Environmental and climatic controlled fractionation of elements in the Mesozoic carbonate sequences of the western Carpathians, 1973, Veizer Jan, Demovic Rudolf,

CaO, MgO, insoluble residue, strontium, barium, manganese and titanium distribution and controls

Colour In Some Nullarbor Plain Speleothems, 1982, Caldwell J. R. , Davey A. G. , Jennings J. N. , Spate A. P.

Chemical and mineralogical analyses of 18 speleothem samples from Nullarbor Plain caves are related to their colours ranging from white to black through browns and reds. Iron, manganese and organic compounds are the pigments responsible but their effect is variable according to their manner of incorporation in the speleothems and possibly also to the intervention of clay minerals. Closer studies are necessary to unravel these aspects and to investigate sequences of colour in speleothem growth.

On the Wad-Minerals from the Cavern Environment., 1983, Kashima Naruhiko

The wad-minerals from limestone caves of Yugoslavia, China and Japan were studied. X-ray diffraction analysis revealed five minerals; birnessite, 10A-manganite, pyrolusite, todorokite and goethite. The heavy metal elements, Mn, Zn, Fe and Cr have been detected by X-ray fluorescence analysis and their contents were roughly determined. The condensation water introduced directly from the covering soils formed by the continental weathering and the deriving corrosive water interaction with limestone could be the input sources of manganese and other metal elements into the system.

Bacterial Deposition of Iron and Manganese Oxides in North American Caves, 1986, Peck, Stewart B.

IRON-MANGANESE FORMATIONS OF THE CAVE ZOLUSHKA, 1987, Volkov S. N. , Smirnov B. I. , Ianchuk E. A. ,

Chemical hydrogeology in natural and contaminated environments, 1989, Back W, Baedecker Mj,

Chemical hydrogeology, including organic and inorganic aspects, has contributed to an increased understanding of groundwater flow systems, geologic processes, and stressed environments. Most of the basic principles of inorganic-chemical hydrogeology were first established by investigations of organic-free, regional-scale systems for which simplifying assumptions could be made. The problems of groundwater contamination are causing a shift of emphasis to microscale systems that are dominated by organic-chemical reactions and that are providing an impetus for the study of naturally occurring and manmade organic material. Along with the decrease in scale, physical and chemical heterogeneity become major controls.Current investigations and those selected from the literature demonstrate that heterogeneity increases in importance as the study site decreases from regional-scale to macroscale to microscale. Increased understanding of regional-scale flow systems is demonstrated by selection of investigations of carbonate and volcanic aquifers to show how application of present-day concepts and techniques can identify controlling chemical reactions and determine their rates; identify groundwater flow paths and determine flow velocity; and determine aquifer characteristics. The role of chemical hydrogeology in understanding geologic processes of macroscale systems is exemplified by selection of investigations in coastal aquifers. Phenomena associated with the mixing zone generated by encroaching sea water include an increase in heterogeneity of permeability, diagenesis of minerals, and formation of geomorphic features, such as caves, lagoons, and bays. Ore deposits of manganese and uranium, along with a simulation model of ore-forming fluids, demonstrate the influence of heterogeneity and of organic compounds on geochemical reactions associated with genesis of mineral deposits. In microscale environments, importance of heterogeneity and consequences of organic reactions in determining the distributions and concentrations cf. constituents are provided by several studies, including infiltration of sewage effluent and migration of creosote in coastal plain aquifers. These studies show that heterogeneity and the dominance of organically controlled reactions greatly increase the complexity of investigations

La grotte du Funiculaire (Le Mesnil-sous-Jumièges, Seine-Maritime), spéléogenèse et étude d’un remplissage ferro-manganique, 1993, Coquerel G. , Lefebvre D. , Rodet J. , Staigre J. C.

The Funicular Cave is a major cave of the Lower Seine Completely excavated 40 years ago by its owner, it presents a spatial organisation model of drains for the paleokarsts of the great valley. Among the infillings, we discovered a brown-black deposit with a surprising concentration of 90% iron and of 7% manganese, without organic matter or nickel mineral.

BACTERIA, FUNGI AND BIOKARST IN LECHUGUILLA CAVE, CARLSBAD-CAVERNS-NATIONAL-PARK, NEW-MEXICO, 1995, Cunningham Ki, Northup De, Pollastro Rm, Wright Wg, Larock Ej,

Lechuguilla Cave is a deep, extensive, gypsum- and sulfur-bearing hypogenic cave in Carlsbad Caverns National Park, New Mexico, most of which (> 90%) lies more than 300 m beneath the entrance. Located in the arid Guadalupe Mountains, Lechuguilla's remarkable state of preservation is partially due to the locally continuous Yates Formation siltstone that has effectively diverted most vadose water away from the cave. Allocthonous organic input to the cave is therefore very limited, but bacterial and fungal colonization is relatively extensive: (1) Aspergillus sp. fungi and unidentified bacteria are associated with iron-, manganese-, and sulfur-rich encrustations on calcitic folia near the suspected water table 466 m below the entrance; (2) 92 species of fungi in 19 genera have been identified throughout the cave in oligotrophic (nutrient-poor) ''soils'' and pools; (3) cave-air condensate contains unidentified microbes; (4) indigenous chemoheterotrophic Seliberius and Caulobacter bacteria are known from remote pool sites; and (5) at least four genera of heterotrophic bacteria with population densities near 5 x 10(5) colony-forming units (CFU) per gram are present in ceiling-bound deposits of supposedly abiogenic condensation-corrosion residues. Various lines of evidence suggest that autotrophic bacteria are present in the ceiling-bound residues and could act as primary producers in a unique subterranean microbial food chain. The suspected autotrophic bacteria are probably chemolithoautotrophic (CLA), utilizing trace iron, manganese, or sulfur in the limestone and dolomitic bedrock to mechanically (and possibly biochemically) erode the substrate to produce residual floor deposits. Because other major sources of organic matter have not been detected, we suggest that these CLA bacteria are providing requisite organic matter to the known heterotrophic bacteria and fungi in the residues. The cavewide bacterial and fungal distribution, the large volumes of corrosion residues, and the presence of ancient bacterial filaments in unusual calcite speleothems (biothems) attest to the apparent longevity of microbial occupation in this cave

Geology and ore genesis of the manganese ore deposits of the Postmasburg manganese-field, South Africa, 1995, Plehweleisen E. , Klemm D. D. ,

GEOLOGY AND ORE GENESIS OF THE MANGANESE ORE-DEPOSITS OF THE POSTMASBURG MANGANESE-FIELD, SOUTH-AFRICA, 1995, Vonplehweleisen E. , Klemm D. D. ,

The Postmasburg Mn/Fe-ores occur exclusively in dolomitic Precambrian sinkhole structures with siliceous breccias and shales as hostrocks. The main manganese minerals are braunite and bixbyite, apart from secondary alteration products of the psilomelane-manganomelane family. Various generations of ore minerals could be identified. The ore mineralization is subdivided into three different genetic types. They are classified either as pure karst deposits or as combined formations of karst origin and shallow marine sedimentation due to the transgression of the Banded Iron Formation (BIF) sea. Post-sedimentary metamorphism is identified as very low grade. The development of the different ore types is illustrated schematically

Karst-hosted fresh-water Paleoproterozoic manganese deposits, Postmasburg, South Africa, 1996, Gutzmer Jens, Beukes Nicolas J. ,

Presence of Rare-Earth Elements in Black Ferromanganese Coatings from V?ntului Cave (Romania), 1997, Onac, B. P. , Pedersen, R. B. , Tysseland, M.

This study examines the rare-earth elements (REEs) found in ferromanganese coatings covering both sandy alluvium and submerged boulders in an underground stream from V?ntului Cave, Romania. The black ferromanganese sediments are mainly composed of birnessite and other poorly-crystallized manganese oxide and hydroxides (pyrolusite, romanechite, todorokite, rhodochrosite) as well as goethite and kaolinite. Scanning electron microscope and EDX analyses performed on the black ferromanganese sediments show the material to have concentrated considerable amounts of REEs (La, Ce, Sm, Nd) in iron-rich spheres that build up botryoidal-like aggregates. The correlation of 143Nd/144Nd ratio for 6 different samples indicates that the REEs were concentrated in the cave environment after being leached from bauxitic and red residual clays from above the cave. Based on our observations, we conclude that an increase in pH resulted in adsorption of REE onto the surface of ferromanganese minerals. This study demonstrates the potential of using Nd isotopes as a tool for paleochemistry studies of the cave environment.

Nouveaux minéraux de fer et de manganèse dans la Grotte du Vent (Monts Padurea Craiului, Roumanie), 1997, Diaconu Gabriel, Morar Mariana

New iron and manganese minerals in the Wind Cave (Padurea Craiului mountains, Romania)

Geology, geochemistry, and origin of the continental karst-hosted supergene manganese deposits in the western Rhodope massif, Macedonia, northern Greece, 1997, Nimfopoulos M. K. , Pattrick R. A. D. , Michailidis K. M. , Polya D. A. , Esson J. ,

Economic Mn-oxide ore deposits of commercial grade occur in the Rhodope massif near Kato Nevrokopi in the Drama region, Northern Greece. The Mn-oxide mineralization has developed by weathering of continental hypogene rhodochrosite-sulphide veins. The vein mineralization is confined by tectonic shear zones between marble and metapelites, extending laterally into the marble as tabular, pod or lenticular oreshoots (up to 50 m x 20 m x 5-10 m). Supergene oxidation of the hypogene mineralization led to the formation of in-situ residual Mn-oxide ore deposits, and secondary infills of Mn-oxide ore in embryonic and well developed karst cavities. Whole rock geochemical profiles across mineralized zones confirm the role of thrusts and faults as solution passageways and stress the importance of these structures in the development of hydrothermal and supergene mineralization at Kato Nevrokopi. Three zones an recognized in the insitu supergene veins: (A) a stable zone of oxidation, where immobile elements form (or substitute in) stable oxide mineral phases, and mobile elements are leached; (B) a transitional (active) zone in which element behavior is strongly influenced by seasonal fluctuations of the groundwater table and variations in pH-Eh conditions; and (C) a zone of permanent flooding, where variations in pH-Eh conditions are minimal. Zone (B) is considered as the source zone for the karst cavity mineralization. During weathering, meteoric waters, which were CO2-rich (P-CO2 similar to 10(-3.8) to 10(-1.4)) and oxygenated (fO(2) -10(-17) for malachite), percolated downward within the veins, causing breakdown and dissolution of sulfides and marble, and oxidation of rhodochrosite to Mn-oxides. Karat cavity formation was favored by the high permeability along thrust zones. Dissolved Mn2 was transported into karst cavities in reduced meteoric waters at the beginning of weathering (pH similar to 4-5), and as Mn(HCO3)(2) in slightly alkaline groundwaters during advanced weathering (pH similar to 6-8). Mn4? precipitation took place by fO(2) increase in ground waters, or pH increase by continuous hydrolysis and carbonate dissolution. In the well developed karst setting, some mobility of elements occurred during and after karst ore formation in the order Na>K>Mg>Sr>Mn>As>Zn>Ba>Al>Fe>Cu>Cd>Pb. (C) 1998 Canadian Institute of Mining, Metallurgy and Petrolem. Published by Elsevier Science Ltd. All rights reserved

Oxidation of organic matter in a karstic hydrologic unit supplied through stream sinks (Loiret, France), 1998, Alberic P, Lepiller M,

The aim of this paper is to appraise the ability of the oxidation of riverine organic matter in the control of limestone dissolution, in a karst network. Biogeochemical processes during infiltration of river water into an alluvial aquifer have already been described for an average flow velocity of 4-5 m d(-1) (Jacobs, L. A., von Gunten, H. R., Keil, R, and Kuslys, M. (1988) Geochemical changes along a river-groundwater infiltration flow path: Glattfelden, Switzerland. Geochim. Cosmochim. Acta 52, 2693-2706; Von Gunten, H. R., Karametaxas, G., Krahenbuhl, U., Kuslys, M., Giovanoli R., Hoehn E. and Keil R. (1991) Seasonal biogeochemical cycles in riverborne groundwater. Geochim. Cosmochim. Acta 55, 3597-3609; Bourg, A. C. M. and Bertin, C. (1993) Quantitative appraisal of biogeochemical chemical processes during the infiltration of river water into an alluvial aquifer. Environ. Sci. Technol. 27, 661-666). Karstic drainage networks, such as in the River Loire-Val d'Orleans hydrologic system (Fig. 1), make possible flow velocities up to 200 m h(-1 a) and provide convenient access to different water samples several tens of km apart, at both extremities of the hydrologic unit (Chery, J.-L. (1983) Etude hydrochimique d'un aquifere karstique alimente par perte de cours d'eau (la Loire): Le systeme des calcaires de Beauce sous le val d'Orleans. These, Universite d'Orleans; Livrozet, E. (1984) Influence des apports de la Loire sur la qualite bacteriologique et chimique de l'aquifere karstique du val d'Orleans. These, Universite d'Orleans). Recharge of the karstic aquifer occurs principally from influent waters from stream sinks, either through coarse alluvial deposits or directly from outcrops of the regional limestone bedrock (Calcaires de Beauce). Recharge by seepage waters From the local catchment basin is small (Zunino, C., Bonnet, M. and Lelong, F. (1980) Le Val d'Orleans: un exemple d'aquifere a alimentation laterale. C. R. somm. Soc. Geol. Fr. 5, 195-199; Gonzalez R. (1992) Etude de l'organisation et evaluation des echanges entre la Loire moyenne et l'aquifere des calcaires de Beauce. These, Universite d'Orleans) and negligible in summer. This karstic hydrologic: system is the largest in France in terms of flow (tens to hundreds of m(3)/s) and provides the main water resource of the city of Orleans. Chemical compositions of influent waters (River Loire) and effluent waters (spring of the river Loiret) were compared, in particular during floods in summer 1992 and 1993 (Figs 2-4). Variation of chloride in the River Loire during the stream rise can be used as an environmental tracer of the underground flow (Fig. 2). Short transit times of about 3 days are detectable (Fig, 2) which are consistent with earlier estimations obtained with chemical tracers (Ref. in Chery, J.-L. (1983) These, Universite d'Orleans). Depending on the hydrological regime of the river, organic carbon discharge ranges between 3-7 and 2-13 mg/l for dissolved and particulate matter respectively (Fig. 3). Eutrophic characteristics and high algal biomasses are found in the River Loire during low water (Lair, N. and Sargos, D. (1993) A 10 year study at four sites of the middle course of the River Loire. I - Patterns of change in hydrological, physical and chemical variables in relation to algal biomass. Hudroecol. Appl. 5, 1-27) together with more organic carbon rich suspended particulate matter than during floods (30-40 C-org % dry weight versus 5-10%). Amounts of total organic carbon and dissolved oxygen (Fig. 3) dramatically decrease during the underground transport, whereas conversely, dissolved calcium, alkalinity and inorganic carbon increase (Fig. 4). Anoxia of outflows map start in April. Dissolution of calcium carbonates along the influent path outweighs closed system calcite equilibrium of inflow river waters (Table 3). The impact of organic matter oxidation on calcite dissolution may be traced by variations of alkalinity and total carbonates in water. Following, Jacobs, L. A., von Gunten, H. R., Keil, R. and Kuslys, M. (1988) Geochemical changes along a river-groundwater infiltration flow path: Glattfelden, Switzerland. Geochim. Cosmochim. Acta 52, 2693-2706), results are shown graphically (Fig. 5). Extent of reactions is controlled by the consumption of dissolved O-2 and nitrate for organic matter oxidation and by the release of Ca2 for calcite dissolution (Table 2). The karstic network is considered to behave like a biological reactor not exchanging with the atmosphere, with steady inhabitant microbial communities (Mariotti A., Landreau A, and Simon B. (1988) N-15 isotope biogeochemisrry and natural denitrification process in groundwater: Application to the chalk aquifer of northern France. Geochim. Cosmochim. Acta 52, 1869-1878; Gounot, A.-M. (1991) Ecologie microbienne des eaux ei des sediments souterrains. Hydrogeologie, 239-248). Thus, energy requirements only are considered, not carbon assimilation. Moreover, there is no necessity to invoke any delay for nitrification enhancement, as observed elsewhere, after waste water discharge into the river (Chesterikoff, A., Garban, B., Billen, G. and Poulin, M. (1992) Inorganic nitrogen dynamics in the River Seine downstream from Paris (France). Biogeochem. 17, 147-164). Main microbial processes are assumed to be aerobic respiration, nitrification and denitrification. Reactions with iron and manganese, real but not quantitatively important, were neglected. Sulphate reduction and methane formation, certainly not active, were not considered. Denitrification, which is suggested by low nitrate and ammonium concentrations and anoxia in the outflow, is known to be rapid enough to be achieved in a short time (Dupain, S. (1992) Denitrification biologique heterotrophe appliquee au traitement des eaux d'alimentation: Conditions de fonclionnement et mise au point d'un procede. These, Universite Claude Bernard, Lyon). Reaction are somewhat arbitrary but conform to general acceptance (Morel, M. M. and Hering, J. G. (1993) Principles and Applications of Aquatic Chemistry. Wiley, New York). Anaerobic ammonium oxidation (Mulder A., van de Graaf, A. A., Robertson, L: A. and Kuenen, J. G. (1995) Anaerobic ammonium oxidation discovered in a denitrifying fluidized bed reactor. FEMS Microbiol. Ecol. 16, 177-184). although possible, was not considered. In fact, C/N ratio of the reactive organic matter has only mild repercussions on the results; i.e. in the same range as the analytical errors for alkalinity and total carbonates. The objective was simply to roughly confront characteristics of outflowing waters and the calculation. Respective roles of aerobes and denitrifiers, for instance, are not certain. Several periods during low water or floods were selected with various ranges for calcium dissolution or nitrate and oxygen concentrations. The result is that in most cases simulation and data are in reasonable accordance (Fig. 5). Amounts of organic matter in River Loire are generally sufficient to sustain the process (Table 3. Particulate organic matter is probably the most reactive. The balance of oxidation of organic matter indicates that about 65 mu g C-org/l.h are oxidized during the transport without much variation with the river regime or organic discharge. It is concluded that limestone dissolution is directly dependent on organic matter oxidation, but variation occurs (7-29 mg CuCO3/l) with the level of bases that can be neutralized in the River Loire water. (C) 1998 Elsevier Science Ltd. All rights reserved