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Enviroscan Ukrainian Institute of Speleology and Karstology

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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 epikarst; epikarst zone is a relatively thick (the thickness may vary significantly, but 15 to 30 meters thick is a good generalization) portion of bedrock that extends from the base of the soil zone and is characterized by extreme fracturing and enhanced solution. it is separated from the phreatic zone by an inactive, relatively waterless interval of bedrock that is locally breached by vadose percolation. significant water storage and transport are known to occur in this zone. synonym: subcutaneous zone.?

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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 isotope (Keyword) returned 481 results for the whole karstbase:
Showing 451 to 465 of 481
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.


Isotopes of Carbon in a Karst Aquifer of the Cumberland Plateau of Kentucky, USA, 2013, Florea Lee J.

In this study, the concentration and isotopic composition of dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) are measured in the karst groundwater of the Otter Creek watershed of the Cumberland Plateau of Kentucky, USA. Comparisons among these data and with the geochemistry of carbonate and gypsum equilibrium reactions reveal that DOC concentration is inversely related to discharge, multiple reaction pathways provide DIC with isotopic enrichment that may be directly related to mineral saturation, and oxidation of reduced sulfur is possible for dissolution. DOC is derived from C3 vegetation with an average δ13C DOC of ‒27‰. DIC in groundwater is derived from both pedogenic CO2  and HCO3 - from dissolved carbonate. At input sites to the karst aquifers DIC concentrations are expectedly low, less than 1 mmol/L, in waters that are undersaturated with respect to calcite. At the output of these karst aquifers DIC concentrations reach 3 mmol/L in waters that are at or above calcite saturation. Values of δ13C DIC range between ‒6.3 and ‒12.4‰ with CO2 degassing and calcite precipitation at some sites obfuscating a simple relationship between δ13C DIC, discharge, and mineral saturation. In addition, concentrations of DIC in sulfur seeps within the watershed range between 2–7 mmol/L with δ13C DIC values in some samples skewed more toward the anticipated value of carbonate bedrock than would be expected from reactions with carbonic acid alone. This suggests that the oxidation of reduced sulfur from shallow oilfield brines liberates bedrock DIC through reactions with sulfuric acid.


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.


Using isotopes of dissolved inorganic carbon species and water to separate sources of recharge in a cave spring, northwestern Arkansas, USA Blowing Spring Cave, 2013, Knierim Katherine J. , Pollock Erik, Hays Phillip D.

Blowing Spring Cave in northwestern Arkansas is representative of cave systems in the karst of the Ozark Plateaus, and stable isotopes of water (δ18O and δ2H) and inorganic carbon (δ13C) were used to quantify soil-water, bedrock-matrix water, and precipitation contributions to cave-spring flow during storm events to understand controls on cave water quality. water samples from recharge-zone soils and the cave were collected from March to May 2012 to implement a multicomponent hydrograph separation approach using δ18O and δ2H of water and dissolved inorganic carbon (δ13C–DIC). During baseflow, median δ2H and δ18O compositions were –41.6‰ and –6.2‰ for soil water and were –37.2‰ and –5.9‰ for cave water, respectively. Median DIC concentrations for soil and cave waters were 1.8 mg/L and 25.0 mg/L, respectively, and median δ 13C–DIC compositions were –19.9‰ and –14.3‰, respectively. During a March storm event, 12.2 cm of precipitation fell over 82 h and discharge increased from 0.01 to 0.59 m3 /s. The isotopic composition of precipitation varied throughout the storm event because of rainout, a change of 50‰ and 10‰ for δ2H and δ18O was observed, respectively. Although, at the spring, δ2H and δ18O only changed by approximately 3‰ and 1‰, respectively. The isotopic compositions of precipitation and pre-event (i.e., soil and bedrock matrix) water were isotopically similar and the two-component hydrograph separation was inaccurate, either overestimating (>100%) or underestimating (<0%) the precipitation contribution to the spring. During the storm event, spring DIC and δ13C–DIC de- creased to a minimum of 8.6 mg/L and –16.2‰, respectively. If the contribution from precipitation was assumed to be zero, soil water was found to contribute between 23 to 72% of the total volume of discharge. Although the assumption of negligible contributions from precipitation is unrealistic, especially in karst systems where rapid flow through conduits occurs, the hydrograph separation using inorganic carbon highlights the importance of considering vadose-zone soil water when analyzing storm chemohydrographs.  


Flow characterization in the Santee Cave system in the Chapel Branch Creek watershed, upper coastal plain of South Carolina, USA., 2013, Edwards A. E. , Amatya D. M. , Williams T. M. , Hitchcock D. R. , James A. L.

Karst watersheds possess both diffuse and conduit flow and varying degrees of connectivity between surface and groundwater over spatial scales that result in complex hydrology and contaminant transport processes. The flow regime and surface-groundwater connection must be properly identified and characterized to improve management in karst watersheds with impaired water bodies, such as the Chapel Branch Creek (CBC), South Carolina watershed, which has a long-term sampling station presently listed on an EPA 303(d) list for phosphorous, pH, and nitrogen. Water from the carbonate limestone aquifer of the Santee Cave system and spring seeps in the CBC watershed were monitored to characterize dominant flow type and surface-groundwater connection by measuring dissolved calcium and magnesium, total suspended solids, volatile suspended solids, alkalinity, pH, specific conductance, and stable isotopes (d18O, d2H). These measurements indicated that the conduit flow to Santee Cave spring was recharged predominantly from diffuse flow, with a slow response of surface water infiltration to the conduit. Qualitative dye traces and stage elevation at Santee Cave spring and the adjacent Lake Marion (equal to the elevation of the flooded portion of CBC) also indicated a relation between fluctuating base level of the CBC reservoir-like embayment and elevation of the Santee Limestone karst aquifer at the spring. Methods described herein to characterize the flow type and surface-groundwater connection in the Santee Cave system can be applied not only to watershed management in the Chapel Branch Creek watershed, but also to the greater region where this carbonate limestone aquifer exists. 


Hypogene karst: speleogenetic mechanisms and geochemical methods of diagnostics , 2013, Dublyansky, Y.

ESR and 230h/234U dating of speleothems from Aladaglar Mountain Range (AMR) in Turkey , 2014, Ulusoya Ülkü, Anbara Gül, Bayarıb Serdar, Uysalc Tonguç

Electron spin resonance (ESR) and 230Th/234U ages of speleothem samples collected from karstic caves located around 3000 m elevation in the Aladağlar Mountain Range (AMR), south-central Turkey, were determined in order to provide new insight and information regarding late Pleistocene climate. ESR ages were validated with the 230Th/234U ages of test samples. The ESR ages of 21 different layers of six speleothem samples were found to range mostly between about 59 and 4 ka, which cover the Marine Oxygen Isotope Stages (MIS) MIS 3 to MIS 1. Among all, only six layers appear to have deposited during MIS 8 and 5. Most of the samples dated were deposited during the late glacial stage (MIS 2). It appears that a cooler climate with a perennial and steady recharge was more conducive to speleothem development rather than a warmer climate with seasonal recharge in the AMR during the late Quaternary. This argument supports previous findings that suggest a two -fold increase in last glacial maximum mean precipitation in Turkey with respect to the present value.


Fingerprinting water-rock interaction in hypogene speleogenesis: potential and limitations of isotopic depth-profiling, 2014, Spötl Ch, Dublyansky Y.

Dissolution processes in karst regions commonly involve (meteoric) water whose stable isotopic (O, H, C) composition is distinctly different from that of the paleowaters from which the host rock (limestone, dolostone) formed. This, in theory, should lead to isotopic alteration of the host rock beyond the active solution surface as the modern karst water is out of isotopic equilibrium with the carbonate rock. No such alteration has been reported, however, in epigenetic karst systems. In contrast, isotopic alteration, commonly referred to as isotopic halos or fronts, are known from various hypogene systems (ore deposits, active hydro­thermal systems, etc.). These empirical observations suggest that stable isotope data may be a diagnostic tool to identify hypogene water-rock interactions particularly in cave systems whose origin is ambiguous.

We have been testing the applicability of this assumption to karst settings by studying the isotopic composition of carbonate host rocks in a variety of caves showing clear-cut hypogene morphologies. Cores drilled into the walls of cave chambers and galleries were stud­ied petrographically and the C and O isotope composition was analyzed along these cores, which typically reached a depth of 0.5 to 1.2 m. We identified three scenarios: (a) no isotopic alteration, (b) a sigmoidal isotope front within a few centimeters of the cave wall, and (c) pervasive isotope alteration throughout the entire core length. Type (a) was found in caves where the rate of cave wall retreat apparently outpaced the rate of isotopic alteration of the wall rock (which is typical, for example, for sulfuric acid speleogenesis). Type (c) was observed in geologically young, porous limestone showing evidence of alteration zones up to 5 m wide. The intermediate type (b) was identified in hypogene karst cavities developed in tight limestone, dolostone and marble.

Our data in conjunction with evidence from speleothems and their geochemical and fluid-inclusion composition suggest that the spa­tial extent of the isotopic alteration front depends on the porosity and permeability, as well as on the saturation state of the water. Wider alteration zones primarily reflect a higher permeability. Shifts are most distinct for oxygen isotopes and less so for carbon, whereby the amplitude depends on a number of variables, including the isotopic composition of unaltered host rock, the isotopic composition of the paleofluid, the temperature, the water/rock ratio, the surface of water-rock contact, the permeability of the rock, and the time available for isotope exchange. If the other parameters can be reasonably constrained, then semi-quantitative temperature estimates of the paleowater can be obtained assuming isotopic equilibrium conditions.

If preserved (scenarios b and c), alteration fronts are a strong evidence of hypogene speleogenesis, and, in conjunction with hypogene precipitates, allow to fingerprint the isotopic and physical parameters of the altering paleofluid. The reverse conclusion is not valid, however; i.e. the lack of evidence of isotopic alteration of the cave wall rock cannot be used to rule out hypogene paleo-water-rock interaction.


PERMIAN HYDROTHERMAL KARST IN KRAKÓW REGION (SOUTHERN POLAND) AND ITS PECULIAR INTERNAL SEDIMENTS, 2014, Gradziński M. , Lewandowska A. , Paszkowski M. , Duliński M. , Nawrocki J. , Żywiecki M.

The development of caves influenced by the deep circulation of water has received increasing interest for the last thirty years. Presently, hypogene caves have been recognized all around the world. Conversely, the ancient examples filled with sediments and representing palaeokarst forms are not so common.
The karst forms and their sediment fillings were encountered in the Dębnik Anticline (Kraków region, Southern Poland) composed of Middle Devonian to Mississippian carbonates. The development of karst slightly postdates the Permian (ca. 300 Ma) volcanic activity in the Kraków region. In this region major transcontinental strike and slip Hamburg-Kraków-Dobruja fault zone induced a series of minor, en echelon, extensional faults, which served as magma passages and guided karst conduits.
The karst forms in the Dębnik Anticline reach several to tens of meters in size. They are filled with: i) massive, subaqueous, coarse crystalline calcite spar; ii) crystalloclastic, bedded limestones; iii) jasper lenses; iv) kaolinitised tuffs. The sediments are characterized by red colouration caused by iron compounds.
Coarse crystalline calcite spar composes beds up to several dozen centimeters in thickness. They are laminated and comprise frutexites type structures. The calcites are interbedded with pinkish-red crystalloclastic limestones, which are built of detritic calcite crystals from silt size to a few millimeters across. Some of the crystals are of skeletal type. Crystalloclastic limestones are normally graded. Both calcite spar and crystalloclastic limestones underwent synsedimentary deformations, which resulted in brecciation and plastic deformations.
The above deposits fill karst forms up to a few metres in lateral extent. However, analogously filled enormously huge (up to around 100 m across) forms were recognized in the early 80s of the last century. Presently, they are completely exploited.
The karst forms were fragments of extensive circulation system. It was fed by waters of elevated temperature, rich in endogenic CO2, which is proved by fluid inclusion analysis and stable isotope investigation. The origin of this system was associated with volcanic activity. The roots of the system are represented by fissures filled with coarse crystalline, red and white calcites of onyx type, which are common in the Dębnik Anticline. Water issuing from this system on the surface caused precipitation of red travertines. These travertines are preserved only as clasts in the Lower Permian conglomerates deposited in the local tectonic depressions.
The study was financed by Ministry of Science and Higher Education project N307 022 31/1746.


HYPOGENE VS EPIGENE CAVES: THE SULFUR AND OXYGEN ISOTOPE FINGERPRINT, 2014, Onac, B. P.

The classical epigene speleogenetic model in which CO2 is considered the main source of acidity has been challenged over the last three decades by observations that revealed cave passages unrelated to groundwater drainage routes and surface topography. Most of these passages show unusual morphologies, such are cupolas, floor feeders (i.e., inlets for deep-seated fluids), and huge irregular-shaped rooms that terminate abruptly, and often a rich and diverse mineral association. A hypogenetic speleogenetic pathway was proposed for this group of caves.
The presence of abundant gypsum deposits in caves with one or more of the passage morphologies listed above, have prompted scientists to suggest a new theory (i.e., sulfuric acid speleogenesis, SAS) of cave development. In the hypogenic SAS model, the source of acidity is the sulfuric acid produced by oxidation of H2S (originating from sulfate reduction or petroleum reservoirs) near or at the water table, where it dissolves the limestone bedrock and precipitates extensive gypsum deposits. SAS is now thoroughly documented from numerous caves around the world, with the best examples coming from the Guadalupe Mountains (NM), Frasassi caves (Italy), selected caves in France, Cueva de Villa Luz (Mexico), and Cerna Valley (SW Romania).
To date, discrimination between epigene and hypogene speleogenetic pathways is made using cave morphology criteria, exotic mineral assemblages, and the predominantly negative δ34S values for the cave sulfates. This presentation highlights the role sulfur and oxygen stable isotope analyses have in discriminating between epigene and hypogene caves.
Based on a number of case studies in caves of the Cerna Valley (Romania), we found that relatively S-depleted isotopic composition of cave minerals alone does not provide enough information to clearly distinguish SAS from other complex speleogenetic pathways. In fact, δ34S values of SAS by-products depend not only on the source of the S, but also on the completeness of S redox reactions. Therefore, similar studies to this are needed to precisely diagnose SAS and to provide information on the S cycle in a given karst system.
Integrating cave mineralogy, passage morphology, and geochemical studies may shed light on the interpretation of polygenetic caves, offering clues to processes, mechanisms, and parameters involved in their genesis (sulfate-dominated).


HELIUM ISOTOPES AS INDICATOR OF CURRENT HYPOGENIC KARST DEVELOPMENT IN TAURIDS KARST REGION, TURKEY, 2014, Ozyurt N. N. , Bayari C. S.

Hypogenic karst development by means of the aggressiveness of hydrothermal fluids driven and fed by mantle heat and mass flux is a known phenomenon. However, in cases when hydrothermal fluid cools down upon thermal conduction in the near-surface environment and is diluted by near-surface cool groundwater, evidences of this phenomenon may be erased completely. Recent data on the isotopes of helium dissolved in cool karst groundwater samples collected from three different karst aquifers in Turkey suggest an apparent mass flux from mantle, as well as from the crust. In the cases considered, helium content from the mantle increases with the increasing age of groundwater. All cases are located nearby the suture zones which may be easing the upward heat and mass flux. Despite sampling difficulties and high analysis costs, helium isotopes dissolved in cool karst groundwater seem to be useful tool to detect the current hypogenesis at the depths of karst aquifers


ISOTOPIC STUDIES OF BYPRODUCTS OF HYPOGENE SPELEOGENESIS AND THEIR CONTRIBUTION TO THE GEOLOGIC EVOLUTION OF THE WESTERN UNITED STATES, 2014, Polyak V. J. , Asmerom Y. , Hill C. A. , Palmer A. N. , Provencio P. P. , Palmer M. V. , Mcintosh W. C. , Decker D. D. , Onac B. P.

Hypogene speleogenesis in the western United States is associated with a deep source of water and gases that rise and mix with shallow aquifer water. Caves are formed below the surface without surface expressions (ie, sinkholes, sinking streams), and byproducts of speleogenesis are precipitated during the late phase of hypogene speleogenesis. These byproducts provide geochemical and geochronological evidence of a region’s geologic history and include gypsum rinds and blocks, elemental sulfur, halloysite-10Å, alunite, natroalunite, and other sulfur-related minerals. The following speleogenetic and speleothemic features are common: alteration rinds, crusts, mammillaries, folia, rafts, and cave spar. The types of hypogene speleogenesis vary and many can be expressed in space and time in relation to paleo-water tables. We identify two general types: (1) H2S-H2SO4-dominated speleogenesis that takes place predominantly near a paleo-water table (a few meters above and below), and (2) CO2-dominated speleogenesis that mostly takes place 10s to 100s of meters below a paleo-water table, with latest-stage imprints within meters of the water table.
The Kane caves in Wyoming, and the Guadalupe Mountains caves in New Mexico and West Texas, are examples of H2S-H2SO4-dominated speleogenesis (also known as sulfuric acid speleogenesis, SAS), where deposits of H2S- and H2SO4-origin are the obvious fingerprints. The Grand Canyon caves in Arizona and Glenwood Caverns in Colorado are examples of CO2-dominated systems, where H2SO4 likely played a smaller role (Onac et al., 2007). Deeper-seated geode-like caves, like the spar caves in the Delaware Basin area, are probably CO2-dominated, and have formed at greater depths (~0.5 ± 0.3 km) below paleo-water tables. Caves in the Black Hills, South Dakota are composite and complex and show evidence for multiple phases of hypogene speleogenesis. In areas such as the Grand Canyon region, these paleo-water tables, when they existed in thick carbonate rock stratigraphy and especially at the top of the thick carbonate rock strata, were likely regionally relatively flat in the larger intact tectonic blocks.
Geochemical studies of these deposits are providing information about the timing of speleogenesis through U-Th, U-Pb, and Ar-dating. In addition, tracer data from isotopes of C, O, S, Sr, and U are indicators of the sources of water and gases involved in speleogenesis. From these studies, novel canyon incision and landscape evolution interpretations are appearing in the literature. Beyond this, the study of these byproduct materials seems to show evidence that the deeply sourced water and gases involved in hypogene speleogenesis in the western United States are generated during tectonic and volcanic activity, and may be related to mantle processes associated with formation of the Rocky Mountains, Colorado Plateau, Basin and Range province, and Rio Grande Rift.


SPELEOGENESIS BY THE SULFIDIC SPRINGS AT NORTHERN SIERRA DE CHIAPAS, MEXICO, BASED ON THEIR WATER CHEMISTRY, 2014, Rosaleslagarde L. , Boston P. J.

Conspicuous brackish sulfidic springs have been described at the northern Sierra the Chiapas, Mexico. These springs are produced by a mixture between regional and local groundwater flow paths. The regional groundwater has an average Total Dissolved Ions of 3081 mg/L so it has a brackish composition. This brackish water is saturated with respect to calcite and dolomite but undersaturated with respect to gypsum, anhydrite and halite. The mass balance and the discharge rate are used to quantify the mass and volume of minerals that are dissolved by the brackish spring water following Appelo and Postma (1993). This quantification will allow comparing the various speleogenetic mechanisms in the area. This is considering the composition of the spring water is relatively constant over time, as it is suggested by periodic measurements at the Cueva de Villa Luz springs during the last 10 years.
Sulfur isotopes in the water are consistent with anhydrite dissolution as the main source of the sulfate to the brackish spring water. Thus, the average 6 mol/L of sulfate in the brackish springs are produced by dissolution of 6 mol of anhydrite after subtracting the sulfate that could result from evapotranspiration of rainwater. Each liter of brackish water dissolved an average of 882 mg of anhydrite, which are equivalent to dissolving 0.36 cm3 of this mineral considering a density of 2.981 g/cm3. Additionally, using the average brackish water discharge rate of 144 L/s, an average of 57 g of anhydrite are being dissolved each second per every liter of brackish water. This is a minimal value because some of the sulfate in the water is used by sulfate-reducing bacteria in the subsurface to produce the hydrogen sulfide in the spring water. The anhydrite subject to dissolution is found interbedded in the Cretaceous carbonates, either from the subsurface at 4,000 m below sea level to the carbonate outcrops.
Similarly, we can calculate the volume of halite that is being dissolved by the brackish springs, considering chloride is a conservative element and subtracting the chloride concentration from the rainwater from that of the spring water following Appelo & Postma (1993). The 22 mol/L of chloride in the brackish water can result from dissolution in the subsurface of 22 moles or 1.3 g of halite per liter of brackish water. This mass of halite dissolved is equal to 0.59 cm3 considering a density of 2.168 g/cm3. Alternatively, 118 g of halite are dissolved per second per each liter of brackish water if we use the average discharge rate of 144 L/s.
Even when the brackish springs are oversaturated with respect to calcite and dolomite, their dissolution is still possible due to the common ion-effect of calcium after anhydrite dissolution and by mixing of waters with different compositions. A range of 10 to 80 % of brackish water from the regional aquifers mixes with fresh water from the local aquifer based on their water chemistry. Additionally, sulfuric acid speleogenesis occurs due to the oxidation of hydrogen sulfide to sulfuric acid.
Finally, the increase in the chloride concentration of the fresh water springs with respect to the concentration in rainwater was used to estimate that from the 4000 mm/y of annual precipitation, only 4%, 158 to 182 mm/y, recharge the aquifers. This low percentage is slightly higher than the 3.3% recharge in marls, marly limestone, silts and clays (Sanz et al., 2011), probably because of the relatively small area of carbonate outcrops over the entire region and the lack of recharge in altitudes higher than 1500 m above sea level.
Sulfuric acid is the most obvious speleogenetic mechanism occurring in the caves of the northern Sierra de Chiapas, Mexico due to the high hydrogen sulfide concentration in the spring water. In addition, the location of the springs at a zone of regional and local discharge where waters from different composition converge and mix, and the amount of mixing calculated suggests mixing is also an important speleogenetic mechanism. However, the depth and the time constrains at which these two hypogenic mechanisms occur is still unknown. The relatively low rainwater recharge rate suggests epigenesis is limited. Most likely, the porosity created by dissolution of anhydrite and halite in the subsurface is occluded by the precipitation of calcite. Chemical modeling and petrography will help to elucidate the order of the reactions occurring in the subsurface.


Linking mineral deposits to speleogenetic processes in Cova des Pas de Vallgornera (Mallorca, Spain)., 2014, Onac B. P. , Fornós J. J. , Merino A. , Ginés J. , Diehl J.

Cova des Pas de Vallgornera (CPV) is the premier cave of the Balearic Archipelago. Over 74 km of passages develop within two carbonate lithofacies (reef front and back reef), which ultimately control the patterns of the cave and to some degree its mineral infilling. The diversity of speleothem-forming minerals is four times greater around or within hypogene-related features (vents, rims, cupolas), compared to any other vadose passages in the cave. The mineralogy of speleothems (crusts, nodules, crystals, earthy masses) associated with hypogene features in the seaward upper maze of Sector F is characterized by the presence of aragonite, ankerite, huntite, clay minerals, and quartz. In the Tragus and Nord sectors, however, the dominant mineral is dolomite, along with aragonite, celestine, huntite, clay minerals, and quartz. Calcite is by far the most ubiquitous mineral throughout the cave. Detailed macroscopic and scanning electron microanalysis and imaging have permitted the investigation of textural relationships between the minerals associated with vents, rims, and vent’s roof and walls. These studies along with morphological and stable isotope analyses confirm that not all minerals are connected with a hypogene stage in the cave evolution, and furthermore, none of them appears to be sulfuric acid by-products. Instead, the mineral assemblages documented in speleothems from CPV clearly support at least three speleogenetic pathways, namely seacoast mixing, ascending of warm groundwaters, and meteoric recharge (vadose). Thus, cave minerals in Cova des Pas de Vallgornera hold the keys to reconstruction and understanding of processes and conditions under which they precipitated, allowing to establish their relationship with various speleogenetic pathways


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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