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Speleology in Kazakhstan

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

New publications on hypogene speleogenesis

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

The deepest terrestrial animal

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

Caves - landscapes without light

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

Did you know?

That acclivity is ascending a slope [16].?

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Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
See all featured articles
Featured articles from other Geoscience Journals
Karst environment, Culver D.C.
Mushroom Speleothems: Stromatolites That Formed in the Absence of Phototrophs, Bontognali, Tomaso R.R.; D’Angeli Ilenia M.; Tisato, Nicola; Vasconcelos, Crisogono; Bernasconi, Stefano M.; Gonzales, Esteban R. G.; De Waele, Jo
Calculating flux to predict future cave radon concentrations, Rowberry, Matt; Marti, Xavi; Frontera, Carlos; Van De Wiel, Marco; Briestensky, Milos
Microbial mediation of complex subterranean mineral structures, Tirato, Nicola; Torriano, Stefano F.F;, Monteux, Sylvain; Sauro, Francesco; De Waele, Jo; Lavagna, Maria Luisa; D’Angeli, Ilenia Maria; Chailloux, Daniel; Renda, Michel; Eglinton, Timothy I.; Bontognali, Tomaso Renzo Rezio
Evidence of a plate-wide tectonic pressure pulse provided by extensometric monitoring in the Balkan Mountains (Bulgaria), Briestensky, Milos; Rowberry, Matt; Stemberk, Josef; Stefanov, Petar; Vozar, Jozef; Sebela, Stanka; Petro, Lubomir; Bella, Pavel; Gaal, Ludovit; Ormukov, Cholponbek;
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Your search for ratios (Keyword) returned 116 results for the whole karstbase:
Showing 106 to 116 of 116
From soil to cave: Transport of trace metals by natural organic matter in karst dripwaters, 2012, Hartland A. , Fairchild I. J. , Lead J. R. , Borsato A. , Baker A. , Frisia S. , Baalousha M.

This paper aims to establish evidence for the widespread existence of metal binding and transport by natural organic matter (NOM) in karst dripwaters, the imprint of which in speleothems may have important climatic significance. We studied the concentration of trace metals and organic carbon (OC) in sequentially filtered dripwaters and soil leachates from three contrasting sites: Poole's Cavern (Derbyshire, UK), Lower Balls Green Mine (Gloucestershire, UK) and Grotta di Ernesto (Trentino, Italy). The size-distribution of metals in the three soils was highly similar, but distinct from that found in fractionated dripwaters: surface-reactive metals were concentrated in the coarse fraction (>100 nm) of soils, but in the fine colloidal (b100 nm) and nominally dissolved (b1 nm) fractions of dripwaters. The concentration of Cu, Ni and Co in dripwater samples across all sites were well correlated (R2=0.84 and 0.70, Cu vs. Ni, Cu vs. Co, respectively), indicating a common association. Furthermore, metal ratios (Cu:Ni, Cu:Co) were consistent with NICA-Donnan n1 humic binding affinity ratios for these metals, consistent with a competitive hierarchy of binding affinity (Cu>Ni>Co) for sites in colloidal or dissolved NOM. Large shifts in Cu:Ni in dripwaters coincided with high fluxes of particulate OC (following peak infiltration) and showed increased similarity to ratios in soils, diagnostic of qualitative changes in NOMsupply (i.e. fresh inputs of more aromatic/hydrophobic soil organic matter (SOM) with Cu outcompeting Ni for suitable binding sites). Results indicate that at high-flows (i.e. where fracture-fed flow dominates) particulates and colloids migrate at similar rates, whereas, in slow seepage-flow dripwaters, particulates (>1 μm) and small colloids (1–100 nm) decouple, resulting in two distinct modes of NOM–metal transport: high-flux and low-flux. At the hyperalkaline drip site PE1 (in Poole's Cavern), high-fluxes of metals (Cu, Ni, Zn, Ti, Mn, Fe) and particulate NOM occurred in rapid, short-lived pulses following peak infiltration events, whereas low-fluxes of metals (Co and V>Cu, Ni and Ti) and fluorescent NOM (b ca. 100 nm) were offset from infiltration events, probably because small organic colloids (1–100 nm) and solutes (b1 nm) were slower to migate through the porous matrix than particulates. These results demonstrate the widespread occurrence of both colloidal and particulate NOM–metal transport in cave dripwaters and the importance of karst hydrology in affecting the breakthrough times of different species. Constraints imposed by soil processes (colloid/particle release), direct contributions of metals and NOM from rainfall, and flow-routing (colloid/particle migration) are expected to determine the strength of correlations between NOM-transported metals in speleothems and climatic signals. Changes in trace metal ratios (e.g. Cu:Ni) in speleothems may encode information on NOMcomposition, potentially aiding in targeting of compound-specific investigations and for the assessment of changes in the quality of soil organic matter.


Radionuclides as natural tracers for the characterization of fluids in regional discharge areas, Buda Thermal Karst, Hungary, 2012, Eross A. , Mdlszonyi J. , Surbeck H. , Horvth . , Goldscheider N. , Csoma A. .

The Buda Thermal Karst (Budapest, Hungary) developed in the regional discharge zone of a carbonate rock aquifer system. High radioactivity of the spring waters has already been reported in 1912, but there has been no detailed study and no consistent explanation for its origin. In this area mixing of cold and hot karst waters was hitherto assigned to be responsible for cave formation. However, the dissimilarity of the discharging waters within Budapest (in the North: Rozsadomb; in the South: Gellert Hill), may suggest also different cave forming processes. The application of radionuclides as natural tracers represents a novel approach to investigate these questions. For this study, we used uranium, radium and radon to identify mixing of fluids in the Buda Thermal Karst system and to infer the temperature and chemical composition of the end members. Chloride as a conservative component allowed the mixing ratios for the sampled waters to be calculated. Their fluid compositions were modeled and through the comparison of modeled and measured values, the end members were validated. As the result of this study, it was possible to characterize the mixing end members for the Rozsadomb area, whereas for the Gellert Hill discharge zone, mixing components could not be identified with the aid of radionuclides. Therefore, it is suggested that different processes are responsible for cave formation in these areas. In the Rozsadomb area, structurally-controlled mixing is the dominant cave forming process, whereas in the Gellert Hill area, due to the lack of mixing members, other processes have to be found, which are responsible for the formation of the caves, such as retrograde calcite solubility and/or geogenic acids, such as H2S. The application of radionuclides thus further supported the differences between the two study areas. This study identified moreover the source of elevated radon content of the waters in the Gellert Hill area in form of iron-hydroxide precipitates that accumulate in the spring caves. These precipitates are highly efficient in adsorbing radium, which generates radon by alpha decay, and hence act as local radon source for the waters. In this study we showed that uranium, radium and radon naturally occurring in groundwater can be used to characterize fluids of different flow systems in regional discharge areas owing to the contrasting geochemical behaviors of these elements


Simulation of flow processes in a large scale karst system with an integrated catchment model (Mike She) Identification of relevant parameters influencing spring discharge, 2012, Doummar J. , Sauter M. , Geyer T.

In a complex environment such as karst systems, it is difficult to assess the relative contribution of the different components of the system to the hydrological system response, i.e. spring discharge. Not only is the saturated zone highly heterogeneous due to the presence of highly permeable conduits, but also the recharge processes. The latter are composed of rapid recharge components through shafts and solution channels and diffuse matrix infiltration, generating a highly complex, spatially and temporally variable input signal. The presented study reveals the importance of the compartments vegetation, soils, saturated zone and unsaturated zone. Therefore, the entire water cycle in the catchment area Gallusquelle spring (Southwest Germany) is modelled over a period of 10 years using the integrated hydrological modelling system Mike She by DHI (2007). Sensitivity analyses show that a few individual parameters, varied within physically plausible ranges, play an important role in reshaping the recessions and peaks of the recharge functions and consequently the spring discharge. Vegetation parameters especially the Leaf Area Index (LAI) and the root depth as well as empirical parameters in the relationship of Kristensen and Jensen highly influence evapotranspiration, transpiration to evaporation ratios and recharge respectively. In the unsaturated zone, the type of the soil (mainly the hydraulic conductivity at saturation in the water retention and hydraulic retention curves) has an effect on the infiltration/evapotranspiration and recharge functions. Additionally in the unsaturated karst, the saturated moisture content is considered as a highly indicative parameter as it significantly affects the peaks and recessions of the recharge curve. At the level of the saturated zone the hydraulic conductivity of the matrix and highly conductive zone representing the conduit are dominant parameters influencing the spring response. Other intermediate significant parameters appear to influence the characteristics of the spring response yet to a smaller extent, as for instance bypass and the parameters a in the Van Genuchten relation for soil moisture content curves.


Environmental Hydrogeological Study of Louros watershed, Epirus, Greece, 2012, Konstantina Katsanou

The present study aims to describe and characterize the Ionian zone karst formation concerning the karstification grade of carbonate formations and the development of aquifers, through the hydrogeological study of Louros River drainage basin, considering hydrological, hydrogeological and meteorological data, as well as major, trace element, rare earth element and isotope concentrations. It also aims to investigate basic karst properties such as storativity, homogeneity, infiltration coefficients and the parameters of the Louros basin hydrological balance.

To accomplish this aim daily discharge measurements obtained from Public Power Corporation at the Pantanassa station during the years 1956-1957, along with random discharge measurements from 15 springs along the basin performed by IGME between the years 1979-1989, daily meteorological data from 18 stations and 18 sets of potentiometric surface measurements from 38 sites were compiled. Additionally, chemical analyses on major and trace element concentrations of 42 rock samples and of five sets of water samples from 64 sampling sites, along with fourteen sets of successive periods in order to study the seasonal variation in the chemical composition of 11 springs and REE concentrations of 116 water samples. Moreover isotope ratios from 129 rain samples collected at five different altitudes, 331 samples of surface and groundwater samples, radon measurements on 21 groundwater samples and microbiological on 46 samples of surface and groundwater were evaluated. Daily runoff and random spring discharge missing data were completed applying the SAC-SMA and MODKARST simulation algorithms and the values of these parameters for the duration of the research (2008-2010) were predicted. The accuracy of the predicted values was tested applying statistical methods but also against observed values from in situ measurements performed during the same period (2008-2010).

Louros River drainage basin is located at the southern part of Epirus and covers an area of 953 km2. It is elongated and together with the adjacent basin of River Arachthos they constitute the major hydrographic systems discharging in the Amvrakikos Gulf. The main morphological features of the basin are elongated mountain ranges and narrow valleys, which are the result of tectonic and other geological processes mainly controlled by the limestone-“flysch” alternations. The length of the river’s major channel, which is parallel to the major folding direction (NNW-SSE), is 73.5 km. The mountainous part of the hydrogeological basin covers an area of 400 km2 and its endpoint was set at the Pantanassa station, where discharge measurements are performed. The underground limits of the basin coincides with the surface one, defined by the flysch outcrops at the western margin of the Ziros-Zalongo fault zone to the South, the application of isotope determinations and hydraulic load distribution maps at the North and East.

Geologically, Louros River drainage basin is composed of the Ionian zone formations. Triassic evaporites constitute the base of the zone overlain by a thick sequence of carbonate and clastic sedimentary rocks deposited from the Late Triassic to the Upper Eocene. In more detail, from base to top, the lithostratigraphical column of the zone includes dolomite and dolomitic limestone, Pantokrator limestone, Ammonitico Rosso, Posidonia Shales, Vigla limestone, Upper Senonian limestone, Palaeocene-Eocene limestone and Oligocene “flysch”. The major tectonic features of the regions are folds with their axes trending SW-NE at the northern part and NNW-SSE to NNE-SSW southern of the Mousiotitsa-Episkopiko-Petrovouni fault system and the strike-slip fault systems of Ziros and Petousi.

The evaluation of the daily meteorological data revealed that December is the most humid month of the year followed by January, whereas July and August are the driest months. Approximately 40-45% of the annual precipitation is distributed during the winter time and 30% during autumn. The mean annual precipitation ranges from 897.4 to 2051.8 mm and the precipitation altitude relationship suggests an increased precipitation with altitude at a rate of 84 mm/100 m. The maximum temperature is recorded during August and it may reach 40°C and the minimum during January. The temperature variation with the altitude is calculated at 0.61°C/100 m. The maximum solarity time is 377.8 h, recorded during July at the Arta station. December displays the highest relative humidity with a value of 84.2% recorded again at the Arta station. The highest wind velocity values are recorded at the Preveza station and similar velocities are also recorded at the Ioannina station. The real evapotranspiration in Louros drainage basin ranges between 27-39%. The potential evapotranspiration was calculated from the Ioannina station meteorological data, which are considered more representative for Louros basin, at 785.8 mm of precipitation according to Thornthwaite and at 722.0 mm according to Penman-Monteith.

According to the SAC-SMA algorithm the total discharge (surficial and underground) for the years 2008-2010 ranges between 61-73% of the total precipitation. The algorithm simulates the vertical percolation of rainwater in both unsaturated and saturated zones taking into account 15 parameters including the tension water capacity of the unsaturated zone, the maximum water storage capacity of both unsaturated and saturated zones, the water amount escaping into deeper horizons and not recorded at the basin’s outlet, the percentage of impermeable ground which is responsible for instant runoff, etc. These parameters are correlated to the hydrograph and are recalculated according to it. Two interesting aspects were pointed out from the discharge measurements and the algorithm application. The first is related to the maximum amount of free water, which can be stored at the basic flow of the karstic system, which is very high for the whole basin, reaching 1200 mm of precipitation and the second is the amount of water filtered to the deeper horizons, which reaches 0.098.

The discharge of individual karstic units was simulated applying the specialized MODKARST code. The code, which transforms precipitation to discharge resolving mathematical equations of non-linear flow using the mass and energy balance, successfully completed the time series of available data of spring discharge measurements for the period between the years 2008-2010.

Additionally, a number of useful parameters including spring recharge, delay period between precipitation and discharge, the storage capacity of the discharge area were also calculated by the MODKARST code. These data enabled the calculation of the annual infiltration coefficient for each one of the 15 springs and for the whole basin; the latter was found to range between 38-50% of annual precipitation. The total supply area was estimated approximately at 395 km2, which is consistent with the area of Louros hydrogeological basin calculated from hydrogeological data.

The 18 sets of water table measurements, each one corresponding to a different period, revealed that the aquifers of the intermediate part of Louros basin, which are developed in Quaternary alluvial sediments, are laterally connected to the carbonate formations of the individual karstic spring units, forming a common aquifer with a common water table.

Groundwater flow follows a general N-S direction from the topographic highs to the coastal area with local minor shifts to NE-SW and NW-SE directions. The artificial lake at the position of the Public Power Corporation’s Dam at the south of the region is directly connected to the aquifer and plays an important role in water-level variation. The water table contours display a higher gradient to the southern part due to the decreased hydraulic conductivity of the limestones close to Agios Georgios village. The decreased hydraulic conductivity is believed to be the reason for the development of the homonymous spring although the hydraulic load distributions suggest the extension of the aquifer to the south and a relation to the water level in Ziros Lake, boreholes and the Priala springs. The hydraulic gradient in the broader region ranges between 4-16‰. The absolute water level variation between dry and humid season ranges from 2 m at the South to 15-20 m to the North with an average of 9 m.

The hydrological balance of Louros River mountainous basin according to the aforementioned data is calculated as follows: The total precipitation between the years 2008-2010 ranged between 5.67E+08-9.8E+08 m3 and the discharge at Pantanassa site between 3.47E+08-6.83E+08 m3. The real evapotransiration ranged between 29-39% of the precipitation. The total discharge (runoff and groundwater) accounted for 61-73% of the precipitation, whereas the basic flow due to the percolation ranged between 34-38%. Considering a mean water level variation of 9 m, between the dry and humid season, the water amount constituting the local storage is 2025Ε+07 m3.

Statistical evaluation on spring discharge data and the recession curves analysis revealed three distinct levels with diverse karstic weathering along Louros basin coinciding to the upper, intermediate and low flow of Louros River, respectively. The developed karstic units are generally complex but simple individual units develop as well. The response of spring discharge to the stored water amounts is immediate but with relatively large duration suggesting the storage of large quantities of water and a well-developed system of karstic conduits, which however has not yet met its complete evolution. The karst spring’s units are homogeneous and each one is distinguished from different recession coefficients.

The three levels of flow are also distinguished from the duration curves, which point to individual units upstream, complex units receiving and transmitting water to the adjacent ones in the middle part and complex that only receive water from the upper. This distinguishment is also enhanced by the groundwater’s major ion concentrations, which reveal Ca-HCO3 water-type upstream, along with the isotopic composition at the same part. The prevalent Ca-HCO3-Cl-SO4 water-type in the middle part, the Na-Ca-Cl-SO4 water-type downstream and isotope variation confirms this distinguishment. Moreover, REE variation is also consistent with the three levels. The assumption of relatively large stored water reserves, which contribute to analogous “memory” of spring karstic units, as pointed out by autocorreletion functions is enhanced from SAC-SMA algorithm which premises an increased capacity at the lower zone of basic flow, as well as from the hydrochemical and isotopic composition of groundwater. Monitoring of the seasonal variation in groundwater composition revealed minor variations of hydrochemical parameters and remarkably stable isotopic composition. Both aspects can be explained by the existence of a considerable water body acting as a retarder to external changes.

The crosscorrelation functions suggest a well-developed karstic system, which however has not yet reached its complete maturity also confirmed from field observations. The same conclusion is extracted from the homogeneous evolution at the interval of each karstic unit as demonstrated from recession curves on spring hydrographs.

The results from hydrochemical analyses also revealed the effect of evaporitic minerals and phosphate-rich rocks in groundwater composition and confirmed the hydraulic relationships between surface and groundwater.

The study of the isotopic composition also contributed to exclude the potential connection between the Ioannina and Louros basins, confirmed the meteoric origin of groundwater and revealed the effect of seawater in the chemical composition of few sampling sites.

The microbiological research only revealed minor incidents of contamination and significant attenuation of microorganisms during periods of high discharge.


Stable isotope (O and C) geochemistry of non-sulfide ZnPb deposits; case study: Chah-Talkh non-sulfide ZnPb deposit (Sirjan, south of Iran), 2013, Rezaeian A. , Rasa I. , Amiri A. , Jafari M. R.

The study of oxygen and carbon isotopic ratios has gained importance to determine the origin of ore-bearing fluids, carbon origin, and also to determine the formation temperature of non-sulfide Pb and Zn minerals. In order to determine the origin of fluids and carbon existing in Zn carbonate minerals in Chah-Talkh deposit, initially the amounts of δ18OSMOW and δ13CPDB changes in various zinc minerals in important deposits in Iran and the world were studied, and then by comparing these values in Chah-Talkh deposit with those of other deposits, the origin of fluids responsible for ore forming, carbon, and formation temperature of Chah-Talkh deposit was determined. The range of δ18OSMOW changes in smithsonite mineral in non-sulfide lead and zinc deposits varies from 18.3 to 31.6 ‰, and δ18OSMOW in hydrozincite mineral varies from 7.8 to 27 ‰. Due to the impossibility of smithsonite sampling from Chah-Talkh deposit (due to it being fine-grained and dispersed), hydrozincite minerals which have high isotopic similarities with smithsonite are used for the isotopic analysis of carbon and oxygen. The range of δ18OSMOW changes in hydrozincite mineral of Chah-Talkh deposit varies from 7.8 to 15.15‰, which places in the domain of metamorphic water. The extensiveness of δ18OSMOW changes in Chah- Talkh indicates the role of at least two fluids in the formation of non-sulfide minerals. The obtained formation temperature of non-sulfide minerals (hydrozincite) in Chah- Talkh deposit is 70 to 100 °C, which indicates the role of metamorphic fluids in the formation of deposit. Complete weathering of sulfide minerals to a depth of 134 m confirms the role of rising metamorphic fluids in the formation of non-sulfide minerals. The δ13CPDB values of Chah-Talkh deposit are set in the range of atmospheric CO2 and carbonate rocks, in which the existence of atmospheric CO2 indicates the role of atmospheric fluids, and the existence of carbonate carbon rock indicates of the role of metamorphic fluids in the precipitation of non-sulfide Zn minerals.


Layer-bounding surfaces in stalagmites as keys to better paleoclimatological histories and chronologies, 2013, Railsback L. B. , Akers P. D. , Wang L. , Holdridge G. A. , Riavo Voarintsoa N.

Petrographic recognition of layer-bounding surfaces in stalagmites offers an important tool in constructing paleoclimate records. Previous petrographic efforts have examined thickness of layers (a possible proxy for annual rainfall) and alternation of layers in couplets (a possible indicator of seasonality). Layer-bounding surfaces, in contrast, delimit series of layers and represent periods of non-deposition, either because of exceptionally wet or exceptionally dry conditions.

Two types of layer-bounding surfaces can be recognized according to explicitly defined petrographic criteria. Type E layer-bounding surfaces are surfaces at which layers have been truncated or eroded at the crest of a stalagmite. Keys to their recognition include irregular termination of layers otherwise present on the stalagmite’s flank, dissolutional cavities, and coatings of non-carbonate detrital materials. Type E surfaces are interpreted to represent wet periods during which drip water became so undersaturated as to dissolve pre-existing stalagmite layers, and thus they necessarily represent hiatuses in the stalagmite record. Type L layer-bounding surfaces are surfaces below which layers become thinner upward and/or layers have lesser lateral extent upward, so that the stalagmite’s layer-specific width decreases. They are thus surfaces of lessened deposition and are interpreted to represent drier conditions in which drip rate slowed so much that little deposition occurred. A Type L surface may, but does not necessarily, represent a hiatus in deposition. However, radiometric age data show that Type L surfaces commonly represent significant hiatuses.

These surfaces are significant to paleoclimate research both for their implications regarding climate change (exceptionally wet or dry conditions) and in construction of chronologies in which other data, such as stable isotope ratios, are placed. With regard to climate change, recognition of these surfaces provides paleoclimatological information that can complement or even substitute for geochemical proxies. With regard to chronologies, recognition of layer- bounding surfaces allows correct placement of hiatuses in chronologies and thus correct placement of geochemical data in time series. Attention to changing thickness of annual layers and thus to accumulation rate can also refine a chronology. A chronology constructed with attention to layer-bounding surfaces and to changing layer thickness is much more accurate than a chronology in which hiatuses are not recognized at such surfaces.


HOW DO APERTURE SIZES IN LIMESTONE VARY FOR THE ONSETS OF TURBULENT FLOW AND FIRST-ORDER DISSOLUTION KINETICS?, 2013, Faulkner Trevor

 

It is commonly stated in the literature that the “breakthrough” point at the transition from slow high-order to fast firstorder dissolution kinetics in limestone occurs at an exit aperture of about one centimetre, and that this coincides with the transition from a wholly laminar flow to a turbulent flow. These relationships are approximately true for a range of conduit geometries in sub-horizontally bedded strata. However, the exit aperture for the onset of turbulence varies with the hydraulic gradient whereas the exit aperture for the onset of first-order kinetics varies with the hydraulic ratio, which is the hydraulic gradient divided by the path length. These transitions only occur at the same exit aperture for planar fissures and cylindrical tubes of lengths 290 m and 452 m. Breakthrough can occur before or after the onset of turbulence. Aperture sizes for breakthrough and turbulence can be over a metre for long and shallow conduits but sub millimetre for short and steep conduits. This paper analyses these relationships for many conduits in natural and artificial conditions and discusses their relevance to the multitude of possible karst situations, where hydraulic ratios can be considered over 17 orders of magnitude.


INVESTIGATIONS INTO THE POTENTIAL FOR HYPOGENE SPELEOGENESIS IN THE CUMBERLAND PLATEAU OF SOUTHEAST KENTUCKY, U.S.A., 2013, Florea Lee J.

 

This manuscript offers preliminary geochemical evidence that investigates the potential for hypogene speleogenesis in the Cumberland Plateau of southeastern Kentucky, U.S.A. The region was traditionally considered a classic example of epigenic karst, but new insights have uncovered tantalizing observations that suggest alternatives to simple carbonic acid speleogenesis. Such first-order observations have included natural petroleum seeps at the surface and in caves, occasional cave morphologies consistent with action of hypogene fluids, and prolific gypsum within cave passages. To this point, geochemical data from caves and springs verify carbonic acid as the primary dissolutional agent; however, these same analyses cannot rule out sulfuric acid as a secondary source of dissolution. In this paper, Principal Component Analysis of ionic data reveals two components that coordinate with parameters associated with “karst water” and shallow brine. In contrast, molar ratios of Ca+ and Mg+ as compared to HCO3 - and SO4 2- closely follow the reaction pathway stipulated by the carbonate equilibria reactions. Despite these data, the role, if any, of hypogene speleogenesis in the karst of the Cumberland Plateau remains inconclusive. It is very likely that carbonic acid dominates speleogenesis; however, contributions from sulfuric acid may influence our understanding of “inception” and carbon flux within these aquifers.


STRONTIUM ISOTOPE RATIOS (87SR/86SR) IN GYPSUM SPELEOTHEMS FROM THE NAICA MINE CAVES (CHIHUAHUA, MEXICO): GENETIC IMPLICATIONS, 2013, Gzquez Fernando, Calaforra Jos Maria, Garcacasco Antonio, Sanna Laura, Forti Paolo

The 87Sr/86Sr ratio of several gypsum speleothems from the caves of the Naica Mine (Chihuahua, Mexico) has been determined in order to evaluate the origin of the saline solution from which they precipitated. The 87Sr/86Sr ratios of the huge selenite crystals from the Cristales Cave (-290 m Level) and of the gypsum core of the “espadas” speleothems from the Espadas Cave (-120 m Level) are 0.707337 and 0.708343, respectively. These values are slightly higher than that of the carbonate host rock (0.7072) as well as that of the Tertiary felsic dikes emplaced in the carbonate sequence (0.7080). They are also lower than those expected for crystallization from seepage water solutions (>0.7090). Therefore, the 87Sr/86Sr values determined for the speleothems at Naica suggest that gypsum in these caves precipitated from a mixture of infiltration water and thermal water. The 87Sr/86Sr ratio of gypsum speleothems is regarded as a useful indicator to infer the rela- tive contribution of meteoric deep thermal water solutions during the genesis of the Naica’s gypsum speleothems.


Environmental controls on organic matter production and transport across surface-subsurface and geochemical boundaries in the Edwards aquifer, Texas, USA, 2013, Hutchins Benjamin T. , Schwartz Benjamin F. , Engel Annette S.

Karst aquifer phreatic zones are energy limited habitats supported by organic matter (OM) flow across physical and geochemical boundaries. Photosynthetic OM enters the Edwards Aquifer of Central Texas via streams sinking along its northeastern border. The southeastern boundary is marked by a rapid transition between oxygenated freshwaters and anoxic saline waters where OM is likely produced by chemolithoautotrophic microbes. Spatial and temporal heterogeneity in OM composition at these boundaries was investigated using isotopic and geochemical analyses. δ13C values for stream fine particulate OM (FPOM) (−33.34‰ to −11.47‰) decreased during regional drought between fall 2010 and spring 2012 (p<0.001), and were positively related to FPOM C:N ratios (r2 =0.47, p<0.001), possibly due to an increasing contribution of periphyton. Along the freshwater-saline water interface (FwSwI), δ 13CFPOM values (−7.23‰ to −58.18‰) correlated to δ13C values for dissolved inorganic carbon (δ13C DIC) (−0.55‰ to −7.91‰) (r2 =0.33, p=0.005) and were depleted relative to δ13C DIC values by 28.44‰, similar to fractionation values attributed to chemolithoautotrophic carbon fixation pathways using DIC as the substrate. δ13CFPOM values also became enriched through time (p<0.001), and δ13C DIC values (r2 =0.43, p<0.001) and δ13CFPOM values (r2 =0.35, p=0.004) at FwSwI sites increased with distance along the southwest-northeast flowpath of the aquifer. Spatial variability in FwSwI δ13C DIC values is likely due to variable sources of acidity driving carbonate dissolution, and the temporal relationship is explained by changes to recharge and aquifer level that affected transport of chemolithoautotrophic OM across the FwSwI.


Groundwater geochemistry observations in littoral caves of Mallorca (western Mediterranean): implications for deposition of phreatic overgrowths on speleothems., 2014, Boop L. M. , Onac B. P. , Wynn J. G. , Fornós J. J. , Rodríguezhomar M. , Merino A.

Phreatic overgrowths on speleothems (POS) precipitate at the air-water interface in the littoral caves of Mallorca, Spain. Mainly composed of calcite, aragonite POS are also observed in specific locations. To characterize the geochemical environment of the brackish upper water column, water samples and salinity values were collected from water profiles (0-2.9 m) in April 2012 and March 2013 near aragonite POS in Cova des Pas de Vallgornera and calcite POS in Coves del Drac (hereafter, Vallgornera and Drac). Degassing of CO2 from the water was evidenced by the existence of lower dissolved inorganic carbon (DIC) concentration and enriched δ13CDIC values in a thin surface layer (the uppermost 0.4 m), which was observed in both profiles from Drac. This process is facilitated by the efficient exchange of cave air with the atmosphere, creating a CO2 partial pressure (pCO2) disparity between the cave water and air, resulting in the precipitation of calcite POS as CO2 degasses from the water. The degassed upper layer was not observed in either profile from Vallgornera, suggesting that less efficient cave ventilation restricts outgassing of CO2, which also results in accumulation of CO2 in the cave atmosphere. The presence of an existing uncorroded POS horizon, as well as higher concentrations and large amplitude fluctuations of cave air pCO2, may indicate that aragonite POS deposition is currently episodic in Vallgornera. Ion concentration data from monthly water samples collected in each cave between October 2012 and March 2013 indicate higher Mg:Ca, Sr:Ca, Ba:Ca and Sr:Mg ratios in Vallgornera. Salinity alone does not appear to be a viable proxy for ions that may promote aragonite precipitation or inhibit calcite precipitation. Instead, these ions may be contributed by more intense bedrock weathering or deep groundwater flow.


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