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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. ...

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That series is a subdivision of rock according to age at which they were laid down in a geologic epoch [16].?

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Karst environment, Culver D.C.
Mushroom Speleothems: Stromatolites That Formed in the Absence of Phototrophs, Bontognali, Tomaso R.R.; D’Angeli Ilenia M.; Tisato, Nicola; Vasconcelos, Crisogono; Bernasconi, Stefano M.; Gonzales, Esteban R. G.; De Waele, Jo
Calculating flux to predict future cave radon concentrations, Rowberry, Matt; Marti, Xavi; Frontera, Carlos; Van De Wiel, Marco; Briestensky, Milos
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Your search for apatite (Keyword) returned 18 results for the whole karstbase:
Showing 1 to 15 of 18
La karstification de l'le haute carbonate de Makatea (Polynsie franaise) et les cycles eustatiques et climatiques quaternaires, 1991, Dessay J. , Pouchan Y. , Girou A. , Humbert L. , Malezieux J.
THE KARST 0F MAKATEA ISLAND (FRENCH POLYNESIA) AND THE CLIMATIC AND GLACIO-EUSTATISM SETTING - Located in the Central Pacific, in the northwestern part of the Tuamotu Archipelago, Makatea island (148 15 W - 15 50 S) is an uplifted, karstic, carbonate construction of Early Miocene age, which reaches 113m in height. From 1906 to 1966, phosphate deposits were exploited on Makatea Island. These phosphate deposits (apatite) overlaid the Miocene series and filled the karstic cavities in the higher regions of the island. Several traces of ancient shorelines can be observed on Makatea: 1/ three different reef formations, which reach about +27m, +7m, +1m above the present mean sea level and respectively dated 400,000 100,000 yr BP, 140,000 30,000 yr BP, between 4,470 150 yr BP and 3,720 13O yr BP; 2/ four distinct marine notch lines on the Early Miocene cliff at about +1m, +7m, +27m and +56m (or +47m on the west coast caused by tilt) above the present mean sea level; 3/ two exposed marine platforms respectively at +29m and +7m above the present mean sea level. The ages of the former makatean shores are inferred by using: (1) the Pacific glacio-eustatic sea-level curve for the last 140,000 yr BP, (2) the Pacific oxygen isotope curve for the last 900,000 yr BP, and (3) a constant uplift rate during the Pleistocene. In this way, according to their age and elevation, the sea-level indicators at about +1m, +7m and +27m (+29m) above the present mean sea level can be respectively related to the Holocene transgression (Flandrian) dated between 6,000 and 1,500 yr BP, to the last Pleistocene interglacial period (Sangamon) dated between about 130,000 and 110,000 yr BP, and to a Middle Pleistocene interglacial period (Yarmouth) dated between about 315,000 and 485,000 yr BP. If we assume that a sea level similar to the present occurred during the Yarmouth inter-glacial period, the uplift rate is valued at 0.085 mm/yr to 0.056 mm/yr. Thus the sea-level associated with the marine notch at about +56m (+47m) may be about 650,000 yr to 1 M.y. old and can be associated with another Pleistocene interglacial period (Aftonian). Consequently, as indicated by the former shores, the sea level fluctuations can be related to the major glacio-eustatic quaternary events. This climatic and eustatic setting is used to explain the karst observed on the Makatea island. Carbonate dissolution and essentially vertical karst genesis were the result of the superposition of several cycles. Each cycle was initially composed of a solution of the carbonates during an interglacial period, followed by a drainage of the saturated solutions during the marine regression associated with the consecutive glacial period. Nevertheless, this scheme is not enough to explain the specific morphology of the makatean karstic cavities and we suggest using insular phosphatisation to explain this karst genesis. It is generally accepted that phosphate rock deposits on coral reef islands are the result of chemical reaction between seabird guano and reef limestone. Furthermore, petrographic and stable isotope studies suggest several generations of phosphorite formation and reworking episodes in the history of these deposits. The primary deposition of phosphates must have begun during a glacial period. This deposition was followed by some redistribution of phosphorites during the interglacial period and by additional precipitation of apatite from meteoric waters. This assumed process of phosphogenesis is consistent with both the field observations and the geodynamic evolution of Makatea. Thus, the particular morphology of the makatean karst can be the result of the dissolution of the carbonates caused by phosphoric acid etching. This acid is derived from the evolution of the phosphorites during the pleistocene interglacial periods.

Brushite, hydroxylapatite, and taranakite from Apulian caves (southern Italy); new mineralogical data, 1991, Fiore S, Laviano R,

Precipitation and alteration of late Cretaceous sedimentary apatites and siderites (Leonie Trough, Bavaria, Germany), 1998, Sattler C. D. , Halbach P. ,
Late Cretaceous sedimentary siderites and fluorapatites of the iron ore deposit 'Leonie' (Bavaria, Germany) have been investigated by geochemical and mineralogical methods to define their origin. The siderites consist to more than 90 mol% of FeCO3. This elemental composition relates to an early diagenetic fresh water depositional environment. The stable isotope geochemistry of carbon and oxygen (delta(18)O: parts per thousand SMOW; delta(13)C: -12 parts per thousand PDB) also supports a siderite genesis in meteoric waters, with carbon originating from oxidation of organic matter. The chemical composition of the fluorapatites is relatively pure and shows a very low elemental substitution for calcium and phosphate. This is the result of an intense epigenetic alteration of the primary carbonate fluorapatite and, thus, cannot be related to specific source aspects. Microscopic investigations and thermodynamic calculations reveal a precursory apatite precipitation before siderite was formed. This process is thought to have removed calcium from karst waters to a level which enables siderite to be precipitated. Because of the data and observations a siderite formation in a stagnant fresh water basin is postulated, while the apatite formation probably was initiated during a connection to the open ocean (Tethys) with temporary marine ingressions. The input of iron and partly of phosphorus and fluorine into the karst basins resulted from the draining of the uplifted easterly mountains of the igneous Bohemian Massif under the influence of a humid warm climate. During the postulated marine ingressions especially phosphorus and fluorine were brought into the system whereas most of the calcium and carbonate reached the karst troughs by dissolution of the Late Jurassic Maim limestones

La grotte et le karst de Cango (Afrique du Sud), 2000, Martini, J. E. J.
The author describes a small karst area in the extreme south of the African Continent, with special reference to the Cango Cave, which is a major tourist attraction. Compared with the other karsts of Southern Africa, this area is unique. The karst is typically exogenic, with caves forming by stream disappearance into swallow holes, where the thalweg intersects steeply dipping Precambrian limestone. Wet caves are vadose, with only short phreatic segments and exhibit rectilinear, longitudinal sections. Passages are low, but wide with bevelled ceilings, often terraced. This peculiar morphology is typical of the caves developing exactly on the water-table and seems to be controlled by the abundance of sediments introduced from the swallow holes. If one excepts a short active lower level, Cango is a dry cave of the same type than the wet ones. It is practically linear in plan and in profile, with a length of 2.6 km from entrance to end for a total of 5.2 km of passages. The age of the speleogenesis has been estimated as early Pleistocene from the entrance elevation, which is in between the altitude of the actual thalweg and the one of the Post African I erosion surface, which started to be eroded during the Upper Pliocene. This relatively young age is in contrast with a Miocene model, which was accepted by most of the previous authors. Cango is well adorned with speleothems, in particular with outstanding abundant shields, monocrystalline stalagmites and pools coated with calcite crystals. In the first chambers from entrance, the speleothems have been deeply corroded by bat guano, with deposition of hydroxylapatite. Previously this corrosion was attributed to resolution due to several rises of the paleowater-table. The meteorology is discussed, in particular the high carbon dioxide, which indicates that the cave is poorly ventilated and which constitutes a problem for management and conservation.

The Dachstein paleosurface and the Augenstein Formation in the Northern Calcareous Alps - a mosaic stone in the geomorphological evolution of the Eastern Alps, 2001, Frisch W, Kuhlemann J, Dunkl I, Szekely B,
The central and eastern areas of the Northern Calcareous Alps (NCA) are characterized by remnants of the Dachstein paleosurface, which formed in Late Eocene (?) to Early Oligocene time and is preserved with limited modification on elevated karst plateaus. In Oligocene time, the Dachstein paleosurface subsided and was sealed by the Augenstein Formation, a terrestrial succession of conglomerates and sandstones, which are only preserved in small remnants on the plateaus, some in an autochthonous position. Thermochronological data suggest a maximum thickness of the Augenstein Formation of >1.3 km, possibly >2 km. The age of the Augenstein Formation is constrained by the overall geological situation as Early Oligocene to earliest Miocene. Fission track age data support an Early Oligocene age of the basal parts of the formation. The source area of the Augenstein Formation consisted predominantly of weakly metamorphic Paleozoic terrains (Greywacke Zone and equivalents) as well as the Late Carboniferous to Scythian siliciclastic base of the NCA to the south of the depositional area. To the west, the Augenstein Formation interfingered with the Tertiary deposits of the Inntal. Sedimentation of the Augenstein Formation was terminated in Early Miocene time in the course of the orogenic collapse of the Eastern Alps. The Augenstein sediments were eroded and redeposited in the foreland Molasse zone. From Pannonian times (similar to 10 Ma) on, the NCA and the denuded Dachstein surface experienced uplift in several pulses. The Dachstein paleosurface has been preserved in areas, in which thick limestone sequences allowed subsurface erosion by cave formation and thus prevented major surface erosion

Mineralogy and geochemistry of trace elements in bauxites: the Devonian Schugorsk deposit, Russia, 2001, Mordberg L. E. , Stanley C. J. , Germann K. ,
Processes of mineral alteration involving the mobilization and deposition of more than 30 chemical elements during bauxite formation and epigenesis have been studied on specimens from the Devonian Schugorsk bauxite deposit, Timan, Russia. Chemical analyses of the minerals were obtained by electron microprobe and element distribution in the minerals was studied by element mapping. Interpretation of these data also utilized high-resolution BSE and SE images. The main rock-forming minerals of the Vendian parent rock are calcite, dolomite, feldspar, aegirine, riebeckite, mica, chlorite and quartz; accessory minerals are pyrite, galena, apatite, ilmenite, monazite, xenotime, zircon, columbite, pyrochlore, chromite, bastnaesite and some others. Typically, the grain-size of the accessory minerals in both parent rock and bauxite is from 1 to 40 {micro}m. However, even within these rather small grains, the processes of crystal growth and alteration during weathering can be determined from the zonal distribution of the elements. The most widespread processes observed are: (1) Decomposition of Ti-bearing minerals such as ilmenite, aegirine and riebeckite with the formation of leucoxene', which is the main concentrator of Nb, Cr, V and W. Crystal growth can be traced from the zonal distribution of Nb (up to 16 wt.%). Vein-like leucoxene' is also observed in association with organics. (2) Weathering of columbite and pyrochlore: the source of Nb in leucoxene' is now strongly weathered columbite, while the alteration of pyrochlore is expressed in the growth of plumbopyrochlore rims around Ca-rich cores. (3) Dissolution of sulphide minerals and apatite and the formation of crandallite group minerals: crandallite' crystals of up to 40 {micro}m size show a very clear zonation. From the core to the rim of a crystal, the following sequence of elements is observed: Ca [->] Ba [->] Ce [->] Pb [->] Sr [->] Nd. Sulphur also shows a zoned but more complicated distribution, while the distribution of Fe is rather variable. A possible source of REE is bastnaesite from the parent rock. More than twelve crandallite type cells can be identified in a single crandallite' grain. (4) Alteration of stoichiometric zircon and xenotime with the formation of metamict solid solution of zircon and xenotime: altered zircon rims also bear large amounts of Sc (up to 3.5 wt.%), Fe, Ca and Al in the form of as yet unidentified inclusions of 1-2 {micro}m. Monazite seems to be the least altered mineral of the profile. In the parent rock, an unknown mineral of the composition (wt.%): ThO2 - 54.8; FeO - 14.6; Y2O5 -2.3; CaO - 2.0; REE - 1.8; SiO2 - 12.2; P2O5 - 2.8; total - 94.2 (average from ten analyses) was determined. In bauxite, another mineral was found, which has the composition (wt.%): ThO2 - 24.9; FeO - 20.5; Y2O5 - 6.7; CaO - 2.0; ZrO - 17.6; SiO2 - 8.8; P2O5 - 5.4; total - 89.3 (F was not analysed; average from nine analyses). Presumably, the second mineral is the result of weathering of the first one. Although the Th content is very high, the mineral is almost free of Pb. However, intergrowths of galena and pyrite are observed around the partially decomposed crystals of the mineral. Another generation of galena is enriched in chalcophile elements such as Cu, Cd, Bi etc., and is related to epigenetic alteration of the profile, as are secondary apatite and muscovite

Dachstein-Altflche, Augenstein-Formation und Hhlenentwicklung - die Geschichte der letzten 35 Millionen Jahre in den zentralen Nrdlichen Kalkalpen., 2002, Frisch W. , Kuhlemann J. , Dunkl I. , Szekely B. , Vennemann T. , Rettenbacher A.
The landscape of the central Northern Calcareous Alps (NCA) is largely determined by the celebrate elevated karst plateaus, which represent relics of the Dachstein paleosurface and can be followed as far as the eastern margin of the NCA. The Dachstein paleosurface formed in late Eocene to early Oligocene times as a karstic hilly landscape. It was modified by later erosional processes to a limited extent only and is preserved as such in the karst plateaus. In the Oligocene, the paleosurface subsided and was sealed by the Augenstein Formation, a terrestrial sequence of conglomerates and sandstones, which are only preserved in small remnants on the plateaus. The poorly and contradictingly defined terms Rax landscape" and Augenstein landscape" are not used any more. From the overall geological situation, the age of the Augenstein Formation can be inferred as Lower Oligocene to early Lower Miocene. Fission track dating on zircon support the Lower Oligocene age of the basal Augenstein sediments (only these are preserved). Their source area was situated in the south and mainly occupied by weakly metamorphosed Paleozoic sequences (Graywacke Zone and its equivalents) and the latest Carboniferous to Lower Triassic siliciclastic base of the NCA. To the west, the Augenstein Formation interfingered with the Tertiary sediments of the Lower Inn Valley. Thermal modeling of fission track data from apatite, which is contained in pebbles as an accessory phase, suggest that the Augenstein Formation attained thicknesses of locally 1.3 km, possibly even more than 2 km. Augenstein sedimentation probably ended in Early Miocene times with the onset of lateral tectonic extrusion in the Eastern Alps, which caused lowering of the relief in the source area and created a new, fault-bounded river network. In the following period, the Augenstein sediments were eroded and redeposited in the foreland molasse basin. From Pannonian times (ca. 10 Ma) on, the central and eastern NCA, and therefore also the Dachstein paleosurface, experienced uplift in pulses. The paleosurface remained preserved in those areas, where thick limestone sequences enabled subsurface erosion in cave systems and considerably reduced surface erosion. Augenstein sediments became washed into the widespread cave systems of the plateau-topped limestone massifs. The arrangement of the caves in three horizons shows that uplift of the NCA occurred in pulses separated from periods of tectonic quiescence. In our model of the evolution of the NCA since the late Eocene, the highest cave system, the surface-near ruin cave system, was probably formed during formation of the Dachstein paleosurface. The largest system, the giant cave system, formed in Upper Miocene times, i.e., in the early stage of the final uplift period of the NCA. The youngest and lowest system, the source cave system, formed in Pliocene to Quaternary times. We aimed to date material from the giant cave system by radiometric methods. U/Pb dating on speleothems from the Mammut cave (Dachstein) and the Eisriesenwelt (Tennengebirge) gave no formation age because of the low U contents; however, the isotope ratios allow to infer that the speleothems formed in pre-Pleistocene time. Quartz pebbles from the Augenstein Formation, washed into the caves before the formation of the speleothems, were analyzer for cosmogenic beryllium and aluminum isotopes in order to date the time of redeposition. The isotope contents, however, did no yield a sufficiently strong signal. Oxygen and carbon isotope ratios were determined on the Eisriesenwelt speleothem in order to receive information on climatic changes during speleothem growth. A 260 mm long core from the outer zone of the speleothem shower limited variation for the temperatures of the seeping rainwater, which caused the speleothems to form. This indicates moderate climate and thus, again, pre-Pleistocene formation of the speleothems. All these results are in accord with the supposed Upper Miocene formation age of the giant cave system. Displacement of a speleothem along a shear plane and normal faults visible on the plateaus by the offset of the actual surface testify young, partly Quaternary tectonics, which affected the NCA.[ausfhrliche Darstellung, geol. Krtchen, Farbbilder, ganzes Heft.]

Blue Bone Analyses as a Contribution to the Study of Bone Taphonomy in San Josecito Cave, Nuevo Leon, Mexico, 2002, Robles, J. , Arroyocabrales, J. , Johnson, E. , Allen, B. L. , Izquierdo, G.
Blue-stained bones, collected along a single stratigraphic level in San Josecito Cave, Nuevo Le?n, M?xico, were analyzed in order to better understand the diagenetic processes that pertained to their formation, and in order to ascertain if those processes could be used in inferring past environmental conditions. Using XRD, two minerals were identified as composing the fossil bone, hydroxylapatite and calcite. INAA, ICPS, XRFS, and colorimetric methods were used to quantify trace elements, including Cu, Sr, Zn, F, and Cl (in descending order). The findings point to the presence of a physical phenomenon produced by transition metal ions impurities, that in turn seems to be associated with physical and chemical processes occurring inside the cave, rather than with outside paleoenvironmental conditions

ENVIRONMENTAL BASELINE GEOCHEMISTRY OF SEDIMENTS AND PERCOLATING WATERS IN THE MODRI] CAVE, CROATIA, 2002, Miko Slobodan, Kuhta Mladen, Kapelj Sanja

A comprehensive study of Modrić cave was undertaken to evaluate the baseline conditions before its utilization for tourism. Silty loams with guano contain abundant quartz, illite and taranakite and minor vivianite and high concentrations of Cu (2869 mg/kg), Zn (951 mg/kg) and Cd (28 mg/kg). Also sediments mixed with guano are enriched with light REE as well as elevated concentrations of U, Th, Rb and Hg. Sediments with bone fragments contain abundant quartz, illite, calcite and hydroxylapatite and minor carndallite and lower contents of heavy metals. All sediments analysed showed various degrees of contamination by Cu and Zn from dispersed guano. Most of the Zn and Cu in cave sediments and the hydroxyl-apatite crusts are mainly controlled by the iron and manganese hydroxide and the organic fractions, the organic fraction plays an important role in sediment samples with direct influence of guano and in hydroxylapatite crusts while in samples with bone fragments the hydroxide control is dominant. Guano influence on the percolating waters was observed in two cases in the left channel where due to the higher content of orthophosphates saturation in respect to hydroxyl-apatite is present.


Dachstein-Altflche, Augenstein-Formation und Hhlenentwicklung - die Geschichte der letzten 35 Millionen Jahre in den zentralen Nrdlichen Kalkalpen, 2002, Frisch W. , Kuhlemann J. , Dunkl I. , Szekely B. , Vennemann T. , Rettenbacher A.
The landscape of the central Northern Calcareous Alps (NCA) is largely determined by the celebrate elevated karst plateaus, which represent relics of the Dachstein paleosurface and can be followed as far as the eastern margin of the NCA. The Dachstein paleosurface formed in late Eocene to early Oligocene times as a karstic hilly landscape. It was modified by later erosional processes to a limited extent only and is preserved as such in the karst plateaus. In the Oligocene, the paleosurface subsided and was sealed by the Augenstein Formation, a terrestrial sequence of conglomerates and sandstones, which are only preserved in small remnants on the plateaus. The poorly and contradictingly defined terms Rax landscape" and Augenstein landscape" are not used any more. From the overall geological situation, the age of the Augenstein Formation can be inferred as Lower Oligocene to early Lower Miocene. Fission track dating on zircon support the Lower Oligocene age of the basal Augenstein sediments (only these are preserved). Their source area was situated in the south and mainly occupied by weakly metamorphosed Paleozoic sequences (Graywacke Zone and its equivalents) and the latest Carboniferous to Lower Triassic siliciclastic base of the NCA. To the west, the Augenstein Formation interfingered with the Tertiary sediments of the Lower Inn Valley. Thermal modeling of fission track data from apatite, which is contained in pebbles as an accessory phase, suggest that the Augenstein Formation attained thicknesses of locally 1.3 km, possibly even more than 2 km. Augenstein sedimentation probably ended in Early Miocene times with the onset of lateral tectonic extrusion in the Eastern Alps, which caused lowering of the relief in the source area and created a new, fault-bounded river network. In the following period, the Augenstein sediments were eroded and redeposited in the foreland molasse basin. From Pannonian times (ca. 10 Ma) on, the central and eastern NCA, and therefore also the Dachstein paleosurface, experienced uplift in pulses. The paleosurface remained preserved in those areas, where thick limestone sequences enabled subsurface erosion in cave systems and considerably reduced surface erosion. Augenstein sediments became washed into the widespread cave systems of the plateau-topped limestone massifs. The arrangement of the caves in three horizons shows that uplift of the NCA occurred in pulses separated from periods of tectonic quiescence. In our model of the evolution of the NCA since the late Eocene, the highest cave system, the surface-near ruin cave system, was probably formed during formation of the Dachstein paleosurface. The largest system, the giant cave system, formed in Upper Miocene times, i.e., in the early stage of the final uplift period of the NCA. The youngest and lowest system, the source cave system, formed in Pliocene to Quaternary times. We aimed to date material from the giant cave system by radiometric methods. U/Pb dating on speleothems from the Mammut cave (Dachstein) and the Eisriesenwelt (Tennengebirge) gave no formation age because of the low U contents; however, the isotope ratios allow to infer that the speleothems formed in pre-Pleistocene time. Quartz pebbles from the Augenstein Formation, washed into the caves before the formation of the speleothems, were analyzer for cosmogenic beryllium and aluminum isotopes in order to date the time of redeposition. The isotope contents, however, did no yield a sufficiently strong signal. Oxygen and carbon isotope ratios were determined on the Eisriesenwelt speleothem in order to receive information on climatic changes during speleothem growth. A 260 mm long core from the outer zone of the speleothem shower limited variation for the temperatures of the seeping rainwater, which caused the speleothems to form. This indicates moderate climate and thus, again, pre-Pleistocene formation of the speleothems. All these results are in accord with the supposed Upper Miocene formation age of the giant cave system. Displacement of a speleothem along a shear plane and normal faults visible on the plateaus by the offset of the actual surface testify young, partly Quaternary tectonics, which affected the NCA.

Sequence of secondary phosphates deposition in a karst environment: evidence from Magurici Cave (Romania), 2003, Onac Bogdan P. , Veres Daniel S. ,
M[IMG]f1.gif' ALT='a' BORDER='0'>gurici Cave hosts a diverse assemblage of minerals. The phosphatization of illite and montmorillonite clay rich sediments, located on the cave's floor, lead to the formation of taranakite and francoanellite. Mineral assemblages precipitated at the boundary between limestone bedrock and guano deposits are dominantly hydroxylapatite, brushite, ardealite, and monetite. A number of sulphate minerals (gypsum, bassanite, mirabilite, and cesanite) were precipitated along with the phosphates, strengthen the physico-chemical conditions of the depositional environment. The major parameters controlling the environments under which these mineral assemblages were deposited are: pH, relative humidity, alkali content, and Ca/P ratio. In addition, this study presents the second worldwide reported occurrence of phosphammite discovered in a cave environment. This rare mineral occurs as small transparent crystals within the guano deposit, precipitated in an early stage from the liquid fraction of guano

Electron Spin Resonance (ESR) Dating In Karst Environments, 2006, Blackwell, Bonnie A. B.

Electron spin resonance (ESR) dating has been developed for many materials, including hydroxyapatite in enamel, bone, and some fish scales, aragonite and calcite in travertine, molluscs, and calcrete, and quartz from ash, which have many potential applications in karst settings. Although the complexity of the signals in some materials has hampered routine application, research is solving these problems to make the method even more widely applicable. When tested against other dating techniques, age agreement has usually been excellent. Generally, the most reliable applications seem to be tooth enamel, some mollusc species, calcite deposits, and quartz minerals. ESR dating uses signals resulting from trapped charges created by radiation in crystalline solids. Ages are calculated by comparing the accumulated dose in the dating sample with the internal and external radiation dose rates produced by natural radiation in and around the sample. For fossils and authigenic minerals, no zeroing is necessary to obtain accurate ages. In sediment which contains reworked mineral clasts, ESR can be used to date the age of the mineral grain itself if it was not zeroed during erosion. For dating the sedimentation age, however, ESR signals must have been zeroed in order to give the correct age. High pressure, heating, and in some minerals, light exposure and grinding can zero an ESR signal, but some like hydroxyapatite have very high stability at surface temperatures. For materials that absorb uranium (U) during their burial history, such as teeth, bones, or mollusc shells, the age calculation considers their U uptake by cross calibrating with U series or U/Pb dating or by assuming different uptake models. Some difficulties in calculating the external dose rate can be overcome by applying the ESR isochron method, in which the sample acts as its own dosimeter. In open-air karst environments, changes in the external dose rate due to altered sediment cover, and hence, changing cosmic dose rates, need to be modelled. For all karst environments, sedimentary water concentration and mineralogical variations with time also need to be considered. Many ESR applications are currently used in karst settings, but several more are also possible.


Continental France and Belgium during the early Cretaceous: paleoweatherings and paleolandforms, 2006, Thiry Medard, Quesnel Florence, Yans Johan, Wyns Robert, Vergari Anne, Theveniaut Herve, Simoncoincon Regine, Ricordel Caroline, Moreau Marie Gabrielle, Giot Denis, Dupuis Christian, Bruxelles Laurent, Barbarand
During the early Cretaceous, successive tectonic phases and several sea level falls resulted in the emersion of the main part of western Europe and the development of thick 'lateritic' weathering. This long period of continental evolution ended with the Upper Cretaceous transgressions. During this period, the exposed lands displayed a mosaic of diverse morphologies and weathered landscapes. Bauxites are the most spectacular paleoweathering features, known for long in southern France. Recently, new residual outcrops have been identified, trapped in the karstic depressions of the Grands Causses. Other bauxitic formations, containing gibbsite, have also been recognised, occurring with the Clay-with-Jurassic-cherts in the southeastern border of the Paris Basin. These bauxitic formations overlay Jurassic limestone and are buried beneath Upper Cretaceous marine deposits. The recognition of bauxites up north into the southern Paris Basin significantly widens the extension of the Lower Cretaceous bauxitic paleolandscapes. On the Hercynian basements thick kaolinitic weathering mantles occur. They have been classically ascribed to the Tertiary. The first datings of these in situ paleosoils, by means of paleomagnetism and/or radiogenic isotopes, record especially early Cretaceous ages. This is the case for the 'Siderolithic' formations on the edges of the French Massif Central, but also for the kaolinitic profiles in the Belgian Ardennes. In the Flanders, the Brabant basement is deeply kaolinised beneath the Upper Cretaceous cover. These paleosoils show polygenetic evolutions. The relief of these basement paleolandscapes may have been significant. There where probably high scarps (often of tectonic origin) reaching 200 m in elevation or beyond, as well as wide surfaces with inselbergs, as in the present day landscapes of tropical Africa and South America. On the Jurassic limestone platforms occur diverse kaolinitic and ferruginous weathering products. Around the Paris Basin they show various facies, ranging from kaolinitic saprolites to ferricretes. Due to the lack of sedimentary cover, the age of these ferruginous and kaolinitic weathering products has been debated for long, most often allocated to the Siderolithic sensu lato (Eocene-Oligocene). Recent datings by paleomagnetism have enabled to date them (Borne de Fer in eastern Paris Basin) back also to the early Cretaceous (130 {} 10 Ma). These wide limestone plateaus show karstified paleolandforms, such as vast closed and flat depressions broken by conical buttes, but also deep sinkholes in the higher areas of the plateaus and piedmonts. The depth of the karst hollows may be indicative of the range of relative paleoelevations. Dissolution holes display seldom contemporaneous karst fillings, thus implying that the karstland had not a thick weathering cover or that this cover had been stripped off before or by the late Cretaceous transgression. Nevertheless, some areas, especially above chert-bearing Jurassic limestone or marl, show weathering products trapped in the karst features or as a thick weathering mantle. In the Paris Basin, the Wealden gutter looked like a wide floodplain in which fluvio-deltaic sands and clays were deposited and on which paleosoils developed during times of non-deposition. The edges of the gutter were shaped as piedmonts linked up with the upstream basement areas. The rivers flowing down to the plain deposited lobes of coarse fluvial sands and conglomerates. The intensity of the weathering, the thickness of the profiles and their maturation are directly dependent on the duration of the emersion and the topographic location relative to the gutter. Near the axis of the gutter, where emersion was of limited duration, the paleoweathering features are restricted to rubefaction and argillization of the Lower Cretaceous marine formations. On the other hand, on the borders of the basin and on the Hercynian basement, where emersion was of longer duration, the weathering profiles are thicker and more intensively developed. The inventory of the Lower Cretaceous paleoweathering features shows the complexity of the continental history of this period. Moreover, the preserved weathering products are only a part of this long lasting period, all the aspects relative to erosion phases are still more difficult to prove and to quantify. In this domain, apatite fission tracks thermochronology (AFTT) can be helpful to estimate the order of magnitude of denudation. Residual testimonies and subsequent transgressions may enable to estimate relative elevations, but in return, we presently have no reliable tool to estimate absolute paleoelevations. In the work presented here, the inventory enabled to draw a continental paleogeographic map showing the nature of the weathering mantles and the paleolandscape features, just as paleoenvironments and paleobathymetry presently appear on marine paleogeographic maps. For the future, the challenge is to make progress in dating the paleoweathering profiles and especially in the resolution of these datings, in order to correlate precisely the continental records with the different events which trigger them (eustatism, climate, regional and global geodynamics). The final goal will be to build up a stratigraphic scale of the 'continental geodynamic and climatic events' in parallel with 'sequential stratigraphy' in the marine realm

Unusual Phosphate Concretions Related to Groundwater Flow in a Continental Environment, 2006, Thiry Medard, Galbois Jean, Schmitt Jean Michel,
Occurrence of phosphate cemented-sandstone concretions in alluvial sand containing archaeological layers implies that they have formed during the last 2000 years. Morphology and petrography of the concretions indicates a relationship with groundwater cementation. The phosphate cement of the concretions consists of concentric isopachous aureoles, about 10 {micro}m thick, that wrap the detrital grains. Aureoles are formed of collophane, the cryptocrystalline or amorphous variety of hydroxyapatite. Geochemical modeling indicates that the apatite cement likely results from the leaching of a preexisting phosphate deposit (bones?) in an acidic soil environment and the precipitation of dissolved phosphate under pH control at the mixing zone of down-moving soil-water with the calcite-saturated groundwater

EVIDENCE FROM CERNA VALLEY CAVES (SW ROMANIA) FOR SULFURIC ACID SPELEOGENESIS: A MINERALOGICAL AND STABLE ISOTOPE STUDY, 2009, Onac B. , Sumrall J. , Wynn J. , Tamas T. , Dormiceanu V. , Cizma? C.

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.


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