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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 metabolic rate is the rate at which a living thing transforms food into energy and body tissue. the higher its metabolic rate, the more food it must consume. most cave animals live at a reduced metabolic rate [23].?

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Featured articles from Cave & Karst Science Journals
Chemistry and Karst, White, William B.
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Karst environment, Culver D.C.
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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 sulfur isotope (Keyword) returned 16 results for the whole karstbase:
Showing 1 to 15 of 16
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

Karstification without carbonic acid; bedrock dissolution by gypsum-driven dedolomitization, 1994, Bischoff Jl, Julia R, Shanks Wc, Rosenbauer Rj,
Aggressive karstification can take place where dolomite and gypsum are in contact with the same aquifer. Gypsum dissolution drives the precipitation of calcite, thus consuming carbonate ions released by dolomite. Lake Banyoles, in northeastern Spain, is a karst lake supplied by sublacustrine springs, and karstic collapse is occurring in the immediate vicinity of the lake. Lake water is dominated by Mg-Ca and SO 4 -HCO 3 , and is supersaturated with calcite that is actively accumulating in lake sediments. Water chemistry, sulfur isotope composition, local stratigraphy, and mass-balance modeling suggest that the primary karst-forming process at Lake Banyoles is dedolomitization of basement rocks driven by gypsum dissolution. Karstification takes place along the subsurface contact between the gypsiferous Beuda Formation and the dolomitic Perafita Formation. This process is here recognized for the first time to cause karstification on a large scale; this is significant because it proceeds without the addition of soil-generated carbonic acid. Gypsum-driven dedolomitization may be responsible for other karstic systems heretofore attributed to soil-generated carbonic acid

Aggressive karstification can take place where dolomite and gypsum are in contact with the same aquifer. Gypsum dissolution drives the precipitation of calcite, thus consuming carbonate ions released by dolomite. Lake Banyoles, in northeastern Spain, is a karst lake supplied by sublacustrine springs, and karstic collapse is occurring in the immediate vicinity of the lake. Lake water is dominated by Mg-Ca and SO4-HCO3, and is supersaturated with calcite that is actively accumulating in lake sediments. Water chemistry, sulfur isotope composition, local stratigrapy, and mass-balance modeling suggest that the primary karst-forming process at Lake Banyoles is dedolomitization of basement rocks driven by gypsum dissolution. Karstification takes place along the subsurface contact between the gypsiferous Beuda Formation and the dolomitic Perafita Formation. This process is here recognized for the first time to cause karstification on a large scale; this is significant because it proceeds without the addition of soil-generated carbonic acid. Gypsum-driven dedolomitization may be responsible for other karstic systems heretofore attributed to soil-generated carbonic acid

Sulfur isotope geochemistry of Southern Appalachian mississippi valley-type deposits, 1996, Jones Henry D. , Kesler Stephen E. , Furman Francis C. , Kyle J. Richard,

Vein and Karst Barite Deposits in the Western Jebilet of Morocco: Fluid Inclusion and Isotope (S, O, Sr) Evidence for Regional Fluid Mixing Related to Central Atlantic Rifting, 2000, Valenza Katia, Moritz Robert, Mouttaqi Abdellah, Fontignie Denis, Sharp Zachary,
Numerous vein and karst barite deposits are hosted by Hercynian basement and Triassic rocks of the western Jebilet in Morocco. Sulfur, oxygen, and strontium isotope analyses of barite, combined with fluid inclusion microthermometry on barite, quartz, and calcite were used to reveal the nature and source of the ore-forming fluids and constrain the age of mineralization. The{delta} 34S values of barite between 8.9 and 14.7 per mil are intermediate between the sulfur isotope signatures of Triassic evaporites and Triassic-Jurassic seawater and lighter [IMG]f1.gif' BORDER='0'>, probably derived from the oxidation of dissolved H2S and leaching of sulfides in the Hercynian basement. The 87Sr/86Sr ratios of barite between 0.7093 and 0.7130 range between the radiogenic strontium isotope compositions of micaceous shale and sandstone and the nonradiogenic isotopic signature of Triassic to Jurassic seawater and Cambrian limestone. The{delta} 18O values of barite between 11 and 15 per mil (SMOW) support mixing between two or more fluids, including Late Triassic to Jurassic seawater or a water dissolving Triassic evaporites along its flow path, hot basinal, or metamorphic fluids with{delta} 18O values higher than 0 per mil and/or meteoric fluids with{delta} 18O values lower than 0 per mil. The general trend of decreasing homogenization temperatures and initial ice melting temperatures with increasing salinities of H2O-NaCl {} CaCl2 fluid inclusions trapped in barite, quartz, and calcite indicates that a deep and hot basinal fluid with salinities lower than 6 wt percent NaCl equiv might have mixed with a cooler surficial solution with a mean salinity of 20 wt percent NaCl equiv. Calcium was leached from the Cambrian limestone and the clastic and mafic volcanic rocks of the Hercynian basement. Alkali feldspars and micas contained in the Cambrain sandstones provided most of the Ba to the hydrothermal system. Vein and karst deposits are modeled as a two-component mixing process in which the temperature and the S and Sr isotope composition of the end members changed during the 220 to 155 Ma interval. The hot basinal fluid remained volumetrically dominant during the entire mineralization process. Differences in mean S, O, and Sr isotope compositions among the barite families are interpreted as reflecting differences in mineralization age. Most barite deposits formed before the Kimmeridgian, except for north-south-oriented vein barite, karst barite, and barite cement in the conglomeratic Upper Jurassic, which were deposited later, possibly around 155 Ma. Similar genetic processes have been described for late Paleozoic to Mesozoic F-Ba vein deposits in western Europe. The vein and karst barite in the western Jebilet of Morocco reveals a wide-scale regional mineralization event related to Central Atlantic rifting

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.

Origin and Significance of Postore Dissolution Collapse Breccias Cemented with Calcite and Barite at the Meikle Gold Deposit, Northern Carlin Trend, Nevada, 2003, Emsbo P, Hofstra Ah,
The final event in a complicated hydrothermal history at the Meikle gold deposit was gold deficient but caused extensive postore dissolution of carbonate, collapse brecciation, and precipitation of calcite and barite crystals in the resulting cavities. Although previously interpreted to be part of the Carlin-type hydrothermal system, crosscutting relationships and U-Th-Pb geochronology constrain this hydrothermal event to late Pliocene time (ca. 2 Ma), nearly 36 Ma after ore formation. Mineralogic, fluid inclusion, and stable isotope data indicate that postore hydrothermal fluids were reduced, H2S-rich, unevolved meteoric waters ({delta}18O = -17{per thousand}) of low temperature (ca. 65{degrees}C). The{delta} 18O values of barite and calcite indicate that these minerals were in isotopic equilibrium, requiring that barite SO4 was derived from the oxidation of reduced sulfur; however, preexisting sulfides in breccia cavities were not oxidized. The{delta} 34S (15{per thousand}) values of barite are higher than those of local bulk sulfide and supergene alunite indicating that SO4 was not derived from supergene oxidation of local sulfide minerals. The 15 per mil {delta}34S value suggests that the H2S in the fluids may have been leached from sulfur-rich organic matter in the local carbonaceous sedimentary rocks. A reduced H2S-rich fluid is also supported by the bright cathodoluminescence of calcite which indicates that it is Mn rich and Fe poor. Calcite has a narrow range of {delta}13C values (0.3-1.8{per thousand}) that are indistinguishable from those of the host Bootstrap limestone, indicating that CO2 in the fluid was from dissolution of the local limestone. These data suggest that dissolution and brecciation of the Bootstrap limestone occurred where H2S-rich fluids encountered more oxidizing fluids and formed sulfuric acid (H2SO4). Intense fracturing in the mine area by previous structural and hydrothermal events probably provided conduits for the descent of oxidized surface water which mixed with the underlying H2S-rich waters to form the dissolving acid. The surface-derived fluid apparently contained sufficient oxygen to produce H2SO4 from H2S but not enough to alter pyrite to Fe oxide. Although H2S is an important gold-transporting ligand, the temperature was too low to transport a significant amount of gold. The presence of analogous calcite- and barite-lined cavities in other Carlin-type deposits suggests that the generation (and oxidation) of H2S-rich meteoric waters was a common phenomenon in north-central Nevada. Previous sulfur isotope studies have also shown that the Paleozoic sedimentary rocks were the principal source of H2S in Devonian sedimentary exhalative-type, Jurassic intrusion-related, Eocene Carlin-type, and Miocene low-sulfidation gold deposits in the region. The similar sulfur source in all of these systems suggests that basin brines, magmatic fluids, and meteoric waters all evolved to be H2S-rich ore fluids by circulation through Paleozoic sedimentary rocks. Thus, although not directly related to gold mineralization, the recent hydrologic history of the deposit provides important clues to earlier ore-forming processes that were responsible for gold mineralization


Nanisivik (Inuit – “the place where they find things’) zinc/lead mine is located at Lat. 73o N in northwestern Baf?n Island. The host rock is a Proterozoic platform carbonate 260-800 m thick, medium to massively bedded and pervasively dolomitized. It rests on mixed shales and shaly dolomites, and is overlain by 150+ m of further shales functioning as an aquitard. These formations were buried by later Proterozoic strata, uplifted, eroded and buried again in a Cambrian sedimentary basin. The ore-grade deposits are contained within a horst block of the dolomites dipping NW at 15o across it. Graben to the north and south are roofed in the overlying shales. The principal deposit, the Main Ore, is of zinc, lead and iron sul?de precipitates plus gangue minerals, chie?y secondary dolomite. It extends for three km E-W along the horst. It is horizontal, at ~300 m above sea level and terminated at both ends by modern valley entrenchments. The Main Ore body is consistently ~100 m in width and ?ve-seven m in depth. This wide ceiling is a nearly planar, horizontal corrosion bevel. The sulfdes scarcely extend above it anywhere. Within the Main Ore two or more generations of tapered ?ns of dolomite in situ extend from both south (updip) and north (downdip) walls into the cavity. Fin surfaces truncate the bedding. Edges of ?ns are sinuous, some meandering with a wavelength of ~50 m. Very sharp, horizontal corrosion notches 20-30 cm high extend into the dolomite walls for at least 20 m (the limit of deep crosscuts in the mine). They are ?lled with layered pyrites which continue out into the ore body as regular sheets truncating earlier, dipping mineral layers until they themselves are truncated by later fillings. One exceptional notch, one meter deep, is at least 350 m in breadth. The ore displays four sedimentary modes: (i) regular layers settled or precipitated onto the cavity floor; (ii) chaotic polymict breccias suggestive of channel cut-and-?ll episodes; (iii) the horizontal pyrite sheets in corrosion notches; (iv) minor metasomatic replacements of dolomite. The ore cavity was created by paragenesis in a channel ?ow mode, with ore and gangue deposition on the floor taking place in tandem with dissolutional cavity creation upwards,. Principal deposition took place when a fluid interface could be rigorously maintained. Fluid inclusions indicate derivation of the metals from exchange reactions with metalliferous sediments (the underlying shales), indicating low water/rock ratios and moderate temperatures. The ore fluids were similar to oil field brines. Sulfur isotope fractionations indicate temperatures of 90-150 +/-40o C, suggesting that the Main Ore formed along a gas/brine interface at a depth of at least 1600 m as a consequence of ?uid expulsion in the subsiding Cambrian sedimentary basin.


Over 30 caves are known to develop in the Jurassic and Cretaceous limestone that outcrops along the lower part of the Cerna Valley and its tributaries in southwestern Romania. There are three features that strike observers when entering most of these caves: a variety of sulfate speleothems, large amounts of bat guano (both fossil and fresh), and unusually high cave temperatures. Such thermal anomalies are rather uncommon in the ordinary cave environment. Along Cerna Valley, however, one can measure temperatures (in some cavities) as high as 40ºC. This situation is due to (i) presence of thermal water pools, (ii) hot water flowing along cave passages, (iii) hot steam rising up fractures from depth.
Seventy-four mineral samples were collected from eight caves in the Cerna Valley. These were investigated by means of X-ray diffraction, scanning electron microscope, and electron microprobe analyses. The minerals identified so far in Sălitrari, Ion Barzoni, Sălitrari 2, Diana, Adam, Despicătura, and Grota cu Aburi caves, are: calcite [CaCO3], aragonite [CaCO3], gypsum [CaSO4•2H2O], anhydrite [CaSO4], pickeringite [MgAl2(SO4)4•22H2O], halotrichite [Fe2+Al2(SO4)4•22H2O], kalinite [KAl(SO4)2•11H2O], melanterite [FeSO4•7H2O], apatite- (Ca(OH) [Ca5(PO4)3(OH)], brushite [CaHPO4•2H2O], darapskite [Na3(SO4)(NO3)•H2O], and nitratine [NaNO3]. The phosphates and nitrates (except for darapskite) were precipitated in a typical vadose environment from reactions between phosphoric solutions supplied by bat guano and limestone bedrock. Most of the sulfates and darapskite are the result of sulfuric acid speleogenesis.
In addition, sulfur isotope measurements (δ34S) on sulfate speleothems and spring waters were undertaken to determine the origin of cave sulfates (i.e., vadose, hypogene, bacteriogenic, etc.). The isotope measurements in the springs show sulfide δ34S ranges from -21.9‰ to 24.0‰ with a mean value of 6.6‰ (n=9), whereas the sulfate δ34S ranges from 16.6‰ to 71.3‰ with a mean value of 30.1‰ (n=10).
Three populations of sulfur isotope values (negative, near zero, and positive) were found in the caves. Samples from Barzoni Cave (the most distant cave from any modern thermal spring) are extremely depleted (-23 to -28‰). Sulfide values of the nearest springs are approximately -20‰. In Sălitrari Cave, the range of values was from -19.8 to +6.5‰. It is more than likely a reflection of the increase in completeness of the reduction of sulfate. The δ34S value of gypsum in Grota cu Aburi (active H2S hot steam cave) was 6.5‰. This value is similar to the sulfur isotopic composition measured in darapskite from Sălitrari Cave; thus, probably documenting earlier sulfuric acid activity in the latter cave.
The final population of caves, especially Despicătura and Diana caves, has enriched sulfur isotope values, which correspond well to the sulfide values of nearby springs. Diana Cave from which Diana 3 spring originates has a sulfide isotopic composition of +19‰, which is approximately the value of the mean of the cave sulfates from Diana Cave. This shows that the cave sulfate isotopic value is controlled by the sulfide, which (after being oxidized) reacts with limestone/marls to produce gypsum or other sulfate minerals.

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

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

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.


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.

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