Towards An Air Quality Standard For Tourist Caves : Studies of Carbon Dioxide Enriched Atmospheres In Gaden - Coral Cave, Wellington Caves, N.S.W., 1981, Osborne, R. Armstrong L.

Carbon dioxide enriched atmospheres are not uncommon in Australian caves and have posed a safety problem for cavers. Carbon dioxide enrichment of a tourist cave's atmosphere is a management problem which can only be approached when standards for air quality are applied. In Gaden - Coral Cave two types of carbon dioxide enrichment are recognised; enrichment by human respiration and enrichment from an external source. Standards for air quality in mines and submersible vehicles are applicable to tourist caves. A maximum allowable concentration of 0.5% carbon dioxide is recommended as the safe, but not the most desirable, air quality standard for tourist caves.

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

Carbon stable isotopic composition of karst soil CO2 in central Guizhon, China, 1999, Zheng L. P. ,

The delta(13)C values of soil CO2 are less than that of atmosphere CO2 in the karst area. On the soil-air interface, the delta(13)C vlaues of soil CO2 decrease with the increase in soil depth; below the soil-air interface, the delta(13)C values of soil CO2 are invariable. The type of vegetation on the land surface has an influence on the delta(13)C values of soil CO2. Due to the activity of soil microbes, the delta(13)C values of soil CO2 are variable dth seasonal change in grass. Isotopic tracer indicates that atmosphere CO2 has a great deal of contribution to soil CO2 at the lower parts of soil profile

Depositional Facies and Aqueous-Solid Geochemistry of Travertine-Depositing Hot Springs (Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, U.S.A.), 2000, Fouke Bw, Farmer Jd, Des Marais Dj, Pratt L, Sturchio Nc, Burns Pc, Discipulo Mk,

Petrographic and geochemical analyses of travertine-depositing hot springs at Angel Terrace, Mammoth Hot Springs, Yellowstone National Park, have been used to define five depositional facies along the spring drainage system. Spring waters are expelled in the vent facies at 71 to 73{degrees}C and precipitate mounded travertine composed of aragonite needle botryoids. The apron and channel facies (43-72{degrees}C) is floored by hollow tubes composed of aragonite needle botryoids that encrust sulfide-oxidizing Aquificales bacteria. The travertine of the pond facies (30-62{degrees}C) varies in composition from aragonite needle shrubs formed at higher temperatures to ridged networks of calcite and aragonite at lower temperatures. Calcite 'ice sheets', calcified bubbles, and aggregates of aragonite needles ('fuzzy dumbbells') precipitate at the air-water interface and settle to pond floors. The proximal-slope facies (28-54{degrees}C), which forms the margins of terracette pools, is composed of arcuate aragonite needle shrubs that create small microterracettes on the steep slope face. Finally, the distal-slope facies (28-30{degrees}C) is composed of calcite spherules and calcite 'feather' crystals. Despite the presence of abundant microbial mat communities and their observed role in providing substrates for mineralization, the compositions of spring-water and travertine predominantly reflect abiotic physical and chemical processes. Vigorous CO2 degassing causes a unit increase in spring water pH, as well as Rayleigh-type covariations between the concentration of dissolved inorganic carbon and corresponding {delta}13C. Travertine {delta}13C and {delta}18O are nearly equivalent to aragonite and calcite equilibrium values calculated from spring water in the higher-temperature ([~]50-73{degrees}C) depositional facies. Conversely, travertine precipitating in the lower-temperature (<[~]50{degrees}C) depositional facies exhibits {delta}13C and {delta}18O values that are as much as 4{per thousand} less than predicted equilibrium values. This isotopic shift may record microbial respiration as well as downstream transport of travertine crystals. Despite the production of H2S and the abundance of sulfide-oxidizing microbes, preliminary {delta}34S data do not uniquely define the microbial metabolic pathways present in the spring system. This suggests that the high extent of CO2 degassing and large open-system solute reservoir in these thermal systems overwhelm biological controls on travertine crystal chemistry

Investigations of microbial origin of karst corrosion of soils depending on different temperatures, 2001, Zambo L. , Horvath G. , Telbisz T. ,

The acids accumulating in soils and controlling the solution of carbonates including the predominant CO2, mostly derive from three processes: i) root respiration of higher plants; ii) decomposition of soil organic matter by microorganisms (microbiota) and iii) other decomposition processes not associated with microbial activities. The solution effect under rendzina soils is primarily used for the dissolution of the enclosed limestone fragments and thus here the solution of bedrock is of limited scale. Below karst soils of high clay content the corrosion of bedrock is more intensive than under rendzinas. On the whole, the amount of carbonates dissolved and transported Into the depths of the karst is smaller than below rendzinas. In each soil type studied the solution caused by microbial activities manifold exceeds the rate of solution resulting from temperature factor but there is a manifest dropping trend from rendzina to clays

Application of carbon isotope for discriminating sources of soil CO2 in karst area, Guizhou, 2001, Li T. Y. , Wang S. J. ,

Using carbon isotope of soil CO2 this paper discussed the sources of soil CO2 in karst area, Guizhou Province, China. Oxidation-decomposition of organic matter, respiration of plant root and activity of microbe are thought to be the major sources of soil CO2. However, in karst area, the contribution of dissolution of underlying carbonate rock to soil CO2 should be considered as in acidic environment. Atmospheric CO2 is the major composition Of Soil CO2 in surface layer of soil profiles and its proportion in Soil CO2 decreases with increase of soil depth. CO2 produced by dissolution of carbonate rock contributes 34%-46% to soil CO2 below the depth of 10cm in the studied soil profiles covered by grass

Soil carbon dioxide in a summer-dry subalpine karst, Marble Mountains, California, USA, 2001, Davis J, Amato P, Kiefer R,

Studies of the seasonality, spatial variation and geomorphic effects of Soil CO2 concentrations in a summer-dry subalpine karst landscape in the Marble Mountains, Klamath National Forest, California, demonstrate the significance of soil moisture as a limiting factor. Modeled actual evapotranspiration (AET) in the four weeks prior to sampling explains 36% of the observed soil-CO2 concentrations, pointing to the importance of root respiration processes in these systems. Late snows are significant in controlling the timing of a snowmelt-initiated pulse of respiration and groundwater. CO2 concentrations were measured at multiple sites in two seasons - 1995 and 1997 - with contrasting patterns of snowmelt. Other than wet-meadow anomalies, where CO2 concentrations reached up to 3.8% in midsummer, alpine meadows on schist were the sites of the highest spring peak concentrations of approximately 1%. Forest sites and sites with thin soils on marble typically peaked at approximately 0.5%, also within a month of snowmelt exposure. Ongoing karstification in the upper bare karst is focused in soil-filled grikes where late-season snowmelt concentrates flow during high-respiration periods, but the lack of active speleothem development suggests that the carbonate solution system is greatly reduced from preglacial periods

Land use change and soil nutrient transformations in the Los Haitises region of the Dominican Republic, 2005, Templer P. H. , Groffman P. M. , Flecker A. S. , Power A. G. ,

We characterized soil cation, carbon (C) and nitrogen (N) transformations within a variety of land use types in the karst region of the northeastern Dominican Republic. We examined a range of soil pools and fluxes during the wet and dry seasons in undisturbed forest, regenerating forest and active agricultural sites within and directly adjacent to Los Haitises National Park. Soil moisture, soil organic matter (SOM), soil cations, leaf litter C and pH were significantly greater in regenerating forest sites than agricultural sites, while bulk density was greater in active agricultural sites. Potential denitrification, microbial biomass C and N, and microbial respiration g(-1) dry soil were significantly greater in the regenerating forest sites than in the active agricultural sites. However, net mineralization, net nitrification, microbial biomass C, and microbial respiration were all significantly greater in the agricultural sites on g(-1) SOM basis. These results suggest that land use is indirectly affecting microbial activity and C storage through its effect on SOM quality and quantity. While agriculture can significantly decrease soil fertility, it appears that the trend can begin to rapidly reverse with the abandonment of agriculture and the subsequent regeneration of forest. The regenerating forest soils were taken out of agricultural use only 5-7 years before our study and already have soil properties and processes similar to an undisturbed old forest site. Compared to undisturbed mogote forest sites, regenerating sites had smaller amounts of SOM and microbial biomass N, as well as lower rates of microbial respiration, mineralization and nitrification g(-1) SOM. Initial recovery of soil pools and processes appeared to be rapid, but additional research must be done to address the long-term rate of recovery in these forest stands. (C) 2004, Elsevier Ltd. All rights reserved

A conceptual model of the flow and distribution of organic carbon in caves, 2007, Simon K. S. , Pipan T. , And Culver D. C.

We present a conceptual model for the movement of organic carbon in karst. We argue that the drainage basin is the most appropriate unit for analyzing energy flux in karst. There are two main inputs in karst basins: 1) localized flow of particulate organic carbon (POC) and dissolved organic carbon (DOC) through sinks and shafts and 2) diffuse flow of POC and DOC from soils and epikarst. After entry, this organic matter is processed and transported before eventual loss through respiration or export from the basin. To begin parameterizing our conceptual model, we estimated carbon fluxes for the first two inputs for two karst basins (Organ Cave in West Virginia and Postojna-Planina Cave System (PPCS) in Slovenia) that have sinking streams and many active epikarst drips. We made a series of measurements of organic carbon, especially DOC in epikarst drip water, cave streams, surface streams sinking into the cave, and at resurgences, which we combined with other published data. In both caves, most of the organic carbon entering through the epikarst was DOC, at concentrations averaging around 1 mg C L21. In both basins, sinking streams accounted for the large majority of DOC input. It is likely that considerable processing of organic carbon occurs within both caves, but more detailed measurements of organic carbon flux at both the basin and stream scale are needed.

Biospeleogenesis, 2013, Barton, H. A.

Microorganisms have shaped the world around us, yet their role in karst processes and speleogenesis remains poorly understood. Biospeleogenesis is the formation of subsurface cavities and caves through the activities of microorganisms, by either respiratory (redox) or metabolic chemistries. In carrying out energy acquisition and the metabolic processes of growth, microorganisms change the local geochemistry of the environment. Such activities can dramatically accelerate speleogenesis and even lead to cave formation in geochemical environments that would otherwise not be conducive to dissolution. The aim of this chapter is to help the reader understand the importance of microbial activity in geochemistry and how such activity can lead to the formation and morphology of caves. The chapter then describes the role that microorganisms are known to have in speleogenesis (carbonic and sulfuric acid biospeleogenesis), hints that such activity may be occurring in newly described cave systems (iron biospeleogenesis), and a potential role in other cave systems (quartzite biospeleogenesis). It is hoped that the reader will gain an understanding of what motivates microorganisms to dramatically change their environment, understand the potential geochemical conditions where such activity could occur, and allow the informed geologist to make predictive statements as to the potential of, and for, biospeleogenesis 

CO2 emission response to different water conditions under simulated karst environment, 2015,

Habitat degradation has been proven to result associated with drought in karst region in south China. However, how this drought condition relates to CO2 efflux is not clear. In this study, we designed a simulated epikarst water–rock (limestone)–soil–plant columns, under varying water levels (treatment), and monitored CO2 concentration and efflux in soil in different seasons during 2011. The results showed that increased soil water greatly enhanced CO2 concentrations. With which treatment with epikarst water (WEW) had higher CO2 concentration than without epikarst water (WOEW). This was particularly high in low soil water treatment and during high temperature in the summer season. Under 30–40 % relative soil water content (RSWC), CO2 concentration in WEW treatment was 1.44 times of WOEW; however, under 90–100 % RSWC, this value was smaller. Comparatively, soil surface CO2 efflux (soil respiration) was 1.29–1.94 lmol m-2 s-1 in WEW and 1.35–2.04 lmol m-2 s-1 in WOEW treatment, respectively. CO2 efflux increased with increasing RSWC, but it was not as sensitive to epikarst water supply as CO2 concentration. WEW tended to weakly influence CO2 efflux under very dry or very wet soil condition and under low temperature. High CO2 efflux in WEW occurred under 50–80 % RSWC during summer. Both CO2 concentrations and CO2 efflux were very sensitive to temperature increase. As a result, at degraded karst environment, increased temperature may enhance CO2 concentration and CO2 emission; meanwhile, the loss of epikarst and soil water deficiency may decrease soil CO2 concentration and CO2 emission, which in turn may decrease karst corrosion.