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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 fault breccia is the assemblage of broken rock fragments frequently found along faults. the fragments may vary in size from inches to feet.?

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Your search for sulfur isotopes (Keyword) returned 8 results for the whole karstbase:
THE OCCURRENCE AND EFFECT OF SULFATE REDUCTION AND SULFIDE OXIDATION ON COASTAL LIMESTONE DISSOLUTION IN YUCATAN CENOTES, 1993, Stoessell R. K. , Moore Y. H. , Coke J. G. ,
Dissolution of carbonate minerals in the coastal halocline is taking place in the karst terrain along the northeastern coast of the Yucatan Peninsula. The dissolution is being accelerated in cenotes (sinkholes) where sulfate reduction and oxidation of the produced sulfide is occurring. Hydrogen-sulfide concentrations ranged from 0.06 to 4 mmolal within the halocline in two sinkholes. Relative to concentrations expected by conservative mixing, fluids with high hydrogen-sulfide concentrations were correlated with low sulfate concentrations, high alkalinities, low pH values, and heavy sulfur isotope values for sulfate. Hydrogen-sulfide concentrations were less than those predicted from sulfate reduction, calculated from deficiencies in measured sulfate concentrations, indicating mobility and loss of aqueous sulfide. Fluids with low hydrogen-sulfide concentrations were correlated with very high calcium concentrations, high strontium and sulfate concentrations, slightly elevated alkalinities, low pH values, and sea-water sulfur isotope values for sulfate. Gypsum dissolution is supported by the sulfur isotopes as the major process producing high sulfate concentrations. However, oxidation of aqueous sulfide to sulfuric acid, resulting in carbonate-mineral dissolution is needed to explain the calcium concentrations, low pH values, and only slightly elevated alkalinities. The halocline may trap hydrogen sulfide that has been stripped from the underlying anoxic salt water. The halocline can act as a stable, physical boundary, holding some of the hydrogen sulfide until it is oxidized back to sulfuric acid through interaction with the overlying, oxygenated fresh water or through the activity of sulfide-oxidizing bacteria

Gypsum deposits in the Frasassi Caves, central Italy, 2003, Galdenzi, S. , Maruoka, T.
The Frasassi Caves are hypogenic caves in central Italy, where H2S-rich groundwater flows in the lowest cave level. Near the water table, the H2S is converted to sulfuric acid by biotic and abiotic processes, which have enhanced cave development. The sulfate generally deposits above the water table as a replacement gypsum crust coating limestone walls or as large gypsum crystals. Although the oxidation of sulfide also occurs below the water table, sulfate saturation is not achieved, therefore, sulfate does not precipitate below the water table. In the upper dry levels of the cave, three main types of ancient gypsum deposits occurs: (1) replacement crusts, similar to the presently forming deposits of the active zone, (2) microcrystalline large and thick floor deposits, and (3) euhedral crystals inside mud. The study of the depositional setting and the analysis of sulfur isotopes in the gypsum and groundwater clearly demonstrate that all the sampled gypsum in the cave formed by H2S oxidation above the water table. Some fraction of small sulfur isotopic differences between H2S in the water and gypsum can be explained by isotopic fractionation during abiotic and/or biotic oxidation of H2S.

Tracing the sources of cave sulfates: a unique case from Cerna Valley, Romania, 2011, Onac Bogdan P. , Wynn Jonathan G. , Sumrall Jonathan B.

In order to reliably distinguish between different genetic processes of cave sulfate formation and to quantify the role of thermo-mineral waters on mineral deposition and cave morphology, it is critical to understand sulfur (S) sources and S transformations during hydrological and speleogenetic processes. Previous work has shown that sulfuric acid speleogenesis (SAS) often produces sulfate deposits with 34S-depleted isotopic signatures compared to those of the original source of S in sulfate rocks. However, 34S-depleted isotopic composition of S-bearing minerals alone does not provide enough information to clearly distinguish SAS from other speleogenetic processes driven by carbonic acid, geothermal heat, or other processes. The isotopic composition (δ18O and δ34S) of sulfate minerals (mainly gypsum) from seven caves of the Cerna Valley (Romania) defines three distinct populations, and demonstrates that the δ34S values of SAS-precipitated cave sulfates depend not only on the source of the S, but also on the H2S:SO4 2− ratio during aqueous S species reactions and mineral precipitation. Population 1 includes sulfates that are characterized by relatively low δ34S values (−19.4 to −27.9‰) with δ18O values between 0.2 and 4.3‰ that are consistent with oxidation of dissolved sulfide produced during methane-limited thermochemical sulfate reduction (TSR) that presently characterizes the chemistry of springs in the upper Cerna Valley. Population 2 of cave sulfates has 34S enriched δ34S values (14.3 to 19.4‰) and more 18O-depleted δ18O values (from −1.8 to −10.0‰). These values argue for oxidation of dissolved sulfide produced during sulfate-limited TSR that presently characterizes the chemistry of springs further downstream in the Cerna Valley. The δ18O values of cave sulfates from Population 1 are consistent with oxidation under more oxic aqueous conditions than those of Population 2. δ34S values of cave sulfates within Population 3 (δ34S: 5.8 to 6.5‰) may be consistent with several scenarios (i.e., pyrite oxidation, oxidation of dissolved sulfide produced during methane-limited TSR coupled with O2-limited oxidation during SAS). However, comparatively 18O-enriched δ18OSO4 values (11.9 to 13.9‰) suggest the majority of this sulfate O was derived from atmospheric O2 in gas-phase oxidation prior to hydration. Thus, the combined use of oxygen- and sulfur-isotope systematics of sulfate minerals precipitated in a variety of cave settings along Cerna Valley may serve as an example of how more complex cave systems can be deconvoluted to allow for more complete recognition of the range of processes and parameters that may be involved in SAS.


Hypogenic contribution to speleogenesis in a predominant epigenic karst system: A case study from the Venetian Alps, Italy, 2012, Tisato Nicola, Sauro Francesco, Bernasconi Stefano M. , Bruijn Rolf H. C. , De Waele Jo

Buso della Rana and Buso della Pisatela are two karstic caves located in north-east Italy. They are part of the same karst system and are developed in the Castelgomberto calcarenitic marine sediments, which were deposited in a shallow Caribbean-type sea during the Eocene. The Buso della Rana-Pisatela system developed mostly at the contact between the Castelgomberto calcarenite and underlying volcanic rocks. The system of caves is ~37 km long and has only three entrances, two of which are semi-artificial. The overlying karst plateau is not directly connected to the Buso della Rana-Pisatela system and, with the exception of one deep abyss, exhibits a rather poorly developed karst. This is unexpected considering the presence at depth of such a large and long cave. Gypsum (CaSO4·2H2O) has locally been observed on the walls of the Buso della Pisatela cave. Energy dispersive X-ray spectroscopy (EDS), performed with a scanning electron microscope (SEM), reveals the presence of sulfur-bearing minerals within the host rock. Gypsum was formed by oxidation of these minerals as indicated by negative δ34S values. The oxidation of sulfide minerals forms a sulfuric-acid solution that dissolves the Castelgomberto calcarenite and, once it is oversaturated in calcium, precipitates as gypsum. The lack of well-developed karst on top of the plateau and the analyses suggest that the formation mechanisms for the Buso della Rana-Pisatela system differ from classical epigenic speleogenesis. The “pyrite-effect” has been recognized in other caves and described in literature. In our case pyrite is responsible of two hypo-speleogenetic processes: i) the dissolution of a portion of the host rock and ii) the enlargement of the karst voids as a consequence of the haloclastic effect.


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

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.


Hypogene Sulfuric Acid Speleogenesis and rare sulfate minerals in Baume Galini`ere Cave (Alpes-de-Haute-Provence, France). Record of uplift, correlative cover retreat and valley dissection, 2015, Audra Philippe, Gґazquez Fernando, Rull Fernando, Bigot Jeanyves, Camus Hubert

The oxidation of hydrocarbons and sulfide sources (H2S, pyrite) produces sulfuric acid that strongly reacts with bedrock, causing limestone dissolution and complex interactions with other minerals from the bedrock or from cave fillings, mainly clays. This type of cave development, known as Sulfuric Acid Speleogenesis (SAS), is a subcategory of hypogene speleogenesis, where aggressive water rises from depth. It also produces uncommon minerals, mainly sulfates, the typical byproducts of SAS. Baume Galinière is located in Southern France, in the Vaucluse spring watershed. This small maze cave displays characteristic SAS features such as corrosion notches, calcite geodes, iron crusts, and various sulfate minerals. Sulfur isotopes of SAS byproducts (jarosite and gypsum) clearly show they derive from pyrite oxidation. Using XRD and micro-Raman spectroscopy, thirteen minerals were identified, including elemental sulfur, calcite, quartz, pyrite, goethite, gypsum, fibroferrite, plus all of the six members of the jarosite subgroup (jarosite, argentojarosite, ammoniojarosite, hydroniumjarosite, natrojarosite, plumbojarosite). The Baume Galinière deposits are the first documented cave occurrence of argentojarosite and the second known occurrence of plumbojarosite, hydronium jarosite, ammoniojarosite, and fibroferrite. In the Vaucluse watershed, there were numerous upwellings of deep water along major faults, located at the contact of the karstic aquifer and the overlying impervious covers. The mixing of deep and meteoric waters at shallow depths caused pyrite depositions in numerous caves, including Baume Galinière. Sulfuric acid speleogenesis occurred later after base-level drop, when the cave was under shallow phreatic conditions then in the vadose zone, with oxidation of pyrites generating sulfuric acid. Attenuated oxidation is still occurring through condensation of moisture from incoming air. Baume Galinière Cave records the position of the semi-impervious paleo-cover and documents its retreat in relationship to valley incision caused by uplift and tilting of the Vaucluse block during the Neogene.


Hypogene Sulfuric Acid Speleogenesis and rare sulfate minerals in Baume Galinière Cave (Alpes-de-Haute-Provence, France). Record .., 2015, Audra P. , Gázquez F. , Rull F. , Bigot J. Y. , Camus H.

The oxidation of hydrocarbons and sulfide sources (H2S, pyrite) produces sulfuric acid that strongly reacts with bedrock, causing limestone dissolution and complex interactions with other minerals from the bedrock or from cave fillings, mainly clays. This type of cave development, known as Sulfuric Acid Speleogenesis (SAS), is a subcategory of hypogene speleogenesis, where aggressive water rises from depth. It also produces uncommon minerals, mainly sulfates, the typical byproducts of SAS. Baume Galinière is located in Southern France, in the Vaucluse spring watershed. This small maze cave displays characteristic SAS features such as corrosion notches, calcite geodes, iron crusts, and various sulfate minerals. Sulfur isotopes of SAS byproducts (jarosite and gypsum) clearly show they derive from pyrite oxidation. Using XRD and micro-Raman spectroscopy, thirteen minerals were identified, including elemental sulfur, calcite, quartz, pyrite, goethite, gypsum, and fibroferrite, plus all of the six members of the jarosite subgroup (jarosite, argentojarosite, ammoniojarosite, hydroniumjarosite, natrojarosite, plumbojarosite). The Baume Galinière deposits are the first documented cave occurrence of argentojarosite and the second known occurrence of plumbojarosite, hydronium jarosite, ammoniojarosite, and fibroferrite. In the Vaucluse watershed, there were numerous upwellings of deep water along major faults, located at the contact of the karstic aquifer and the overlying impervious covers. The mixing of deep and meteoric waters at shallow depths caused pyrite depositions in numerous caves, including Baume Galinière. Sulfuric Acid Speleogenesis occurred later after base-level drop, when the cave was under shallow phreatic conditions then in the vadose zone, with oxidation of pyrites generating sulfuric acid. Attenuated oxidation is still occurring through condensation of moisture from incoming air. Baume Galinière Cave records the position of the semi-impervious paleo-cover and documents its retreat in relationship to valley incision caused by uplift and tilting of the Vaucluse block during the Neogene.


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