were mixed just before passage through a tube (analogous to a soda-straw stalactite) and allowed to drip onto a surface, analogous to a stalagmite. Growth rates were comparable with linear extension rates of natural speleothems.Analytical spots gave reproducible analyses in later analytical cycles after ablation of surface calcite with Na and Mg contamination. Different crystals from the same experiment tended to show positive covariation of Na and Mg with negative covariation with Sr. This may be due to the presence of growth hillocks with vicinal faces with differential partitioning behaviour.The result for the partition coefficient for Mg (DMg) at 25[deg]C is 0.031 0.004, which is quantitatively in good agreement with the trends of previous workers. At 15[deg]C, the result is 0.019 0.003. The temperature dependency is higher than experimental data on seawater-analogue solutions, but lower than a previous estimate based on a comparison of speleothem chemistry with single water analyses.Data for DSr are mainly in the range of 0.057 to 0.078, with a possible weak dependency on growth rate, consistent with previous experimental work. Absolute values are higher than studies in Mg-free saline solutions, which is attributed mainly to salinity effects. Values of DSr are nevertheless somewhat lower than in natural caves, which may relate to crystal growth factors.Mg partition coefficient values should allow robust determination of solution Mg/Ca compositions in enclosed caves, which are at constant temperature on the decadal timescale. The inferred sensitivity of DSr to growth rate factors implies that Sr values should be interpreted more cautiously. Muted changes could relate entirely to growth rate variations, whereas changes of large magnitude imply a control by solution composition. The absence of local (tens of micron scale) antipathetic variations in Sr and Mg in studied natural speleothems, implies that intracrystalline zoning phenomena, if present, are on a finer scale in those natural materials compared with experimental products

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