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Sample records for abiotic marine calcite

  1. The. delta. sup 18 O record of Phanerozoic abiotic marine calcite cements

    SciTech Connect

    Lohmann, K.C.; Walker, J.C.G. )

    1989-04-01

    Monomineralic, abiotic marine cements formed in low-latitude Phanerozoic reefs provide the direction and amplitude of secular variation of {delta}{sup 13}C and {delta}{sup 18}O in marine calcite and defines two end member compositions - 580 to 360 my ({minus}7 to {minus}5{per thousand}{delta}{sup 18}O{sub PDB}) and 360 to present ({minus}3 to 0{per thousand}{delta}{sup 18}O{sub PDB}). Sampling of the Devono-Carboniferous transition (375-320 my) at several global sites reveals a rapid change in carbonate isotopic compositions. Bracketed within Fammenian to Early Visean-aged strata, a 7 to 15 my time interval, this shift corresponds to a 2% offset in mean {delta}{sup 13}C and 3-4% offset in {delta}{sup 18}O. The abruptness of such change, and its overall correlation with variations in {sup 87}Sr/{sup 86}Sr, {delta}{sup 34}S, {delta}{sup 13}C, and Li/Al ratios in marine sediments suggests a primary offset in marine water composition.

  2. delta. sup 18 O values, sup 87 Sr/ sup 86 Sr and Sr/Mg ratios of Late Devonian abiotic marine calcite: Implications for the composition of ancient seawater

    SciTech Connect

    Carpenter, S.J.; Lohmann, K.C.; Walter, L.M.; Huston, J.G.; Halliday, A.N. ); Holden, P. )

    1991-07-01

    Late Devonian (Frasnian) abiotic marine calcite has been microsampled and analyzed for {sup 87}Sr/{sup 86}Sr ratios, {delta}{sup 18}O and {delta}{sup 13}C values, and minor element concentrations. Portions of marine cement crystals from the Alberta and Canning Basins have escaped diagenetic alteration and preserve original marine {delta}{sup 18}O values ({minus}4.8{per thousand} {plus minus} 0.5, PDB), {delta}{sup 13}C values (+2.0 to +3.0{per thousand}, PDB), {sup 87}Sr/{sup 86}Sr ratios (0.70805 {plus minus} 3), and Sr/Mg weight ratios (0.04 to 0.05). Marine {sup 87}Sr/{sup 86}Sr ratios are globally consistent and can be correlated within the Alberta Basin, and among the Alberta, Canning, and Williston Basins. Correlation of isotopic and chemical data strengthen the conclusion that marine cements from the Leduc Formation preserve original marine {delta}{sup 18}O values which are 3 to 4{per thousand} lower than those of modern marine cements. These low {delta}{sup 18}O values are best explained by precipitation from {sup 18}O-depleted seawater and not be elevated seawater temperature or diagenetic alteration. For comparison with Devonian data, analogous data were collected from Holocene Mg-calcite and aragonite marine cements from Enewetak Atoll, Marshall Islands. Mg-calcite and aragonite marine cements are in isotopic equilibrium with ambient seawater, and Mg-calcite cements are homogeneous with respect to Sr and Mg contents. Comparison of Sr and Mg contents of analogous Devonian and Holocene marine cements suggests that the Mg/Ca ratio of Late Devonian seawater was significantly lower and that the Sr/Ca ratio was significantly higher than that of modern seawater.

  3. Magnesium stable isotope fractionation in marine biogenic calcite and aragonite

    NASA Astrophysics Data System (ADS)

    Wombacher, F.; Eisenhauer, A.; Böhm, F.; Gussone, N.; Regenberg, M.; Dullo, W.-Chr.; Rüggeberg, A.

    2011-10-01

    This survey of magnesium stable isotope compositions in marine biogenic aragonite and calcite includes samples from corals, sclerosponges, benthic porcelaneous and planktonic perforate foraminifera, coccolith oozes, red algae, and an echinoid and brachiopod test. The analyses were carried out using MC-ICP-MS with an external repeatability of ±0.22‰ (2SD for δ 26Mg; n = 37), obtained from a coral reference sample (JCp-1). Magnesium isotope fractionation in calcitic corals and sclerosponges agrees with published data for calcitic speleothems with an average Δ 26Mg calcite-seawater = -2.6 ± 0.3‰ that appears to be weakly related to temperature. With one exception ( Vaceletia spp.), aragonitic corals and sclerosponges also display uniform Mg isotope fractionations relative to seawater with Δ 26Mg biogenic aragonite-seawater = -0.9 ± 0.2. Magnesium isotopes in high-Mg calcites from red algae, echinoids and perhaps some porcelaneous foraminifera as well as in all low-Mg calcites (perforate foraminifera, coccoliths and brachiopods) display significant biological influences. For planktonic foraminifera, the Mg isotope data is consistent with the fixation of Mg by organic material under equilibrium conditions, but appears to be inconsistent with Mg removal from vacuoles. Our preferred model, however, suggests that planktonic foraminifera synthesize biomolecules that increase the energetic barrier for Mg incorporation. In this model, the need to remove large quantities of Mg from vacuole solutions is avoided. For the high-Mg calcites from echinoids, the precipitation of amorphous calcium carbonate may be responsible for their weaker Mg isotope fractionation. Disregarding superimposed biological effects, it appears that cation light isotope enrichments in CaCO 3 principally result from a chemical kinetic isotope effect, related to the incorporation of cations at kink sites. In this model, the systematics of cation isotope fractionations in CaCO 3 relate to the

  4. Review: geological and experimental evidence for secular variation in seawater Mg/Ca (calcite-aragonite seas) and its effects on marine biological calcification

    NASA Astrophysics Data System (ADS)

    Ries, J. B.

    2010-09-01

    Synchronized transitions in the polymorph mineralogy of the major reef-building and sediment-producing calcareous marine organisms and abiotic CaCO3 precipitates (ooids, marine cements) throughout Phanerozoic time are believed to have been caused by tectonically induced variations in the Mg/Ca ratio of seawater (molar Mg/Ca>2="aragonite seas", <2="calcite seas"). Here, I assess the geological evidence in support of secular variation in seawater Mg/Ca and its effects on marine calcifiers, and review a series of recent experiments that investigate the effects of seawater Mg/Ca (1.0-5.2) on extant representatives of calcifying taxa that have experienced variations in this ionic ratio of seawater throughout the geologic past. Secular variation in seawater Mg/Ca is supported by synchronized secular variations in (1) the ionic composition of fluid inclusions in primary marine halite, (2) the mineralogies of late stage marine evaporites, abiogenic carbonates, and reef- and sediment-forming marine calcifiers, (3) the Mg/Ca ratios of fossil echinoderms, molluscs, rugose corals, and abiogenic carbonates, (4) global rates of tectonism that drive the exchange of Mg2+ and Ca2+ along zones of ocean crust production, and (5) additional proxies of seawater Mg/Ca including Sr/Mg ratios of abiogenic carbonates, Sr/Ca ratios of biogenic carbonates, and Br concentrations in marine halite. Laboratory experiments have revealed that aragonite-secreting bryopsidalean algae and scleractinian corals and calcite-secreting coccolithophores exhibit higher rates of calcification and growth in experimental seawaters formulated with seawater Mg/Ca ratios that favor their skeletal mineral. These results support the assertion that seawater Mg/Ca played an important role in determining which hypercalcifying marine organisms were the major reef-builders and sediment-producers throughout Earth history. The observation that primary production increased along with calcification within the bryopsidalean

  5. Marine low-magnesian calcite cement from periphery of Mururoa atoll

    SciTech Connect

    Aissaoui, D.M.

    1989-03-01

    Reef-associated rudstones and grainstones from the periphery of Mururoa atoll (Pacific Ocean 21/degrees/50'N-138/degrees/50'W) are significantly more cemented than their lagoonal counterparts. With increasing depth, the centrifugal distribution of the marine lithification is associated with a change in the cement composition. Peripheral facies above 500 m are cemented by three types of high-magnesian calcite (HMC) with distinct mole % MgCO/sub 3/: 14.4-16.9 for fibrous crusts, 7.6-13.5 for bladed cement, and 4.3-11.2 for sparitic, stubby forms. Large pores favor fibrous HMC; small, isolated pores are preferential sites for sparitic HMC, the bladed HMC occurring in association with the two end members of this morphological and geochemical variation. Below 500 m, marine HMCs are progressively replaced by acicular crystals forming fringes less than 100 ..mu..m thick around original grains. Individual crystals are 10-80 ..mu..m long and 2-10 ..mu..m wide. These acicular crystals are low-magnesian calcite (LMC) with less than 3.9 mole % MgCO/sub 3/ and up to 1470 ppm strontium. The marine origin of LMC from the deep periphery of Mururoa atoll is deduced from (1) continuous occurrence over more than 200 m within a major shallowing-upward sequence; (2) absence of emergence within this sequence; (3) strontium content similar to that of marine HMC; and (4) deep infiltration of cold marine waters that may have favored the precipitation of magnesium-depleted calcite along the periphery of the atoll. Recognition of marine LMC cementation at Mururoa atoll indicates LMC is not an exclusive indicator of meteoric diagenesis. Marine LMC cementation may have been more common than previously reported in ancient carbonates, and all acicular LMC cements are not necessarily secondary.

  6. Biomineralization processes of calcite induced by bacteria isolated from marine sediments

    PubMed Central

    Wei, Shiping; Cui, Hongpeng; Jiang, Zhenglong; Liu, Hao; He, Hao; Fang, Nianqiao

    2015-01-01

    Biomineralization is a known natural phenomenon associated with a wide range of bacterial species. Bacterial-induced calcium carbonate precipitation by marine isolates was investigated in this study. Three genera of ureolytic bacteria, Sporosarcina sp., Bacillus sp. and Brevundimonas sp. were observed to precipitate calcium carbonate minerals. Of these species, Sporosarcina sp. dominated the cultured isolates. B. lentus CP28 generated higher urease activity and facilitated more efficient precipitation of calcium carbonate at 3.24 ± 0.25 × 10−4 mg/cell. X-ray diffraction indicated that the dominant calcium carbonate phase was calcite. Scanning electron microscopy showed that morphologies of the minerals were dominated by cubic, rhombic and polygonal plate-like crystals. The dynamic process of microbial calcium carbonate precipitation revealed that B. lentus CP28 precipitated calcite crystals through the enzymatic hydrolysis of urea, and that when ammonium ion concentrations reached 746 mM and the pH reached 9.6, that favored calcite precipitation at a higher level of 96 mg/L. The results of this research provide evidence that a variety of marine bacteria can induce calcium carbonate precipitation, and may influence the marine carbonate cycle in natural environments. PMID:26273260

  7. Seawater fluid inclusions preserved within Cambrian-Ordovician marine cements indicate Cambrian-Ordovician seawater precipitated low-magnesium calcite

    SciTech Connect

    Johnson, W.J.; Goldstein, R.H. . Dept. of Geology)

    1992-01-01

    The San Saba Member of the Wilberns Formation (Llano Uplift, Texas) contains a series of Late Cambrian-Early Ordovician hardgrounds. Bladed low-Mg calcite cements are truncated at hardground surfaces and overlain by shallow marine limestones, indicating a syndepositional shallow marine origin. Primary one-phase fluid inclusions within bladed cements have marine salinities, suggesting that these low-Mg calcite cements formed as a precipitate from Late Cambrian and Early Ordovician seawater and have not undergone recrystallization. Stable isotope analysis of the bladed cement yields delta O-18 values that cluster between [minus]5.6--[minus]6.0 ([per thousand] PDB) which is comparable to those previously reported for Early Ordovician marine calcite. The delta C-13 values are more positive than those reported for this time interval (0.6--1.3 [per thousand] PDB). Trace element analysis indicates that strontium content ranges from 200 to 2,200 ppm. Iron ranges from below detection by electron microprobe to 800 ppm. Mg is generally below detection, however, cements in one hardground display Mg contents that increase progressively toward pore centers. Trace element data lack covariance that would suggest recrystallization. In addition, closed system recrystallization cannot be supported here due to a lack of microdolomite inclusions. Stable isotope, trace element, and fluid inclusion data are consistent with submarine cementation at or below the sediment-water interface. These cements have not undergone significant recrystallization and preserve a primary low Mg calcite mineralogy. These data suggest that early Paleozoic seawater differed chemically from modern seawater. Moreover, preservation of ancient seawater, within fluid inclusions, may provide a direct means of determining those differences.

  8. Protective function of nitric oxide on marine phytoplankton under abiotic stresses.

    PubMed

    Li, Peifeng; Liu, Chun-Ying; Liu, Huanhuan; Zhang, Qiang; Wang, Lili

    2013-09-01

    As an important signaling molecule, nitric oxide (NO) plays diverse physiological functions in plants, which has gained particular attention in recent years. We investigated the roles of NO in the growth of marine phytoplankton Platymonas subcordiforms and Skeletonema costatum under abiotic stresses. The growth of these two microalgae was obviously inhibited under non-metal stress (sodium selenium, Na2SeO3), heavy metal stress (lead nitrate, Pb(NO3)2), pesticide stress (methomyl) and UV radiation stress. After the addition of different low concentrations of exogenous NO (10(-10)-10(-8) mol L(-1)) twice each day during cultivation, the growth of these two microalgae was obviously promoted. Results showed that NO could relieve the oxidative stresses to protect the growth of the two microalgae. For different environmental stress, there is a different optimum NO concentration for marine phytoplankton. It is speculated that the protective effect of NO is related to its antioxidant ability. PMID:23810732

  9. Synchronous barium peaks in high-resolution profiles of calcite and aragonite marine bivalve shells

    NASA Astrophysics Data System (ADS)

    Gillikin, David Paul; Lorrain, Anne; Paulet, Yves-Marie; André, Luc; Dehairs, Frank

    2008-10-01

    Barium/calcium profiles of bivalve shells are characterized by flat background signals periodically interrupted by sharp peaks, with the background signals correlated with water Ba/Ca. To test if the peaks are an environmental signal related to productivity, we analyzed high-resolution Ba/Ca profiles in bivalve shells that grew adjacent to one another. Two aragonitic Saxidomus giganteus show remarkable similarity over a decade of growth, clearly indicating an environmental forcing. Four calcitic Pecten maximus shells also record synchronous Ba/Ca peaks, again indicating an exogenous control. The Ba/Ca peaks, however, start ~40 days after the crash of a bloom, while sedimentation takes place immediately following the bloom. Barite formation in settling phytoplankton flocs, as has been previously proposed, is clearly not the cause of these peaks. Other possible causes, such as dissolved Ba in ambient water, spawning, shell organic matter content, and kinetic growth rate effects are also discussed, but none provide satisfactory explanations. Background shell Ba partition coefficients (Ba/Cacarbonate/Ba/Cawater) for both the calcitic shells (0.18) and aragonitic shells (0.16) are similar to that previously reported for the calcitic Mytilus edulis (~0.1). We suggest that Ba/Ca peaks in bivalve shells are caused by an as yet undetermined environmental forcing, while background Ba/Ca levels are a good indication of dissolved Ba/Ca in the water; both are independent of shell mineralogy.

  10. On the use of abiotic surrogates to describe marine benthic biodiversity

    NASA Astrophysics Data System (ADS)

    McArthur, M. A.; Brooke, B. P.; Przeslawski, R.; Ryan, D. A.; Lucieer, V. L.; Nichol, S.; McCallum, A. W.; Mellin, C.; Cresswell, I. D.; Radke, L. C.

    2010-06-01

    A growing need to manage marine biodiversity sustainably at local, regional and global scales cannot be met by applying existing biological data. Abiotic surrogates of biodiversity are thus increasingly valuable in filling the gaps in our knowledge of biodiversity patterns, especially identification of hotspots, habitats needed by endangered or commercially valuable species and systems or processes important to the sustained provision of ecosystem services. This review examines the use of abiotic variables as surrogates for patterns in benthic biodiversity with particular regard to how variables are tied to processes affecting species richness and how easily those variables can be measured at scales relevant to resource management decisions. Direct gradient variables such as salinity, oxygen concentration and temperature can be strong predictive variables for larger systems, although local stability of water quality may prevent usefulness of these factors at fine spatial scales. Biological productivity has complex relationships with benthic biodiversity and although the development of local and regional models cannot accurately predict outside the range of their biological sampling, remote sensing may provide useful information. Indeed, interpolated values are available for much of the world's seas, and these are continually being refined by the collection of remote sensing and field data. Sediment variables often exhibit complex relationships with benthic biodiversity. The strength of the relationship between any one sediment variable and biodiversity may depend on the state of another sediment variable in that system. Percentage mud, percentage gravel, rugosity and compaction hold the strongest independent predictive power. Rugosity and the difference between gravel and finer sediments can be established using acoustic methods, but to quantify grain size and measure compaction, a sample is necessary. Pure spatial variables such as latitude, longitude and depth

  11. Suboxic to anoxic diagenesis of platform-marginal ooids and bladed-to-fibrous calcite from the middle Ordovician Ottosee Formation (east Tennessee)

    SciTech Connect

    Tobin, K.J.; Walker, K.R.; Srinivasan, K.; Steinhauff, D.M.

    1996-02-01

    The oolite member of the Ottosee Formation (early Caradoc) has bladed-to-fibrous calcite cement that formed under oxygen-depleted conditions atypical of most abiotic marine precipitates. The sequence of early diagenetic events was as follows: (1) ooid formation, (2) precipitation of rare turbid marine cement, (3) minor dissolution of ooids and initial marine cement, (4) precipitation of translucent bladed-to-fibrous calcite, and (5) stabilization of metastable components, such as ooids and turbid marine cements. Ooids and turbid marine cements precipitated from oxic fluids. Minor dissolution of ooids and turbid marine cements was associated with aerobic degradation of organic material, which decreased alkalinity through generation of CO{sub 2}. Translucent bladed-to-fibrous calcite precipitated from suboxic to anoxic marine fluids that were modified by bacterially mediated Mn{sup 4+}, Fe{sup 3+}, and SO{sub 4}{sup 2-} reduction. Translucent bladed-to-fibrous cement was originally low-magnesian calcite and has {delta}{sup 13}C and {delta}{sup 18}O values near other Caradoc marine values. Conversely, ooids and turbid marine calcite had a metastable magnesian calcite mineralogy. These components were dramatically altered by stabilization as reflected by negative {delta}{sup 13}C and {delta}{sup 18}O ooid values. Mineralogical stabilization of ooids and turbid marine cements mainly postdated bladed-to-fibrous calcite formation. 64 refs., 8 figs., 2 tabs.

  12. Tetravalent uranium in calcite.

    SciTech Connect

    Sturchio, N. C.; Antonio, M. R.; Soderholm, L.; Sutton, S. R.; Brannon, J. C.; Univ. of Chicago; Washington Univ.

    1998-08-14

    X-ray absorption spectroscopy and x-ray fluorescence microprobe studies of 35-million-year-old calcite from a Mississippi Valley-type zinc ore deposit indicate substitution of tetravalent uranium for divalent calcium. Thus, tetravalent uranium has a stable location in calcite deposited under reducing conditions. This result validates uranium-series dating methods (including uranium/lead dating) for ancient calcite and shows that calcite provides a sink for uranium in deep groundwater aquifers and anoxic lacustrine and marine basins.

  13. Tetravalent uranium in calcite

    PubMed

    Sturchio; Antonio; Soderholm; Sutton; Brannon

    1998-08-14

    X-ray absorption spectroscopy and x-ray fluorescence microprobe studies of 35-million-year-old calcite from a Mississippi Valley-type zinc ore deposit indicate substitution of tetravalent uranium for divalent calcium. Thus, tetravalent uranium has a stable location in calcite deposited under reducing conditions. This result validates uranium-series dating methods (including uranium/lead dating) for ancient calcite and shows that calcite provides a sink for uranium in deep groundwater aquifers and anoxic lacustrine and marine basins. PMID:9703507

  14. The Effect of Abiotic Factors on Marine Animal Body Size Evolution

    NASA Astrophysics Data System (ADS)

    Wang, X. F.; Wong, W.; Heim, N.; Payne, J.

    2015-12-01

    While there is evidence of a general increase in body size over time, there has been no comprehensive attempt to determine the influence of abiotic factors on body size. Although an increase in maximum body size has been observed during and after the Precambrian oxidation events in the Late Archean and at the onset of the Cambrian, these observations took into account the appearance of eukaryotic life and multicellular life respectively. Using a database of marine animal body sizes spanning the Phanerozoic, we conducted a series of Pearson product-moment correlation tests with igneous rock weathering (Strontium-87: Strontium-86), rate of carbon cycle (δ13C), temperature (δ18O), CO2 concentration, sulfate mineral weathering (δ34S), atmospheric oxygen concentration, and sea level as independent variables, and mean body size as the dependent variable. Our test yielded a correlation coefficient of 0.81 between δ18O and body size, and -0.78 between rCO2 and body size; since δ18O is inversely correlated with temperature, these results indicate that both temperature and CO2 have strong inverse relationships with body size. Atmospheric oxygen yielded a correlation coefficient of 0.09, demonstrating that it ceased to play an influential role in shaping body sizes following the start of the Phanerozoic.

  15. Stable isotope composition of calcite fossils and bulk carbonate as a proxy for the reconstruction of Jurassic marine environments

    NASA Astrophysics Data System (ADS)

    Arabas, A. Z.

    2012-12-01

    Changes in global ocean productivity may be studied by means of carbon isotope analyses of marine carbonates. The analyses of the isotopic composition of carbonate oxygen are a basis for seawater temperature reconstructions, which are indicative of environmental and climatic changes. In this study we use carbon and oxygen isotope composition for the evaluation of the environmental changes in the Pieniny Klippen Basin (PKB) during the Jurassic. PKB is a narrow and long structure separating the Outer and Central Carpathians. The sample set includes the stratigraphically well-dated bulk carbonates and calcite fossils from several outcrops in Polish, Slovakian and Ukrainian parts of the PKB. Sample screening for the state of preservation was conducted using cathodoluminescence microscopy and optical emission spectrometry method. The aims of the project are: (i) to reconstruct the evolution of sea water temperatures using the oxygen isotope composition and Mg/Ca and Sr/Ca ratios of the belemnite rostra; (ii) to trace the secular changes in the carbonate carbon isotope composition in order to present temporal variations in δ13C values of Jurassic bulk carbonates and belemnite rostra; (iii) to compare the obtained δ13C curves with the previously reported records of the isotope composition of carbonate carbon. Preliminary results of the study show that: (i) a negative excursion of the bulk carbonate δ13C curve during the Toarcian may correspond to the Toarcian Oceanic Anoxic Event; (ii) high Middle Oxfordian δ13C values of bulk carbonate and calcite fossils correspond to the global positive isotope excursion in carbonate carbon; (iii) for Upper Jurassic belemnite δ18O values range from -0.8 to 0.4 ‰VPDB what implies temperatures of 13 ± 2°C.

  16. Isotopic fractionation of cadmium into calcite

    NASA Astrophysics Data System (ADS)

    Horner, Tristan J.; Rickaby, Rosalind E. M.; Henderson, Gideon M.

    2011-12-01

    Cadmium mimics the distribution of the macronutrient phosphate in the oceans, and has uses as a palaeoproxy of past ocean circulation and nutrient utilization. Isotopic analyses of dissolved Cd in modern seawater show potential as a new tool for disentangling phytoplankton utilization of Cd from abiotic processes, such as ocean mixing. Extending this information into the past requires the Cd isotope signal to be captured and faithfully preserved in a suitable sedimentary archive. However, the role that environmental factors, such as temperature, may play in controlling Cd isotope fractionation into such archives has not been assessed. To this end, we have performed controlled inorganic CaCO 3 precipitation experiments in artificial seawater solutions. We grew calcite under different precipitation rates, temperatures, salinities, and ambient [Mg 2 + ], before measuring Cd isotopic compositions by double spike MC-ICPMS. We find that the isotopic fractionation factor for Cd into calcite ( α-C) in seawater is always less than one (i.e. light isotopes of Cd are preferred in calcite). The fractionation factor has a value of 0.99955 ± 0.00012 and shows no response to temperature, [Mg 2 + ], or precipitation rate across the range studied. The constancy of this fractionation in seawater suggests that marine calcites may provide a record of the local seawater composition, without the need to correct for effects due to environmental variables. We also performed CaCO 3 growth in freshwater and, in contrast to calcite precipitated from artificial seawater solutions, no isotopic offset was recorded between the growth solution and calcite ( α-Cd=1.0000±0.0001). Cadmium isotope fractionation during calcite growth can be explained by a kinetic isotope effect during the largely unidirectional incorporation of Cd at the mineral surface. Further, the rate of Cd uptake and isotopic fractionation can be modulated by increased ion blocking of crystal surface sites at high salinity

  17. Early diagenetic high-magnesium calcite and dolomite indicate that coal balls formed in marine or brackish water: Stratigraphic and paleoclimatic implications

    NASA Astrophysics Data System (ADS)

    Raymond, Anne

    2016-04-01

    Coal balls are carbonate and pyrite permineralizations of peat that contain three-dimensional plant fossils preserved at the cellular level. Coal balls, which occur in Pennsylvanian and earliest Permian equatorial coals, provide a detailed record of terrestrial ecology and tropical climate during the Late Paleozoic Ice Age; yet their depositional environment remains controversial. The exquisite preservation of some coal-ball fossils, e.g. pollen with pollen tubes and leaves with mesophyll, indicates rapid formation. The presence of abundant, cement-filled, void spaces within and between the plant debris in most coal balls indicates that they formed in uncompacted peat, near the surface of the mire. Botanical, taphonomic and isotopic evidence point to a freshwater origin for coal balls. The nearest living relatives of coal ball plants (modern lycopsids, sphenopsids, marratialean ferns and conifers) grow in fresh water. Coal-ball peat contains a high percentage of aerial debris, similar to modern freshwater peat. The stable oxygen isotopes of coal-ball carbonate (δ18O = 16 to 3 per mil) suggest a freshwater origin. However, the widespread occurrence of marine invertebrates and early diagenetic framboidal pyrite in coal balls suggests that many formed in close proximity to marine water. Indeed, carbonate petrology points to a marine or brackish water origin for the first-formed carbonate cements in coal balls. Petrographic and geochemical (microprobe) analysis of coal-ball carbonates in Pennsylvanian coals from the midcontinent of North America (Western Interior Basin, West Pangaea) and the Ruhr and Donets Basins (East Pangaea) indicate that the first formed carbonate is either radaxial, nonstochiometric dolomite or high magnesium calcite (9 - 17 mol % MgCO3, indicating precipitation in marine or brackish water. Although both primary dolomite and high magnesium calcite can form in lacustrine settings, the lakes in which these minerals form occur in carbonate terranes

  18. The effects of atmospheric [CO2] on carbon isotope fractionation and magnesium incorporation into biogenic marine calcite

    NASA Technical Reports Server (NTRS)

    Vieira, Veronica

    1997-01-01

    The influences of atmospheric carbon dioxide on the fractionation of carbon isotopes and the magnesium incorporation into biogenic marine calcite were investigated using samples of the calcareous alga Amphiroa and benthic foraminifer Sorites grown in the Biosphere 2 Ocean system under variable atmospheric CO2 concentrations (approximately 500 to 1200 ppm). Carbon isotope fractionation was studied in both the organic matter and the skeletal carbonate. Magnesium analysis was to be performed on the carbonate removed during decalcification. These data have not been collected due to technical problems. Carbon isotope data from Amphiroa yields a linear relation between [CO2] and Delta(sup 13)C(sub Corg)values suggesting that the fractionation of carbon isotopes during photosynthesis is positively correlated with atmospheric [CO2]. [CO2] and Delta(sup 13)C(sub Corg) values for Sorites produce a relation that is best described by a hyperbolic function where Delta(sup 13)C(sub Corg) values increase between 300 and 700 ppm and decrease from 700 to 1200 ppm. Further investigation of this relation and Sorites physiology is needed.

  19. Microbiological and abiotic processes in modelling longer-term marine corrosion of steel.

    PubMed

    Melchers, Robert E

    2014-06-01

    Longer term exposure of mild steel in natural (biotic) waters progresses as a bimodal function of time, both for corrosion mass loss and for pit depth. Recent test results, however, found this also for immersion in clean fresh, almost pure and triply distilled waters. This shows chlorides or microbiological activity is not essential for the electrochemical processes producing bimodal behaviour. It is proposed that the first mode is aerobic corrosion that eventually produces a non-homogeneous corroded surface and rust coverage sufficient to allow formation of anoxic niches. Within these, aggressive autocatalytic reduction then occurs under anoxic abiotic conditions, caused by sulfide species originating from the MnS inclusions typical in steels. This is consistent with Wranglen's model for abiotic anoxic crevice and pitting corrosion without external aggressive ions. In biotic conditions, metabolites from anaerobic bacterial activity within and near the anoxic niches provides additional (sulfide) species to contribute to the severity of corrosion. Limited observational evidence that supports this hypothesis is given but further investigation is required to determine all contributor(s) to the cathodic current for the electrochemical reaction. The results are important for estimating the contribution of microbiological corrosion in infrastructure applications. PMID:24067447

  20. Diagenesis of fibrous magnesian calcite marine cement: Implications for the interpretation of δ18O and δ13C values of ancient equivalents

    NASA Astrophysics Data System (ADS)

    Frank, Tracy D.; Lohmann, Kyger C.

    1996-07-01

    Fibrous, high Mg-calcite (HMC) marine cement from the Pliocene Hope Gate Formation, Jamaica occurs as 1-2 mm thick isopachous coatings on skeletal grains in local occurrences of Halimeda grainstone and is commonly syntaxially overgrown by clear, prismatic low Mg-calcite (LMC) interpreted as a mixing zone cement. The presence of inclusions at discrete levels in the fibrous marine cement produces internal growth banding wherein clear, inclusion-free zones alternate with cloudy, inclusion-rich zones. Clear zones have uniform Mg contents (13.7 ± 0.2 mol% MgCO 3) and stable isotopic compositions ( δ18O = 0.8 ± 0.1%; δ13C = 3.2 ± 0.1%) consistent with a marine origin. In contrast, inclusion-rich zones contain fine-scale intergrowths of LMC, dolomite, and HMC, and have carbon and oxygen isotopic compositions that define a linear mixing trend between compositions of inclusion-free HMC and prismatic LMC cement overgrowths. Petrographic observations indicate that the mixing trend defined by isotopic data from inclusion-rich zones is related to the addition of large volumes of secondary LMC as cement in primary pore space, as intergrowths among fibers of primary HMC marine cement, and/or as replacements of primary HMC crystallites. Dolomite is present in inclusion-rich zones in volumes generally compatible with amounts predicted to result from the closed-system stabilization of HMC to LMC and dolomite. In addition, isotopic and geochemical data from some areas of inclusion-rich zones are consistent with mass balance constraints assuming a closed-system, which require that bulk isotopic and geochemical compositions are retained. These relations suggest that small remnants of HMC in inclusion-rich zones of Hope Gate marine cement have altered to LMC and dolomite while isolated from system pore fluids, such that primary marine isotopic signatures were imparted on diagenetic products. Similar petrographic, geochemical, and isotopic relations have been noted in ancient

  1. Abiotic causes of the great mass extinction of marine biota at the Triassic-Jurassic boundary

    NASA Astrophysics Data System (ADS)

    Barash, M. S.

    2015-05-01

    In the interval of the Triassic-Jurassic boundary up to 80% of marine species became extinct. The main hypotheses on the causes of this mass extinction are reviewed. The extinction was triggered by a powerful eruption of basalts in the Central Atlantic Magmatic Province. In addition, several impact craters have been found. Extraterrestrial factors resulted in two main sequences of events: terrestrial, leading to strong volcanism, and extraterrestrial (impact events). They produced similar effects: emissions of harmful chemical compounds and aerosols. Consequences included the greenhouse effect, darkening of the atmosphere (which prevented photosynthesis), stagnation of the oceans, and anoxia. Biological productivity decreased; food chains collapsed. As a result, all vital processes were disturbed, and a large portion of the biota went extinct.

  2. Growth rate controlled barium partitioning in calcite and aragonite

    NASA Astrophysics Data System (ADS)

    Goetschl, Katja Elisabeth; Mavromatis, Vasileios; Baldermann, Andre; Purgstaller, Bettina; Dietzel, Martin

    2016-04-01

    The barium (Ba) content and the Ba/Ca molar ratios in biogenic and abiotic carbonates have been widely used from the scientific community as a geochemical proxy especially in marine and early diagenetic settings. The Ba content of carbonate minerals has been earlier associated to changes in oceanic circulation that may have been caused by upwelling, changes in weathering regimes and river-runoff as well as melt water discharge. The physicochemical controls of Ba ion incorporation in the two most abundant CaCO3 polymorphs found in Earth's surface environments, i.e. calcite and aragonite, have adequately been studied only for calcite. These earlier studies (i.e. [1]) suggest that at increasing growth rate, Ba partitioning in calcite is increasing as well. In contrast, to date the effect of growth rate on the partitioning of Ba in aragonite remains questionable, despite the fact that this mineral phase is the predominant carbonate-forming polymorph in shallow marine environments. To shed light on the mechanisms controlling Ba ion uptake in carbonates in this study we performed steady-state Ba co-precipitation experiments with calcite and aragonite at 25°C. The obtained results for the partitioning of Ba in calcite are in good agreement with those reported earlier by [1], whereas those for aragonite indicate a reduction of Ba partitioning at elevated aragonite growth rates, with the partitioning coefficient value between solid and fluid to be approaching the unity. This finding is good agreement with the formation of a solid solution in the aragonite-witherite system, owing to the isostructural crystallography of the two mineral phases. Moreover, our data set provides new insights that are required for reconstructing the evolution of the Ba content of pristine marine versus diagenetically altered carbonate minerals commonly occurring in marine subfloor settings, as the thermodynamically less stable aragonite will transform to calcite enriched in Ba, whilst affecting

  3. Molecular evidence for abiotic sulfurization of dissolved organic matter in marine shallow hydrothermal systems

    NASA Astrophysics Data System (ADS)

    Gomez-Saez, Gonzalo V.; Niggemann, Jutta; Dittmar, Thorsten; Pohlabeln, Anika M.; Lang, Susan Q.; Noowong, Ann; Pichler, Thomas; Wörmer, Lars; Bühring, Solveig I.

    2016-10-01

    recirculation in Milos seafloor. The four most effective potential sulfurization reactions were those exchanging an O atom by one S atom in the formula or the equivalent + H2S reaction, correspondingly exchanging H2O, H2 and/or O2 by a H2S molecule. Our study reveals novel insights into DOS dynamics in marine hydrothermal environments and provides a conceptual framework for molecular-scale mechanisms in organic sulfur geochemistry.

  4. Improvement of lipid production in the marine strains Alexandrium minutum and Heterosigma akashiwo by utilizing abiotic parameters.

    PubMed

    Fuentes-Grünewald, C; Garcés, E; Alacid, E; Sampedro, N; Rossi, S; Camp, J

    2012-01-01

    Two different strains of microalgae, one raphidophyte and one dinoflagellate, were tested under different abiotic conditions with the goal of enhancing lipid production. Whereas aeration was crucial for biomass production, nitrogen deficiency and temperature were found to be the main abiotic parameters inducing the high-level cellular accumulation of neutral lipids. Net neutral lipid production and especially triacylglycerol (TAG) per cell were higher in microalgae (>200% in Alexandrium minutum, and 30% in Heterosigma akashiwo) under treatment conditions (25°C; 330 μM NaNO(3)) than under control conditions (20°C; 880 μM NaNO(3)). For both algal species, oil production (free fatty acids plus TAG fraction) was also higher under treatment conditions (57 mg L(-1) in A. minutum and 323 mg L(-1) in H. akashiwo). Despite the increased production and accumulation of lipids in microalgae, the different conditions did not significantly change the fatty acids profiles of the species analyzed. These profiles consisted of saturated fatty acids (SAFA) and polyunsaturated fatty acids (PUFA) in significant proportions. However, during the stationary phase, the concentrations per cell of some PUFAs, especially arachidonic acid (C20:4n6), were higher in treated than in control algae. These results suggest that the adjustment of abiotic parameters is a suitable and one of the cheapest alternatives to obtain sufficient quantities of microalgal biomass, with high oil content and minimal changes in the fatty acid profile of the strains under consideration. PMID:21766212

  5. Seawater Mg/Ca controls polymorph mineralogy of microbial CaCO3: a potential proxy for calcite-aragonite seas in Precambrian time.

    PubMed

    Ries, J B; Anderson, M A; Hill, R T

    2008-03-01

    A previously published hydrothermal brine-river water mixing model driven by ocean crust production suggests that the molar Mg/Ca ratio of seawater (mMg/Ca(sw)) has varied significantly (approximately 1.0-5.2) over Precambrian time, resulting in six intervals of aragonite-favouring seas (mMg/Ca(sw) > 2) and five intervals of calcite-favouring seas (mMg/Ca(sw) < 2) since the Late Archaean. To evaluate the viability of microbial carbonates as mineralogical proxy for Precambrian calcite-aragonite seas, calcifying microbial marine biofilms were cultured in experimental seawaters formulated over the range of Mg/Ca ratios believed to have characterized Precambrian seawater. Biofilms cultured in experimental aragonite seawater (mMg/Ca(sw) = 5.2) precipitated primarily aragonite with lesser amounts of high-Mg calcite (mMg/Ca(calcite) = 0.16), while biofilms cultured in experimental calcite seawater (mMg/Ca(sw) = 1.5) precipitated exclusively lower magnesian calcite (mMg/Ca(calcite) = 0.06). Furthermore, Mg/Ca(calcite )varied proportionally with Mg/Ca(sw). This nearly abiotic mineralogical response of the biofilm CaCO3 to altered Mg/Ca(sw) is consistent with the assertion that biofilm calcification proceeds more through the elevation of , via metabolic removal of CO2 and/or H+, than through the elevation of Ca2+, which would alter the Mg/Ca ratio of the biofilm's calcifying fluid causing its pattern of CaCO3 polymorph precipitation (aragonite vs. calcite; Mg-incorporation in calcite) to deviate from that of abiotic calcification. If previous assertions are correct that the physicochemical properties of Precambrian seawater were such that Mg/Ca(sw) was the primary variable influencing CaCO3 polymorph mineralogy, then the observed response of the biofilms' CaCO3 polymorph mineralogy to variations in Mg/Ca(sw), combined with the ubiquity of such microbial carbonates in Precambrian strata, suggests that the original polymorph mineralogy and Mg/Ca(calcite )of well

  6. Hydrothermal calcite in the Elephant Moraine

    SciTech Connect

    Faure, G.; Taylor, K.S.; Jones, L.M.

    1986-01-01

    In the course of geologic mapping of the Elephant Moraine on the east antarctic ice sheet, Faure and Taylor (1985) collected several specimens of black botryoidal calcite, composed of radiating acicular crystals that resemble stromatolites. Calcite from this and other specimens is significantly enriched in strontium-87 (the strontium-87/strontium-86 ratio equals 0.71417 +/- 0.00002), carbon-12 (delta carbon-13 equals -22.9 parts per thousand, PDB standard) and oxygen-16 (delta oxygen-18 equals -21.1 parts per thousand, standard mean ocean water) compared with calcite of marine origin. The enrichment in carbon-12 is similar to that of calcite associated with coal in the Allan Hills. The enrichment in oxygen-16 indicates that the calcite from the Elephant Moraine could only have precipitated in isotopic equilibrium with glacial melt water. Therefore, the temperature at which the black calcite precipitated from water of that isotope composition was about 85/sup 0/C. A temperature of this magnitude implies that the black calcite formed as a result of volcanic activity under the east antarctic ice sheet. The enrichment of the black calcite in carbon-12 suggests that it formed in part from carbon dioxide derived from the coal seams of the Weller Formation in the Beacon Supergroup. The isotopic composition of strontium in the black calcite is similar to that of carbonate beds and concretions in the Beacon rocks of southern Victoria Land. A volcanic-hydrothermal origin is also consistent with the very low total organic carbon content of 0.15% in the calcite.

  7. Effect of organic ligands on Mg partitioning and Mg isotope fractionation during low-temperature precipitation of calcite

    NASA Astrophysics Data System (ADS)

    Mavromatis, Vasileios; Immenhauser, Adrian; Buhl, Dieter; Purgstaller, Bettina; Baldermann, Andre; Dietzel, Martin

    2016-04-01

    Calcite growth experiments have been performed at 25 oC and 1 bar pCO2 in the presence of aqueous Mg and six organic ligands in the concentration range from 10‑5 to 10‑3 M. These experiments were performed in order to quantify the effect of distinct organic ligands on the Mg partitioning and Mg stable isotope fractionation during its incorporation in calcite at similar growth rates normalized to total surface area. The organic ligands used in this study comprise of (i) acetate acid, (ii) citrate, (iii) glutamate, (iv) salicylate, (v) glycine and (vi) ethylenediaminetetraacetic acid (EDTA), containing carboxyl- and amino-groups. These fuctional groups are required for bacterial activity and growth as well as related to biotic and abiotic mineralization processes occurring in sedimentary and earliest diagenetic aquatic environments (e.g. soil, cave, lacustrine, marine). The results obtained in this study indicate that the presence of organic ligands promotes an increase in the partition coefficient of Mg in calcite (DMg = (Mg/Ca)calcite (Mg/Ca)fluid). This behaviour can be explained by the temporal formation of aqueous Mg-ligand complexes that are subsequently adsorbed on the calcite surfaces and thereby reducing the active growth sites of calcite. The increase of DMg values as a function of the supersaturation degree of calcite in the fluid phase can be described by the linear equation LogDMg =0.3694 (±0.0329)×SIcalcite - 1.9066 (±0.0147); R2=0.92 In contrast, the presence of organic ligands, with exception of citrate, does not significantly affect the Mg isotope fractionation factor between calcite and reactive fluid (Δ26Mgcalcite‑fluid = -2.5 ±0.1). Citrate likely exhibits larger fractionation between the Mg-ligand complexes and free aqueous Mg2+, compared to the other organic ligands studied in this work, as evidenced by the smaller Δ26Mgcalcite‑fluid values. These results indicate that in Earth's surface calcite precipitating environments that are

  8. Fibrous calcite from the Middle Ordovician Holston Formation (east Tennessee)

    SciTech Connect

    Tobin, K.J.; Walker, K.R. . Dept. of Geological Sciences)

    1993-03-01

    Fibrous calcite from buildups, which occur near the top of the Middle Ordovician Holston Formation, were examined from two localities near Knoxville, TN (Alcoa Highway and Deanne Quarry). Buildups at these localities were deposited under open-marine conditions, slightly down-slope from the platform edge. Fibrous calcite (mainly radiaxial fibrous) occur most commonly as cements in mainly stromatactis structures present in bioherms and intergranular porosity in beds that flank bioherms. Fibrous calcite is interpreted to have been precipitated in a marine setting. Fibrous calcite is uniformly turbid or banded with interlayered turbid and clearer cement. Fibrous calcite most commonly shows patchy or blotchy dull-non-luminescence under cathodoluminescence. Bands of uniformly non-luminescent and relatively bright luminescent calcite are present. [delta][sup 13]C compositions of fibrous calcite vary little (0.6 to 1.0%) but [delta][sup 18]O values are highly variable ([minus]4.8 to [minus]7.1%). Post-marine cement consists of ferroan and non-ferroan, dull luminescent equant calcite ([delta][sup 13]C = 0.3 to 0.8; [delta][sup 18]O = [minus]8.6 to [minus]11.5) and is interpreted as precipitated in a deep meteoric or burial setting. Depleted [delta][sup 18]O compositions of fibrous calcite reflect addition of post-depositional calcite during stabilization. Most enriched [delta][sup 13]C and [delta][sup 18]O fibrous calcite composition are similar to enriched values from other Middle Ordovician southern Appalachian buildups (other localities of Holston (TN) and Effna (VA) formations) ([delta][sup 13]C = 0.3 to 0.8; [delta][sup 18]O = [minus]3.9 to [minus]4.8) and may reflect fibrous calcite precipitated in isotopic equilibrium with Middle Ordovician sea water.

  9. High surface area calcite

    NASA Astrophysics Data System (ADS)

    Schultz, L. N.; Andersson, M. P.; Dalby, K. N.; Müter, D.; Okhrimenko, D. V.; Fordsmand, H.; Stipp, S. L. S.

    2013-05-01

    Calcite (CaCO3) is important in many fields—in nature, because it is a component of aquifers, oil reservoirs and prospective CO2 storage sites, and in industry, where it is used in products as diverse as paper, toothpaste, paint, plastic and aspirin. It is difficult to obtain high purity calcite with a high surface area but such material is necessary for industrial applications and for fundamental calcite research. Commercial powder is nearly always contaminated with growth inhibitors such as sugars, citrate or pectin and most laboratory synthesis methods deliver large precipitates, often containing vaterite or aragonite. To address this problem, we (i) adapted the method of carbonating a Ca(OH)2 slurry with CO2 gas to develop the first simple, cheap, safe and reproducible procedure using common laboratory equipment, to obtain calcite that reproducibly had a surface area of 14-17 m2/g and (ii) conducted a thorough characterization of the product. Scanning electron microscopy (SEM) revealed nanometer scale, rhombohedral crystals. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR) confirmed highly crystalline, pure calcite that more closely resembles the dimensions of the biogenic calcite produced by algae in coccoliths than other methods for synthesizing calcite. We suggest that this calcite is useful when purity and high surface area are important.

  10. Microbially-Mediated Subsurface Calcite Precipitation for Removal of Hazardous Divalent Cations

    SciTech Connect

    Colwell, Frederick S.; Smith, R.W.; Ferris, F. Gratn; Ingram, Jani C.; Reysenbach, A.-L.; Fujita, Yoshiko; Tyler, T.L.; Taylor, J.L.; Banta, A.; Delwiche, M.E.; McLing, T.; Cortez, Marnie, M.; Watwood, M.E.

    2003-03-27

    We are investigating microbially-mediated acceleration of calcite precipitation and co-precipitation of hazardous divalent cations (e.g., 90Sr) in calcite saturated subsurface systems. In theory, the addition of urea to an aquifer or vadose zone and its subsequent hydrolysis by indigenous microbes will cause an increase in alkalinity, pH and calcite precipitation. Lab studies indicated the ability of various bacteria to precipitate calcite through urea hydrolysis and that incorporation of strontium in biogenically-formed calcite is greater than in abiotically formed calcite. Results from a field experiment in a pristine location in the Snake River Plain aquifer involving the phased addition of molasses and then urea showed increases in total cell numbers, rate of urea hydrolysis and calcite formation during the study. The combined diagnostic approaches of microbiology, molecular ecology and analytical chemistry demonstrate the feasibility of this biogeochemical manipulation for subsurface remediation at arid Western DOE sites such as Hanford and INEEL.

  11. Mineralogical and isotopic record of biotic and abiotic diagenesis of the Callovian-Oxfordian clayey formation of Bure (France)

    NASA Astrophysics Data System (ADS)

    Lerouge, C.; Grangeon, S.; Gaucher, E. C.; Tournassat, C.; Agrinier, P.; Guerrot, C.; Widory, D.; Fléhoc, C.; Wille, G.; Ramboz, C.; Vinsot, A.; Buschaert, S.

    2011-05-01

    The Callovian-Oxfordian (COx) clayey unit is being studied in the Eastern part of the Paris Basin at depths between 400 and 500 m depth to assess of its suitability for nuclear waste disposal. The present study combines new mineralogical and isotopic data to describe the sedimentary history of the COx unit. Petrologic study provided evidence of the following diagenetic mineral sequence: (1) framboidal pyrite and micritic calcite, (2) iron-rich euhedral carbonates (ankerite, sideroplesite) and glauconite (3) limpid calcite and dolomite and celestite infilling residual porosity in bioclasts and cracks, (4) chalcedony, (5) quartz/calcite. Pyrite in bioturbations shows a wide range of δ 34S (-38‰ to +34.5‰), providing evidence of bacterial sulphate reduction processes in changing sedimentation conditions. The most negative values (-38‰ to -22‰), measured in the lower part of the COx unit indicate precipitation of pyrite in a marine environment with a continuous sulphate supply. The most positive pyrite δ 34S values (-14‰ up to +34.5‰) in the upper part of the COx unit indicate pyrite precipitation in a closed system. Celestite δ 34S values reflect the last evolutionary stage of the system when bacterial activity ended; however its deposition cannot be possible without sulphate supply due to carbonate bioclast dissolution. The 87Sr/ 86Sr ratio of celestite (0.706872-0.707040) is consistent with deposition from Jurassic marine-derived waters. Carbon and oxygen isotopic compositions of bulk calcite and dolomite are consistent with marine carbonates. Siderite, only present in the maximum clay zone, has chemical composition and δ 18O consistent with a marine environment. Its δ 13C is however lower than those of marine carbonates, suggesting a contribution of 13C-depleted carbon from degradation of organic matter. δ 18O values of diagenetic chalcedony range between +27‰ and +31‰, suggesting precipitation from marine-derived pore waters. Late calcite

  12. Strontium incorporation into calcite generated by bacterial ureolysis

    NASA Astrophysics Data System (ADS)

    Fujita, Yoshiko; Redden, George D.; Ingram, Jani C.; Cortez, Marnie M.; Ferris, F. Grant; Smith, Robert W.

    2004-08-01

    Strontium incorporation into calcite generated by bacterial ureolysis was investigated as part of an assessment of a proposed remediation approach for 90Sr contamination in groundwater. Urea hydrolysis produces ammonium and carbonate and elevates pH, resulting in the promotion of calcium carbonate precipitation. Urea hydrolysis by the bacterium Bacillus pasteurii in a medium designed to mimic the chemistry of the Snake River Plain Aquifer in Idaho resulted in a pH rise from 7.5 to 9.1. Measured average distribution coefficients (D EX) for Sr in the calcite produced by ureolysis (0.5) were up to an order of magnitude higher than values reported in the literature for natural and synthetic calcites (0.02-0.4). They were also higher than values for calcite produced abiotically by ammonium carbonate addition (0.3). The precipitation of calcite in these experiments was verified by X-ray diffraction. Time-of-flight secondary ion mass spectrometry (ToF SIMS) depth profiling (up to 350 nm) suggested that the Sr was not merely sorbed on the surface, but was present at depth within the particles. X-ray absorption near edge spectra showed that Sr was present in the calcite samples as a solid solution. The extent of Sr incorporation appeared to be driven primarily by the overall rate of calcite precipitation, where faster precipitation was associated with greater Sr uptake into the solid. The presence of bacterial surfaces as potential nucleation sites in the ammonium carbonate precipitation treatment did not enhance overall precipitation or the Sr distribution coefficient. Because bacterial ureolysis can generate high rates of calcite precipitation, the application of this approach is promising for remediation of 90Sr contamination in environments where calcite is stable over the long term.

  13. A novel determination of calcite dissolution kinetics in seawater

    NASA Astrophysics Data System (ADS)

    Subhas, Adam V.; Rollins, Nick E.; Berelson, William M.; Dong, Sijia; Erez, Jonathan; Adkins, Jess F.

    2015-12-01

    We present a novel determination of the dissolution kinetics of inorganic calcite in seawater. We dissolved 13 C -labeled calcite in unlabeled seawater, and traced the evolving δ13 C composition of the fluid over time to establish dissolution rates. This method provides sensitive determinations of dissolution rate, which we couple with tight constraints on both seawater saturation state and surface area of the dissolving minerals. We have determined dissolution rates for two different abiotic calcite materials and three different grain sizes. Near-equilibrium dissolution rates are highly nonlinear, and are well normalized by geometric surface area, giving an empirical dissolution rate dependence on saturation state (Ω) of: This result substantiates the non-linear response of calcite dissolution to undersaturation. The bulk dissolution rate constant calculated here is in excellent agreement with those determined in far from equilibrium and dilute solution experiments. Plots of dissolution versus undersaturation indicates the presence of at least two dissolution mechanisms, implying a criticality in the calcite-seawater system. Finally, our new rate determination has implications for modeling of pelagic and seafloor dissolution. Nonlinear dissolution kinetics in a simple 1-D lysocline model indicate a possible transition from kinetic to diffusive control with increasing water depth, and also confirm the importance of respiration-driven dissolution in setting the shape of the calcite lysocline.

  14. Alginic Acid Accelerates Calcite Dissolution

    NASA Astrophysics Data System (ADS)

    Perry, T. D.; Duckworth, O. W.; McNamara, C. J.; Martin, S. T.; Mitchell, R.

    2003-12-01

    Accelerated carbonate weathering through biological activity affects both geochemical cycling and the local pH and alkalinity of terrestrial and marine waters. Microbes affect carbonate dissolution through metabolic activity, production of acidic or chelating exudates, and cation binding by cell walls. Dissolution occurs within microbial biofilms - communities of microorganisms attached to stone in an exopolymer matrix. We investigated the effect of alginic acid, a common biological polymer produced by bacteria and algae, on calcite dissolution using a paired atomic force microscopy/flow-through reactor apparatus. The alginic acid caused up to an order of magnitude increase in dissolution rate at 3 < pH < 12. Additionally, the polymer preferentially binds to the obtuse pit steps and increases step velocity. We propose that the polymer is actively chelating surficial cations reducing the activation energy and increasing dissolution rate. The role of biologically produced polymers in mineral weathering is important in the protection of cultural heritage materials and understanding of marine and terrestrial systems.

  15. Elastic constants of calcite

    USGS Publications Warehouse

    Peselnick, L.; Robie, R.A.

    1962-01-01

    The recent measurements of the elastic constants of calcite by Reddy and Subrahmanyam (1960) disagree with the values obtained independently by Voigt (1910) and Bhimasenachar (1945). The present authors, using an ultrasonic pulse technique at 3 Mc and 25??C, determined the elastic constants of calcite using the exact equations governing the wave velocities in the single crystal. The results are C11=13.7, C33=8.11, C44=3.50, C12=4.82, C13=5.68, and C14=-2.00, in units of 1011 dyncm2. Independent checks of several of the elastic constants were made employing other directions and polarizations of the wave velocities. With the exception of C13, these values substantially agree with the data of Voigt and Bhimasenachar. ?? 1962 The American Institute of Physics.

  16. Uranyl incorporation in natural calcite.

    SciTech Connect

    Kelly, S. D.; Newville, M. G.; Cheng, L.; Kemner, K. M.; Sutton, S. R.; Fenter, P.; Sturchio, N. C.; Spotl, C.; Environmental Research; Univ. of Chicago; Univ. of Illiois at Chicago; Univ. of Innsbruck

    2003-01-01

    The occurrence of trace amounts of uranyl in natural calcite has posed a long-standing problem in crystal chemistry because of speculation that the size and shape of the uranyl ion may preclude its incorporation in a stable lattice position in calcite. This also defines an important environmental problem because of its bearing on the transport and sequestration of uranyl released from nuclear facilities and uranium mining operations. Calcite is a nearly ubiquitous mineral in soils and groundwater aquifers. X-ray absorption spectroscopy and X-ray fluorescence microprobe studies of uranium in relatively U-rich {approx}13700-year-old calcite from a speleothem in northernmost Italy indicate substitution of uranyl for a calcium and two adjacent carbonate ions in calcite. These new data imply that uranyl has a stable lattice position in natural calcite, indicating that it may be reliably sequestered in calcite over long time scales.

  17. in situ Calcite Precipitation for Contaminant Immobilization

    SciTech Connect

    Yoshiko Fujita; Robert W. Smith

    2009-08-01

    in situ Calcite Precipitation for Contaminant Immobilization Yoshiko Fujita (Yoshiko.fujita@inl.gov) (Idaho National Laboratory, Idaho Falls, Idaho, USA) Robert W. Smith (University of Idaho-Idaho Falls, Idaho Falls, Idaho, USA) Subsurface radionuclide and trace metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE’s greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent trace ions, such as the short-lived radionuclide strontium-90, is co-precipitation in calcite. Calcite, a common mineral in the arid western U.S., can form solid solutions with trace metals. The rate of trace metal incorporation is susceptible to manipulation using either abiotic or biotic means. We have previously demonstrated that increasing the calcite precipitation rate by stimulating the activity of urea hydrolyzing microorganisms can result in significantly enhanced Sr uptake. Urea hydrolysis causes the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity, and also by liberating the reactive cations from the aquifer matrix via exchange reactions involving the ammonium ion derived from urea: H2NCONH2 + 3H2O ? 2NH4+ + HCO3- + OH- urea hydrolysis >X:2Ca + 2NH4+ ? 2>X:NH4 + Ca2+ ion exchange Ca2+ + HCO3- + OH- ? CaCO3(s) + H2O calcite precipitation where >X: is a cation exchange site on the aquifer matrix. This contaminant immobilization approach has several attractive features. Urea hydrolysis is catalyzed by the urease enzyme, which is produced by many indigenous subsurface microorganisms. Addition of foreign microbes is unnecessary. In turn the involvement of the native microbes and the consequent in situ generation of reactive components in the aqueous phase (e.g., carbonate and Ca or Sr) can allow dissemination of the reaction over a larger volume and/or farther away from an amendment injection point, as compared to direct addition of the reactants at

  18. On the complex conductivity signatures of calcite precipitation

    SciTech Connect

    Wu, Yuxin; Hubbard, Susan; Williams, Kenneth Hurst; Ajo-Franklin, Jonathan

    2009-11-01

    Calcite is a mineral phase that frequently precipitates during subsurface remediation or geotechnical engineering processes. This precipitation can lead to changes in the overall behavior of the system, such as flow alternation and soil strengthening. Because induced calcite precipitation is typically quite variable in space and time, monitoring its distribution in the subsurface is a challenge. In this research, we conducted a laboratory column experiment to investigate the potential of complex conductivity as a mean to remotely monitor calcite precipitation. Calcite precipitation was induced in a glass bead (3 mm) packed column through abiotic mixing of CaCl{sub 2} and Na{sub 2}CO{sub 3} solutions. The experiment continued for 12 days with a constant precipitation rate of {approx}0.6 milimole/d. Visual observations and scanning electron microscopy imaging revealed two distinct phases of precipitation: an earlier phase dominated by well distributed, discrete precipitates and a later phase characterized by localized precipitate aggregation and associated pore clogging. Complex conductivity measurements exhibited polarization signals that were characteristic of both phases of calcite precipitation, with the precipitation volume and crystal size controlling the overall polarization magnitude and relaxation time constant. We attribute the observed responses to polarization at the electrical double layer surrounding calcite crystals. Our experiment illustrates the potential of electrical methods for characterizing the distribution and aggregation state of nonconductive minerals like calcite. Advancing our ability to quantify geochemical transformations using such noninvasive methods is expected to facilitate our understanding of complex processes associated with natural subsurface systems as well as processes induced through engineered treatments (such as environmental remediation and carbon sequestration).

  19. Magnesium incorporation in calcite in the presence of organic ligands

    NASA Astrophysics Data System (ADS)

    Mavromatis, Vasileios; Baldermann, Andre; Purgstaller, Bettina; Dietzel, Martin

    2015-04-01

    The formation of authigenic Mg-calcites in marine early diagenetic environments is commonly driven by a bio-induced process, the anaerobic oxidation of methane (AOM), which provides inorganic carbon required for the precipitation of such authigenic carbonates. In such settings the availability of major and/or trace divalent metal cations (Me2+) incorporated in calcite and their aqueous speciation are controlled by the presence of aqueous organic molecules that are produced either as (by-)products of biological activity (i.e. exopolymeric substances) or during degradation of allochthonous organic matter in the sediments. Despite the fact that the presence of aqueous organic ligands strongly affects the growth rates and the mineralogy of precipitating CaCO3 polymorphs, till now no study addresses the role of Me2+-ligand aqueous complexes on the extent of Mg and/or other trace element content of Mg-calcites. In order to shed light on this process, relevant to authigenic calcite formation in organic-rich marine sediments and continental soils, we precipitated calcite in the presence of aqueous Mg and a variety of low molecular weight carboxylic- and aminoacids. Our experimental data indicate that the presence of organic ligands augments significantly the saturation state of calcite in the parent fluid during its precipitation. Moreover, they suggest that the higher the ligand concentration, the higher the obtained distribution coefficient of Mg in calcite. The latter is directly proportional to the ratio of Mg2+/Ca2+ aqueous ions for all ligands used. Hydrogeochemical modelling of the aqueous fluids indicate that the observed correlation can be explained by the stronger complexation of Ca2+ with organic ligands compared to Mg2+, which results in higher availability of Mg2+ vs. Ca2+ aqueous ions. Overall the obtained results suggest that the higher the organic ligand aqueous concentration the higher the Mg content of calcite forming from this fluid. These findings are

  20. Zinc isotope fractionation during adsorption on calcite

    NASA Astrophysics Data System (ADS)

    Dong, S.; Wasylenki, L. E.

    2013-12-01

    Zinc is an important element as a nutrient in the marine biosphere. However, our understanding of its biogeochemical cycling in the oceans is relatively limited. The Zn stable isotope system holds the promise of providing novel insights, since published Zn isotopic values for various natural samples reveal significant fractionations in the marine environment. Surface seawater, basalts, shales, deep-sea clay sediments, sediment trap material, bulk plankton and zooplankton samples, and eolian dust fall within a tight range (δ66/64Zn from -0.1 to 0.5‰), but modern ferromanganese crusts (δ66/64Zn from 0.5 to 1.2‰), as well as carbonates (δ66/64Zn from 0.3 to 1.4‰), are notably enriched in heavy Zn isotopes [1-4]. In this study we seek to constrain the mechanism by which carbonates are enriched in heavier isotopes. In particular, we have conducted experiments to quantify isotope fractionation during adsorption of Zn onto the surfaces of calcite crystals that are in equilibrium with solution. The adsorption experiments were carried out in a series of small-volume batch reactions in a clean laboratory environment, using high-purity reagents and calcite seed crystals. The calcite was equilibrated with the solution prior to addition of Zn at atmospheric CO2 pressure (i.e., in air) for 5 days until a stable pH of 8.3 was reached. Later, a small aliquot of dissolved ZnCl2 was added such that the solution remained undersaturated with respect to hydrozincite. Experimental duration varied among the replicates from 6 to 144 hours, and then all solids and solutions were separated by filtration, purified by ion exchange chromatography, and analyzed by MC-ICP-MS. Zn adsorbed on calcite is isotopically heavier than in the co-existing solutions, with Δ68/66Zncalcite-solution of approximately 0.3‰. The variation of Δ68/66Zncalcite-solution beyond 24 hours is insignificant, so we infer that isotopic equilibrium is reached by this time. Previous work strongly suggests that a

  1. Radiaxial-fibrous calcites of shallow subsurface diagenetic origin

    SciTech Connect

    Mazzullo, S.J.; Bischoff, W.D.; Lobitzer, H.

    1989-03-01

    Radiaxial-fibrous calcites (RFC) in marine carbonates are generally considered syndepositional cements. In Upper Triassic and basal Liassic reef and platform limestones in Austria (Steinplatte complex), however, isopachous RFC is demonstrably a postdepositional diagenetic component that precipitated in shallow-burial phreatic environments during a time of periodic meteoric exposure. Isopachous RFC occurs solely within solution cavities and is interlayered with internal red sediment; discontinuities due to leaching separate sequential generations of RFC in the rocks. Accordingly, one possibility is that the RFC was originally low-magnesium calcite that precipitated in the meteoric phreatic zone during lowstands. Such calcites contain relatively low magnesium concentrations (average 0.87 mole % MgCO/sub 3/) and are /sup 18/O depleted (average - 5.81 /per thousand/ PDB). However, most other RFC cements in the sequence average slightly higher magnesium comparable to crinoidal calcites (1.13 mole % MgCO/sub 3/), are less depleted in /sup 18/O (average - 1.88 /per thousand/ PDB), and are partly dolomitized. Additionally, all the RFC cements are enriched in /sup 13/C to values similar to that of Triassic and Jurassic seawater (+ 2.86 /per thousand/ PDB) and are nonluminescent. Trace element studies indicate alteration of the rocks in partly closed, rock-dominated diagenetic systems. By these facts, the authors favor a precursor high-magnesium calcite mineralogy for the RFC cements, which possibly precipitated during highstands when meteoric pore waters were replaced by marine fluids. Thus, the geochemical trends observed are likely due to variations in the degree of meteoric alteration of high-magnesium calcite RFC rather than to differences in original mineralogy.

  2. What controls boron incorporation into foraminiferal calcite?

    NASA Astrophysics Data System (ADS)

    Allen, K. A.; Hoenisch, B.; Eggins, S. M.; Rosenthal, Y.; Spero, H. J.

    2012-12-01

    In recent years, the ratio of boron to calcium (B/Ca) in foraminiferal calcite has emerged as a new and promising candidate for reconstructing marine carbonate chemistry. In addition to the expected primary control of aqueous borate and bicarbonate concentrations, calcification temperature and aqueous carbonate ion ([CO32-]) appear to exert secondary influences on B/Ca, based on sediment coretop data. In these studies, partitioning of B between seawater and calcite was described by an empirical coefficient, KD, and application of temperature- and [CO32-]-dependent KD calibrations to fossil calcite yielded pCO2 reconstructions that appeared consistent with ice-core records. Identification of controlling parameters from coretop samples alone can be difficult because many environmental parameters covary in the surface ocean (e.g., temperature and [CO32-]). To quantify the different controls on B/Ca, we performed culture experiments with live planktic foraminifers that enabled us to test the respective influences of pH, temperature, salinity, dissolved boron, and dissolved inorganic carbon. Unlike prior studies, we did not discern any influence of temperature on B partitioning. This result prompted us to reconsider KD calibrations and their corresponding pH and pCO2 reconstructions. The new culture calibrations (salinity and carbonate system) allow prediction of coretop planktic foraminiferal B/Ca from surface seawater properties, suggesting that these culture relationships are applicable to specimens growing in the open ocean. Benthic foraminiferal B/Ca, however, is not well-described by planktic culture calibrations. Instead, it is most closely correlated with bottom water carbonate saturation (ΔCO32-), suggesting that planktic and benthic foraminifera may incorporate B via different mechanisms. Here, we discuss existing B/Ca calibrations and KD-based pH reconstructions, and suggest directions for proxy applications and further development.

  3. Aragonite / Calcite seas and the evolution of biomineralization

    NASA Astrophysics Data System (ADS)

    Balthasar, Uwe

    2015-04-01

    The vast majority of marine invertebrate skeletons are composed of the CaCO3 polymorphs aragonite and calcite, yet the influence of seawater composition on the evolution of calcareous skeletal composition is poorly understood. The main theoretical framework in which the evolution of CaCO3 shell mineralogy is assessed is the aragonite-calcite sea hypothesis with conventional thinking suggesting that a threshold in the marine Mg:Ca ratio determines CaCO3 polymorph formation. I present data from CaCO3 precipitation experiments to show that the concept of a distinct threshold is misleading because Mg:Ca ratio and temperature combined result in a Phanerozoic continuum of co-existing aragonite-calcite seas with aragonite-facilitating conditions existing throughout the Phanerozoic in shallow warm-water (>20° C) environments. The stable reservoir of aragonite-favouring conditions in shallow warm water environments potentially explains the trend of increasing occurrences of skeletal aragonite throughout the Phanerozoic, particularly in the context of the 'out of the tropics' hypothesis. By contrast, the most prominent fluctuations with respect to aragonite-calcite sea conditions can be expected to have occurred in mid- to high latitudes.

  4. Removal of organic magnesium in coccolithophore calcite

    NASA Astrophysics Data System (ADS)

    Blanco-Ameijeiras, S.; Lebrato, M.; Stoll, H. M.; Iglesias-Rodriguez, M. D.; Méndez-Vicente, A.; Sett, S.; Müller, M. N.; Oschlies, A.; Schulz, K. G.

    2012-07-01

    Coccolithophore calcite refers to the plates of calcium carbonate (CaCO3) produced by the calcifying phytoplankton, coccolithophores. The empirical study of the elemental composition has a great potential in the development of paleoproxies. However, the difficulties to separate coccolithophore carbonates from organic phases hamper the investigation of coccoliths magnesium to calcium ratios (Mg/Ca) in biogeochemical studies. Magnesium (Mg) is found in organic molecules in the cells at concentrations up to 400 times higher than in inorganically precipitated calcite in present-day seawater. The aim of this study was to optimize a reliable procedure for organic Mg removal from coccolithophore samples to ensure reproducibility in measurements of inorganic Mg in calcite. Two baseline methods comprising organic matter oxidations with (1) bleach and (2) hydrogen peroxide (H2O2) were tested on synthetic pellets, prepared by mixing reagent grade CaCO3 with organic matter from the non-calcifying marine algae Chlorella autotrophica and measured with an ICP-AES (inductively coupled plasma-atomic emission spectrometer). Our results show that treatments with a reductive solution [using hydroxylamine-hydrochloride (NH2OH·HCl + NH4OH)] followed by three consecutive oxidations (using H2O2) yielded the best cleaning efficiencies, removing >99% of organic Mg in 24 h. P/Ca and Fe/Ca were used as indicators for organic contamination in the treated material. The optimized protocol was tested in dried coccolithophore pellets from batch cultures of Emiliania huxleyi, Calcidiscus leptoporus and Gephyrocapsa oceanica. Mg/Ca of treated coccolithophores were 0.151 ± 0.018, 0.220 ± 0.040, and 0.064 ± 0.023 mmol/mol, respectively. Comparison with Mg/Ca literature coccolith values, suggests a tight dependence on modern seawater Mg/Ca, which changes as a consequence of different seawater origins (<10%). The reliable determination of Mg/Ca and Sr/Ca, and the low levels of organic contamination

  5. Diagnosing Abiotic Degradation

    EPA Science Inventory

    The abiotic degradation of chlorinated solvents in ground water can be difficult to diagnose. Under current practice, most of the “evidence” is negative; specifically the apparent disappearance of chlorinated solvents with an accumulation of vinyl chloride, ethane, ethylene, or ...

  6. Calcite formation in soft coral sclerites is determined by a single reactive extracellular protein.

    PubMed

    Rahman, M Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-09-01

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called "calcite and aragonite seas." Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that -OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature. PMID:21768106

  7. Calcite Formation in Soft Coral Sclerites Is Determined by a Single Reactive Extracellular Protein*

    PubMed Central

    Rahman, M. Azizur; Oomori, Tamotsu; Wörheide, Gert

    2011-01-01

    Calcium carbonate exists in two main forms, calcite and aragonite, in the skeletons of marine organisms. The primary mineralogy of marine carbonates has changed over the history of the earth depending on the magnesium/calcium ratio in seawater during the periods of the so-called “calcite and aragonite seas.” Organisms that prefer certain mineralogy appear to flourish when their preferred mineralogy is favored by seawater chemistry. However, this rule is not without exceptions. For example, some octocorals produce calcite despite living in an aragonite sea. Here, we address the unresolved question of how organisms such as soft corals are able to form calcitic skeletal elements in an aragonite sea. We show that an extracellular protein called ECMP-67 isolated from soft coral sclerites induces calcite formation in vitro even when the composition of the calcifying solution favors aragonite precipitation. Structural details of both the surface and the interior of single crystals generated upon interaction with ECMP-67 were analyzed with an apertureless-type near-field IR microscope with high spatial resolution. The results show that this protein is the main determining factor for driving the production of calcite instead of aragonite in the biocalcification process and that –OH, secondary structures (e.g. α-helices and amides), and other necessary chemical groups are distributed over the center of the calcite crystals. Using an atomic force microscope, we also explored how this extracellular protein significantly affects the molecular-scale kinetics of crystal formation. We anticipate that a more thorough investigation of the proteinaceous skeleton content of different calcite-producing marine organisms will reveal similar components that determine the mineralogy of the organisms. These findings have significant implications for future models of the crystal structure of calcite in nature. PMID:21768106

  8. Kinetic and thermodynamic factors controlling the distribution of SO32- and Na+ in calcites and selected aragonites

    USGS Publications Warehouse

    Busenberg, E.; Niel, Plummer L.

    1985-01-01

    Significant amounts of SO42-, Na+, and OH- are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO42-. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na+, but very low concentrations of SO42-. The SO42- content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na+ and SO42- increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO42- beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO42- is the same as that of aragonite. Na+ appears to have very little effect on the solubility product of calcites. The amounts of Na+ and SO42- incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient (D) of SO42- in calcite at 25.0??C and 0.50 molal NaCl is described by the equation D = k0 + k1R where k0 and k1 are constants equal to 6.16 ?? 10-6 and 3.941 ?? 10-6, respectively, and R is the rate of crystal growth of calcite in mg??min-1??g-1 of seed. The data on Na+ are consistent with the hypothesis that a significant amount of Na+ occupies interstitial positions in the calcite structure. The distribution of Na+ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na+ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na+ contents of calcites are not very accurate indicators of environmental salinities. ?? 1985.

  9. Abiotic origin of biopolymers

    NASA Technical Reports Server (NTRS)

    Oro, J.; Stephen-Sherwood, E.

    1976-01-01

    A variety of methods have been investigated in different laboratories for the polymerization of amino acids and nucleotides under abiotic conditions. They include (1) thermal polymerization; (2) direct polymerization of certain amino acid nitriles, amides, or esters; (3) polymerization using polyphosphate esters; (4) polymerization under aqueous or drying conditions at moderate temperatures using a variety of simple catalysts or condensing agents like cyanamide, dicyandiamide, or imidazole; and (5) polymerization under similar mild conditions but employing activated monomers or abiotically synthesized high-energy compounds such as adenosine 5'-triphosphate (ATP). The role and significance of these methods for the synthesis of oligopeptides and oligonucleotides under possible primitive-earth conditions is evaluated. It is concluded that the more recent approach involving chemical processes similar to those used by contemporary living organisms appears to offer a reasonable solution to the prebiotic synthesis of these biopolymers.

  10. Subaerial meteoric calcitization and lithification of high-magnesian calcite muds, Belize

    SciTech Connect

    Mazzullo, S.J.; Bischoff, W.D. )

    1991-03-01

    Holocene ({lt}1000-1500 yrs old) high-magnesian calcite-dominated muddy sediments (1 m thick) on subaerially exposed cays in northern Belize are in the process of being converted to low-magnesian calcite micrite. Mineralogic stabilization and attendant lithification result from interaction of the sediments with meteoric fluids believed to be derived from seasonal upward discharge through subjacent Pleistocene limestones. The initial marine-derived sediments, composed of {gt}85% HMC (and minor skeletal aragonite), consist of mud and associated soritid and miliolid foraminifera both with MgCO{sub 3} content of 11-15 mol%, and isotopic compositions of -1.0 to -2.5{per thousand} PDB (O), 0 to +1.5{per thousand} PDB (C). With depth, lithified LMC crusts appear in the section, and the Mg concentration of the sediments and associated crusts decreases rapidly to 3 mol% or less, with a corresponding isotopic depletion to values approaching -7.0{per thousand} (O) and -5.8{per thousand} (C). Concomitantly there is progressive dissolution of skeletal aragonite in the sediments, reduction of porosity due to cementation by LMC, and in the muds, a decrease in Sr and increase in Mn contents. The resultant petrofabric of these lithified LMC deposits, derived from the alteration of HMC-dominated muds, is characterized by micrite with patches of pore-filling micritic and microsparitic LMC cements. Such a fabric is similar to and can be confused easily with calcitized aragonite-dominated precursor muds, except for the relative rarity in the samples examined of aragonite relicts in component microspar and/or pseudospar.

  11. Dislocation Creep in Magnesium Calcite

    NASA Astrophysics Data System (ADS)

    Xu, L.; Xiao, X.; Evans, B. J.

    2003-12-01

    To investigate the effect of dissolved Mg on plastic deformation of calcite, we performed triaxial deformation experiments on synthetic calcite with varying amount of Mg content. Mixtures of powders of calcite and dolomite were isostatically hot pressed (HIP) at 850° C and 300 MPa confining pressure for different intervals (2 to 20hrs) resulting in homogeneous aggregates of high-magnesium calcite; Mg content varied from 0.07 to 0.17 mol%. Creep tests were performed at differential stresses from 20 to 160 MPa at 700 to 800° C. Grain sizes before and after deformation were determined from the images obtained from scanning electron microscope (SEM) and optical microscope. Grain sizes are in the range of 5 to 20 microns depending on the HIP time, and decrease with increasing magnesium content. Both BSE images and chemical analysis suggest that all dolomite are dissolved and the Mg distribution is homogeneous through the sample, after 2 hrs HIP. At stresses below 40 MPa, the samples deformed in diffusion region (Coble creep), as described previously by Herwegh. The strength decreases with increasing magnesium content, owing to the difference of grain size. At stresses above 80 MPa, the stress exponent is greater than 3, indicating an increased contribution of dislocation creep. The transition between diffusion to dislocation creep occurs at higher stresses for the samples with higher magnesium content and smaller grain size. Preliminary data suggests a slight increase in strength with increasing magnesium content, but more tests are needed to verify this effect. In a few samples, some strain weakening may have been evident. The activation energy in the transition region (at 80 MPa) is ˜200 KJ/mol with no dependence on magnesium content, agreeing with previous measurements of diffusion creep in natural and synthetic marbles.

  12. Nickel and manganese interaction with calcite

    SciTech Connect

    Doner, H; Zavarin, M

    1999-08-09

    Many divalent metal cations sorb to calcite surfaces and incorporate into calcite to varying degrees. Since calcite may sorb trace elements in the environment, the factors controlling metal-calcite interactions are critical to understanding element cycling. The interaction of divalent metal cations with calcite can be critical to toxic metal immobilization, nutrient cycling, interpretation of past redox conditions, tracing fluid flow, for example. Sorption of Ni and Mn on calcite surfaces was studied by Zachara et al.. At any particular pH, the sorption of Mn on calcite was greater than Ni. This was attributed in part to the similarity of divalent Mn and Ca with respect to ion size. Although direct spectroscopic evidence was not available, sorption/desorption results suggested that Mn quickly forms a surface precipitate or solid solution while Ni forms a hydrated surface complex that may incorporate into calcite much more slowly via recrystallization. Because Mn(II) ionic radius is similar to that of Ca(II) (0.80 versus 1.0{angstrom}), and because MnCO{sub 3} has a structure similar to calcite, it is likely that Mn can substitute directly for Ca in the calcite structure. The ionic radius of Ni(II) is significantly smaller (0.69{angstrom}) and Ni(OH){sub 2} precipitation is likely to be favored in most systems. For Ni, direct substitution for Ca is less likely or may require more significant calcite lattice deformation.

  13. Transformation of Mg-bearing amorphous calcium carbonate to Mg-calcite - In situ monitoring

    NASA Astrophysics Data System (ADS)

    Purgstaller, Bettina; Mavromatis, Vasileios; Immenhauser, Adrian; Dietzel, Martin

    2016-02-01

    The formation of Mg-bearing calcite via an amorphous precursor is a poorly understood process that is of relevance for biogenic and abiogenic carbonate precipitation. In order to gain an improved insight on the controls of Mg incorporation in calcite formed via an Mg-rich amorphous calcium carbonate (Mg-ACC) precursor, the precipitation of Mg-ACC and its transformation to Mg-calcite was monitored by in situ Raman spectroscopy. The experiments were performed at 25.0 ± 0.03 °C and pH 8.3 ± 0.1 and revealed two distinct pathways of Mg-calcite formation: (i) At initial aqueous Mg/Ca molar ratios ⩽ 1:6, Mg-calcite formation occurs via direct precipitation from solution. (ii) Conversely, at higher initial Mg/Ca molar ratios, Mg-calcite forms via an intermediate Mg-rich ACC phase. In the latter case, the final product is a calcite with up to 20 mol% Mg. This Mg content is significant higher than that of the Mg-rich ACC precursor phase. Thus, a strong net uptake of Mg ions from the solution into the crystalline precipitate throughout and also subsequent to ACC transformation is postulated. Moreover, the temporal evolution of the geochemical composition of the reactive solution and the Mg-ACC has no significant effect on the obtained "solubility product" of Mg-ACC. The enrichment of Mg in calcite throughout and subsequent to Mg-ACC transformation is likely affected by the high aqueous Mg/Ca ratio and carbonate alkalinity concentrations in the reactive solution. The experimental results have a bearing on the formation mechanism of Mg-rich calcites in marine early diagenetic environments, where high carbonate alkalinity concentrations are the rule rather than the exception, and on the insufficiently investigated inorganic component of biomineralisation pathways in many calcite secreting organisms.

  14. Uranium Isotope Fractionation During Coprecipitation with Aragonite and Calcite

    NASA Astrophysics Data System (ADS)

    Chen, X.; Romaniello, S. J.; Herrmann, A. D.; Wasylenki, L. E.; Anbar, A. D.

    2014-12-01

    Natural variations in the 238U/235U ratio of marine carbonates may provide a useful way of constraining past variations in ocean redox conditions. However, before applying this novel redox proxy, it is essential to explore possible isotopic fractionation during U coprecipitation with aragonite and calcite. We investigated these effects in laboratory experiments. Aragonite and calcite coprecipitation experiments were conducted at pH 8.5±0.1 using a constant addition method [1]. More than 90% of the U was incorporated into the solid phase at the end of each experiment. Samples were purified using UTEVA chemistry and δ238/235U was measured using 233U-236U double-spike MC-ICP-MS with a precision of ±0.10‰ [2]. The aragonite experiment demonstrated a 238U/235U Rayleigh fractionation factor of α=1.00008±0.00002 with the 238U preferentially incorporated. In contrast, the calcite experiment demonstrated no resolvable U isotope fractionation (α=1.00001±0.00003). To determine if U isotopes are affected during the early diagenetic conversion of aragonite to calcite, natural carbonate samples were collected along an aragonite-calcite transition across a single coral head in the Key Largo limestone, and characterized for U concentration and δ238/235U [3]. We found that the mean δ238/235U in aragonite (-0.33±0.07‰ 2se) was slightly heavier than that in calcite (-0.37±0.02‰ 2se). Further work is needed to address the mechanisms leading to differential isotopic fractionation of U(VI) during incorporation into aragonite and calcite. Possible drivers include differences in coordination in the crystal structure or equilibrium isotopic fractionation between various aqueous U(VI) species prior to incorporation. [1] Reeder et al. (2001) GCA 65, 3491-3503. [2] Weyer et al., (2008) GCA 72, 345-359. [3] Gill et al., (2008) GCA 72, 4699-4722.

  15. Isotopic composition of a calcite-cemented layer in the Lower Jurassic Bridport Sands, southern England: Implications for formation of laterally extensive calcite-cemented layers

    SciTech Connect

    Bjoerkum, P.A. ); Walderhaug, O. )

    1993-07-01

    [delta][sup 18]O[sub PDB] and [delta][sup 13]C[sub PDB] values have been measured on 107 calcite cement samples from a laterally extensive (> 3 km) and continuous calcite-cemented layer 0.5 m thick in the coastal exposures of the Lower Jurassic shallow-marine Bridport Sands in Dorset, southern England. The samples were taken from a two-dimensional grid with 10-cm horizontal and vertical spacing between samples and along individual vertical lines across the calcite-cemented layer, [delta][sup 18]O[sub PDB] values vary between [minus]4.8% and [minus]9.2% and decrease radially outwards from points with lateral spacings on the order of 0.5-1 m in the middle of the calcite-cemented layer. The [delta][sup 18]O[sub PDB] values therefore indicate that the calcite-cemented layer was formed by merging of concretions. All [delta][sup 13]C[sub PDB] values measured are in the narrow range [minus]2.2% to [minus]0.5%, which suggests that the dominant source of calcite cement in the layer was biogenic carbonate.

  16. FUNGI AND HYDROCARBONS IN THE MARINE ENVIRONMENT

    EPA Science Inventory

    Hydrocarbons from various sources--anthropogenic pollution, marine seeps, marine algae, atmospheric fallout and terrestrial runoff--enter the ocean daily. These complex hydrocarbon mixtures are dispersed and degraded by abiotic and biogenic processes. Most commonly, bacteria are ...

  17. Mg-calcite dissolution in carbonate sediments: role in ocean acidification

    NASA Astrophysics Data System (ADS)

    Drupp, P. S.; De Carlo, E. H.; Mackenzie, F. T.

    2014-12-01

    An array of porewater wells at two locations on Hawaiian reefs have been utilized to obtain interstitial pore fluid from various depths in permeable sandy sediments. The total alkalinity (AT) and pH (total scale) were measured for each sample (depths 0, 2, 4, 6, 8, 12, 16, 20, 30, 40, and 60 cm) as well as calcium, magnesium, and strontium concentrations. Ca2+ and Mg2+ concentrations co-vary and appear to be directly related to AT and pH. The ratio of the change in calcium and magnesium (ΔCa, ΔMg) between the overlying water column and the porewater indicates that an 18 mol % Mg-calcite phase is dissolving within the sediment column. This could represent the dissolution of coralline algae such as Porolithon or Lithothamnion both of which produce ~18% Mg-calcite skeletons and are present on Hawaiian reefs. The small changes in Mg concentrations from dissolution/precipitation of high Mg-calcites is typically difficult to measure against the high background matrix of seawater and to our knowledge these data represent some of the first magnesium concentrations measured in permeable sediments. Saturation state (Ω) for Mg-calcites was calculated using both sets of stoichiometric solubility products (K) widely accepted in the literature. Depending on the K used, most of the porewater was undersaturated with respect to the high Mg calcites (>12%). Saturation states were determined using an ion activity product (IAP) calculated from the measured values of calcium and magnesium. This produces a more accurate Ω than assuming calcium and magnesium concentrations based on salinity, as is typically done in surface waters. As surface water becomes more corrosive to carbonate minerals due to enhanced ocean acidification through the next century, it is expected that dissolution of both biogenic high Mg-calcites and abiotic Mg-calcite cements will increase, potentially destabilizing reef framework and altering the biogeochemical cycling of carbon in these environments.

  18. Calcite production by coccolithophores in the south east Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Beaufort, L.; Couapel, M.; Buchet, N.; Claustre, H.; Goyet, C.

    2008-08-01

    BIOSOPE cruise covered an oceanographic transect through the centre of the South Pacific Gyre (SPG) from the Marquesas archipelago to the Peru-Chile upwelling (PCU). Water samples from 6 depths in the euphotic zone were collected at 20 stations. The concentrations of suspended calcite particles, coccolithophores cells and detached coccoliths were estimated together with size and weight using an automatic polarizing microscope, a digital camera, and a collection of softwares performing morphometry and pattern recognition. Some of these softwares are new and described here for the first time. The coccolithophores standing stocks were usually low and reached maxima west of the PCU. The coccoliths of Emiliania huxleyi, Gephyrocapsa spp. and Crenalithus spp. (Order Isochrysidales) represented more than 30% of all the suspended calcite particles detected in the size range 0.1 46 μm (22% of PIC in term of calcite weight). These species grew preferentially in the Chlorophyll maximum zone. In the SPG their maximum cell concentrations were recorded between depth of 150 and 200 m, which is unusually deep for these taxa. The weight of coccoliths and coccospheres were correlated to their size. Large and heavy coccoliths and coccospheres were found in regions with relatively high fertility in the Marquises Island and in the PCU. Small and light coccoliths and coccospheres were found west of the PCU. This distribution is strongly related to ocean chemistry in particular to alkalinity and to carbonate ions concentration. The biotic (coccolithophores production) influence on calcification is mainly driven at the local scale (depth) whereas the abiotic (carbonate chemistry) plays its most important role at the regional (horizontal) level. Here 94% of the variability of coccolith and coccosphere weight can be explained by a change in 7 environmental variables.

  19. Stabilities of calcite and aragonite

    USGS Publications Warehouse

    Christ, C.L.; Hostetler, P.B.; Siebert, R.M.

    1974-01-01

    A revaluation of the 25° C activity-product constants of calcite (KC) and aragonite (KA) was made on the basis of the known solubilities of these phases for which the activity of total dissolved calcium was corrected for the presence of the ion pair CaHCO3+ in the aqueous phase. The value of the dissociation constant of CaHCO3+ was taken to be 10-1.225±0.02. This value, combined with values of the analytical concentrations in solutions with partial pressure PCO2 =0.97 atmosphere, leads to KC=l0-8.52±0.04 and KA= 10-8.36±0.04. Based on these K values, standard free energies of formation of calcite and aragonite were calculated to be -270,144±375 and -269,926±375 calories mole-1, (-1,130,282±1,569 and -1,129,370±1,569 joules mole-1), respectively. From the 25°C K values, using appropriate entropy and heat capacity data, values of KC and KA were calculated over the temperature range 0° to 200°C. Possible errors in interpretation of measured pH values and inferred PCO2values and the bearing of these errors on calculations of K values are discussed.

  20. Fluid mediated transformation of aragonitic cuttlebone to calcite

    NASA Astrophysics Data System (ADS)

    Perdikouri, C.; Kasioptas, A.; Putnis, A.

    2009-04-01

    up of interconnected chambers. The aragonite grown during biomineralization of the cuttlebone is interlaced with a β-chitin organic phase that provides the framework for the morphology that is observed. Experiments carried out with the same constant conditions but for different periods of time have revealed the evolution of the transformation to calcite. At shorter reaction times the product was made up of calcite powder and of well preserved aragonite septa, as was confirmed by powder X-ray diffraction. In other words, the vertical pillars appear to react at faster rates than the horizontal septa. It has been reported by Florek et al. 2008 that the septa contain higher quantities of β-chitin. The aim of this study is the investigation of these observations and the determination of the effect of the organic component on the kinetics of the aragonite to calcite transformation. Florek M., Fornal E., Gómez-Romero P., Zieba E., Paszkowicz W., Lekki J.,Nowak J., Kuczumow A. Materials Science and Engineering C, In Press (2008) Perdikouri C., Kasioptas A., Putnis C.V., Putnis A. Mineralogical Magazine 72, 111-114 (2008) Putnis A., Putnis C.V. Solid State Chemistry 180, 1783-1786 (2007) Topor N. D., Tolokonnikova L. I., Kadenatsi B. M. Journal of Thermal Analysis 20, 169-174 (1981) Vongsavat V., Winotai P., Meejoo S. Nuclear Instruments and Methods in Physics Research B 243, 167-173 (2006) Wolf G., Lerchner J., Schmidt H., Gamsjäger H., Königsberger E., Schmidt P. Journal of Thermal Analysis 46, 353-359 (1996) Yoshioka S., Ohde S., Kitano Y., Kanamori N. Marine Chemistry 18, 35-48 (1986)

  1. Influence of temperature on the composition of magnesian calcite overgrowths precipitated from sea water

    SciTech Connect

    Mucci, A.

    1987-07-01

    A constant disequilibrium technique was used to determine the composition of magnesian calcite overgrowths precipitated on pure calcite seeds from artificial sea water at 5, 25 and 40/sup 0/C. The amount of magnesium incorporated in the overgrowths at a given temperature is independent of the precipitation rate over a wide range of saturation states and is believed to correspond to a composition in true equilibrium with sea water. The distribution coefficient of magnesium, D/sub Mg/sup 2 +///sup c/, in the magnesian calcite overgrowths increases almost linearly with temperature, being 0.0121 +- 0.0013 at 5/sup 0/C, 0.0172 +- 0.0022 at 25/sup 0/C, and 0.0271 +- 0.0013 at 40/sup 0/C. These values apply only to magnesian calcites precipitated from standard composition sea water, since a previous study has shown D/sub Mg/sup 2 +///sup c/ to be a function of the (Mg/sup 2 +/)(Ca/sup 2 +/) ratio in the parent solution. Results of this study are compared with values reported previously by other workers, and with the compositional distribution of naturally occurring magnesian calcite cements and ooids found in sea water. It appears that variations in temperature are not sufficient to account for the compositional variability of naturally occurring inorganic marine magnesian calcite cements.

  2. Abiotic Buildup of Ozone

    NASA Astrophysics Data System (ADS)

    Domagal-Goldman, S. D.; Meadows, V. S.

    2010-10-01

    Two of the best biosignature gases for remote detection of life on extrasolar planets are oxygen (O2) and its photochemical byproduct, ozone (O3). The main reason for their prominence as biosignatures is that large abiotic fluxes of O2 and O3 are not considered sustainable on geological and astronomical timescales. We show here how buildup of O3 can occur on planets orbiting M stars, even in the absence of the large biological fluxes. This is possible because the destruction of O2 and O3 is driven by UV photochemistry. This chemistry is much slower on planets around these stars, due to the smaller incident UV flux. Because the destruction of these gases is slower, O3 can build up to detectable levels even if the O3 source is small. We will present atmospheric profiles of these gases for planets around AD Leo (an M dwarf) as well as spectra that show the implications for missions such as Darwin and the Terrestrial Planet Finder (TPF).

  3. Calcite saturation in eastern UK rivers.

    PubMed

    Neal, Colin

    2002-01-23

    Calcite saturation in eastern UK rivers is assessed in relation to the potential kinetic inhibition of calcite precipitation. Two well established inhibitors are considered: soluble reactive phosphorus (SRP, i.e. inorganic monomeric phosphorus); and dissolved organic carbon (DOC). The rivers show a range of calcite saturation levels from approximately 1hundredth to approximately 100-fold. The greatest range occurs for the northernmost river considered, the Tweed, where the waters range from highly unsaturated to highly oversaturated. The lowest range occurs for the most southerly rivers (the Great Ouse and the Thames) where the waters are consistently oversaturated with respect to calcite. The contrasting patterns relate to a greater diversity of water quality within the northern regions. Thus, during the winter, the main waters are derived from the upland areas with acidic soils and low weathering rates. During the summer baseflow periods, groundwater inputs are more important and high photosynthesis results in particularly high pHs and calcite oversaturation. In contrast, for the southern rivers, the main source of water during both the summer baseflow and the winter highflow periods comes from calcium carbonate rich aquifer sources. Statistical analysis of pH vs. the logarithm of the calcite saturation index for each river indicates strong linear features with individual gradients of approximately 1. This linearity results from an autocorrelation (the logarithm of the saturation index is calculated from the pH) and this indicates that calcite solubility controls are not operative in any of the rivers examined. A comparison of calcite saturation levels and SRP and DOC concentrations show a pattern inconsistent with kinetic hindrance, although some structure is observed, probably due to the mixing reactions between point and diffuse sources of water with contrasting chemistry. PMID:11846076

  4. Do organic ligands affect calcite dissolution rates?

    NASA Astrophysics Data System (ADS)

    Oelkers, Eric H.; Golubev, Sergey V.; Pokrovsky, Oleg S.; Bénézeth, Pascale

    2011-04-01

    Steady state Iceland-spar calcite dissolution rates were measured at 25 °C in aqueous solutions containing 0.1 M NaCl and up to 0.05 M dissolved bicarbonate at pH from 7.9 to 9.1 in the presence of 13 distinct dissolved organic ligands in mixed-flow reactors. The organic ligands considered in this study include those most likely to be present in either (1) aquifers at the conditions pertinent to CO 2 sequestration or (2) soil/early diagenetic environments: acetate, phthalate, citrate, EDTA 4-, succinate, D-glucosaminate, L-glutamate, D-gluconate, 2,4-dihydroxybenzoate, 3,4-dihydroxybenzoate, fumarate, malonate, and gallate. Results show that the presence of <0.05 mol/kg of these organic anions changes calcite dissolution rates by less than a factor of 2.5 with the exception of citrate and EDTA 4-. The presence of 0.05 mol/kg citrate and EDTA 4- increases calcite dissolution rates by as much as a factor of 35 and 500, respectively, compared to rates in organic anion-free solutions. Further calcite dissolution experiments were performed in the presence of organic polymers similar to bacterial exudates, cell exopolysaccharides, and analogs of microbial cell envelopes: alginate, lichen extract, humic acid, pectin, and gum xanthan. In no case did the presence of <100 ppm of these organics change calcite dissolution rates by more than a factor of 2.5. Results obtained in this study suggest that the presence of aqueous organic anions negligibly affects calcite forward dissolution rates in most natural environments. Some effect on calcite reactivity may be observed, however, by the presence of organic anions if they change substantially the chemical affinity of the fluid with respect to calcite.

  5. Diffusion of Ca and Mg in Calcite

    SciTech Connect

    Cygan, R.T.; Fisler, D.K.

    1999-02-10

    The self-diffusion of Ca and the tracer diffusion of Mg in calcite have been experimentally measured using isotopic tracers of {sup 25}Mg and {sup 44}Ca. Natural single crystals of calcite were coated with a thermally-sputtered oxide thin film and then annealed in a CO{sub 2} gas at one atmosphere total pressure and temperatures from 550 to 800 C. Diffusion coefficient values were derived from the depth profiles obtained by ion microprobe analysis. The resultant activation energies for Mg tracer diffusion and Ca self-diffusion are respectively: E{sub a}(Mg) = 284 {+-} 74 kJ/mol and E{sub a}(Ca) = 271 {+-} 80 kJ/mol. For the temperature ranges in these experiments, the diffusion of Mg is faster than Ca. The results are generally consistent in magnitude with divalent cation diffusion rates obtained in previous studies and provide a means of interpreting the thermal histories of carbonate minerals, the mechanism of dolomitization, and other diffusion-controlled processes. The results indicate that cation diffusion in calcite is relatively slow and cations are the rate-limiting diffusing species for the deformation of calcite and carbonate rocks. Application of the calcite-dolomite geothermometer to metamorphic assemblages will be constrained by cation diffusion and cooling rates. The direct measurement of Mg tracer diffusion in calcite indicates that dolomitization is unlikely to be accomplished by Mg diffusion in the solid state but by a recrystallization process.

  6. Nickel adsorption on chalk and calcite

    NASA Astrophysics Data System (ADS)

    Belova, D. A.; Lakshtanov, L. Z.; Carneiro, J. F.; Stipp, S. L. S.

    2014-12-01

    Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite and chalk and pH ranging from 7.7 to 8.8, explored the influence of initial concentration and the amount and type of sorbent on Ni uptake. Adsorption increases with increased surface area and pH. A surface complexation model describes the data well. Stability constants for the Ni surface complex are log KNi = - 1.12 on calcite and log KNi = - 0.43 and - 0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts of polysaccharides and clay nanoparticles on the chalk surface.

  7. Nickel adsorption on chalk and calcite.

    PubMed

    Belova, D A; Lakshtanov, L Z; Carneiro, J F; Stipp, S L S

    2014-12-01

    Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite and chalk and pH ranging from 7.7 to 8.8, explored the influence of initial concentration and the amount and type of sorbent on Ni uptake. Adsorption increases with increased surface area and pH. A surface complexation model describes the data well. Stability constants for the Ni surface complex are log KNi=-1.12 on calcite and log KNi=-0.43 and -0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts of polysaccharides and clay nanoparticles on the chalk surface. PMID:25300061

  8. Tropical Silurian Paleotemperatures from Clumped Isotope Analysis of Coexisting Dolomite and Calcite

    NASA Astrophysics Data System (ADS)

    Winkelstern, I. Z.; Lohmann, K. C.

    2013-12-01

    In many instances, pervasive diagenetic alteration of original material prevents the use of quantitative climate proxies on Paleozoic or older rocks. As an inherently diagenetic phase, dolomite may provide a more resilient paleotemperature resource. The Δ47 carbonate clumped isotope thermometer has been shown to be an accurate paleothermometer and, in a limited way, has been shown to be applicable to dolomites. The shallow water carbonates of the Pipe Creek Jr. Reef in central Indiana offer an opportunity to test the viability of the technique in ancient dolomite. After formation in the late Silurian, a sea level drop resulted in a diagenetic sequence of meteoric phreatic alteration of marine cement and biotic components, which included precipitation of dolomite cements inter-grown within the meteoric phreatic calcite cement. This was post-dated by a coarse void filling calcite spar formed at burial temperatures of ~100°C (based on fluid inclusion analysis). Preliminary analyses of coexisting dolomite and calcite suggest that near-surface temperatures are preserved in dolomites despite having experienced elevated thermal diagenetic effects.. In contrast, co-existing early-formed calcites exhibit resetting of earth surface temperatures to elevated values. Δ47 measurements in dolomites yield temperatures around 30°C using the Guo et al., (2009) theoretical calibration. This contrasts with analyses of early (original) and late (hydrothermal) calcites, which record temperatures greater than ~80°C using the Δ47-calcite calibration of Dennis and Schrag (2010). These data support the hypothesis that dolomite can be a more resilient paleotemperature proxy relative to calcite in deep-time studies. Temperatures from dolomites compare reasonably with other late Silurian paleoclimate studies, and offer insight into regional-scale paleoclimate.

  9. Controls on variation of calcite content in arkose beds of the Sangre de Cristo Formation, (Pennsylvanian-Permian) Colorado

    SciTech Connect

    Wysong, J.R.; Bain, R.J. . Dept. of Geology)

    1994-04-01

    Arkosic conglomerates and sandstones of the Pennsylvanian-Permian Sangre de Cristo Formation of south-central Colorado were deposited on alluvial plains and nearshore marine shelves adjacent to the highlands of the Ancestral Rocky Mountains. Thin limestone units occur locally, however calcite content of arkoses varies independent of these limestones. The thinly bedded to laminated arkoses contain abundant detrital orthoclase and plagioclase feldspars, micas and quartz. Authigenic clay (kaolinite) and calcite occur both as void-filling cement and replacement of feldspars. Fine-grained arkoses possess more calcite and authigenic clay than their coarse-grained counterparts. Calcite occurs as plagioclase replacement in fine-grained samples whereas in coarse-grained rocks it fills interstitial voids. Calcite content in fine-grained arkoses is low where laminae are preserved and increases with the presence of bioturbation. Diagenetic processes responsible for calcite and clay content of these arkoses were controlled by several factors including original sediment texture, composition, and grain orientation. Plagioclase has been altered to produce calcite and clay more than orthoclase. Permeability of coarse-grained rocks was higher and resulted in primarily void-filling cement. In fine-grained arkoses, permeability was less and water remained in contact with grains longer thereby altering plagioclase. Aligned mica grains of laminae retarded flow and impeded diagenetic alteration whereas bioturbation disrupted grain orientation thereby enhancing diagenesis.

  10. Low-magnesium calcite produced by coralline algae in seawater of Late Cretaceous composition.

    PubMed

    Stanley, Steven M; Ries, Justin B; Hardie, Lawrence A

    2002-11-26

    Shifts in the MgCa ratio of seawater driven by changes in midocean ridge spreading rates have produced oscillations in the mineralogy of nonskeletal carbonate precipitates from seawater on time scales of 10(8) years. Since Cambrian time, skeletal mineralogies of anatomically simple organisms functioning as major reef builders or producers of shallow marine limestones have generally corresponded in mineral composition to nonskeletal precipitates. Here we report on experiments showing that the ambient MgCa ratio actually governs the skeletal mineralogy of some simple organisms. In modern seas, coralline algae produce skeletons of high-Mg calcite (>4 mol % MgCO(3)). We grew three species of these algae in artificial seawaters having three different MgCa ratios. All of the species incorporated amounts of Mg into their skeletons in proportion to the ambient MgCa ratio, mimicking the pattern for nonskeletal precipitation. Thus, the algae calcified as if they were simply inducing precipitation from seawater through their consumption of CO(2) for photosynthesis; presumably organic templates specify the calcite crystal structure of their skeletons. In artificial seawater with the low MgCa ratio of Late Cretaceous seas, the algae in our experiments produced low-Mg calcite (<4 mol % MgCO(3)), the carbonate mineral formed by nonskeletal precipitation in those ancient seas. Our results suggest that many taxa that produce high-Mg calcite today produced low-Mg calcite in Late Cretaceous seas. PMID:12399549

  11. Calcite dissolution in two deep eutrophic lakes

    SciTech Connect

    Ramisch, F.; Dittrich, M.; Mattenberger, C.; Wehrli, B.; Wueest, A.

    1999-10-01

    The calcium cycle, in particular carbonate dissolution, was analyzed in two deep eutrophic lakes, Lago di Lugano (288 m maximum depth) and Sempachersee (87 m) located in Switzerland. A box model approach was used to calculate calcite dissolution in the water column and at the sediment-water interface based on various lake monitoring data such as sediment traps, sediment cores, water and pore-water interface based on various lake monitoring data such as sediment traps, sediment cores, water and pore-water analysis. A model for stationary conditions allowing the calculation of calcite dissolution in the water column for a given particle size distribution was developed. The relative values of the simulated flux were consistent with sediment trap observations. The best fit of the dissolution rate constant of sinking calcite in Lago di Lugano was on the same order of magnitude (3 {center{underscore}dot} 10{sup {minus}10} kg{sup 1/3} s{sup {minus}1}) as published laboratory values for this surface controlled process. Both lakes show a similar specific calcite precipitation rate of 170 g Ca m{sup {minus}2} a{sup {minus}1}. The diffusive flux across the sediment-water interface amounts to about 15 and 10% of total calcite precipitation in Sempachersee and Lago di Lugano, respectively. However, 61% of the precipitated calcite is dissolved in the water column of Lago di Lugano compared to only 13% in Sempachersee. These results point towards the importance of grain size distributions and settling times in stratified deep waters as the two most important factors determining calcite retention in sediments of hard water lakes.

  12. Abiotic Nitrous Oxide Production in Natural and Artificial Seawater

    NASA Astrophysics Data System (ADS)

    Ochoa, H.; Stanton, C. L.; Cavazos, A. R.; Ostrom, N. E.; Glass, J. B.

    2014-12-01

    The ocean contributes approximately one third of global sources of nitrous oxide (N2O) to the atmosphere. While nitrification is thought to be the dominant pathway for marine N2O production, mechanisms remain unresolved. Previous studies have carried the implicit assumption that marine N2O originates directly from enzymatic sources. However, abiotic production of N2O is possible via chemical reactions between nitrogenous intermediates and redox active trace metals in seawater. In this study, we investigated N2O production and isotopic composition in treatments with and without added hydroxylamine (NH2OH) and nitric oxide (NO), intermediates in microbial oxidation of ammonia to nitrite, and Fe(III). Addition of substrates to sterile artificial seawater was compared with filtered and unfiltered seawater from Sapelo Island, coastal Georgia, USA. N2O production was observed immediately after addition of Fe(III) in the presence of NH2OH at pH 8 in sterile artificial seawater. Highest N2O production was observed in the presence of Fe(III), NO, and NH2OH. The isotopomer site preference of abiotically produced N2O was consistent with previous studies (31 ± 2 ‰). Higher abiotic N2O production was observed in sterile artificial seawater (salinity: 35 ppt) than filtered Sapelo Island seawater (salinity: 25 ppt) whereas diluted sterile artificial seawater (18 ppt) showed lowest N2O production, suggesting that higher salinity promotes enhanced abiotic N2O production. Addition of Fe(III) to unfiltered Sapelo Island seawater stimulated N2O production. The presence of ammonia-oxidizing archaea (AOA), which lack known N2O producing enzymes, in Sapelo Island seawater was confirmed by successful amplification of the archaeal amoA gene, whereas ammonia-oxidizing bacteria (AOB), which contain N2O-producing enzymes were undetected. Given the few Fe-containing proteins present in AOA, it is likely that Fe(III) addition promoted N2O production via an abiotic vs. enzymatic N2O mechanism

  13. Calibration of the calcite-water oxygen-isotope geothermometer at Devils Hole, Nevada, a natural laboratory

    USGS Publications Warehouse

    Coplen, T.B.

    2007-01-01

    The ??18O of ground water (-13.54 ?? 0.05 ???) and inorganically precipitated Holocene vein calcite (+14.56 ?? 0.03 ???) from Devils Hole cave #2 in southcentral Nevada yield an oxygen isotopic fractionation factor between calcite and water at 33.7 ??C of 1.02849 ?? 0.00013 (1000 ln ??calcite-water = 28.09 ?? 0.13). Using the commonly accepted value of ???(??calcite-water)/???T of -0.00020 K-1, this corresponds to a 1000 ln ??calcite-water value at 25 ??C of 29.80, which differs substantially from the current accepted value of 28.3. Use of previously published oxygen isotopic fractionation factors would yield a calcite precipitation temperature in Devils Hole that is 8 ??C lower than the measured ground water temperature. Alternatively, previously published fractionation factors would yield a ??18O of water, from which the calcite precipitated, that is too negative by 1.5 ??? using a temperature of 33.7 ??C. Several lines of evidence indicate that the geochemical environment of Devils Hole has been remarkably constant for at least 10 ka. Accordingly, a re-evaluation of calcite-water oxygen isotopic fractionation factor may be in order. Assuming the Devils Hole oxygen isotopic value of ??calcite-water represents thermodynamic equilibrium, many marine carbonates are precipitated with a ??18O value that is too low, apparently due to a kinetic isotopic fractionation that preferentially enriches 16O in the solid carbonate over 18O, feigning oxygen isotopic equilibrium.

  14. The Alkaline Dissolution Rate of Calcite.

    PubMed

    Colombani, Jean

    2016-07-01

    Due to the widespread presence of calcium carbonate on Earth, several geochemical systems, among which is the global CO2 cycle, are controlled to a large extent by the dissolution and precipitation of this mineral. For this reason, the dissolution of calcite has been thoroughly investigated for decades. Despite this intense activity, a consensual value of the dissolution rate of calcite has not been found yet. We show here that the inconsistency between the reported values stems mainly from the variability of the chemical and hydrodynamic conditions of measurement. The spreading of the values, when compared in identical conditions, is much less than expected and is interpreted in terms of sample surface topography. This analysis leads us to propose benchmark values of the alkaline dissolution rate of calcite compatible with all the published values, and a method to use them in various chemical and hydrodynamic contexts. PMID:27282839

  15. Abiotic Organic Chemistry in Hydrothermal Systems.

    NASA Astrophysics Data System (ADS)

    Simoneit, B. R.; Rushdi, A. I.

    2004-12-01

    Abiotic organic chemistry in hydrothermal systems is of interest to biologists, geochemists and oceanographers. This chemistry consists of thermal alteration of organic matter and minor prebiotic synthesis of organic compounds. Thermal alteration has been extensively documented to yield petroleum and heavy bitumen products from contemporary organic detritus. Carbon dioxide, carbon monoxide, ammonia and sulfur species have been used as precursors in prebiotic synthesis experiments to organic compounds. These inorganic species are common components of hot spring gases and marine hydrothermal systems. It is of interest to further test their reactivities in reductive aqueous thermolysis. We have synthesized organic compounds (lipids) in aqueous solutions of oxalic acid, and with carbon disulfide or ammonium bicarbonate at temperatures from 175-400° C. The synthetic lipids from oxalic acid solutions consisted of n-alkanols, n-alkanoic acids, n-alkyl formates, n-alkanones, n-alkenes and n-alkanes, typically to C30 with no carbon number preferences. The products from CS2 in acidic aqueous solutions yielded cyclic thioalkanes, alkyl polysulfides, and thioesters with other numerous minor compounds. The synthesis products from oxalic acid and ammonium bicarbonate solutions were homologous series of n-alkyl amides, n-alkyl amines, n-alkanes and n-alkanoic acids, also to C30 with no carbon number predominance. Condensation (dehydration) reactions also occur under elevated temperatures in aqueous medium as tested by model reactions to form amide, ester and nitrile bonds. It is concluded that the abiotic formation of aliphatic lipids, condensation products (amides, esters, nitriles, and CS2 derivatives (alkyl polysulfides, cyclic polysulfides) is possible under hydrothermal conditions and warrants further studies.

  16. Interaction of alcohols with the calcite surface.

    PubMed

    Bovet, N; Yang, M; Javadi, M S; Stipp, S L S

    2015-02-01

    A clearer understanding of calcite interactions with organic molecules would contribute to a range of fields including harnessing the secrets of biomineralisation where organisms produce hard parts, increasing oil production from spent reservoirs, remediating contaminated soils and drinking water aquifers and improving manufacturing methods for industrial products such as pigments, soft abrasives, building materials and optical devices. Biomineralisation by some species of blue green algae produces beautifully elaborate platelets of calcite where the individual crystals are of nanometer scale. Controlling their growth requires complex polysaccharides. Polysaccharide activity depends on the functionality of OH groups, so to simplify the system in order to get closer to a molecular level understanding, we investigated the interaction of OH from a suite of alcohols with clean, freshly cleaved calcite surfaces. X-ray photoelectron spectroscopy (XPS) provided binding energies and revealed the extent of surface coverage. Molecular dynamics (MD) simulations supplemented with information about molecule ordering, orientation and packing density. The results show that all alcohols studied bond with the calcite surface through the OH group, with their carbon chains sticking away in a standing-up orientation. Alcohol molecules are closely packed and form a well-ordered monolayer on the surface. PMID:25533590

  17. Carbon isotope fractionation in synthetic magnesian calcite

    NASA Astrophysics Data System (ADS)

    Jimenez-Lopez, Concepción; Romanek, Christopher S.; Caballero, Emilia

    2006-03-01

    Mg-calcite was precipitated at 25 °C in closed system, free-drift experiments, from solutions containing NaHCO 3, CaCl 2 and MgCl 2. The carbon stable isotope composition of bulk solid and solution were analyzed from subsamples collected during time course experiments of 24 h duration. Considering only the Mg-content and δ 13C values for the bulk solid, the carbon isotope fractionation factor for the Mg-calcite-HCO 3(aq)- system (as 103lnα) increased with average mol percentage of Mg (X Mg) in the solid at a rate of (0.024 ± 0.011) per mol% MgCO 3. Extrapolation of this relationship to the pure calcite end member yields a value of 0.82 ± 0.09, which is similar to published values for the calcite-HCO 3(aq)- system. Although 103lnα did not vary for precipitation rates that ranged from 10 3.21 to 10 4.60 μmol m -2 h -1, it was not possible to hold Mg-content of the solid constant, so kinetic effect on 10 3 ln α could not be evaluated from these experiments.

  18. Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

    ERIC Educational Resources Information Center

    Wilkinson, Bruce H.

    1982-01-01

    Discusses causes of cyclicity in cratonic carbonate sequences and evidence for and potential significance of postulated primary calcite sediment components in past Paleozoic seas, outlining problems, focusing on models explaining existing data, and identifying background. Future sedimentary geologists will need to address these and related areas…

  19. Trigonal dendritic calcite crystals forming from hot spring waters at Waikite, North Island, New Zealand

    SciTech Connect

    Jones, B.; Renault, R.W.; Rosen, M.R.

    2000-05-01

    Amorphous silica and calcite form the deposits in the vent and on the discharge apron of Waikite Spring 100 (WS-100), which is located in the Waikite Geothermal area on North Island, New Zealand. These precipitates formed from spring water that has a temperature of >90 C and a pH of 8.1--8.8. The opaline silica is restricted to areas around the vent where cooling and evaporation of the spring water triggered precipitation. The calcite deposits in the spring vent and on the discharge apron are formed of large (up to 15 cm long) asymmetrical dendrite crystals that are characterized by multiple levels of branching. Branches grew preferentially from the downflow side of their parent branch. All branches have a trigonal transverse cross section except in areas where competition for growth space induced merger of neighboring crystals. The primary branches of the dendrite crystals are (sub)perpendicular to the substrate even in areas where the discharge apron slopes at a high angle (up to 80{degree}). On the steeper parts of the discharge apron, the plate-like primary branches form the floors of the small terrace pools whereas their distal edges form the rims of the pools. Growth of these dendrite crystals is attributed to abiotic processes. High levels of saturation with respect to calcite were caused by rapid CO{sub 2} degassing of the sheets of spring water that flowed down the steep discharge apron. Calcite crystals with different crystal morphologies characterize other springs near this spring. The variation in crystal morphologies from spring to spring is attributed to different levels of saturation that are related to the initial PCO{sub 2} of the spring water upon discharge and the rate of CO{sub 2} degassing at each spring.

  20. Oxygen isotope fractionation in synthetic magnesian calcite

    NASA Astrophysics Data System (ADS)

    Jiménez-López, Concepción; Romanek, Christopher S.; Huertas, F. Javier; Ohmoto, Hiroshi; Caballero, Emilia

    2004-08-01

    Mg-bearing calcite was precipitated at 25°C in closed system free-drift experiments from solutions containing NaHCO 3, CaCl 2 and MgCl 2. The chemical and isotope composition of the solution and precipitate were investigated during time course experiments of 24-h duration. Monohydrocalcite and calcite precipitated early in the experiments (<8 h), while Mg-calcite was the predominant precipitate (>95%) thereafter. Solid collected at the end of the experiments displayed compositional zoning from pure calcite in crystal cores to up to 23 mol% MgCO 3 in the rims. Smaller excursions in Mg were superimposed on this chemical record, which is characteristic of oscillatory zoning observed in synthetic and natural solid-solution carbonates of differing solubility. Magnesium also altered the predominant morphology of crystals over time from the {104} to {100} and {110} growth forms. The oxygen isotope fractionation factor for the magnesian-calcite-water system (as 10 3lnα Mg-cl-H 2O ) displayed a strong dependence on the mol% MgCO 3 in the solid phase, but quantification of the relationship was difficult due to the heterogeneous nature of the precipitate. Considering only the Mg-content and δ 18O values for the bulk solid, 10 3lnα Mg-cl-H 2O increased at a rate of 0.17 ± 0.02 per mol% MgCO 3; this value is a factor of three higher than the single previous estimate (Tarutani T., Clayton R.N., and Mayeda T. K. (1969) The effect of polymorphims and magnesium substitution on oxygen isotope fractionation between calcium carbonate and water. Geochim. Cosmochim. Acta 33, 987-996). Nevertheless, extrapolation of our relationship to the pure calcite end member yielded a value of 27.9 ± 0.02, which is similar in magnitude to published values for the calcite-water system. Although no kinetic effect was observed on 10 3lnα Mg-cl-H 2O for precipitation rates that ranged from 10 3.21 to 10 4.60 μmol · m -2 · h -1, it was impossible to disentangle the potential effect(s) of

  1. Alkaline flocculation of Phaeodactylum tricornutum induced by brucite and calcite

    DOE PAGESBeta

    Vandamme, Dries; Pohl, Philip I.; Beuckels, Annelies; Foubert, Imogen; Brady, Patrick Vane; Muylaert, Koenraad; Hewson, John C.

    2015-08-20

    Alkaline flocculation holds great potential as a low-cost harvesting method for marine microalgae biomass production. Alkaline flocculation is induced by an increase in pH and is related to precipitation of calcium and magnesium salts. In this study, we used the diatom Phaeodactylum tricornutum as model organism to study alkaline flocculation of marine microalgae cultured in seawater medium. Flocculation started when pH was increased to 10 and flocculation efficiency reached 90% when pH was 10.5, which was consistent with precipitation modeling for brucite or Mg(OH)2. Compared to freshwater species, more magnesium is needed to achieve flocculation (>7.5 mM). Zeta potential measurementsmore » suggest that brucite precipitation caused flocculation by charge neutralization. When calcium concentration was 12.5 mM, flocculation was also observed at a pH of 10. Furthermore, zeta potential remained negative up to pH 11.5, suggesting that precipitated calcite caused flocculation by a sweeping coagulation mechanism.« less

  2. Brine induced low-Magnesium calcite formation at cold seeps

    NASA Astrophysics Data System (ADS)

    Feng, Dong; Roberts, Harry; Joye, Samantha; Heydari, Ezat

    2013-04-01

    Low-Mg calcite (LMC; < 5 mol% Mg), commonly observed during time intervals of "calcite seas," since the beginning of the Paleozoic Era, is a good indicator of low Mg/Ca ratio (< 2) in seawater. Calcite seas were coincident with times of active seawater-basalt interactions along mid-ocean ridges at high temperatures, which extract Mg from seawater and release Ca to it. In the modern aragonite sea, most carbonate minerals precipitate at the seafloor, including deposits from cold seep environments are primarily either aragonite or high-Mg calcite (HMC). Here, we report the finding of non-skeletal LMC from cold seeps in Alaminos Canyon block 601 (AC 601), 2200 m below the sea surface on northern Gulf of Mexico (GOM) continental slope. Low-Mg calcite usually represents the only carbonate mineral in the studied samples. Dominant allochems in these seep carbonates are peloids, grain aggregates, pelagic forams, and fragments of mollusks and echinoids. The limestone is heavily cemented. The observed cements include micrite, microspar, mosaic, bladed, fan, and needle cements. The dissolution of grains and cements was observed. Not only originally aragonitic mollusks shells, but also carbonate cement have been dissolved. The aerobic oxidation of reduced chemical species such as methane and H2S is responsible for an increase in pCO2 and a decrease of pH, leading to local carbonate dissolution. The occurrence of oxic conditions is confirmed by the presence of negative Ce anomalies of the carbonates. Further, we report on analyses showing that the ambient porewater Mg/Ca ratio actually governs the carbonate mineralogy. The occurrence of LMC may be attributed to the brine fluids, which is relatively Mg-depleted (Mg/Ca mole ratio is below 0.7) compared to pore fluid of the subsurface sediments from the reference site (Mg/Ca mole ratio is above 4.1) that usually produce HMC. The 87Sr/86Sr values of LMC (mean = 0.708001, sd = 0.000034, n=2) are significantly lower than that of the

  3. Carbon export and transfer to depth across the Southern Ocean Great Calcite Belt

    NASA Astrophysics Data System (ADS)

    Rosengard, S. Z.; Lam, P. J.; Balch, W. M.; Auro, M. E.; Pike, S.; Drapeau, D.; Bowler, B.

    2015-02-01

    Sequestration of carbon by the marine biological pump depends on the processes that alter, remineralize and preserve particulate organic carbon (POC) during transit to the deep ocean. Here, we present data collected from the Great Calcite Belt, a calcite-rich band across the Southern Ocean surface, to compare the transformation of POC in the euphotic and mesopelagic zones of the water column. The 234Th-derived export fluxes and size-fractionated concentrations of POC, particulate inorganic carbon (PIC), and biogenic silica (BSi) were measured from the upper 1000 m of 27 stations across the Atlantic and Indian sectors of the Great Calcite Belt. POC export out of the euphotic zone was correlated with BSi export. PIC export was not, but did correlate positively with POC flux transfer efficiency. Moreover, regions of high BSi concentrations, which corresponded to regions with proportionally larger particles, exhibited higher attenuation of >51 μm POC concentrations in the mesopelagic zone. The interplay among POC size partitioning, mineral composition and POC attenuation suggests a more fundamental driver of POC transfer through both depth regimes in the Great Calcite Belt. In particular, we argue that diatom-dominated communities produce large and labile POC aggregates, which generate high export fluxes but also drive more remineralization in the mesopelagic zone. We observe the opposite in communities with smaller calcifying phytoplankton, such as coccolithophores. We hypothesize that these differences are influenced by inherent differences in the lability of POC exported by different phytoplankton communities.

  4. Carbon export and transfer to depth across the Southern Ocean Great Calcite Belt

    NASA Astrophysics Data System (ADS)

    Rosengard, S. Z.; Lam, P. J.; Balch, W. M.; Auro, M. E.; Pike, S.; Drapeau, D.; Bowler, B.

    2015-07-01

    Sequestration of carbon by the marine biological pump depends on the processes that alter, remineralize, and preserve particulate organic carbon (POC) during transit to the deep ocean. Here, we present data collected from the Great Calcite Belt, a calcite-rich band across the Southern Ocean surface, to compare the transformation of POC in the euphotic and mesopelagic zones of the water column. The 234Th-derived export fluxes and size-fractionated concentrations of POC, particulate inorganic carbon (PIC), and biogenic silica (BSi) were measured from the upper 1000 m of 27 stations across the Atlantic and Indian sectors of the Great Calcite Belt. POC export out of the euphotic zone was correlated with BSi export. PIC export was not, but did correlate positively with POC flux transfer efficiency. Moreover, regions of high BSi concentrations, which corresponded to regions with proportionally larger particles, exhibited higher attenuation of > 51 μm POC concentrations in the mesopelagic zone. The interplay among POC size partitioning, mineral composition, and POC attenuation suggests a more fundamental driver of POC transfer through both depth regimes in the Great Calcite Belt. In particular, we argue that diatom-rich communities produce large and labile POC aggregates, which not only generate high export fluxes but also drive more remineralization in the mesopelagic zone. We observe the opposite in communities with smaller calcifying phytoplankton, such as coccolithophores. We hypothesize that these differences are influenced by inherent differences in the lability of POC exported by different phytoplankton communities.

  5. Dissolution Kinetics of Biogenic Magnesian Calcites

    NASA Astrophysics Data System (ADS)

    Thompson, R.; Guidry, M.; Mackenzie, F. T.; De Carlo, E. H.

    2014-12-01

    Ocean acidification (OA) is a serious concern for the health of calcifying ecosystems in the near future. During the past century, surface ocean pH has decreased by ~0.1 pH units, and is expected to decrease further by 0.3-0.4 pH units by the end of this century. The process of OA will likely result in both decreased calcification rates and increased rates of carbonate mineral dissolution, particularly involving the magnesian calcite (Mg-calcite) calcifiers found in shallow-water reef and other carbonate environments. Many Mg-calcite compositions are the most soluble of the carbonate phases commonly found in reef environments (often comprising much of the cementation and structure within a reef), and are therefore potentially the most susceptible to dissolution processes associated with OA. However, the dissolution kinetics of these phases is poorly known, limiting our ability to understand their behavior in nature. Laboratory experiments designed to investigate the mechanisms and dissolution rates of biogenic Mg-calcite mineral phases in distilled water and seawater over a range of CO2 and T conditions were conducted employing both batch and fluidized-bed reactor systems and using a variety of cleaned and annealed biogenic Mg-calcite phases. Our initial results have shown that the dissolution rate at 298 K and a pCO2 of ~350 ppm of the crustose coralline alga Amphiroa rigida (~20 mol% MgCO3) in seawater undersaturated with respect to this phase is 3.6 μmol g-1 hr-1, nearly 50% greater than that under similar conditions for aragonite. This rate and the derived experimental rate law are consistent with the preliminary findings of Walter and Morse (1985). Additional kinetic (and also solubility) data will be presented for the following species: Chiton tuberculatus (~0-4 mol% MgCO3); Echinometra mathei and/or Lytechinus variegatus (~8-12 mol% MgCO3); Homotrema rubrum (12-16 mol% MgCO3); and Lithothamnion sp. (~18-24 mol% MgCO3). Quantification of the rates of

  6. Calcite growth-rate inhibition by fulvic acid and magnesium ion—Possible influence on biogenic calcite formation

    USGS Publications Warehouse

    Reddy, Michael M.

    2012-01-01

    Increases in ocean surface water dissolved carbon dioxide (CO2) concentrations retard biocalcification by reducing calcite supersaturation (Ωc). Reduced calcification rates may influence growth-rate dependent magnesium ion (Mg) incorporation into biogenic calcite modifying the use of calcifying organisms as paleoclimate proxies. Fulvic acid (FA) at biocalcification sites may further reduce calcification rates. Calcite growth-rate inhibition by FA and Mg, two common constituents of seawater and soil water involved in the formation of biogenic calcite, was measured separately and in combination under identical, highly reproducible experimental conditions. Calcite growth rates (pH=8.5 and Ωc=4.5) are reduced by FA (0.5 mg/L) to 47% and by Mg (10−4 M) to 38%, compared to control experiments containing no added growth-rate inhibitor. Humic acid (HA) is twice as effective a calcite growth-rate inhibitor as FA. Calcite growth rate in the presence of both FA (0.5 mg/L) and Mg (10−4 M) is reduced to 5% of the control rate. Mg inhibits calcite growth rates by substitution for calcium ion at the growth site. In contrast, FA inhibits calcite growth rates by binding multiple carboxylate groups on the calcite surface. FA and Mg together have an increased affinity for the calcite growth sites reducing calcite growth rates.

  7. Frictional behavior of talc-calcite mixtures

    NASA Astrophysics Data System (ADS)

    Giorgetti, C.; Carpenter, B. M.; Collettini, C.

    2015-09-01

    Faults involving phyllosilicates appear weak when compared to the laboratory-derived strength of most crustal rocks. Among phyllosilicates, talc, with very low friction, is one of the weakest minerals involved in various tectonic settings. As the presence of talc has been recently documented in carbonate faults, we performed laboratory friction experiments to better constrain how various amounts of talc could alter these fault's frictional properties. We used a biaxial apparatus to systematically shear different mixtures of talc and calcite as powdered gouge at room temperature, normal stresses up to 50 MPa and under different pore fluid saturated conditions, i.e., CaCO3-equilibrated water and silicone oil. We performed slide-hold-slide tests, 1-3000 s, to measure the amount of frictional healing and velocity-stepping tests, 0.1-1000 µm/s, to evaluate frictional stability. We then analyzed microstructures developed during our experiments. Our results show that with the addition of 20% talc the calcite gouge undergoes a 70% reduction in steady state frictional strength, a complete reduction of frictional healing and a transition from velocity-weakening to velocity-strengthening behavior. Microstructural analysis shows that with increasing talc content, deformation mechanisms evolve from distributed cataclastic flow of the granular calcite to localized sliding along talc-rich shear planes, resulting in a fully interconnected network of talc lamellae from 20% talc onward. Our observations indicate that in faults where talc and calcite are present, a low concentration of talc is enough to strongly modify the gouge's frictional properties and specifically to weaken the fault, reduce its ability to sustain future stress drops, and stabilize slip.

  8. Origin of micro-rhombic calcite matrix within Cretaceous reservoir rock, West Stuart City Trend, Texas

    NASA Astrophysics Data System (ADS)

    Perkins, Ronald D.

    1989-07-01

    Cores from four wells from the West Stuart City Trend in La Salle and Webb Counties, Texas, were analyzed to define depositional and diagenetic facies and to determine factors controlling porosity distribution. In all, 1187 ft (362 m) of core and 220 thin sections were examined in detail and supplemented by SEM analyses of fractured surfaces and plastic casts of pore systems. A comparison of lithofacies and ecologic facies to permeability and porosity values compiled from core data revealed that zones with permeabilities greater than 0.1 md and porosities of at least 6% were associated with rudistid grainstones cemented by isopachous, submarine cement and packstones with a finely crystalline rhombic calcite matrix. Isotopic and trace element analyses of both isopachous submarine cements and micro-rhombic matrix suggest a common origin. The precursor to the micro-rhombic calcite is believed to have been peloidal, high-magnesian calcite. This internal marine sediment may be analogous to the peloidal fabrics that have been reported from Holocene and Pleistocene carbonates. Diagenetic equilibration of both submarine cements and peloidal infill is believed to have occurred during burial either in marine pore waters at elevated temperatures or in restricted flow, phreatic freshwaters.

  9. Origin of epigenetic calcite in coal from Antarctica and Ohio based on isotope compositions of oxygen, carbon and strontium

    USGS Publications Warehouse

    Faure, G.; Botoman, G.

    1984-01-01

    Isotopic compositions of oxygen, carbon and strontium of calcite cleats in coal seams of southern Victoria Land, Antarctica, and Tuscarawas County, Ohio, contain a record of the conditions a the time of their formation. The Antarctic calcites (?? 18O(SMOW) = +9.14 to +11.82%0) were deposited from waters enriched in 16O whose isotopic composition was consistent with that of meteoric precipitation at low temperature and high latitude. The carbon of the calcite cleats (?? 13C(PDB) = -15.6 to -16.9%0) was derived in part from the coal (?? 13C(PDB) = -23.5 to -26.7%0) as carbon dioxide and by oxidation of methane or other hydrocarbon gases. The strontium ( 87Sr 86Sr = 0.71318-0.72392) originated primarily from altered feldspar grains in the sandstones of the Beacon Supergroup. Calcite cleats in the Kittaning No. 6 coal seam of Ohio (?? 18O(SMOW) = +26.04 to +27.79%0) were deposited from waters that had previously exchanged oxygen, possibly with marine carbonate at depth. The carbon (?? 13C(PDB) = 0.9 to +2.4%0) is enriched in 13C even though that cleats were deposited in coal that is highly enriched in 12C and apparently originated from marine carbonates. Strontium in the cleats ( Sr 87 0.71182-0.71260) is not of marine origin but contains varying amounts of radiogenic 87Sr presumably derived from detrital Rb-bearing minerals in the adjacent sedimentary rocks. The results of this study suggest that calcite cleats in coal of southern Victoria Land, Antarctica, were deposited after the start of glaciation in Cenozoic time and that those in Ohio precipitated from formation waters derived from the underlying marine carbonate rocks, probably in the recent geologic past. ?? 1984.

  10. Biogenic calcite granules--are brachiopods different?

    PubMed

    Pérez-Huerta, Alberto; Dauphin, Yannicke; Cusack, Maggie

    2013-01-01

    Brachiopods are still one of the least studied groups of organisms in terms of biomineralization despite recent studies indicating the presence of highly complex biomineral structures, particularly in taxa with calcitic shells. Here, we analyze the nanostructure of calcite biominerals, fibers and semi-nacre tablets, in brachiopod shells by high-resolution scanning electron microscopy (SEM) and atomic force microscopy (AFM). We demonstrate that basic mechanisms of carbonate biomineralization are not uniform within the phylum, with semi-nacre tablets composed of spherical aggregates with sub-rounded granules and fibers composed of large, triangular or rod-like particles composed of small sub-rounded granules (40-60 nm). Additionally, proteinaceous envelopes surrounding calcite fibers have been shown for the first time to have a dual function: providing a micro-environment in which granules are produced and acting as the organic template for particle orientation as fiber components. In summary, these new findings in brachiopod shells reveal a complex and distinctive style of biomineralization among carbonate-producing organisms. PMID:23026148

  11. Calcite cements in the modern Floridan aquifer

    SciTech Connect

    Hammes, U.; Budd, D.A. )

    1991-03-01

    Calcite cements in the Ocala (Eocene) and Suwannee (Oligocene) formations, southwestern Floridan aquifer have been studied to determine updip to downdip variations in cement chemistries and cathodoluminescence within a modern regional confined aquifer. Interparticle, intraparticle, and fracture-fill cements comprise 5-15% of the limestones. Five different calcite cement morphologies are distinguishable and occur throughout the aquifer: (1) circumgranular microspar, (2) fine- to medium-crystalline rhombs, (3) medium-crystalline syntaxial overgrowths on echinoderms, (4) fine-crystalline pore-filling mosaics, and (5) micrite. Type 5 occurs only below former exposure surfaces. Volumetrically, type 3 is the most important and type 4 is the least. Cathodoluminescence observations reveal only nonluminescent cements updip and an increase in luminescent zones and luminescent intensity downdip. Updip nonluminescent cements have very low Fe and Mn concentrations, but high Mg and Sr concentrations. These relations are interpreted to reflect oxidizing conditions and high rock/water interaction. Fe and Mn concentrations increase and Sr and Mg contents decrease downdip. These trends are interpreted to reflect reducing conditions, cross-formational flow, and slower rock/water interaction. Downdip cathodoluminescence zonations consist of a broad nonluminescent zone, followed by a thin bright orange zone, and then a dull luminescence zone. These geochemical and luminescent patterns along a regional flow line in the confined Floridan aquifer have many similarities to those observed in calcite cements described from ancient aquifers.

  12. Observations and Experiments on Carbonate Secretion in "Calcite Seas": Why Massive Chalk Deposits Formed in Late Cretaceous Time

    NASA Astrophysics Data System (ADS)

    Stanley, S. M.; Ries, J. B.; Hardie, L. A.

    2003-12-01

    It is now well-established that oscillations in the Mg/Ca ratio of seawater, driven by changes in spreading rates along mid-ocean ridges, have determined the mineralogy of nonskeletal marine carbonate precipitation throughout earth history. Low-Mg calcite has formed at Mg/Ca ratios < 2 ("calcite seas"), and aragonite has formed at ratios > 2 ("aragonite seas"). High-Mg calcite (mole % Mg > 4) has formed by itself at Mg/Ca ratios of 1-2, and along with aragonite at ratios above 2. We report here on experiments rooted in the paleontological observation that the carbonate mineralogy of major reef-building and sediment-producing organisms has tended to correspond to that of nonskeletal precipitates throughout Phanerozoic time. Earlier experiments showed that, with changes in the Mg/Ca ratio of ambient seawater, the Mg content of calcite in coralline algae varies like that of nonskeletal calcite precipitates. New experiments reveal that many kinds of calcite-secreting marine animals exhibit similar mineralogical trends, but with varying partition coefficients. Other experiments address the effects of seawater chemistry on productivity. One can predict that secretion of calcium carbonate will facilitate growth of algae because it releases carbon dioxide that can be used in photosynthesis. Indeed, we found that Halimeda, a major producer of aragonite sediment in present-day aragonite seas, grows less rapidly when living at ambient Mg/Ca ratios below the modern marine level of 5.2. Conversely, calcareous nannoplankton, which secrete calcite, become much more productive when ambient Mg/Ca ratios are below unity and associated concentrations of Ca are high. Such conditons characterized the extreme calcite seas of Late Cretaceous time, when nannoplankton formed massive chalk deposits throughout the world. Thus, we attribute the formation of these deposits, which gave the Cretaceous Period its name, to seawater chemistry. Calcareous nannoplankton in modern seas are adapted to

  13. Environmental controls for the precipitation of different fibrous calcite cement fabrics

    NASA Astrophysics Data System (ADS)

    Ritter, Ann-Christine; Wiethoff, Felix; Neuser, Rolf D.; Richter, Detlev K.; Immenhauser, Adrian

    2016-04-01

    Abiogenic calcite cements are widely used as climate archives. They can yield information on environmental change and climate dynamics at the time when the sediment was lithified in a (marine) diagenetic environment. Radiaxial-fibrous (RFC) and fascicular-optic fibrous (FOFC) calcite cements are two very common and similar pore-filling cement fabrics in Palaeozoic and Mesozoic carbonate rocks (Richter et al., 2011) and in Holocene Mg-calcitic speleothems (Richter et al., 2015). Both fabrics are characterised by distinct crystallographic properties. Current research has shown that these fabrics are often underexplored and that a careful combination of conservative and innovative proxies allows for a better applicability of these carbonate archives to paleoenvironmental reconstructions (Ritter et al., 2015). A main uncertainty in this context is that it is still poorly understood which parameters lead to the formation of either RFC or FOFC and if differential crystallographic parameters affect proxy data from these fabrics. This study aims at a better understanding of the environmental factors that may control either RFC or FOFC precipitation. Therefore, suitable samples (a stalagmite and a Triassic marine cement succession), each with clearly differentiable layers of RFC and FOFC, were identified and analysed in high detail using a multi-proxy approach. Detailed thin section and cathodoluminescence analysis of the samples allowed for a precise identification of layers consisting solely of either RFC or FOFC. Isotopic (δ13C, δ18O) as well as trace elemental compositions have been determined and the comparison of data obtained from these different carbonate archives sheds light on changes in environmental parameters during RFC or FOFC precipitation. References: Richter, D.K., et al., 2011. Radiaxial-fibrous calcites: A new look at an old problem. Sedimentary Geology, 239, 26-36 Richter, D.K., et al., 2015. Radiaxial-fibrous and fascicular-optic Mg-calcitic cave

  14. Genetic diversity in pollen abiotic stress tolerance

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Genetic diversity in reproductive abiotic stress tolerance has been investigated by cotton breeders throughout the public and private sectors. The primary focus of these studies has been the evaluation of abiotic stress responses during the development of the flower prior to anthesis. Sterility in...

  15. Genetic Diversity in Pollen Abiotic Stress Tolerance

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Genetic diversity in reproductive abiotic stress tolerance has been investigated by cotton breeders throughout the public and private sectors. The primary focus of these studies has been the evaluation of abiotic stress responses during the development of the flower prior to anthesis. Sterility in...

  16. Spectroscopic characterization of natural calcite minerals

    NASA Astrophysics Data System (ADS)

    Gunasekaran, S.; Anbalagan, G.

    2007-11-01

    The FT-IR, FT-Raman, NMR spectral data of ten different limestone samples have been compared. FT-IR and FT-Raman spectral data show that calcium carbonate in limestone, principally in the form of calcite, as identified by its main absorption bands at 1426, 1092, 876 and 712 cm -1. The sharp diffractions at the d-spacings, 3.0348, 1.9166 and 1.8796 confirm the presence of calcite structure and the calculated lattice parameters are: a = 4.9781 Å, c = 17.1188 Å. The range of 13C chemical shifts for different limestone samples is very small, varying from 198.38 to 198.42 ppm. The observed chemical shifts are consistent with the identical C-O bonding in different limestone samples. 27Al MAS NMR spectra of the samples exhibit a central line at 1 ppm and another line at 60 ppm corresponding to octahedral and tetrahedral Al ions, respectively. The five component resonances were observed in 29Si MAS NMR spectrum of limestone and these resonances were assigned to Si (4 Al), Si (3 Al), Si (2 Al), Si (1 Al) and Si (0 Al) from low field to high field.

  17. A Reacidification Model for Acidified Lakes Neutralized With Calcite

    NASA Astrophysics Data System (ADS)

    Sverdrup, Harald; Warfvinge, Per

    1985-09-01

    In lake liming operations in Sweden, acidified lakes are reclaimed by neutralization with calcite powder. The amount added is intended to neutralize the water column as well as to delay the reacidification. The reacidification of limed lakes is dependent on the dilution of the dissolved calcium carbonate with time and, for a limited period of time, the dissolution of calcite from the lake sediments. Calcite on the lake bottom will, in addition to being covered by sedimentation, become inactivated by precipitates of humus and clay minerals clogging the calcite surfaces. A model has been developed to calculate the reacidification of a limed lake which includes the following mechanisms: (1) the dissolution of calcite and a subsequent neutralization of acid water, (2) owing to the increase inpH value, occurrence of precipitation of humus and dissolved metals onto the calcite surface and inhibition of the dissolution of calcite (3) reversible sorbtion of calcium from the water column by sediments not covered with calcite, and (4) diffusive transport through a boundary bottom layer to the water column. In a first approach the lake was modeled as a continuously stirred tank. The equations were derived from a mass balance and the dissolution kinetics for calcite to describe the long-term development ofpH, alkalinity, and calcium concentration in the lake. The differential equations describing the mechanisms were solved with the help of a computer code. The model accurately describes the reacidification and the mass balances observed in several limed lakes.

  18. Sorption and desorption of arsenate and arsenite on calcite

    NASA Astrophysics Data System (ADS)

    Sø, Helle U.; Postma, Dieke; Jakobsen, Rasmus; Larsen, Flemming

    2008-12-01

    The adsorption and desorption of arsenate (As(V)) and arsenite (As(III)) on calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic concentrations were kept low (<33 μM) to avoid surface precipitation. The results show that little or no arsenite sorbs on calcite within 24 h at an initial As concentration of 0.67 μM. In contrast, arsenate sorbs readily and quickly on calcite. Likewise, desorption of arsenate from calcite is fast and complete within hours, indicating that arsenate is not readily incorporated into the calcite crystal lattice. The degree of arsenate sorption depends on the solution chemistry. Sorption increases with decreasing alkalinity, indicating a competition for sorption sites between arsenate and (bi)carbonate. pH also affects the sorption behavior, likely in response to changes in arsenate speciation or protonation/deprotonation of the adsorbing arsenate ion. Finally, sorption is influenced by the ionic strength, possibly due to electrostatic effects. The sorption of arsenate on calcite was modeled successfully using a surface complexation model comprising strong and weak sites. In the model, the adsorbing arsenate species were HAsO4- and CaHAsO40. The model was able to correctly predict the adsorption of arsenate in the wide range of calcite-equilibrated solutions used in the batch experiments and to describe the non-linear shape of the sorption isotherms. Extrapolation of the experimental results to calcite bearing aquifers suggests a large variability in the mobility of arsenic. Under reduced conditions, arsenite, which does not sorb on calcite, will dominate and, hence, As will be highly mobile. In contrast, when conditions are oxidizing, arsenate is the predominant species and, because arsenate adsorbs strongly on calcite, As mobility will be significantly retarded. The estimated

  19. Uranium isotope fractionation during coprecipitation with aragonite and calcite

    NASA Astrophysics Data System (ADS)

    Chen, Xinming; Romaniello, Stephen J.; Herrmann, Achim D.; Wasylenki, Laura E.; Anbar, Ariel D.

    2016-09-01

    Natural variations in 238U/235U of marine calcium carbonates might provide a useful way of constraining redox conditions of ancient environments. In order to evaluate the reliability of this proxy, we conducted aragonite and calcite coprecipitation experiments at pH ∼7.5 and ∼8.5 to study possible U isotope fractionation during incorporation into these minerals. Small but significant U isotope fractionation was observed in aragonite experiments at pH ∼8.5, with heavier U isotopes preferentially enriched in the solid phase. 238U/235U of dissolved U in these experiments can be fit by Rayleigh fractionation curves with fractionation factors of 1.00007 + 0.00002/-0.00003, 1.00005 ± 0.00001, and 1.00003 ± 0.00001. In contrast, no resolvable U isotope fractionation was observed in an aragonite experiment at pH ∼7.5 or in calcite experiments at either pH. Equilibrium isotope fractionation among different aqueous U species is the most likely explanation for these findings. Certain charged U species are preferentially incorporated into calcium carbonate relative to the uncharged U species Ca2UO2(CO3)3(aq), which we hypothesize has a lighter equilibrium U isotope composition than most of the charged species. According to this hypothesis, the magnitude of U isotope fractionation should scale with the fraction of dissolved U that is present as Ca2UO2(CO3)3(aq). This expectation is confirmed by equilibrium speciation modeling of our experiments. Theoretical calculation of the U isotope fractionation factors between different U species could further test this hypothesis and our proposed fractionation mechanism. These findings suggest that U isotope variations in ancient carbonates could be controlled by changes in the aqueous speciation of seawater U, particularly changes in seawater pH, PCO2 , Ca2+, or Mg2+ concentrations. In general, these effects are likely to be small (<0.13‰), but are nevertheless potentially significant because of the small natural range of

  20. Neptunium(V) adsorption to calcite.

    PubMed

    Heberling, Frank; Brendebach, Boris; Bosbach, Dirk

    2008-12-12

    The migration behavior of the actinyl ions U(VI)O2(2+), Np(V)O2+ and Pu(V,VI)O2(+,2+) in the geosphere is to a large extend controlled by sorption reactions (inner- or outer-sphere adsorption, ion-exchange, coprecipitation/structural incorporation) with minerals. Here NpO2+ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0-9.4) and concentration (0.4 microM-40 microM) conditions. pH is adjusted by variation of CO2 partial pressure. Adsorption is found to be pH dependent with maximal adsorption at pH 8.3 decreasing with increasing and decreasing pH. pH dependence of adsorption decreases with increasing Np(V) concentration. EXAFS data of neptunyl adsorbed to calcite and neptunyl in the supernatant shows differences in the Np(V)-O-yl distance, 1.85+/-0.01 angstroms for the adsorbed and 1.82+/-0.01 angstroms for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45+/-0.02 angstroms. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46+/-0.01 angstroms. An additional feature in the adsorbed species' R-space spectrum can be related to carbonate neighbours, 3 to 6 carbon backscatterers (C-eq) at 3.05+/-0.03 angstroms and 3 to 6 oxygen backscatterers (O-eq2) at 3.31+/-0.02 angstroms. The differences in the Np(V)-O-yl distance and the C-eq and O-eq2 backscatterers which are only present for the adsorbed species indicate inner-sphere bonding of the adsorbed neptunyl species to the calcite surface. Experiments on adsorption kinetics indicate that after a fast surface adsorption process a continuous slow uptake occurs which may be explained by incorporation via surface dissolution and reprecipitation processes. This is also indicated by the part irreversibility of the adsorption as shown by increased KD values after desorption compared to adsorption. PMID:18973965

  1. A Microkinetic Model of Calcite Step Growth.

    PubMed

    Andersson, M P; Dobberschütz, S; Sand, K K; Tobler, D J; De Yoreo, J J; Stipp, S L S

    2016-09-01

    In spite of decades of research, mineral growth models based on ion attachment and detachment rates fail to predict behavior beyond a narrow range of conditions. Here we present a microkinetic model that accurately reproduces calcite growth over a very wide range of published experimental data for solution composition, saturation index, pH and impurities. We demonstrate that polynuclear complexes play a central role in mineral growth at high supersaturation and that a classical complexation model is sufficient to reproduce measured rates. Dehydration of the attaching species, not the mineral surface, is rate limiting. Density functional theory supports our conclusions. The model provides new insights into the molecular mechanisms of mineral growth that control biomineralization, mineral scaling and industrial material synthesis. PMID:27532505

  2. Dissolution of coccolithophorid calcite by microzooplankton and copepod grazing

    NASA Astrophysics Data System (ADS)

    Antia, A. N.; Suffrian, K.; Holste, L.; Müller, M. N.; Nejstgaard, J. C.; Simonelli, P.; Carotenuto, Y.; Putzeys, S.

    2008-01-01

    Independent of the ongoing acidification of surface seawater, the majority of the calcium carbonate produced in the pelagial is dissolved by natural processes above the lysocline. We investigate to what extent grazing and passage of coccolithophorids through the guts of copepods and the food vacuoles of microzooplankton contribute to calcite dissolution. In laboratory experiments where the coccolithophorid Emiliania huxleyi was fed to the rotifer Brachionus plicatilis, the heterotrophic flagellate Oxyrrhis marina and the copepod Acartia tonsa, calcite dissolution rates of 45-55%, 37-53% and 5-22% of ingested calcite were found. We ascribe higher loss rates in microzooplankton food vacuoles as compared to copepod guts to the strongly acidic digestion and the individual packaging of algal cells. In further experiments, specific rates of calcification and calcite dissolution were also measured in natural populations during the PeECE III mesocosm study under differing ambient pCO2 concentrations. Microzooplankton grazing accounted for between 27 and 70% of the dynamic calcite stock being lost per day, with no measurable effect of CO2 treatment. These measured calcite dissolution rates indicate that dissolution of calcite in the guts of microzooplankton and copepods can account for the calcite losses calculated for the global ocean using budget and model estimates.

  3. Control of carbonate alkalinity on Mg incorporation in calcite: Insights on the occurrence of high Mg calcites in diagenetic environments

    NASA Astrophysics Data System (ADS)

    Purgstaller, Bettina; Mavromatis, Vasileios; Dietzel, Martin

    2015-04-01

    High Mg calcites (HMC), with up to 25 mol % of Mg, are common features in early diagenetic environments and are frequently associated with bio-induced anaerobic oxidation of methane (AOM). Such archives hold valuable information about the biogeochemical processes occurring in sedimentary environments in the geological past. Despite the frequency AOM-induced HMC observed in marine diagenetic settings and their potential role in dolomitization, only a minor number of experimental studies has been devoted on deciphering their formation conditions. Thus, in order to improve our understanding on the formation mechanism of HMC induced by elevated carbonate ion concentrations, we precipitated HMC by computer controlled titration of a (Mg,Ca)Cl2 solution at different Mg/Ca ratios into a NaHCO3 solution under precisely defined physicochemical conditions (T = 25.00 ±0.03°C; pH = 8.3 ±0.1). The formation of carbonates was monitored at a high temporal resolution using in situ Raman spectroscopy as well as by continuous sampling and analyzing of precipitates and reactive solutions. We identified two distinct mechanisms of HMC formation. In solutions with molar Mg/Ca ratios ≤ 1/8 calcium carbonate was precipitated as crystalline phases directly from homogeneous solution. In contrast, higher Mg/Ca ratios induced the formation of Mg-rich ACC (up to 10 mol % of Mg), which was subsequently transformed to HMC with up 20 mol % of Mg. Our experimental results highlight that the finally formed HMC has a higher Mg content than the ACC precursor phase. Considering experimental data for Mg containing ACC transformation to crystalline calcium carbonate from literature, the continuous enrichment of Mg in the precipitate throughout transformation of amorphous to crystalline CaCO3 most likely occurs due to the high carbonate alkalinity (DIC about 0.1 M) of our reactive solutions. The Mg incorporation into calcite lattice seems to be favored by intensive supply of carbonate ions as

  4. Abiotic ammonification and gross ammonium photoproduction in the upwelling system off central Chile (36° S)

    NASA Astrophysics Data System (ADS)

    Rain-Franco, A.; Muñoz, C.; Fernandez, C.

    2012-12-01

    We investigated the production of ammonium via photodegradation of dissolved organic matter (DOM) in the coastal upwelling system off central Chile (36° S). Photoammonification experiments were carried out using exudates obtained from representative diatom species (Chaetoceros muelleri and Thalassiosira minuscule) and natural marine DOM under simulated solar radiation conditions. Additionally, we evaluated the use of photoproduced ammonium by natural microbial communities and separated ammonium oxidizing archaea and bacteria by using GC-7 as an inhibitor of the archaeal community. We found photoammonification operating at two levels: via the transformation of DOM by UV radiation (abiotic ammonification) and via the simultaneous occurrence of abiotic phototransformation and biological remineralization of DOM into NH4+ (referred as gross photoproduction of NH4+). The maximum rates of abiotic ammonification reached 0.057 μmol L-1 h-1, whereas maximum rates of gross photoproduction reached 0.746 μmol L-1 h-1. Our results also suggest that ammonium oxidizing archaea could dominate the biotic remineralization induced by photodegradation of organic matter and consequently play an important role in the local N cycle. Abiotic ammonium photoproduction in coastal upwelling systems could support between 7 and 50% of the spring-summer phytoplankton NH4+ demand. Surprisingly, gross ammonium photoproduction (remineralization induced by abiotic ammonification) might support 50 to 180% of spring-summer phytoplankton NH4+ assimilation.

  5. Calcite-accumulating large sulfur bacteria of the genus Achromatium in Sippewissett Salt Marsh.

    PubMed

    Salman, Verena; Yang, Tingting; Berben, Tom; Klein, Frieder; Angert, Esther; Teske, Andreas

    2015-11-01

    Large sulfur bacteria of the genus Achromatium are exceptional among Bacteria and Archaea as they can accumulate high amounts of internal calcite. Although known for more than 100 years, they remain uncultured, and only freshwater populations have been studied so far. Here we investigate a marine population of calcite-accumulating bacteria that is primarily found at the sediment surface of tide pools in a salt marsh, where high sulfide concentrations meet oversaturated oxygen concentrations during the day. Dynamic sulfur cycling by phototrophic sulfide-oxidizing and heterotrophic sulfate-reducing bacteria co-occurring in these sediments creates a highly sulfidic environment that we propose induces behavioral differences in the Achromatium population compared with reported migration patterns in a low-sulfide environment. Fluctuating intracellular calcium/sulfur ratios at different depths and times of day indicate a biochemical reaction of the salt marsh Achromatium to diurnal changes in sedimentary redox conditions. We correlate this calcite dynamic with new evidence regarding its formation/mobilization and suggest general implications as well as a possible biological function of calcite accumulation in large bacteria in the sediment environment that is governed by gradients. Finally, we propose a new taxonomic classification of the salt marsh Achromatium based on their adaptation to a significantly different habitat than their freshwater relatives, as indicated by their differential behavior as well as phylogenetic distance on 16S ribosomal RNA gene level. In future studies, whole-genome characterization and additional ecophysiological factors could further support the distinctive position of salt marsh Achromatium. PMID:25909974

  6. No extreme bipolar glaciation during the main Eocene calcite compensation shift.

    PubMed

    Edgar, Kirsty M; Wilson, Paul A; Sexton, Philip F; Suganuma, Yusuke

    2007-08-23

    Major ice sheets were permanently established on Antarctica approximately 34 million years ago, close to the Eocene/Oligocene boundary, at the same time as a permanent deepening of the calcite compensation depth in the world's oceans. Until recently, it was thought that Northern Hemisphere glaciation began much later, between 11 and 5 million years ago. This view has been challenged, however, by records of ice rafting at high northern latitudes during the Eocene epoch and by estimates of global ice volume that exceed the storage capacity of Antarctica at the same time as a temporary deepening of the calcite compensation depth approximately 41.6 million years ago. Here we test the hypothesis that large ice sheets were present in both hemispheres approximately 41.6 million years ago using marine sediment records of oxygen and carbon isotope values and of calcium carbonate content from the equatorial Atlantic Ocean. These records allow, at most, an ice budget that can easily be accommodated on Antarctica, indicating that large ice sheets were not present in the Northern Hemisphere. The records also reveal a brief interval shortly before the temporary deepening of the calcite compensation depth during which the calcite compensation depth shoaled, ocean temperatures increased and carbon isotope values decreased in the equatorial Atlantic. The nature of these changes around 41.6 million years ago implies common links, in terms of carbon cycling, with events at the Eocene/Oligocene boundary and with the 'hyperthermals' of the Early Eocene climate optimum. Our findings help to resolve the apparent discrepancy between the geological records of Northern Hemisphere glaciation and model results that indicate that the threshold for continental glaciation was crossed earlier in the Southern Hemisphere than in the Northern Hemisphere. PMID:17713530

  7. Transformation of echinoid Mg calcite skeletons by heating

    NASA Astrophysics Data System (ADS)

    Dickson, J. A. D.

    2001-02-01

    Interambularcral plates of echinoid Heterocentrotus trigonarius, composed of Mg calcite 1 (≈14 mol% MgCO 3), were heated in three timed series of experiments at 300°C. Dried plate fragments and fragments with added water were heated separately in pressurized bombs. X-ray powder diffractometry, unit cell dimensions, and phase compositions are used to monitor reaction progress. After 10 h heating in the bombs dolomite (43.5 mol% MgCO 3) and Mg calcite appear (4-7 mol% MgCO 3); by 20 h all Mg calcite 1 is consumed, and at 120 h dolomite composition has evolved to ≈47 mol% MgCO 3 and calcite to ≈2 mol% MgCO 3. Whole plates heated at 300°C in an open muffle furnace develop dolomite (≈42 mol% MgCO 3) and Mg calcite 2 (≈6 mol% MgCO 3) after 10 h and remain compositionally invariant throughout subsequent heating to 620 h. Limited skeletal water catalyzes the early reaction but escapes from the open furnace and consequently reaction ceases after ≈10 h. The experimentally produced dolomite has relative Mg-Ca ordering of 75% to 79%. The stabilization of echinoid Mg calcite by heating at 300°C to a mixture of dolomite and calcite occurs through a dissolution/precipitation reaction. The alteration fabric produced within the stereom consists of irregularly shaped, branched dolomite crystals > 5 μm homoaxially set in a calcite 2 (bomb) or Mg calcite 2 (furnace) matrix. Round and tubular pores 1 to 5 μm are randomly distributed throughout this fabric. The stereom pore system remains intact during furnace heating but is destroyed during heating in bombs. The texture of experimentally stabilized echinoid skeletons is different from that of fossil echinoderms that are composed of microrhomic dolomite homoaxially set in a single calcite crystal.

  8. Influence of temperature and CO2 on the strontium and magnesium composition of coccolithophore calcite

    NASA Astrophysics Data System (ADS)

    Müller, M. N.; Lebrato, M.; Riebesell, U.; Ramos, J. Barcelos e.; Schulz, K. G.; Blanco-Ameijeiras, S.; Sett, S.; Eisenhauer, A.; Stoll, H. M.

    2013-10-01

    Marine calcareous sediments provide a fundamental basis for paleoceanographic studies aiming to reconstruct past oceanic conditions and understand key biogeochemical element cycles. Calcifying unicellular phytoplankton (coccolithophores) are a major contributor to both carbon and calcium cycling by photosynthesis and the production of calcite (coccoliths) in the euphotic zone and the subsequent long-term deposition and burial into marine sediments. Here we present data from controlled laboratory experiments on four coccolithophore species and elucidate the relation between the divalent cation (Sr, Mg and Ca) partitioning in coccoliths and cellular physiology (growth, calcification and photosynthesis). Coccolithophores were cultured under different seawater temperature and carbonate chemistry conditions. The partition coefficient of strontium (DSr) was positively correlated with both carbon dioxide (pCO2) and temperature but displayed no coherent relation to particulate organic and inorganic carbon production rates. Furthermore, DSr correlated positively with cellular growth rates when driven by temperature but no correlation was present when changes in growth rates were pCO2-induced. The results demonstrate the complex interaction between environmental forcing and physiological control on the strontium partitioning in coccolithophore calcite. The partition coefficient of magnesium (DMg) displayed species-specific differences and elevated values under nutrient limitation. No conclusive correlation between coccolith DMg and temperature was observed but pCO2 induced a rising trend in coccolith DMg. Interestingly, the best correlation was found between coccolith DMg and chlorophyll a production suggesting that chlorophyll a and calcite associated Mg originate from the same intracellular pool. These results give an extended insight into the driving factors that lead to variations in the coccolith Mg / Ca ratio and can be used for Sr / Ca and Mg / Ca paleoproxy

  9. Dating of the time of sedimentation using U-Pb ages for paleosol calcite

    SciTech Connect

    Rasbury, E.T.; Hanson, G.N.; Meyers, W.J.

    1997-04-01

    We have sampled paleosol horizons from a continuous core of a rapidly deposited Late Pennsylvanian-Early Permian marine shelf section in Texas. USA. The paleosols occur on the tops of shoaling upward cycles and, based on current time constraints, these cycles average 250 ka and cannot represent longer than 400 ka. As the unconformity which is represented by the paleosol can only be a fraction of the time allowed for deposition of the cycle, the age of minerals that form in the paleosol is effectively the time of sedimentation. The uncertainty on the {sup 238}U-{sup 206}Pb age of brown paleosol calcite from one exposure surface is only 1 Ma. Reported uncertainties on Paleozoic boundaries are greater than 10 Ma. Our early results suggest that the marine sedimentary record may be dated to a precision of 1 Ma with U-Pb analyses of carefully selected paleosol calcite. These results have implications for vastly improving time resolution of the rock record. 21 refs., 3 figs., 1 tab.

  10. Indications for the past redox environments in deep groundwaters from the isotopic composition of carbon and oxygen in fracture calcite, Olkiluoto, SW Finland.

    PubMed

    Sahlstedt, Elina; Karhu, Juha A; Pitkanen, Petteri

    2010-09-01

    In paleohydrogeological studies, the geochemical and isotope geochemical composition of fracture calcites can be utilised to gain information about the evolution of the composition of deep groundwaters in crystalline bedrock. The aim of our study was to investigate the latest hydrogeochemical evolution of groundwaters in the crystalline bedrock at Olkiluoto, which is the planned site for deep geological disposal of spent nuclear fuel. Samples were collected from drill cores intercepting water-conducting fractures at the upper ~500 m of the bedrock. The latest fracture calcite generations were identified using optical microscopy and electron microprobe. They occur as thin ~10-200 μm crusts or small euhedral crystals on open fracture surfaces. These latest calcite fillings were carefully sampled and analysed for the isotopic composition on carbon and oxygen. In addition, fluid inclusion homogenisation temperatures were determined on selected calcite samples. Fluid inclusion data indicated a low temperature of formation for the latest fracture calcite fillings. The δ(18)O values of calcite in these fracture fillings vary only slightly, from-7.3 to-11.5 ‰ (Vienna Pee Dee Belemnite, VPDB), whereas the δ(13)C values fluctuate widely, from-30 to+31 ‰ (VPDB). The δ(13)C values of latest calcite fillings show a systematic pattern with depth, with high and variable δ(13)C values below 50 m. The high δ(13)C values indicate active methanogenesis during the formation of the latest calcite fillings. In contrast, the present-day methanic redox environment is restricted to depths below 200-300 m. It is possible that the shift in the redox environment at Olkiluoto has occurred during infiltration of SO2-(4)-rich marine waters, the latest of such events being the infiltration of brackish waters of the Littorina Sea stage of the Baltic Sea at ~8000-3000 BP. PMID:20665300

  11. Calcite growth kinetics: Modeling the effect of solution stoichiometry

    NASA Astrophysics Data System (ADS)

    Wolthers, Mariëtte; Nehrke, Gernot; Gustafsson, Jon Petter; Van Cappellen, Philippe

    2012-01-01

    Until recently the influence of solution stoichiometry on calcite crystal growth kinetics has attracted little attention, despite the fact that in most aqueous environments calcite precipitates from non-stoichiometric solution. In order to account for the dependence of the calcite crystal growth rate on the cation to anion ratio in solution, we extend the growth model for binary symmetrical electrolyte crystals of Zhang and Nancollas (1998) by combining it with the surface complexation model for the chemical structure of the calcite-aqueous solution interface of Wolthers et al. (2008). To maintain crystal stoichiometry, the rate of attachment of calcium ions to step edges is assumed to equal the rate of attachment of carbonate plus bicarbonate ions. The model parameters are optimized by fitting the model to the step velocities obtained previously by atomic force microscopy (AFM, Teng et al., 2000; Stack and Grantham, 2010). A variable surface roughness factor is introduced in order to reconcile the new process-based growth model with bulk precipitation rates measured in seeded calcite growth experiments. For practical applications, we further present empirical parabolic rate equations fitted to bulk growth rates of calcite in common background electrolytes and in artificial seawater-type solutions. Both the process-based and empirical growth rate equations agree with measured calcite growth rates over broad ranges of ionic strength, pH, solution stoichiometry and degree of supersaturation.

  12. Uranyl incorporation into calcite and aragonite: XAFS and luminescence studies

    SciTech Connect

    Reeder, R.J.; Nugent, M.; Lamble, G.M.; Tait, C.D.; Morris, D.E.

    2000-02-15

    X-ray absorption, luminescence, and Raman spectroscopic studies of U(VI)-containing calcite and aragonite show that the UO{sub 2}{sup 2+} ion, the dominant and mobile form of dissolved uranium in near-surface waters, has a disordered and apparently less stable coordination environment when incorporated into calcite in comparison to aragonite, both common polymorphs of CaCO{sub 3}. Their findings suggest that calcite, a widely distributed authigenic mineral in soils and near-surface sediments and a principal weathering product of concrete-based containment structures, is not likely to be a suitable host for the long-term sequestration of U(VI). The more stable coordination provided by aragonite suggests that its long-term retention should be favored in this phase, until it inverts to calcite. Consequently, future remobilization of U(VI) coprecipitated with calcium carbonate minerals should not be ruled out in assessments of contaminated sites. Their observation of a similar equatorial coordination of UO{sub 2}{sup 2+} in aragonite and the dominant aqueous species [UO{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}}] but a different coordination in calcite indicates that a change in UO{sub 2}{sup 2+} coordination is required for its incorporation into calcite. This may explain the observed preferential uptake of U(VI) by aragonite relative to calcite.

  13. Reconstructing Cambro-Ordovician Seawater Composition using Clumped Isotope Paleothermometry on Calcitic and Phosphatic Brachiopods

    NASA Astrophysics Data System (ADS)

    Bergmann, K.; Robles, M.; Finnegan, S.; Hughes, N. C.; Eiler, J. M.; Fischer, W. W.

    2012-12-01

    A secular increase in δ18O values of marine fossils through early Phanerozoic time raises questions about the evolution of climate and the water cycle. This pattern suggests two end-member hypotheses 1) surface temperatures during early Paleozoic time were very warm, in excess of 40°C (tropical MAT), or 2) the isotopic composition of seawater increased by up to 7-8‰. It has been difficult to evaluate these hypotheses because the δ18O composition of fossils depends on both temperature and the δ18O of water. Furthermore, primary isotopic signatures can be overprinted by diagenetic processes that modify geological materials. This too could explain the decrease in δ18O values of marine fossils with age. Carbonate clumped isotope thermometry can constrain this problem by providing an independent measure of crystallization temperature and, when paired with classical δ18O paleothermometry, can determine the isotopic composition of the fluid the mineral last equilibrated with. Combined with traditional tools, this method has the potential to untangle primary isotopic signatures from diagenetic signals. We measured the isotopic ordering of CO3 groups (Δ47) substituted into the phosphate lattice of phosphatic brachiopods in Cambrian strata. Phosphatic fossils are generally less soluble than carbonates in surface and diagenetic environments, and so are hypothesized to provide a more robust record of primary growth conditions. They also provide an archive prior to the rise of thick shelled calcitic fossils during the Ordovician Radiation. Additionally, measurements of the δ18O of the CO3 groups can be compared with the δ18O of PO4 groups to test whether their mutual fractionation is consistent with primary growth and the apparent temperature recorded by carbonate clumped isotope measurements. We are constructing a phosphatic brachiopod calibration for carbonate clumped isotope thermometry, and Δ47 values of CO2 extracted from modern phosphatic brachiopods suggest

  14. Calcite surface structure and reactivity: molecular dynamics simulations and macroscopic surface modelling of the calcite-water interface.

    PubMed

    Wolthers, M; Di Tommaso, D; Du, Z; de Leeuw, N H

    2012-11-21

    Calcite-water interactions are important not only in carbon sequestration and the global carbon cycle, but also in contaminant behaviour in calcite-bearing host rock and in many industrial applications. Here we quantify the effect of variations in surface structure on calcite surface reactivity. Firstly, we employ classical Molecular Dynamics simulations of calcite surfaces containing an etch pit and a growth terrace, to show that the local environment in water around structurally different surface sites is distinct. In addition to observing the expected formation of more calcium-water interactions and hydrogen-bonds at lower-coordinated sites, we also observed subtle differences in hydrogen bonding around acute versus obtuse edges and corners. We subsequently used this information to refine the protonation constants for the calcite surface sites, according to the Charge Distribution MUltiSite Ion Complexation (CD-MUSIC) approach. The subtle differences in hydrogen bonding translate into markedly different charging behaviour versus pH, in particular for acute versus obtuse corner sites. The results show quantitatively that calcite surface reactivity is directly related to surface topography. The information obtained in this study is not only crucial for the improvement of existing macroscopic surface models of the reactivity of calcite towards contaminants, but also improves our atomic-level understanding of mineral-water interactions. PMID:23042085

  15. Initial responses of carbonate-rich shelf sediments to rising atmospheric pCO2 and “ocean acidification”: Role of high Mg-calcites

    NASA Astrophysics Data System (ADS)

    Morse, John W.; Andersson, Andreas J.; Mackenzie, Fred T.

    2006-12-01

    Carbonate-rich sediments at shoal to shelf depths (<200 m) represent a major CaCO 3 reservoir that can rapidly react to the decreasing saturation state of seawater with respect to carbonate minerals, produced by the increasing partial pressure of atmospheric carbon dioxide ( pCO 2) and "acidification" of ocean waters. Aragonite is usually the most abundant carbonate mineral in these sediments. However, the second most abundant (typically ˜24 wt%) carbonate mineral is high Mg-calcite (Mg-calcite) whose solubility can exceed that of aragonite making it the "first responder" to the decreasing saturation state of seawater. For the naturally occurring biogenic Mg-calcites, dissolution experiments have been used to predict their "stoichiometric solubilities" as a function of mol% MgCO 3. The only valid relationship that one can provisionally use for the metastable stabilities for Mg-calcite based on composition is that for the synthetically produced phases where metastable equilibrium has been achieved from both under- and over-saturation. Biogenic Mg-calcites exhibit a large offset in solubility from that of abiotic Mg-calcite and can also exhibit a wide range of solubilities for biogenic Mg-calcites of similar Mg content. This indicates that factors other than the Mg content can influence the solubility of these mineral phases. Thus, it is necessary to turn to observations of natural sediments where changes in the saturation state of surrounding waters occur in order to determine their likely responses to the changing saturation state in upper oceanic waters brought on by increasing pCO 2. In the present study, we investigate the responses of Mg-calcites to rising pCO 2 and "ocean acidification" by means of a simple numerical model based on the experimental range of biogenic Mg-calcite solubilities as a function of Mg content in order to bracket the behavior of the most abundant Mg-calcite phases in the natural environment. In addition, observational data from Bermuda

  16. A simplified methodology to approach the complexity of foraminiferal calcite oxygen-isotope data - model comparison

    NASA Astrophysics Data System (ADS)

    Roche, Didier; Waelbroeck, Claire

    2016-04-01

    Since the pioneering work of Epstein (Epstein et al., 1953), numerous calcite isotopic records from the ocean have been used to attempt reconstructing paleoclimatic information. Additional to the well known complexity brought by the fact that foraminiferal calcite records both temperature and isotopic composition of the surrounding oceanic waters, an additional effect for surface - dwelling foraminifers is the fact that two different species do not have the same habitat and may thus record different signals. This is obvious when comparing paleoclimatic records where different species have been measured for the isotopic composition of the calcite. The difference in habitat produces a three dimensional spatial complexity (a foraminifera living in preferred climatic conditions at a specific location, but also at a specific depth, sometimes far from the surface) but also a temporal uncertainty (foraminifers generally live for only a few weeks and their growth season may be evolving through time with climate change). While the different species habitats potentially contain a wealth of information that could be used to better understand the sequences of climate change, this has seldom been used in modeling studies, most models deriving calcite isotopic signal from surface and annual mean conditions (e.g. Roche et al., 2014). In the present work, we propose a reduced complexity approach to compute the calcite for several planktonic foraminifers from climate model simulations under pre-industrial conditions. We base our approach on simple functions describing the temperature dependence of the different species growth rates (Lombard et al., 2009) and on probability of presence based on the physical variables computed in the climate model. We present a comparison to available sediment traps and core tops data as a validation of the methodology, focusing on the possibility for future applicability towards inversion of the signal measured in oceanic sediment cores. References

  17. Calcite crystal growth rate inhibition by polycarboxylic acids

    USGS Publications Warehouse

    Reddy, M.M.; Hoch, A.R.

    2001-01-01

    Calcite crystal growth rates measured in the presence of several polycarboxyclic acids show that tetrahydrofurantetracarboxylic acid (THFTCA) and cyclopentanetetracarboxylic acid (CPTCA) are effective growth rate inhibitors at low solution concentrations (0.01 to 1 mg/L). In contrast, linear polycarbocylic acids (citric acid and tricarballylic acid) had no inhibiting effect on calcite growth rates at concentrations up to 10 mg/L. Calcite crystal growth rate inhibition by cyclic polycarboxyclic acids appears to involve blockage of crystal growth sites on the mineral surface by several carboxylate groups. Growth morphology varied for growth in the absence and in the presence of both THFTCA and CPTCA. More effective growth rate reduction by CPTCA relative to THFTCA suggests that inhibitor carboxylate stereochemical orientation controls calcite surface interaction with carboxylate inhibitors. ?? 20O1 Academic Press.

  18. Thermoluminescence dating of calcite shells in the pectinidae family

    NASA Astrophysics Data System (ADS)

    Ninagawa, Kiyotaka; Adachi, Kenji; Uchimura, Noboru; Yamamoto, Isao; Wada, Tomonori; Yamashita, Yoshihiko; Takashima, Isao; Sekimoto, Katsuhisa; Hasegawa, Hiroichi

    Previously we investigated the thermoluminescence (TL) of a calcite shell, Pectinidae Pecten (Notovola) albicans (Schröter) (abbreviated to albicans), and we found that TL dating was possible for fossil calcite shells of albicans from 5 × 10 5 years ago to the present. In the present work, we investigate the TL emission spectra and the first glow-growth of 5 other species in the Pectinidae family, and it is found that the TL characteristics of these species are the same as those of the albicans. This means that the application of TL dating can be extended to these species. Furthermore, we tried to date fossil calcite shells older than 5 × 10 5 years ago, and we found that the upper limit for TL dating of fossil calcite shells is about 6 × 10 5 years.

  19. Paleoclimatic and paleohydrologic records from secondary calcite: Yucca Mountain, Nevada

    SciTech Connect

    Whelan, J.F.; Stuckless, J.S.; Moscati, R.J.; Vaniman, D.T.

    1994-12-31

    Stable isotope analyses of calcite and opal, fluid inclusion formation conditions and gas compositions, Sr isotope ratios, and REE compositions all support formation of secondary calcite in the unsaturated zone of Yucca Mountain from infiltration of surface-derived (and soil zone buffered) waters of meteoric origin. Detailed sampling of growth-banding preserved by the secondary calcite should provide a record of past variations in the stable isotope chemistry of these infiltrating waters, and, hence, of precipitation at Yucca Mountain, i.e., a proxy of past climate at Yucca Mountain. The precision of this record depends on how well it can be dated. The distribution and texture of secondary calcite occurrences, if mapped in careful detail from existing bore hole samples and underground workings (as exposures become accessible), could provide a time/space map of fracture and fault unsaturated-zone ground water flow-paths during past wetter climates which might prevail in the future with change in climate.

  20. A 250,000-year climatic record from great basin vein calcite: Implications for Milankovitch theory

    USGS Publications Warehouse

    Winograd, I.J.; Szabo, B. J.; Coplen, T.B.; Riggs, A.C.

    1988-01-01

    A continuous record of oxygen-18 (??18O) variations in the continental hydrosphere during the middle-to-late Pleistocene has been obtained from a uranium-series dated calcitic vein in the southern Great Basin. The vein was deposited from ground water that moved through Devils Hole - an open fault zone at Ash Meadows, Nevada - between 50 and 310 ka (thousand years ago). The configuration of the ??18O versus time curve closely resembles the marine and Antarctic ice core (Vostok) ??18O curves; however, the U-Th dates indicate that the last interglacial stage (marine oxygen isotope stage 5) began before 147 ?? 3 ka, at least 17,000 years earlier than indicated by the marine ??18O record and 7,000 years earlier than indicated by the less well dated Antarctic ??18O record. This discrepancy and other differences in the timing of key climatic events suggest that the indirectly dated marine ??18O chronology may need revision and that orbital forcing may not be the principal cause of the Pleistocene ice ages.

  1. A 250,000-Year Climatic Record from Great Basin Vein Calcite: Implications for Milankovitch Theory

    NASA Astrophysics Data System (ADS)

    Winograd, Isaac J.; Szabo, Barney J.; Coplen, Tyler B.; Riggs, Alan C.

    1988-12-01

    A continuous record of oxygen-18 (δ 18O) variations in the continental hydrosphere during the middle-to-late Pleistocene has been obtained from a uranium-series dated calcitic vein in the southern Great Basin. The vein was deposited from ground water that moved through Devils Hole--an open fault zone at Ash Meadows, Nevada--between 50 and 310 ka (thousand years ago). The configuration of the δ 18O versus time curve closely resembles the marine and Antarctic ice core (Vostok) δ 18O curves; however, the U-Th dates indicate that the last interglacial stage (marine oxygen isotope stage 5) began before 147 ± 3 ka, at least 17,000 years earlier than indicated by the marine δ 18O record and 7,000 years earlier than indicated by the less well dated Antarctic δ 18O record. This discrepancy and other differences in the timing of key climatic events suggest that the indirectly dated marine δ 18O chronology may need revision and that orbital forcing may not be the principal cause of the Pleistocene ice ages.

  2. A 250,000-year climatic record from great basin vein calcite: implications for milankovitch theory.

    PubMed

    Winograd, I J; Coplen, T B; Szabo, B J; Riggs, A C

    1988-12-01

    A continuous record of oxygen-18 (delta(18)O) variations in the continental hydrosphere during the middle-to-late Pleistocene has been obtained from a uranium-series dated calcitic vein in the southern Great Basin. The vein was deposited from ground water that moved through Devils Hole-an open fault zone at Ash Meadows, Nevada-between 50 and 310 ka (thousand years ago). The configuration of the delta(18)O versus time curve closely resembles the marine and Antarctic ice core (Vostok) delta(18)O curves; however, the U-Th dates indicate that the last interglacial stage (marine oxygen isotope stage 5) began before 147 +/- 3 ka, at least 17,000 years earlier than indicated by the marine delta(18)O record and 7,000 years earlier than indicated by the less well dated Antarctic delta(18)O record. This discrepancy and other differences in the timing of key climatic events suggest that the indirectly dated marine delta(18)O chronology may need revision and that orbital forcing may not be the principal cause of the Pleistocene ice ages. PMID:17817073

  3. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    SciTech Connect

    Chapman, Piers; *Morse, John W.

    2010-11-15

    1. Objective The general objective of this research was to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, carbon dioxide partial pressure (pCO2), and modest ranges of T and P. This would be done by studying both reaction rates and solubility from changes in solution chemistry. Also, nanoscale observations of calcite surface morphology and composition would be made to provide an understanding of rate controlling mechanisms.

  4. Methanogenic calcite, 13C-depleted bivalve shells, and gas hydrate from a mud volcano offshore southern California

    USGS Publications Warehouse

    Hein, J.R.; Normark, W.R.; McIntyre, B.R.; Lorenson, T.D.; Powell, C.L., II

    2006-01-01

    Methane and hydrogen sulfide vent from a cold seep above a shallowly buried methane hydrate in a mud volcano located 24 km offshore southern California in?? 800 m of water. Bivalves, authigenic calcite, and methane hydrate were recovered in a 2.1 m piston core. Aragonite shells of two bivalve species are unusually depleted in 13C (to -91??? ??13C), the most 13C-depleted shells of marine macrofauna yet discovered. Carbon isotopes for both living and dead specimens indicate that they used, in part, carbon derived from anaerobically oxidized methane to construct their shells. The ??13C values are highly variable, but most are within the range -12??? to -91???. This variability may be diagnostic for identifying cold-seep-hydrate systems in the geologic record. Authigenic calcite is abundant in the cores down to ???1.5 m subbottom, the top of the methane hydrate. The calcite is depleted in 13C (??13C = -46??? to -58???), indicating that carbon produced by anaerobically oxidized methane is the main source of the calcite. Methane sources include a geologic hydrocarbon reservoir from Miocene source rocks, and biogenic and thermogenic degradation of organic matter in basin sediments. Oxygen isotopes indicate that most calcite formed out of isotopic equilibrium with ambient bottom water, under the influence of gas hydrate dissociation and strong methane flux. High metal content in the mud volcano sediment indicates leaching of basement rocks by fluid circulating along an underlying fault, which also allows for a high flux of fossil methane. ?? 2006 Geological Society of America.

  5. Calcite Farming at Hollow Ridge Cave: Calibrating Net Rainfall and Cave Microclimate to Dripwater and Calcite Chemical Variability

    NASA Astrophysics Data System (ADS)

    Tremaine, D. M.; Kilgore, B. P.; Froelich, P. N.

    2012-04-01

    Stable isotope (δ18O and δ13C) and trace element records in cave speleothems are often interpreted as climate changes in rainfall amount or source, cave air temperature, overlying vegetation and atmospheric pCO2. However, these records are difficult to verify without in situ calibration of changes in cave microclimate (e.g., net rainfall, interior ventilation changes) to contemporaneous variations in dripwater and speleothem chemistry. In this study at Hollow Ridge Cave (HRC) in Marianna, Florida (USA), cave dripwater, bedrock, and modern calcite (farmed in situ) were collected in conjunction with continuous cave air pCO2, temperature, barometric pressure, relative humidity, radon-222 activity, airflow velocity and direction, rainfall amount, and drip rate data [1]. We analyzed rain and dripwater δD and δ18O, dripwater Ca2+, pH, δ13C and TCO2, cave air pCO2 and δ13C, and farmed calcite δ18O and δ13C to examine the relationships among rainwater isotopic composition, cave air ventilation, cave air temperature, calcite growth rate and seasonal timing, and calcite isotopic composition. Farmed calcite δ13C decreases linearly with distance from the front entrance to the interior of the cave during all seasons, with a maximum entrance-to-interior gradient of Δδ13C = -7‰ . A whole-cave "Hendy test" at distributed contemporaneous farming sites reveals that ventilation induces a +1.9 ± 0.96‰ δ13C offset between calcite precipitated in a ventilation flow path and out of flow paths. Farmed calcite δ18O exhibits a +0.82 ± 0.24‰ offset from values predicted by both theoretical calcite-water calculations and by laboratory-grown calcite [2]. Unlike calcite δ13C, oxygen isotopes show no ventilation effects and are a function only of temperature. Combining our data with other speleothem studies, we find a new empirical relationship for cave-specific water-calcite oxygen isotope fractionation across a range of temperatures and cave environments: 1000 ln α = 16

  6. ABIOTIC ORGANIC REACTIONS AT MINERAL SURFACES

    EPA Science Inventory

    Abiotic organic reactions, such as hydrolysis, elimination, substitution, redox, and polymerization reactions, can be influenced by surfaces of clay and primary minerals, and of metal oxides. This influence is due to adsorption of the reactants to surface Lewis and Bronsted sites...

  7. Abiotic Bromination of Soil Organic Matter.

    PubMed

    Leri, Alessandra C; Ravel, Bruce

    2015-11-17

    Biogeochemical transformations of plant-derived soil organic matter (SOM) involve complex abiotic and microbially mediated reactions. One such reaction is halogenation, which occurs naturally in the soil environment and has been associated with enzymatic activity of decomposer organisms. Building on a recent finding that naturally produced organobromine is ubiquitous in SOM, we hypothesized that inorganic bromide could be subject to abiotic oxidations resulting in bromination of SOM. Through lab-based degradation treatments of plant material and soil humus, we have shown that abiotic bromination of particulate organic matter occurs in the presence of a range of inorganic oxidants, including hydrogen peroxide and assorted forms of ferric iron, producing both aliphatic and aromatic forms of organobromine. Bromination of oak and pine litter is limited primarily by bromide concentration. Fresh plant material is more susceptible to bromination than decayed litter and soil humus, due to a labile pool of mainly aliphatic compounds that break down during early stages of SOM formation. As the first evidence of abiotic bromination of particulate SOM, this study identifies a mechanistic source of the natural organobromine in humic substances and the soil organic horizon. Formation of organobromine through oxidative treatments of plant material also provides insights into the relative stability of aromatic and aliphatic components of SOM. PMID:26468620

  8. Marine botany. Second edition

    SciTech Connect

    Dawes, C.J.

    1998-12-01

    Marine plants are a diverse group that include unicellular algae, seaweeds, seagrasses, salt marshes, and mangrove forests. They carry out a variety of ecological functions and serve as the primary producers in coastal wetlands and oceanic waters. The theme that connects such a wide variety of plants is their ecology, which was also emphasized in the 1981 edition. The goal of this revision is to present taxonomic, physiological, chemical, and ecological aspects of marine plants, their adaptations, and how abiotic and biotic factors interact in their communities. The data are presented in a concise, comparative manner in order to identify similarities and differences between communities such as salt marsh and mangroves or subtidal seaweeds and seagrasses. To accomplish this, the text is organized into five chapters that introduce the marine habitats, consider abiotic and biotic factors, and anthropogenic influences on the communities followed by seven chapters that deal with microalgae, seaweeds, salt marshes, mangroves, seagrasses, and coral reefs. Two appendixes are included; one presents simple field techniques and the other is a summary of seaweed uses.

  9. Controls on Calcite Solubility in Metamorphic and Magmatic Fluids

    NASA Astrophysics Data System (ADS)

    Manning, C. E.; Eguchi, J.; Galvez, M.

    2015-12-01

    Calcite is an important hydrothermal alteration product in a wide range of environments. The role of calcite in hydrothermal alteration depends on its solubility in geologic fluids, especially H2O. At ambient T and P, calcite solubility is low and it exhibits well-known declining, or "reverse", solubility with rising T. However, experimental and theoretical studies show that increasing P yields higher solubility and restricts the region of reverse solubility behavior to higher temperature. At 0.2 GPa the reverse solubility region lies at T>600°C; at 0.5 GPa, >800°C. Thus, whereas calcite possesses relatively low solubility in pure H2O in shallow hydrothermal systems (typically <10 ppm C), it is substantially more soluble at conditions of middle and lower crustal metamorphism and magmatism, reaching concentrations ≥1000 ppm. At the higher P of subduction zones, aragonite solubility in H2O is even greater. Thus, neglecting other solubility controls, calcite precipitation is favored as crustal fluids cool and/or decompress. However, the solubility of calcite in H2O also depends strongly on other solutes, pH, and fO2. Sources of alkalinity decrease calcite solubility. In contrast, sources of acidity such as CO2 and Cl increase solubility. Crustal fluids can be enriched in alkali halides such as NaCl. Calcite solubility increases with increasing salt content at a given P and T. From approximately seawater salinity to salt saturation, the fluid behaves as a dilute molten salt and calcite solubility increases as the square of the salt mole fraction regardless of the alkali (Li, Na, K, Cs) or halogen (F, Cl, Br, I) considered. Similar behavior is seen in mixed salt solutions. At lower salinities, solubility behavior is as expected in dilute electrolyte solutions. The transition from dilute electrolyte to molten salt is fundamental to the properties of crustal fluids. Reduction of carbonate species or CO2 in the fluid to CH4, which is common during serpentinization of

  10. Polygenetic Karsted Hardground Omission Surfaces in Lower Silurian Neritic Limestones: a Signature of Early Paleozoic Calcite Seas

    NASA Astrophysics Data System (ADS)

    James, Noel P.; Desrochers, André; Kyser, Kurt T.

    2015-04-01

    Exquisitely preserved and well-exposed rocky paleoshoreline omission surfaces in Lower Silurian Chicotte Formation limestones on Anticosti Island, Quebec, are interpreted to be the product of combined marine and meteoric diagenesis. The different omission features include; 1) planar erosional bedding tops, 2) scalloped erosional surfaces, 3) knobs, ridges, and swales at bedding contacts, and 4) paleoscarps. An interpretation is proposed that relates specific omission surface styles to different diagenetic-depositional processes that took place in separate terrestrial-peritidal-shallow neritic zones. Such processes were linked to fluctuations in relative sea level with specific zones of diagenesis such as; 1) karst corrosion, 2) peritidal erosion, 3) subtidal seawater flushing and cementation, and 4) shallow subtidal deposition. Most surfaces are interpreted to have been the result of initial extensive shallow-water synsedimentary lithification that were, as sea level fell, altered by exposure and subaerial corrosion, only to be buried by sediments as sea level rose again. This succession was repeated several times resulting in a suite of recurring polyphase omission surfaces through many meters of stratigraphic section. Synsedimentary cloudy marine cements are well preserved and are thus interpreted to have been calcitic originally. Aragonite components are rare and thought to have to have been dissolved just below the Silurian seafloor. Large molluscs that survived such seafloor removal were nonetheless leached and the resultant megamoulds were filled with synsedimentary calcite cement. These Silurian inner neritic-strandline omission surfaces are temporally unique. They are part of a suite of marine omission surfaces that are mostly found in early Paleozoic neritic carbonate sedimentary rocks. These karsted hardgrounds formed during a calcite-sea time of elevated marine carbonate saturation and extensive marine cement precipitation. The contemporaneous greenhouse

  11. An explanation for the 18O excess in Noelaerhabdaceae coccolith calcite

    NASA Astrophysics Data System (ADS)

    Hermoso, M.; Minoletti, F.; Aloisi, G.; Bonifacie, M.; McClelland, H. L. O.; Labourdette, N.; Renforth, P.; Chaduteau, C.; Rickaby, R. E. M.

    2016-09-01

    Coccoliths have dominated the sedimentary archive in the pelagic environment since the Jurassic. The biominerals produced by the coccolithophores are ideally placed to infer sea surface temperatures from their oxygen isotopic composition, as calcification in this photosynthetic algal group only occurs in the sunlit surface waters. In the present study, we dissect the isotopic mechanisms contributing to the "vital effect", which overprints the oceanic temperatures recorded in coccolith calcite. Applying the passive diffusion model of carbon acquisition by the marine phytoplankton widely used in biogeochemical and palaeoceanographic studies, our results suggest that the oxygen isotope offsets from inorganic calcite in fast dividing species Emiliania huxleyi and Gephyrocapsa oceanica originates from the legacy of assimilated 18O-rich CO2 that induces transient isotopic disequilibrium to the internal dissolved inorganic carbon (DIC) pool. The extent to which this intracellular isotopic disequilibrium is recorded in coccolith calcite (1.5 to +3‰ over a 10 to 25 °C temperature range) is set by the degree of isotopic re-equilibration between CO2 and water molecules before intracellular mineralisation. We show that the extent of re-equilibration is, in turn, set by temperature through both physiological (dynamics of the utilisation of the DIC pool) and thermodynamic (completeness of the re-equilibration of the relative 18O-rich CO2 influx) processes. At the highest temperature, less ambient aqueous CO2 is present for algal growth, and the consequence of carbon limitation is exacerbation of the oxygen isotope vital effect, obliterating the temperature signal. This culture dataset further demonstrates that the vital effect is variable for a given species/morphotype, and depends on the intricate relationship between the environment and the physiology of biomineralising algae.

  12. Surface chemistry allows for abiotic precipitation of dolomite at low temperature

    NASA Astrophysics Data System (ADS)

    Roberts, Jennifer A.; Kenward, Paul A.; Fowle, David A.; Goldstein, Robert H.; González, Luis A.; Moore, David S.

    2013-09-01

    Although the mineral dolomite is abundant in ancient low-temperature sedimentary systems, it is scarce in modern systems below 50 °C. Chemical mechanism(s) enhancing its formation remain an enigma because abiotic dolomite has been challenging to synthesize at low temperature in laboratory settings. Microbial enhancement of dolomite precipitation at low temperature has been reported; however, it is still unclear exactly how microorganisms influence reaction kinetics. Here we document the abiotic synthesis of low-temperature dolomite in laboratory experiments and constrain possible mechanisms for dolomite formation. Ancient and modern seawater solution compositions, with identical pH and pCO2, were used to precipitate an ordered, stoichiometric dolomite phase at 30 °C in as few as 20 d. Mg-rich phases nucleate exclusively on carboxylated polystyrene spheres along with calcite, whereas aragonite forms in solution via homogeneous nucleation. We infer that Mg ions are complexed and dewatered by surface-bound carboxyl groups, thus decreasing the energy required for carbonation. These results indicate that natural surfaces, including organic matter and microbial biomass, possessing a high density of carboxyl groups may be a mechanism by which ordered dolomite nuclei form. Although environments rich in organic matter may be of interest, our data suggest that sharp biogeochemical interfaces that promote microbial death, as well as those with high salinity may, in part, control carboxyl-group density on organic carbon surfaces, consistent with origin of dolomites from microbial biofilms, as well as hypersaline and mixing zone environments.

  13. Calcite-graphite thermometry of the Franklin Marble, New Jersey Highlands

    USGS Publications Warehouse

    Peck, W.H.; Volkert, R.A.; Meredith, M.T.; Rader, E.L.

    2006-01-01

    We present new stable-isotope data for the Mesoproterozoic Franklin Marble from outcrops along an 80-km traverse parallel to and across strike of the structural grain of the western New Jersey Highlands. Calcite and dolomite from marble have an average ??13C of 0.35??? ?? 0.73??? PDB (n = 46) and a more limited range than other Mesoproterozoic marbles from the Adirondacks and the Canadian Grenville Province. The small range of ??13C values from the New Jersey samples is consistent with the preservation of a primary marine isotopic signature and limited postdepositional isotopic modification, except proximal to Zn or Fe ore deposits and fault zones. Fractionations between calcite and well-formed graphite (??13C[Cal-Gr]) for analyzed Franklin Marble samples average 3.31???. ?? 0.25??? (n = 34), and dolomite-graphite fractionations average 3.07??? ?? 0.30??? (n = 6). Taken together, these indicate an average temperature of 769?? ?? 43??C during metamorphism associated with the Ottawan Orogeny in the New Jersey Highlands. Thus, carbon isotope fractionations demonstrate that the Franklin Marble was metamorphosed at granulite facies conditions. Metamorphic temperatures are relatively constant for the area sampled and overprint the metamorphosed carbonatehosted Zn-Fe-Mn ore deposits. The results of this study support recent work proposing that pressure and temperature conditions during Ottawan orogenesis did not vary greatly across faults that partition the Highlands into structural blocks. ?? 2006 by The University of Chicago. All rights reserved.

  14. Microstructures and elastic properties of sheared calcite flowstone

    NASA Astrophysics Data System (ADS)

    Mitrovic, Ivanka; Grasemann, Bernhard; Plan, Lukas; Tesei, Telemaco; Baron, Ivo

    2016-04-01

    Flowstone is a monomineralic rock precipitated along cave walls and floors, composed of columnar centimeter-scale calcite crystals with strong growth orientation perpendicular to the growth surface. Broken and scratched flowstone can serve as evidence for active faulting and has been found in several alpine caves in Austria. In order to understand the fault mechanics, and associated potential earthquake hazard, experimentally deformed flowstone is studied using microstructural analysis and EBSD-measured physical properties of calcite crystals. For that purpose, we have performed sliding experiments using a rock deformation biaxial apparatus on rectangular blocks of flowstone that were sheared perpendicular to the calcite growth direction. The experiments were performed under room conditions, with sub-seismic sliding velocity (0.001-0.01 mm/s) and constant effective normal stress (3-10 MPa). The deformed samples show diverse brittle features, including high fracture density, the development of calcite-rich fault gouge with Riedel shears within a foliated cataclasite, and drastic grain size reduction down to nm-scale grains. The dominant plastic microstructure is mechanical twinning. Due to the strong growth orientation of calcite in flowstone, crystals can be bent due to shearing. We examine the bending by applying orientation distribution, Schmid factor and elasticity tensor calculations using MTEX Toolbox from EBSD data. In this unique case the flowstone deformation experiments bridge the gap between single crystal and rock powder experiments. This study is supported by the Austrian Science Foundation: SPELEOTECT project (P25884-N29).

  15. A Raman spectroscopic comparison of calcite and dolomite

    NASA Astrophysics Data System (ADS)

    Sun, Junmin; Wu, Zeguang; Cheng, Hongfei; Zhang, Zhanjun; Frost, Ray L.

    2014-01-01

    Raman spectroscopy was used to characterize and differentiate the two minerals calcite and dolomite and the bands related to the mineral structure. The (CO3)2- group is characterized by four prominent Raman vibrational modes: (a) the symmetric stretching, (b) the asymmetric deformation, (c) asymmetric stretching and (d) symmetric deformation. These vibrational modes of the calcite and dolomite were observed at 1440, 1088, 715 and 278 cm-1. The significant differences between the minerals calcite and dolomite are observed by Raman spectroscopy. Calcite shows the typical bands observed at 1361, 1047, 715 and 157 cm-1, and the special bands at 1393, 1098, 1069, 1019, 299, 258 and 176 cm-1 for dolomite are observed. The difference is explained on the basis of the structure variation of the two minerals. Calcite has a trigonal structure with two molecules per unit cell, and dolomite has a hexagonal structure. This is more likely to cause the splitting and distorting of the carbonate groups. Another cause for the difference is the cation substituting for Mg in the dolomite mineral.

  16. Nuclear anomalies in the buccal cells of calcite factory workers

    PubMed Central

    2010-01-01

    The micronucleus (MN) assay on exfoliated buccal cells is a useful and minimally invasive method for monitoring genetic damage in humans. To determine the genotoxic effects of calcite dust that forms during processing, MN assay was carried out in exfoliated buccal cells of 50 (25 smokers and 25 non-smokers) calcite factory workers and 50 (25 smokers and 25 non-smokers) age- and sex-matched control subjects. Frequencies of nuclear abnormalities (NA) other than micronuclei, such as binucleates, karyorrhexis, karyolysis and ‘broken eggs', were also evaluated. Micronuclei and the other aforementioned anomalies were analysed by two way analysis of covariance. The linear correlations between the types of micronucleus and nuclear abnormalities were determined by Spearman's Rho. There was a positive correlation between micronuclei and other types of nuclear abnormalities in accordance with the Spearman's Rho test. Results showed statistically significant difference between calcite fabric workers and control groups. MN and NA frequencies in calcite fabric workers were significantly higher than those in control groups (p < 0.05). The results of this study indicate that calcite fabric workers are under risk of significant cytogenetic damage. PMID:21637497

  17. Reactive oxygen species in abiotic stress signaling.

    PubMed

    Jaspers, Pinja; Kangasjärvi, Jaakko

    2010-04-01

    Reactive oxygen species (ROS) are known to accumulate during abiotic stresses, and different cellular compartments respond to them by distinctive profiles of ROS formation. In contrast to earlier views, it is becoming increasingly evident that even during stress, ROS production is not necessarily a symptom of cellular dysfunction but might represent a necessary signal in adjusting the cellular machinery to the altered conditions. ROS can modulate many signal transduction pathways, such as mitogen-activated protein kinase cascades, and ultimately influence the activity of transcription factors. However, the picture of ROS-mediated signaling is still fragmentary and the issues of ROS perception as well as the signaling specificity remain open. Here, we review some of the recent advances in plant abiotic stress signaling with emphasis on processes known to be affected heavily by ROS. PMID:20028478

  18. Abiotic immobilization/detoxification of recalcitrant organics

    SciTech Connect

    Whelan, G. ); Sims, R.C. )

    1990-11-01

    In contrast to many remedial techniques that simply transfer hazardous wastes from one part of the environment to another (e.g., off-site landfilling), in situ restoration may offer a safe and cost-effective solution through transformation (to less hazardous products) or destruction of recalcitrant organics. Currently, the US Environmental Protection Agency and US Department of Energy are encouraging research that addresses the development of innovative alternatives for hazardous-waste control. One such alternative is biotic and abiotic immobilization and detoxification of polynuclear aromatic hydrocarbons (PNAs) as associated with the soil humification process. This paper discusses (1) the possibility of using abiotic catalysis (with manganese dioxide) to polymerize organic substances; (2) aspects associated with the thermodynamics and kinetics of the process, and (3) a simple model upon which analyses may be based. 36 refs., 7 figs., 3 tabs.

  19. Chemistry and kinetics of calcite dissolution in passive treatment systems

    SciTech Connect

    Rose, A.W.

    1999-07-01

    Reaction of calcite with AMD is a key remediation process in anoxic limestone drains, (ALD), SAPS, and many wetlands, but predictions of effluent quality are currently based mainly on rules of thumb and prior experience. The PHREEQC computer program can be used to calculate the progress of this and similar reactions, and aid in understanding, design and evaluation of these systems. At pH values less than 5, calcite dissolution rates are strongly influenced by transport parameters such as flow velocity. Estimated calcite dissolution rates from ALD's and column experiments indicate little change in rate with pH, in contrast to published data for well stirred lab experiments. The dissolution rate is affected by concentration of SO{sub 4}, Fe, Al, Ca, P, and other trace solutes. The optimum contact time and sizing of ALD's will be dependent on these and possibly other parameters. Additional experiments are needed to evaluate these dependencies.

  20. Monoclinic deformation of calcite crystals at ambient conditions

    NASA Astrophysics Data System (ADS)

    Przeniosło, R.; Fabrykiewicz, P.; Sosnowska, I.

    2016-09-01

    High resolution synchrotron radiation powder diffraction shows that the average crystal structure of calcite at ambient conditions is described with the trigonal space group R 3 bar c but there is a systematic hkl-dependent Bragg peak broadening. A modelling of this anisotropic peak broadening with the microstrain model from Stephens (1999) [15] is presented. The observed lattice parameters' correlations can be described by assuming a monoclinic-type deformation of calcite crystallites. A quantitative model of this monoclinic deformation observed at ambient conditions is described with the space group C 2 / c . The monoclinic unit cell suggested at ambient conditions is related with the monoclinic unit cell reported in calcite at high pressure (Merrill and Bassett (1975) [10]).

  1. Time and metamorphic petrology: Calcite to aragonite experiments

    USGS Publications Warehouse

    Hacker, B.R.; Kirby, S.H.; Bohlen, S.R.

    1992-01-01

    Although the equilibrium phase relations of many mineral systems are generally well established, the rates of transformations, particularly in polycrystalline rocks, are not. The results of experiments on the calcite to aragonite transformation in polycrystalline marble are different from those for earlier experiments on powdered and single-crystal calcite. The transformation in the polycrystalline samples occurs by different mechanisms, with a different temperature dependence, and at a markedly slower rate. This work demonstrates the importance of kinetic studies on fully dense polycrystalline aggregates for understanding mineralogic phase changes in nature. Extrapolation of these results to geological time scales suggests that transformation of calcite to aragonite does not occur in the absence of volatiles at temperatures below 200??C. Kinetic hindrance is likely to extend to higher temperatures in more complex transformations.

  2. Microbially Induced Calcite Precipitation for Subsurface Immobilization of Contaminants

    NASA Astrophysics Data System (ADS)

    Smith, R. W.; Fujita, Y.; Ginn, T. R.; Hubbard, S. S.; Dafflon, B.; Delwiche, M.; Gebrehiwet, T.; Henriksen, J. R.; Peterson, J.; Taylor, J. L.

    2011-12-01

    Subsurface radionuclide and metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of the greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent trace ions, such as the short-lived radionuclide 90Sr, is co-precipitation in calcite. We have found that calcite precipitation and co-precipitation of Sr can be accelerated by the activity of urea hydrolyzing microorganisms, that higher calcite precipitation rates can result in increased Sr partitioning, and that nutrient additions can stimulate ureolytic activity. To extend our understanding of microbially induced calcite precipitation (MICP) in an aquifer setting a continuous recirculation field experiment evaluating MICP was conducted at the Integrated Field Research Challenge (IFRC) site located at Rifle, CO. In this experiment, groundwater extracted from an onsite well was amended with urea (total mass of 42.5 kg) and molasses (a carbon and electron donor) and re-injected into a well approximately 4 meters up-gradient for a period of 12 days followed by 10 months of groundwater sampling and monitoring. Crosshole radar and electrical tomographic data were collected prior, during, and after the MICP treatment. The urea and molasses treatment resulted in an enhanced population of sediment associated urea hydrolyzing organisms as evidenced by increases in the number of ureC gene copies, increases in 14C urea hydrolysis rates, and long-term observations of ammonium (a urea hydrolysis product) in the injection, extraction and down gradient monitoring wells. Permeability changes and increases in the calcite saturation indexes in the well field suggest that mineral precipitation has occurred; ongoing analysis of field samples seeks to confirm this. Changes in dielectric constant and electrical conductivity were used to interpret the spatiotemporal distribution of the injectate and subsequent calcite precipitation. Modeling activities are underway to

  3. Is bicarbonate stable in and on the calcite surface?

    NASA Astrophysics Data System (ADS)

    Andersson, M. P.; Rodriguez-Blanco, J. D.; Stipp, S. L. S.

    2016-03-01

    We have used density functional theory with the COSMO-RS implicit solvent model to predict the pKa for the deprotonation of bicarbonate to carbonate, i.e. HCO3- <=> CO32- + H+, when HCO3- is included in, and adsorbed on, a calcite surface. We have used cluster models (80-100 atoms) to represent the flat {10.4} surface, acute steps, obtuse steps, two types of kinks on the acute step and two types of kinks on the obtuse steps. Based on the predicted pKa values, which range from -6.0 to 2.4 depending on the surface site, we conclude that bicarbonate deprotonates to carbonate when it is in calcite even when pH in solution is very low. This is true for all surface sites, even for solutions where 2.4 < pH < 6.35, where H2CO30 is the dominant dissolved species. When bicarbonate is adsorbed on calcite, the predicted pKa for deprotonation is 7.5, which is ∼3 pH units lower than in aqueous solution, 10.35. This means that adsorbed carbonate is stable even when the concentration of dissolved CO32- is several orders of magnitude lower. This has a significant effect on surface charge and thus the behaviour of the calcite surface. Our results help explain the potential determining behaviour of the carbonate species in calcite-water systems, particularly in the pH range where the bicarbonate species dominates in water and where the carbonate species dominates at the surface, i.e. when 7.5 < pH < 10.35. Our atomic scale data for the various calcite surface sites provide the needed input to improve and constrain surface complexation modelling and are especially useful for predicting behaviour in systems where experiments are difficult or impossible, such as at high temperature and pressure.

  4. Small scale shear zone in calcite: AMS and microstructure

    NASA Astrophysics Data System (ADS)

    Roxerová, Zuzana; Machek, Matěj; Kusbach, Vladimír; Racek, Martin; Silva, Pedro F.

    2016-04-01

    Two structural profiles across thin shear zone in calcite from quarry in Estremoz (Portugal) were studied to find a relationship between AMS and strain in natural rocks. The mesoscopic fabric is characterized by the change from the subhorizontal coarse-grained foliation towards the ~2cm-wide shear zone center with subvertical fine-grained foliation. In microstructure, the shear zone records dynamic recrystallization of calcite aggregate which resulted in development of porphyroclastic microstructure with increasing proportion of fine-grained recrystallized matrix towards the shear zone center. Two distinct crystallographic preferred orientations of calcite were recorded. One related with porphyroclasts, characterized by subvertical orientation of calcite axes and another associated with recrystallized matrix showing subhorizontal calcite axes orientation. The magnetic susceptibility ranges from -8e-6SI to 9e-6SI, with the average -4e-6SI. The majority of the rock mass is diamagnetic, corresponding well with the thermomagnetic curves, with local paramagnetic accumulations in form of thin bands. The AMS of the both profiles exhibits stable subvertical foliation bearing vertical lineation which is locally alternated by the medium-angle foliation. We interpret the AMS fabric pattern which is perpendicular to the mineral one as a type of inverse AMS fabric, due to high iron content in major part of calcite grains The magnetic and microstructural description of the shear zone is accompanied by numerical modeling of AMS based on CPO and different proportion of porphyroclasts, matrix and mica for purposes of deciphering the influence of present microstructural features on AMS.

  5. Sulfated Macromolecules as Templates for Calcite Nucleation and Growth

    NASA Astrophysics Data System (ADS)

    David, M.; Passalacqua, K.; Neira, A. C.; Fernandez, M. S.

    2003-12-01

    Mineralization of egg and seashells is controlled by an intimate association of inorganic materials with organic macromolecules. Among them, particular polyanionic sulfated macromolecules referred to as proteoglycans have been described to be involved in the calcification of these biominerals. The sulfated moieties of the proteoglycans are part of polymer chains constituted of building-blocks of disaccharide units, referred to as sulfated glycosaminoglycans (GAGs), which are covalently attached to a protein core. By using a sitting drop crystallization assay under controlled conditions of time, pH and reactants concentration, we have tested several sulfated and non-sulfated GAGs (i.e.: dermatan and keratan sulfate, hyaluronic acid and heparin), differing in their sulfonate and carboxylate degree and pattern, in their ability to modify calcium carbonate crystal morphology as observed under scanning electron microscopy. Without the addition of GAGs, regular \\{104\\} rhombohedral calcite crystals were obtained. When hyaluronic acid (HA), a non-sulfated but carboxylated GAG, was added, 20 mm long piles of unmodified calcite crystals were observed. When desulfated dermatan, which is an epimeric form of HA but shorter polymer, having their carboxylate groups in an inverted configuration, was added, isolated rhombohedral \\{104\\} calcite crystals showing rounded corners with planes oriented parallel to the c axis were observed. When dermatan sulfated was added, isolated calcite crystals exhibit a columnar morphology as a \\{hk0\\} cylinder with three \\{104\\} faces forming a cap at both ends. Heparin activity depends on the fraction added. Fast-moving heparin fraction (FM), is an undersulfated, low-molecular-weight heterogeneous polymer, while slow-moving heparin fraction (SM) is an high-molecular-weight homogeneous polymer rich in trisulfated-disaccharide units. When FM was added, isolated calcite crystals displayed rhombohedrical \\{104\\} faces but flat corners of

  6. Shallow burial dolomitization of Mid-Cenozoic, cool-water, calcitic deep-shelf limestones, southern Australia

    SciTech Connect

    James. N.P. ); Bone, Y. ); Kyser, T.K. )

    1991-03-01

    Oligocene to middle Miocene, deep-shelf, bryozoan-rich limestones across southern Australia are variably replaced by green to orange, Ca-rich, zoned, medium-crystalline, sucrosic dolomite. The degree of replacement varies from scattered rhombs in limestone to complete dolostones a few tens of meters in thickness and a few kilometers in lateral extent. Dolostone texture ranges from dense and well lithified to completely unlithified, resembling a loose sand of dolomite rhombs. Dolomitization is fabric specific; calcite and Mg-calcite bryozoans are either the last components to be replaced or are molds. The timing and locale of dolomitization are tightly constrained; Sr isotopes indicate a middle to late Miocene age while clasts of dolostone in overlying Pliocene limestones above a regional unconformity confirm a shallow-burial, pre-Pliocene origin. {delta}{sup 13}C and {delta}{sup 18}O values support a marine source for the carbonate; the influence of meteoric fluids appears to have been negligible. Quaternary exposure has resulted in local dedolomitization and/or subaerial erosion, especially in the Murray basin. These rocks are excellent analogues for localized, lenticular dolostone bodies in calcite-rich Paleozoic platform carbonates.

  7. Pore water evolution during sediment burial from isotopic and mineral chemistry of calcite, dolomite and siderite concretions

    NASA Astrophysics Data System (ADS)

    Curtis, C. D.; Coleman, M. L.; Love, L. G.

    1986-10-01

    Coal measures often contain concretions; segregations of diagenetic minerals originally formed within unconsolidated sediments. Three different types (calcite/pyrite, dolomite/pyrite and siderite) occurring spatially quite close together in the Central Pennine Region of England vary widely in carbon isotope composition (+10.35%. > δ13C > -21.49%.) and in major cation chemistry (Ca, Mg, Fe, Mn). Within some siderite concretions, very high Mn/Fe ratios were found in central subsamples; these were also most enriched in 13C. The Fe/Mg ratio decreases systematically from centre to edge (early, shallow to deeper, later precipitation). The calcite/pyrite and dolomite/pyrite concretions developed completely prior to significant burial. Both have high Mn/Fe ratios but negative δ 13C values (calcite -21.49%., dolomite -8.67 to -10.48%.). All of these patterns can be equated precisely with theories of pore water evolution developed on the basis of geochemical investigations of modem sediments. Microbial processes (sulphate reduction, methanogenesis) contributed significantly, as did thermal decarboxylation (to siderite precipitated at considerable burial depth). Mn(IV) and Fe(III) acted differentially as oxidants; producing CO 2 and increasing alkalinity. The interplay of fresh and marine depositional waters is seen most obviously in the presence or absence of sulphate reduction. This controlled mineral type (iron sulphide or carbonate) as well as isotopic and mineral chemistry.

  8. Influence of temperature and CO2 on the strontium and magnesium composition of coccolithophore calcite

    NASA Astrophysics Data System (ADS)

    Müller, M. N.; Lebrato, M.; Riebesell, U.; Ramos, J. Barcelos e.; Schulz, K. G.; Blanco-Ameijeiras, S.; Sett, S.; Eisenhauer, A.; Stoll, H. M.

    2014-02-01

    Marine calcareous sediments provide a fundamental basis for palaeoceanographic studies aiming to reconstruct past oceanic conditions and understand key biogeochemical element cycles. Calcifying unicellular phytoplankton (coccolithophores) are a major contributor to both carbon and calcium cycling by photosynthesis and the production of calcite (coccoliths) in the euphotic zone, and the subsequent long-term deposition and burial into marine sediments. Here we present data from controlled laboratory experiments on four coccolithophore species and elucidate the relation between the divalent cation (Sr, Mg and Ca) partitioning in coccoliths and cellular physiology (growth, calcification and photosynthesis). Coccolithophores were cultured under different seawater temperature and carbonate chemistry conditions. The partition coefficient of strontium (DSr) was positively correlated with both carbon dioxide (pCO2) and temperature but displayed no coherent relation to particulate organic and inorganic carbon production rates. Furthermore, DSr correlated positively with cellular growth rates when driven by temperature but no correlation was present when changes in growth rates were pCO2-induced. Our results demonstrate the complex interaction between environmental forcing and physiological control on the strontium partitioning in coccolithophore calcite and challenge interpretations of the coccolith Sr / Ca ratio from high-pCO2 environments (e.g. Palaeocene-Eocene thermal maximum). The partition coefficient of magnesium (DMg) displayed species-specific differences and elevated values under nutrient limitation. No conclusive correlation between coccolith DMg and temperature was observed but pCO2 induced a rising trend in coccolith DMg. Interestingly, the best correlation was found between coccolith DMg and chlorophyll a production, suggesting that chlorophyll a and calcite associated Mg originate from the same intracellular pool. These and previous findings indicate that Mg

  9. Stable carbon isotopes and lipid biomarkers provide new insight into the formation of calcite and siderite concretions in organic-matter rich deposits

    NASA Astrophysics Data System (ADS)

    Baumann, Lydia; Birgel, Daniel; Wagreich, Michael; Peckmann, Jörn

    2015-04-01

    Carbonate concretions from two distinct settings have been studied for their petrography, stable carbon and oxygen isotopes, and lipid biomarker content. Carbonate concretions are in large part products of microbial degradation of organic matter, as for example by sulfate-reducing bacteria, iron-reducing bacteria, and methanogenic archaea. For these prokaryotes certain lipid biomarkers such as hopanoids, terminally-branched fatty acids (bacteria) and isoprenoids (archaea) are characteristic. Two different types of concretions were studied: a) Upper Miocene septarian calcite concretions of the southern Vienna Basin embedded in brackish sediments represented by partly bituminous calcareous sands, silts and clays; b) Paleocene-Eocene siderite concretions enclosed in marine, sandy to silty turbidites with varying carbonate contents and marl layers from the Upper Gosau Subgroup in northern Styria. Calcite concretions consist of abundant calcite microspar (80-90 vol.%), as well as detrital minerals and iron oxyhydroxides. The septarian cracks show beginning cementation with dog-tooth calcite to varying degrees. Framboidal pyrite occurs in some of the calcite concretions, pointing to bacterial sulfate reduction. Siderite concretions consist of even finer carbonate crystals, mainly siderite (40-70 vol.%) but also abundant ferroan calcite, accompanied by iron oxyhydroxides and detrital minerals. The δ13C values of the calcite concretions (-6.8 to -4.1o ) most likely reflect a combination of bacterial organic matter oxidation and input of marine biodetrital carbonate. The δ18O values range from -8.9 to -7.8o agreeing with a formation within a meteoric environment. The surrounding host sediment shows about 1-2o higher δ13C and δ18O values. The siderite δ13C values (-11.1 to -7.5o ) point to microbial respiration of organic carbon and the δ18O values (-3.5 to +2.2o ) agree with a marine depositional environment. In contrast to the calcite concretions, the stable isotope

  10. The mechanism of Zn sup 2+ adsorption on calcite

    SciTech Connect

    Zachara, J.M. ); Kittrick, J.A.; Harsh, J.B. )

    1988-09-01

    The adsorption of Zn{sup 2+} on calcite (CaCO{sub 3(s)}) was investigated from aqueous solutions in equilibrium with CaCO{sub 3(s)} and undersaturated with respect to Zn{sub 5}(OH){sub 6}(CO{sub 3}){sub 2(s)}. Zinc adsorption occurred via exchange with Ca{sub 2+} in a surface-adsorbed layer on calcite. The validity of this exchange reaction was supported by adsorption isotherm and constant concentration experiments, where Ca{sup 2+}{sub aq} was varied by systematically changing the pH and CO{sub 2(g)}. Greater adsorption of Zn{sup 2+} occurred at higher pH and Co{sub 2(g)} levels, where Ca{sup 2+} activities were lowest. Sites available for Zn{sup 2+} sorption were less than 10% of Ca{sup 2+} sites on the calcite surface. Surface exchange of Zn{sup 2+} did not affect the solubility of calcite. Zinc sorption was apparently independent of surface charge, which suggested that the surface complex had covalent character. Desorption and isotopic exchange experiments indicated that the surface complex remained hydrated and labile as Zn{sup 2+} was rapidly exchangeable with Ca{sup 2+}. Careful analysis of the adsorption data showed that Zn{sup 2+} and ZnOH{sup +} were the sorbing species.

  11. Incorporation of Eu(III) into Calcite under Recrystallization conditions.

    PubMed

    Hellebrandt, S E; Hofmann, S; Jordan, N; Barkleit, A; Schmidt, M

    2016-01-01

    The interaction of calcite with trivalent europium under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). We conducted batch studies with a reaction time from seven days up to three years with three calcite powders, which differed in their specific surface area, recrystallization rates and impurities content. With increase of the recrystallization rate incorporation of Eu(3+) occurs faster and its speciation comes to be dominated by one species with its excitation maximum at 578.8 nm, so far not identified during previous investigations of this process under growth and phase transformation conditions. A long lifetime of 3750 μs demonstrates complete loss of hydration, consequently Eu must have been incorporated into the bulk crystal. The results show a strong dependence of the incorporation kinetics on the recrystallization rate of the different calcites. Furthermore the investigation of the effect of different background electrolytes (NaCl and KCl) demonstrate that the incorporation process under recrystallization conditions strongly depends on the availability of Na(+). These findings emphasize the different retention potential of calcite as a primary and secondary mineral e.g. in a nuclear waste disposal site. PMID:27618958

  12. Utricular otoconia of some amphibians have calcitic morphology

    NASA Technical Reports Server (NTRS)

    Pote, K. G.; Ross, M. D.

    1993-01-01

    This report concerns the morphological features of otoconia removed from the inner ear of four amphibian species. Results from scanning electron microscopic examination are compared based on the site of origin. These results show that utricular otoconia have a mineral structure that mimics calcite, rather than the widely accepted idea that they are mineralized by calcium carbonate of the aragonite polymorph.

  13. Atomistic simulation of the differences between calcite and dolomite surfaces

    SciTech Connect

    Titiloye, J.O.; Leeuw, N.H. de; Parker, S.C.

    1998-08-01

    Atomistic simulation methods have been used to calculate and compare the surface structures and energies of the {l_brace}10{bar 1}4{r_brace}, {l_brace}0001{r_brace}, {l_brace}10{bar 1}0{r_brace}, {l_brace}11{bar 2}0{r_brace} and {l_brace}10{bar 1}1{r_brace} surfaces of calcite and dolomite and to evaluate their equilibrium morphologies. The calcite {l_brace}10{bar 1}4{r_brace} and the dolomite {l_brace}10{bar 1}0{r_brace} and {l_brace}11{bar 2}0{r_brace} surfaces are the most stable crystal planes. Investigation of the segregation of Mg and Ca ions in the dolomite crystal shows a clear preference for Ca{sup 2+} ions at the surface sites and for Mg{sup 2+} ions in the bulk sites and hence growth onto dolomite results in calcium carbonate or high magnesian calcite crystals which helps explain the difficulty in crystallizing dolomite vs. calcite under laboratory conditions.

  14. Isolation and identification of Pseudomonas azotoformans for induced calcite precipitation.

    PubMed

    Heidari Nonakaran, Siamak; Pazhouhandeh, Maghsoud; Keyvani, Abdullah; Abdollahipour, Fatemeh Zahra; Shirzad, Akbar

    2015-12-01

    Biomineralization is a process by which living organisms produce minerals. The extracellular production of these biominerals by microbes has potential for various bioengineering applications. For example, crack remediation and improvement of durability of concrete is an important goal for engineers and biomineral-producing microbes could be a useful tool in achieving this goal. Here we report the isolation, biochemical characterization and molecular identification of Pseudomonas azotoformans, a microbe that produces calcite and which potentially be used to repair cracks in concrete structures. Initially, 38 bacterial isolates were isolated from soil and cements. As a first test, the isolates were screened using a urease assay followed by biochemical tests for the rate of urea hydrolysis, calcite production and the insolubility of calcite. Molecular amplification and sequencing of a 16S rRNA fragment of selected isolates permitted us to identify P. azotoformans as a good candidate for preparation of biotechnological concrete. This species was isolated from soil and the results show that among the tested isolates it had the highest rate of urea hydrolysis, produced the highest amount of calcite, which, furthermore was the most adhesive and insoluble. This species is thus of interest as an agent with the potential ability to repair cracks in concrete. PMID:26386580

  15. NMR spectroscopic study of organic phosphate esters coprecipitated with calcite

    NASA Astrophysics Data System (ADS)

    Phillips, Brian L.; Zhang, Zelong; Kubista, Laura; Frisia, Silvia; Borsato, Andrea

    2016-06-01

    Organic phosphorus incorporated in calcite during laboratory precipitation experiments and in natural cave deposits was investigated by solid-state NMR spectroscopy. For calcite precipitated in the presence of organic phosphoesters of varying size and functionality, solid-state 31P{1H} CP/MAS NMR shows that the phosphoesters were incorporated intact into the solid. Systematic changes in the 31P NMR chemical shift of the phosphate group were observed between the solid phosphoester and that incorporated in the solid precipitate, yielding 31P NMR chemical shifts of the coprecipitates in the range of +1.8 to -2.2 ppm. These chemical shifts are distinct from that of similarly prepared calcite coprecipitated with inorganic phosphate, 3.5 ppm. Only minor changes were noted in the phosphoester 31P chemical shift anisotropy (CSA) which suggests no significant change in the local structure of the phosphate group, which is dominated by C-O-P bonding. Close spatial proximity of the organic phosphate group to calcite structural components was revealed by 31P/13C rotational echo double resonance (REDOR) experiments for coprecipitates prepared with 13C-labeled carbonate. All coprecipitates showed significant 31P dephasing effects upon 13C-irradiation, signaling atomic-scale proximity to carbonate carbon. The dephasing rate for smaller organophosphate molecules is similar to that observed for inorganic phosphate, whereas much slower dephasing was observed for larger molecules having long and/or bulky side-chains. This result suggests that small organic molecules can be tightly enclosed within the calcite structure, whereas significant structural disruption required to accommodate the larger organic molecules leads to longer phosphate-carbonate distances. Comparison of 31P NMR spectroscopic data from the synthetic coprecipitates with those from calcite moonmilk speleothems indicates that phosphorus occurs mainly as inorganic orthophosphate in the natural deposits, although small

  16. Proton/calcium ion exchange behavior of calcite.

    PubMed

    Villegas-Jiménez, Adrián; Mucci, Alfonso; Paquette, Jeanne

    2009-10-21

    The characterization of the proton sorptive properties of calcite in aqueous solutions at 25 +/- 1 degrees C over a relatively wide range of chemical conditions (7.16 calcite surface (species identified by "(exc)"), , that leads to a transient, "apparent" incongruent dissolution regime and the formation of a stable calcium-deficient, proton-enriched layer within the calcite lattice under circum-neutral and alkaline regimes at standard conditions. The 2H(+)/Ca(2+) ion exchange is quantitatively described by the Langmuir-power exchange function under the Vanselow convention: where n = 1 and log(10)K(ex) = 13.0 +/- 0.3. This calcite behavior, never reported before, masks surface equilibria and directly impacts the aqueous speciation of carbonate-rock systems with poor CO(2)(g) ventilation (e.g., aquifers, pore and deep sea waters, industrial reactors) via the buffering of pH and calcite dissolution. In contrast, at fixed pCO(2) conditions, aqueous speciation remains unaffected upon CO(2)(g) sequestration resulting from ion exchange-induced calcite precipitation: ([triple bond]CaCO3)2(exc) + CO2(g) + H2O <==> [triple bond]Ca(HCO3)2(exc) + CaCO3(s). Accordingly, reliable predictions of aqueous speciation in natural or engineered calcite-containing systems at variable pCO(2) conditions must consider this exchange reaction and the associated K(ex). The postulated proton/calcium exchange may have far

  17. Experimental study of the replacement of calcite by calcium sulphates

    NASA Astrophysics Data System (ADS)

    Ruiz-Agudo, E.; Putnis, C. V.; Hövelmann, J.; Álvarez-Lloret, P.; Ibáñez-Velasco, A.; Putnis, A.

    2015-05-01

    Among the most relevant mineral replacement reactions are those involving sulphates and carbonates, which have important geological and technological implications. Here it is shown experimentally that during the interaction of calcite (CaCO3) cleavage surfaces with sulphate-bearing acidic solutions, calcite is ultimately replaced by gypsum (CaSO4 2H2O) and anhydrite (CaSO4), depending on the reaction temperature. Observations suggest that this occurs most likely via an interface-coupled dissolution-precipitation reaction, in which the substrate is replaced pseudomorphically by the product. At 120 and 200 °C gypsum and/or bassanite (CaSO4·0.5H2O) form as precursor phases for the thermodynamically stable anhydrite. Salinity promotes the formation of less hydrated precursor phases during the replacement of calcite by anhydrite. The reaction stops before equilibrium with respect to calcite is reached and during the course of the reaction most of the bulk solutions are undersaturated with respect to the precipitating phase(s). A mechanism consisting of the dissolution of small amounts of solid in a thin layer of fluid at the mineral-fluid interface and the subsequent precipitation of the product phase from this layer is in agreement with these observations. PHREEQC simulations performed in the framework of this mechanism highlight the relevance of transport and surface reaction kinetics on the volume change associated with the CaCO3-CaSO4 replacement. Under our experimental conditions, this reaction occurs with a positive volume change, which ultimately results in passivation of the unreacted substrate before calcite attains equilibrium with respect to the bulk solution.

  18. On the Shock Behavior of Calcite: Recent Results from MEMIN Experiments

    NASA Astrophysics Data System (ADS)

    Hamann, C.; Hecht, L.; Deutsch, A.

    2015-09-01

    Hypervelocity impact and laser melting experiments, aiming at a better understanding of the shock behavior of calcite, suggest that both melting and decomposition of calcite can occur at P-T conditions commensurate with impact processes.

  19. Impact-Induced Devolatilization or Melting of Calcite? Or Both? Answers from MEMIN Experiments

    NASA Astrophysics Data System (ADS)

    Hamann, C.; Hecht, L.; Deutsch, A.

    2015-07-01

    Calcite was experimentally shocked in a series of MEMIN hypervelocity impact and laser melting experiments. Evidence for the formation of calcite melts in both types of experiments is presented and discussed.

  20. Alkaline flocculation of Phaeodactylum tricornutum induced by brucite and calcite

    SciTech Connect

    Vandamme, Dries; Pohl, Philip I.; Beuckels, Annelies; Foubert, Imogen; Brady, Patrick Vane; Muylaert, Koenraad; Hewson, John C.

    2015-08-20

    Alkaline flocculation holds great potential as a low-cost harvesting method for marine microalgae biomass production. Alkaline flocculation is induced by an increase in pH and is related to precipitation of calcium and magnesium salts. In this study, we used the diatom Phaeodactylum tricornutum as model organism to study alkaline flocculation of marine microalgae cultured in seawater medium. Flocculation started when pH was increased to 10 and flocculation efficiency reached 90% when pH was 10.5, which was consistent with precipitation modeling for brucite or Mg(OH)2. Compared to freshwater species, more magnesium is needed to achieve flocculation (>7.5 mM). Zeta potential measurements suggest that brucite precipitation caused flocculation by charge neutralization. When calcium concentration was 12.5 mM, flocculation was also observed at a pH of 10. Furthermore, zeta potential remained negative up to pH 11.5, suggesting that precipitated calcite caused flocculation by a sweeping coagulation mechanism.

  1. Outside the pH box: Boron isotopes in synthetic calcite precipitated under varying solution chemistry

    NASA Astrophysics Data System (ADS)

    Farmer, J. R.; Uchikawa, J.; Penman, D. E.; Hoenisch, B.; Zeebe, R. E.

    2015-12-01

    Boron isotopic measurements (δ11B) in marine carbonates are a powerful tool for reconstructing past ocean carbon chemistry and the carbon cycle. Boron systematics in marine carbonates are rooted in the equilibrium dissociation of dissolved boron in seawater, but existing evidence from biogenic carbonates (corals, planktic and benthic foraminifers) suggests somewhat variable controls on boron concentration and δ11B. Synthetic precipitation experiments provide an opportunity to study boron systematics without biological interference, and recent studies (e.g., Uchikawa et al., 2015, GCA v150, 171-191) suggest that boron incorporation (measured as B/Ca ratios) into synthetic carbonates varies both with the elemental composition of experimental seawater and precipitation rate. Here we extend the geochemical characterization of synthetic calcite by investigating the influences of changing solution chemistry (pH, [Ca2+], [DIC] and [B]) and precipitation rate on their boron isotopic composition. Our results will be evaluated in the context of carbonate precipitation rates, modes of boron incorporation, and changing seawater chemistry through geologic time.

  2. Fracture-aperture alteration induced by calcite precipitation

    NASA Astrophysics Data System (ADS)

    Jones, T.; Detwiler, R. L.

    2013-12-01

    Mineral precipitation significantly alters the transport properties of fractured rock. Chemical solubility gradients that favor precipitation induce mineral growth, which decreases the local aperture and alters preferential flow paths. Understanding the resulting development of spatial heterogeneities is necessary to predict the evolution of transport properties in the subsurface. We present experimental results that quantify the relationship between mineral precipitation and aperture alteration in a transparent analog fracture, 7.62cm x 7.62cm, with a uniform aperture of ~200 μm. Prior to flow experiments, a pump circulated a super-saturated calcite solution over the bottom glass, coating the glass surface with calcite. This method of seeding resulted in clusters of calcite crystals with large reactive surface area and provided micro-scale variability in the aperture field. A continuous flow syringe pump injected a reactive fluid into the fracture at 0.5 ml/min. The fluid was a mixture of sodium bicarbonate (NaHCO3, 0.02M) and calcium chloride (CaCl2 0.0004M) with a saturation index, Ω, of 8.51 with respect to calcite. A strobed LED panel backlit the fracture and a high-resolution CCD camera monitored changes in transmitted light intensity. Light transmission techniques provided a quantitative measurement of fracture aperture over the flow field. Results from these preliminary experiments showed growth near the inlet of the fracture, with decreasing precipitation rates in the flow direction. Over a period of two weeks, the fracture aperture decreased by 17% within the first 4mm of the inlet. Newly precipitated calcite bridged individual crystal clusters and smoothed the reacting surface. This observation is an interesting contradiction to the expectation of surface roughening induced by mineral growth. Additionally, the aperture decreased uniformly across the width of the fracture due to the initial aperture distribution. Future experiments of precipitation

  3. Characterization of various stages of calcitization in Porites sp corals from uplifted reefs — Case studies from New Caledonia, Vanuatu, and Futuna (South-West Pacific)

    NASA Astrophysics Data System (ADS)

    Rabier, Cécile; Anguy, Yannick; Cabioch, Guy; Genthon, Pierre

    2008-11-01

    This study focuses on the processes of calcitization under meteoric conditions based on observations and analyses of a series of subaerial fossil corals of the genus Porites collected from emerged Holocene and Pleistocene reefs in the Pacific Ocean. We can establish two types of low-magnesian calcite (LMC) precipitates according to their textural characteristics after their transformation from the initial aragonitic skeleton to the calcitized corals. In the first variety (LMC1), the calcite contains remnants of the original exoskeleton structure ( in situ insoluble organic tissues, pieces of aragonite needles) while in the second variety (LMC2) — filling the primary inter-skeletal macro-pores — such relicts are not present. Such textural segregation is faithfully reflected in the elemental data on some parts of calcitized corals. LMC1 is characterized by Mg 2+, Sr 2+, and Mn 2+ compositions inherited from the aragonite precursor, indicating a formation in a semi-closed intra-skeleton diagenetic environment in disequilibrium with the meteoric bulk aquifer water. LMC2 has a chemistry indicative of equilibrium with ambient bulk meteoric water. These chemical characteristics can be likened to a two-fold mechanism: a fine-scale process — neomorphism — typified by the concomitant dissolution of intra-fabric aragonite and re-precipitation of the LMC1 resulting from the 'biogenic' skeleton and marine waters, followed by the cementation of the inter-fabric macro-voids by an allochthonous subaerial and meteoric LMC2. In the other parts of calcitized corals, LMC1 and LMC2 have similar trace element contents in Mg 2+ and Sr 2+. The chemical data are consistent with formation by partial skeletal dissolution followed eventually by cementation of primary voids (LMC2) and secondary voids (LMC1) by calcite in equilibrium with meteoric bulk aquifer water. These two mechanisms of the calcitization of skeletal aragonite mainly differ in the space and time length-scales of the

  4. Tuning hardness in calcite by incorporation of amino acids.

    PubMed

    Kim, Yi-Yeoun; Carloni, Joseph D; Demarchi, Beatrice; Sparks, David; Reid, David G; Kunitake, Miki E; Tang, Chiu C; Duer, Melinda J; Freeman, Colin L; Pokroy, Boaz; Penkman, Kirsty; Harding, John H; Estroff, Lara A; Baker, Shefford P; Meldrum, Fiona C

    2016-08-01

    Structural biominerals are inorganic/organic composites that exhibit remarkable mechanical properties. However, the structure-property relationships of even the simplest building unit-mineral single crystals containing embedded macromolecules-remain poorly understood. Here, by means of a model biomineral made from calcite single crystals containing glycine (0-7 mol%) or aspartic acid (0-4 mol%), we elucidate the origin of the superior hardness of biogenic calcite. We analysed lattice distortions in these model crystals by using X-ray diffraction and molecular dynamics simulations, and by means of solid-state nuclear magnetic resonance show that the amino acids are incorporated as individual molecules. We also demonstrate that nanoindentation hardness increased with amino acid content, reaching values equivalent to their biogenic counterparts. A dislocation pinning model reveals that the enhanced hardness is determined by the force required to cut covalent bonds in the molecules. PMID:27135858

  5. U(VI) behaviour in hyperalkaline calcite systems

    NASA Astrophysics Data System (ADS)

    Smith, Kurt F.; Bryan, Nicholas D.; Swinburne, Adam N.; Bots, Pieter; Shaw, Samuel; Natrajan, Louise S.; Mosselmans, J. Frederick W.; Livens, Francis R.; Morris, Katherine

    2015-01-01

    The behaviour of U(VI) in hyperalkaline fluid/calcite systems was studied over a range of U(VI) concentrations (5.27 × 10-5 μM to 42.0 μM) and in two high pH systems, young and old synthetic cement leachate in batch sorption experiments. These systems were selected to be representative of young- (pH 13.3) and old-stage (pH 10.5) leachate evolution within a cementitious geological disposal facility. Batch sorption experiments, modelling, extended X-ray absorption fine structure spectroscopy, electron microscopy, small angle X-ray scattering and luminescence spectroscopy were used to define the speciation of U(VI) across the systems of study. At the lowest concentrations (5.27 × 10-5 μM 232U(VI)) significant U removal was observed for both old and young cement leachates, and this was successfully modelled using a first order kinetic adsorption modelling approach. At higher concentrations (>4.20 μM) in the young cement leachate, U(VI) showed no interaction with the calcite surface over an 18 month period. Small angle X-ray scattering techniques indicated that at high U concentrations (42.0 μM) and after 18 months, the U(VI) was present in a colloidal form which had little interaction with the calcite surface and consisted of both primary and aggregated particles with a radius of 7.6 ± 1.1 and 217 ± 24 Å, respectively. In the old cement leachate, luminescence spectroscopy identified two surface binding sites for U(VI) on calcite: in the system with 0.21 μM U(VI), a liebigite-like Ca2UO2(CO3)3 surface complex was identified; at higher U(VI) concentrations (0.42 μM), a second binding site of undetermined coordination was identified. At elevated U(VI) concentrations (>2.10 μM) in old cement leachate, both geochemical data and luminescence spectroscopy suggested that surface mediated precipitation was controlling U(VI) behaviour. A focused ion beam mill was used to create a section across the U(VI) precipitate-calcite interface. Transmission electron

  6. Tuning hardness in calcite by incorporation of amino acids

    NASA Astrophysics Data System (ADS)

    Kim, Yi-Yeoun; Carloni, Joseph D.; Demarchi, Beatrice; Sparks, David; Reid, David G.; Kunitake, Miki E.; Tang, Chiu C.; Duer, Melinda J.; Freeman, Colin L.; Pokroy, Boaz; Penkman, Kirsty; Harding, John H.; Estroff, Lara A.; Baker, Shefford P.; Meldrum, Fiona C.

    2016-08-01

    Structural biominerals are inorganic/organic composites that exhibit remarkable mechanical properties. However, the structure-property relationships of even the simplest building unit--mineral single crystals containing embedded macromolecules--remain poorly understood. Here, by means of a model biomineral made from calcite single crystals containing glycine (0-7 mol%) or aspartic acid (0-4 mol%), we elucidate the origin of the superior hardness of biogenic calcite. We analysed lattice distortions in these model crystals by using X-ray diffraction and molecular dynamics simulations, and by means of solid-state nuclear magnetic resonance show that the amino acids are incorporated as individual molecules. We also demonstrate that nanoindentation hardness increased with amino acid content, reaching values equivalent to their biogenic counterparts. A dislocation pinning model reveals that the enhanced hardness is determined by the force required to cut covalent bonds in the molecules.

  7. The effect of sulfated polysaccharides on the crystallization of calcite superstructures

    NASA Astrophysics Data System (ADS)

    Fried, Ruth; Mastai, Yitzhak

    2012-01-01

    Calcite with unique morphology and uniform size has been successfully synthesized in the presence of classes of polysaccharides based on carrageenans. In the crystallization of calcite, the choice of different carrageenans, (iota, lambda and kappa), as additives concedes systematic study of the influence of different chemical structures and particularly molecular charge on the formation of CaCO 3 crystals. The uniform calcite superstructures are formed by assemblies and aggregation of calcite crystals. The mechanism for the formation of calcite superstructures was studied by a variety of techniques, SEM, TEM, XRD, time-resolved conductivity and light scattering measurements, focusing on the early stages of crystals' nucleation and aggregation.

  8. Abiotic Methane Synthesis: Caveats and New Results

    NASA Astrophysics Data System (ADS)

    Zou, R.; Sharma, A.

    2005-12-01

    The role of mineral interaction with geochemical fluids under hydrothermal conditions has invoked models of geochemical synthesis of organic molecules at deep crustal conditions. Since Thomas Gold's (1992) hypothesis of the possibility of an abiotic organic synthesis, there have been several reports of hydrocarbon formation under high pressure and temperature conditions. Several previous experimental studies have recognized that small amounts of methane (and other light HC compounds) can be synthesized via catalysis by transition metals: Fe, Ni (Horita and Berndt, 1999 Science) and Cr (Foustavous and Seyfried, 2004 Science). In light of these pioneering experiments, an investigation of the feasibility of abiotic methane synthesis at higher pressure conditions in deep geological setting and the possible role of catalysis warrants a closer look. We conducted three sets of experiments in hydrothermal diamond anvil cell using FeO nanopowder, CaCO 3 and water at 300° - 600° C and 0.5 - 5 GPa : (a) with stainless steel gasket, (b) gold-lined gasket, and (c) gold-lined gasket with added Fe and Ni nanopowder. The reactions were monitored in-situ using micro-Raman spectroscopy with 532nm and 632nm lasers. The solids phases were characterized in-situ using synchrotron X-ray diffraction at CHESS-Cornell and quenched products with an electron microprobe. Interestingly, a variable amount of hydrocarbon was observed only in runs with stainless steel gasket and with Fe, Ni nanoparticles. Experiments with gold-lined reactors did not show any hydrocarbon formation. Added high resolution microscopy of the products and their textural relationship within the diamond cell with Raman spectroscopy data show that the hydrocarbon (methane and other light fractions) synthesis is a direct result of transition metal catalysis, rather than wustite - calcium carbonate reaction as recently reported by Scott et al (2004, PNAS). The author will further present new results highlighting abiotic

  9. Generation of RNA in abiotic conditions.

    NASA Astrophysics Data System (ADS)

    di Mauro, Ernesto

    Generation of RNA in abiotic conditions. Ernesto Di Mauro Dipartimento di Genetica Bi-ologia Molecolare, Universit` "Sapienza" Roma, Italy. a At least four conditions must be satisfied for the spontaneous generation of (pre)-genetic poly-mers: 1) availability of precursors that are activated enough to spontaneously polymerize. Preliminary studies showed that (a) nucleic bases and acyclonucleosides can be synthesized from formamide H2NCOH by simply heating with prebiotically available mineral catalysts [last reviewed in (1)], and that b) nucleic bases can be phosphorylated in every possible posi-tion [2'; 3'; 5'; cyclic 2',3'; cyclic 3',5' (2)]. The higher stability of the cyclic forms allows their accumulation. 2) A polymerization mechanism. A reaction showing the formation of RNA polymers starting from prebiotically plausible precursors (3',5' cyclic GMP and 3', 5'cyclic AMP) was recently reported (3). Polymerization in these conditions is thermodynamically up-hill and an equilibrium is attained that limits the maximum length of the polymer produced to about 40 nucleotides for polyG and 100 nucleotides for polyA. 3) Ligation of the synthesized oligomers. If this type of reaction could occur according to a terminal-joining mechanism and could generate canonical 3',5' phosphodiester bonds, exponential growth would be obtained of the generated oligomers. This type of reaction has been reported (4) , limited to homogeneous polyA sequences and leading to the production of polyA dimers and tetramers. What is still missing are: 4) mechanisms that provide the proof of principle for the generation of sequence complexity. We will show evidence for two mechanisms providing this proof of principle for simple complementary sequences. Namely: abiotic sequence complementary-driven terminal ligation and sequence-complementary terminal growth. In conclusion: all the steps leading to the generation of RNA in abiotic conditions are satisfied. (1) R Saladino, C Crestini, F

  10. Use of coupled passivants and consolidants on calcite mineral surfaces

    SciTech Connect

    Nagy, K.L.; Cygan, R.T.; Brinker, C.J.; Ashley, C.S.; Scotto, C.S.

    1997-02-01

    Deterioration of monuments, buildings, and works of art constructed of carbonate-based stone potentially can be arrested by applying a combination of chemical passivants and consolidants that prevent hydrolytic attack and mechanical weakening. The authors used molecular modeling and laboratory synthesis to develop an improved passivating agent for the calcite mineral surface based on binding strength and molecular packing density. The effectiveness of the passivating agent with and without a linked outer layer of consolidant against chemical weathering was determined through leaching tests conducted with a pH-stat apparatus at pH 5 and 25 C. For the range of molecules considered, modeling results indicate that the strongest-binding passivant is the trimethoxy dianionic form of silylalkylaminocarboxylate (SAAC). The same form of silylalkylphosphonate (SAP) is the second strongest binder and the trisilanol neutral form of aminoethylaminopropylsilane (AEAPS) is ranked third. Short-term leaching tests on calcite powders coated with the trisilanol derivative of SAAC, the triethoxy neutral form of SAP, and the trimethoxy neutral form of AEAPS show that the passivant alone does not significantly slow the dissolution rate. However, all passivants when linked to the sol consolidant result in decreased rates. Combined AEAPS plus consolidant results in a coating that performs better than the commercial product Conservare{reg_sign} OH and at least as well as Conservare{reg_sign} H. The modeling results indicate that there may be a threshold binding energy for the passivant above which the dissolution rate of calcite is actually enhanced. More strongly-binding passivants may aid in the dissolution mechanism or dissociate in aqueous solution exposing the calcite surface to water.

  11. Calcite mylonites in the Central Alpine ``root zone''

    NASA Astrophysics Data System (ADS)

    Heitzmann, Peter

    1987-04-01

    North of the Insubric line, in the Central Alpine "root zone", carbonate rocks are concentrated in very narrow zones and have been metamorphosed under amphibolite facies conditions by the Tertiary Lepontine metamorphism (grain size ~1 mm). Post-metamorphic deformation under greenschist facies conditions produced calcite mylonite bands a few millimeters to tens of meters wide in these marble zones. Microstructural development begins with twin formation, bending of twin boundaries, grain and twin boundary migration and recrystallization in high stress regions. Progressive mylonitization—by dynamic recrystallization—results in a microstructure with elongated calcite crystals (long axis 20-50 μm, axial ration 1:4). In this fine-grained matrix, porphyroclasts of calcite, quartz, white mica, biotite, diopside, tremolite, scapolite and plagioclase are preserved. Ultra-mylonite bands in pure calcite rocks show an even finer grain size of 5-10 μm. Lattice preferred orientation is not present in the undeformed marbles, but it develops during mylonitization. The c-axis orientation in the mylonites forms an asymmetric point maximum. In the ultra-mylonite no preferred orientation is left. It is concluded from microstructural and textural aspects, that during mylonitization, dislocation creep accompanied by dynamic recrystallization were the most important processes, whilst grain-boundary sliding was the dominant mechanism during the formation of the ultra-mylonites. Shear-sense determinations indicate a horizontal right-lateral strike-slip shear system. This is in good agreement with evidence regarding other movements along the Insubric line which can be observed in ductile and brittle shear zones.

  12. Interaction of copper with the surface of calcite

    SciTech Connect

    Franklin, M.L.; Morse, J.W.

    1981-05-01

    The interaction of Cu ions in solution with the surface of calcite has been studied in a range of solutions from pure water to seawater. Observations of the uptake of Cu from solution onto calcite indicates that the process is rapid and strong in both distilled water and seawater. In distilled water, Cu uptake is directly proportional to the concentration of Cu in solution; Cu/sub s/ = K/sub s/Cu/sub 1/. This Cu/sub s/ dependence on Cu/sub 1/ is linear over the entire Cu concentration range studied (0.1 to 200 ..mu..M). Results do not indicate the formation of a precipitate of either malachite or copper carbonate. In seawater, the uptake of Cu is also directly proportional to the concentration of Cu/sub 1/ up to a limiting value of approximately 13 ..mu..M. The average value for K/sub s/ in seawater, 0.24 +- 0.06 (Cu/sub 1/ less than or equal to 13 ..mu..M), is approximately an order of magnitude less than in distilled water. This is probably the result of smaller Cu/sub 1/ activity coefficients and increased site competition by other ions in seawater. Attempts to increase the Cu/sub 1/ concentration above 13 ..mu..M resulted in the additional Cu being deposited on the surface of the calcite. A possible explanation for this behavior is the formation of a precipitate of malachite on the calcite surface. The value of K/sub s/ decreased slightly with increasing solid to solution ratios in seawater.

  13. The effect of dissolved magnesium on diffusion creep in calcite

    NASA Astrophysics Data System (ADS)

    Herwegh, Marco; Xiao, Xiaohui; Evans, Brian

    2003-07-01

    We experimentally tested a series of synthetic calcite marbles with varying amounts of dissolved magnesium in a standard triaxial deformation machine at 300 MPa confining pressure, temperatures between 700 and 850°C, stresses between 2 and 100 MPa, and strain rates between 10 -7 and 10 -3 s -1. The samples were fabricated by hot isostatic pressing of a mixture of calcite and dolomite at 850°C and 300 MPa. The fabrication protocol resulted in a homogeneous, fine-grained high-magnesian calcite aggregate with minimal porosity and with magnesium contents between 0.07 and 0.17 mol% MgCO 3. At stresses below 40 MPa the samples deformed with linear viscosity that depended inversely on grain size to the 3.26±0.51 power, suggesting that the mechanisms of deformation were some combination of grain boundary diffusion and grain boundary sliding. Because small grain sizes tended to occur in the high-magnesium calcite, the strength also appeared to vary inversely with magnesium content. However, the strength at constant grain size does not depend on the amount of dissolved magnesium, and thus, the impurity effect seems to be indirect. At stresses higher than 40 MPa, the aggregates become non-linearly viscous, a regime we interpret to be dislocation creep. The transition between the two regimes depends on grain size, as expected. The activation energy for diffusion creep is 200±30 kJ/mol and is quite similar to previous measurements in natural and synthetic marbles deformed at similar conditions with no added magnesium.

  14. Earthworm-produced calcite granules: A new terrestrial palaeothermometer?

    NASA Astrophysics Data System (ADS)

    Versteegh, Emma A. A.; Black, Stuart; Canti, Matthew G.; Hodson, Mark E.

    2013-12-01

    In this paper we show for the first time that calcite granules, produced by the earthworm Lumbricus terrestris, and commonly recorded at sites of archaeological interest, accurately reflect temperature and soil water δ18O values. Earthworms were cultivated in an orthogonal combination of two different (granule-free) soils moistened by three types of mineral water and kept at three temperatures (10, 16 and 20 °C) for an acclimatisation period of three weeks followed by transfer to identical treatments and cultivation for a further four weeks. Earthworm-secreted calcite granules were collected from the second set of soils. δ18O values were determined on individual calcite granules (δ18Oc) and the soil solution (δ18Ow). The δ18Oc values reflect soil solution δ18Ow values and temperature, but are consistently enriched by 1.51 (± 0.12)‰ in comparison to equilibrium in synthetic carbonates. The data fit the equation 1000 ln α = [20.21 ± 0.92] (103 T-1) - [38.58 ± 3.18] (R2 = 0.95; n = 96; p < 0.0005). As the granules are abundant in modern soils, buried soils and archaeological contexts, and can be dated using U-Th disequilibria, the developed palaeotemperature relationship has enormous potential for application to Holocene and Pleistocene time intervals.

  15. Alternative origins for nannobacteria-like objects in calcite

    NASA Astrophysics Data System (ADS)

    Kirkland, Brenda L.; Lynch, F. Leo; Rahnis, Michael A.; Folk, Robert L.; Molineux, Ian J.; McLean, Robert J. C.

    1999-04-01

    More than 40 calcite-precipitation experiments were performed under sterile conditions in order to investigate the origins of 25 300 nm spherical-, rod-, and ovoid-shaped objects that have been widely interpreted as evidence of nanometer-scale life (i.e., nannobacteria). Individual experiments included the addition of soluble organic compounds, common species of eubacteria, or phage-induced eubacterial lysates. These experiments indicate that many of the nanometer-scale objects have inorganic or nonnannobacterial origins. In the precipitation experiments, calcite formed euhedral crystals 50 800 nm in diameter and smaller (<50 nm) anhedral or rounded particles or protocrystals. The small anhedral or rounded solids resembled nannobacteria. The relative amount of anhedral or rounded calcite was greatest in experiments with a dissolved organic component. These controlled experiments are in accord with observations that rounded nanometer-scale objects are more common in minerals formed in organic-rich environments. Bacterial fragments occur as rounded to irregularly shaped particles that included cell-wall fragments, expulsed cytoplasm, and relict capsules that also closely resembled nannobacteria. Acid etching of the large euhedral crystals produced in the precipitation experiments also resulted in the formation of nanometer-scale features that resembled nannobacteria in natural carbonates. The shapes of the etching artifacts vary as a function of the strength of the acid and the duration of etching. Much caution is advisable in interpreting the origin of rounded features <50 nm.

  16. Calcite deposition at Miravalles geothermal field, Costa Rica

    SciTech Connect

    Vaca, L.; Alvarado, A.; Corrales, R. )

    1989-01-01

    The calcite deposition problem at Miravalles has been studied since it was observed in the first three wells drilled on the slopes of the Miravalles Volcano. Long-term tests have been carried out to study reservoir characteristics. The change in the production behavior of the wells with the restriction imposed by the deposited calcite has been studied trying to evaluate and quantify the scaling problem. Work is being done on predictions of the deposition rate, location and distribution of the deposited mineral inside the wells. This work was compared with real data obtained from caliper logs of the wells before and after production. The feasibility of the first 55 MW power plant has been demonstrated. It was considered that the solution for the calcite problem is the reaming during discharge of the wells trying at the same time to minimize the cleaning interventions with a new well design. It is believed, due to the thermodynamics and chemical characteristics of the extracted fluids, that it is possible to find a non-deposition zone which will permit the drilling of wells without a scaling problem.

  17. Synthetic Calcite as a Scaffold for Osteoinductive Bone Substitutes.

    PubMed

    Chróścicka, Anna; Jaegermann, Zbigniew; Wychowański, Piotr; Ratajska, Anna; Sadło, Jarosław; Hoser, Grażyna; Michałowski, Sławomir; Lewandowska-Szumiel, Malgorzata

    2016-07-01

    Although a wide variety of biomaterials have been already proposed for use in bone tissue engineering, there is still need for man-made materials, which would combine support for osteogenesis with simplicity desirable for upscaling and costs reduction. In this study we have shown that synthetic calcite may serve as a scaffold for human osteoblasts transplantation. A simple dynamic system allows uniform and effective cell distribution. Cell viability and osteogenic phenotype were confirmed by XTT assay, alkaline phosphatase activity and selected osteoblast-specific genes expression. Extracellular matrix deposited by cells improved elasticity and made the whole system similar to the flexible composite material rather than to the brittle ceramic implants. It was revealed in the compression tests and also by the improved samples handling. Subcutaneous implantation of the cell-seeded calcite scaffolds to immunodeficient mice resulted in mineralized bone formation, which was confirmed histologically and by EPR analysis. The latter we propose as a method supplementary to histological analysis, for bone regeneration investigations. It specifically confirms the presence of bone mineral with a unique sensitivity and using bulk samples, which eliminates the risk of missing the material in the preparation. Our study resulted in development of a new osteogenic tissue engineered product based on man-made calcite. PMID:26666226

  18. Rheological characterization of the influence of PVOH on calcite suspensions.

    PubMed

    Eriksson, Rasmus; Kokko, Annaleena; Rosenholm, Jarl B

    2010-06-01

    Flow properties of the calcite/poly(vinyl alcohol) (PVOH) system were studied and related to the microstructure of the suspension. Adsorption of PVOH on calcite was confirmed, and it results in a shift of the slipping plane out from the surface. The charge density at the surface is assumed to remain unchanged. Since the PVOH used is only partially hydrolyzed, the most likely adsorption conformation consists of residual acetate groups adsorbed to the surface and vinylalcohol groups extending outward from the surface as loops and tails. The microstructure and flow properties of the calcite/PVOH system was found to go through several different stages as a function of PVOH concentration. At low PVOH concentrations a gradual weakening of the initially formed floc network is observed as a function of PVOH concentration. Further addition of PVOH eventually leads to breakdown of the flocs which results in a sterically stabilized suspension with a very low viscosity. This state persists for a narrow concentration range of PVOH, and increasing the PVOH concentration over a certain limit leads to a second gradual increase in viscosity. The system is believed not to undergo reflocculation at high PVOH concentrations as judged from the nonelastic nature of the suspensions. Instead, the polymers form a viscous matrix in the solution while the particles remain well-dispersed. At high enough PVOH concentration, the free volume available for the particles is greatly reduced, and the viscosity increases sharply. PMID:20345110

  19. Interactions of salicylic acid derivatives with calcite crystals.

    PubMed

    Ukrainczyk, Marko; Gredičak, Matija; Jerić, Ivanka; Kralj, Damir

    2012-01-01

    Investigation of basic interactions between the active pharmaceutical compounds and calcium carbonates is of great importance because of the possibility to use the carbonates as a mineral carrier in drug delivery systems. In this study the mode and extent of interactions of salicylic acid and its amino acid derivates, chosen as pharmaceutically relevant model compounds, with calcite crystals are described. Therefore, the crystal growth kinetics of well defined rhombohedral calcite seed crystals in the systems containing salicylic acid (SA), 5-amino salicylic acid (5-ASA), N-salicyloil-l-aspartic acid (N-Sal-Asp) or N-salicyloil-l-glutamic acid (N-Sal-Glu), were investigated. The precipitation systems were of relatively low initial supersaturation and of apparently neutral pH. The data on the crystal growth rate reductions in the presence of the applied salicylate molecules were analyzed by means of Cabrera & Vermileya's, and Kubota & Mullin's models of interactions of the dissolved additives and crystal surfaces. The crystal growth kinetic experiments were additionally supported with the appropriate electrokinetic, spectroscopic and adsorption measurements. The Langmuir adsorption constants were determined and they were found to be in a good correlation with values obtained from crystal growth kinetic analyses. The results indicated that salicylate molecules preferentially adsorb along the steps on the growing calcite surfaces. The values of average spacing between the adjacent salicylate adsorption active sites and the average distance between the neighboring adsorbed salicylate molecules were also estimated. PMID:21963207

  20. Geobacillus thermoglucosidasius endospores function as nuclei for the formation of single calcite crystals.

    PubMed

    Murai, Rie; Yoshida, Naoto

    2013-05-01

    Geobacillus thermoglucosidasius colonies were placed on an agar hydrogel containing acetate, calcium ions, and magnesium ions, resulting in the formation of single calcite crystals (calcites) within and peripheral to the plating area or parent colony. Microscopic observation of purified calcites placed on the surface of soybean casein digest (SCD) nutrient medium revealed interior crevices from which bacterial colonies originated. Calcites formed on the gel contained [1-(13)C]- and [2-(13)C]acetate, demonstrating that G. thermoglucosidasius utilizes carbon derived from acetate for calcite formation. During calcite formation, vegetative cells swam away from the parent colony in the hydrogel. Hard-agar hydrogel inhibited the formation of calcites peripheral to the parent colony. The calcite dissolved completely in 1 M HCl, with production of bubbles, and the remaining endospore-like particles were easily stained with Brilliant green dye. The presence of DNA and protein in calcites was demonstrated by electrophoresis. We propose that endospores initiate the nucleation of calcites. Endospores of G. thermoglucosidasius remain alive and encapsulated in calcites. PMID:23455343

  1. Chemistry and petrography of calcite in the KTB pilot borehole, Bavarian Oberpfalz, Germany

    USGS Publications Warehouse

    Komor, S.C.

    1995-01-01

    The KTB pilot borehole in northeast Bavaria, Germany, penetrates 4000 m of gneiss, amphibolite, and subordinate calc-silicate, lamprophyre and metagabbro. There are three types of calcite in the drilled section: 1) metamorphic calcite in calc-silicate and marble; 2) crack-filling calcite in all lithologies; and 3) replacement calcite in altered minerals. Crack-filling and replacement calcite postdate metamorphic calcite. Multiple calcite generations in individual cracks suggest that different generations of water repeatedly flowed through the same cracks. Crack-filling mineral assemblages that include calcite originally formed at temperatures of 150-350??C. Presently, crack-filling calcite is in chemical and isotopic equilibrium with saline to brackish water in the borehole at temperatures of ???120??C. The saline to brackish water contains a significant proportion of meteoric water. Re-equilibration of crack-filling calcite to lower temperatures means that calcite chemistry tells us little about water-rock interactions in the crystal section of temperatures higher than ~120??C. -from Author

  2. Geobacillus thermoglucosidasius Endospores Function as Nuclei for the Formation of Single Calcite Crystals

    PubMed Central

    Murai, Rie

    2013-01-01

    Geobacillus thermoglucosidasius colonies were placed on an agar hydrogel containing acetate, calcium ions, and magnesium ions, resulting in the formation of single calcite crystals (calcites) within and peripheral to the plating area or parent colony. Microscopic observation of purified calcites placed on the surface of soybean casein digest (SCD) nutrient medium revealed interior crevices from which bacterial colonies originated. Calcites formed on the gel contained [1-13C]- and [2-13C]acetate, demonstrating that G. thermoglucosidasius utilizes carbon derived from acetate for calcite formation. During calcite formation, vegetative cells swam away from the parent colony in the hydrogel. Hard-agar hydrogel inhibited the formation of calcites peripheral to the parent colony. The calcite dissolved completely in 1 M HCl, with production of bubbles, and the remaining endospore-like particles were easily stained with Brilliant green dye. The presence of DNA and protein in calcites was demonstrated by electrophoresis. We propose that endospores initiate the nucleation of calcites. Endospores of G. thermoglucosidasius remain alive and encapsulated in calcites. PMID:23455343

  3. Surface chemistry allows for abiotic precipitation of dolomite at low temperature

    PubMed Central

    Roberts, Jennifer A.; Kenward, Paul A.; Fowle, David A.; Goldstein, Robert H.; González, Luis A.; Moore, David S.

    2013-01-01

    Although the mineral dolomite is abundant in ancient low-temperature sedimentary systems, it is scarce in modern systems below 50 °C. Chemical mechanism(s) enhancing its formation remain an enigma because abiotic dolomite has been challenging to synthesize at low temperature in laboratory settings. Microbial enhancement of dolomite precipitation at low temperature has been reported; however, it is still unclear exactly how microorganisms influence reaction kinetics. Here we document the abiotic synthesis of low-temperature dolomite in laboratory experiments and constrain possible mechanisms for dolomite formation. Ancient and modern seawater solution compositions, with identical pH and pCO2, were used to precipitate an ordered, stoichiometric dolomite phase at 30 °C in as few as 20 d. Mg-rich phases nucleate exclusively on carboxylated polystyrene spheres along with calcite, whereas aragonite forms in solution via homogeneous nucleation. We infer that Mg ions are complexed and dewatered by surface-bound carboxyl groups, thus decreasing the energy required for carbonation. These results indicate that natural surfaces, including organic matter and microbial biomass, possessing a high density of carboxyl groups may be a mechanism by which ordered dolomite nuclei form. Although environments rich in organic matter may be of interest, our data suggest that sharp biogeochemical interfaces that promote microbial death, as well as those with high salinity may, in part, control carboxyl-group density on organic carbon surfaces, consistent with origin of dolomites from microbial biofilms, as well as hypersaline and mixing zone environments. PMID:23964124

  4. Genetic Dissection of Abiotic Stress Tolerance in Sorghum

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sorghum, the fifth most important cereal crop in the world is a highly versatile crop and an excellent model species due to its overall tolerance to a number of abiotic stress conditions. To gain a better understanding of the physiological and genetic basis of abiotic stress tolerance in sorghum w...

  5. Cell wall remodeling under abiotic stress

    PubMed Central

    Tenhaken, Raimund

    2015-01-01

    Plants exposed to abiotic stress respond to unfavorable conditions on multiple levels. One challenge under drought stress is to reduce shoot growth while maintaining root growth, a process requiring differential cell wall synthesis and remodeling. Key players in this process are the formation of reactive oxygen species (ROS) and peroxidases, which initially cross-link phenolic compounds and glycoproteins of the cell walls causing stiffening. The function of ROS shifts after having converted all the peroxidase substrates in the cell wall. If ROS-levels remain high during prolonged stress, OH°-radicals are formed which lead to polymer cleavage. In concert with xyloglucan modifying enzymes and expansins, the resulting cell wall loosening allows further growth of stressed organs. PMID:25709610

  6. Improved abiotic stress tolerance of bermudagrass by exogenous small molecules.

    PubMed

    Chan, Zhulong; Shi, Haitao

    2015-01-01

    As a widely used warm-season turfgrass in landscapes and golf courses, bermudagrass encounters multiple abiotic stresses during the growth and development. Physiology analysis indicated that abiotic stresses induced the accumulation of ROS and decline of photosynthesis, resulting in increased cell damage and inhibited growth. Proteomic and metabolomic approaches showed that antioxidant enzymes and osmoprotectant contents (sugar, sucrose, dehydrin, proline) were extensively changed under abiotic stress conditions. Exogenous application of small molecules, such as ABA, NO, CaCl2, H2S, polyamine and melatonin, could effectively alleviate damages caused by multiple abiotic stresses, including drought, salt, heat and cold. Based on high through-put RNA seq analysis, genes involved in ROS, transcription factors, hormones, and carbohydrate metabolisms were largely enriched. The data indicated that small molecules induced the accumulation of osmoprotectants and antioxidants, kept cell membrane integrity, increased photosynthesis and kept ion homeostasis, which protected bermudagrass from damages caused by abiotic stresses. PMID:25757363

  7. Interaction of copper with the surface of calcite

    SciTech Connect

    Franklin, M.L.; Morse, J.W.

    1981-12-01

    The interaction of Cu ions in solution with the surface of calcite has been studied in a range of solutions from pure water to seawater. Observations of the uptake of Cu from solution onto calcite indicates that the process is rapid and strong in both distilled water and seawater. In distilled water, Cu uptake is directly proportional to the concentration of Cu in solution; Cu/sub s/ = K/sub s/Cu/sub 1/. The average value for K/sub s/ is 3.5 +- 1.7. The Cu/sub s/ dependence on Cu/sub 1/ is linear over the entire Cu concentration range studied (0.1 to 200 ..mu..M). Results do not indicate the formation of a precipitate of either malachite or copper carbonate. A precipitate of the form Cu/sub x/Ca/sub 1-x/CO/sub 3/ may be deposited onto the calcite surface in distilled water. The value of K/sub s/ in distilled water decreased sharply over the solid to solution ratio range of 0.1 to 2 g CaCO/sub 3/ 1/sup -1/. This was followed by a small change in K/sub s/ for solid to solution ratios in the range of 2 to 10 g CaCO/sub 3/ 1/sup -1/. In seawater, the uptake of Cu is also directly proportional to the concentration of Cu/sub 1/ up to a limiting value of approximately 13 ..mu..M. The average value for K/sub s/ in seawater, 0.24 +- 0.06 (Cu/sub 1/ less than or equal to 13 ..mu..M), is approximately an order of magnitude less than in distilled water. This is probably the result of smaller Cu/sub 1/ activity coefficients and increased site competition by other ions in seawater. Attempts to increase the Cu/sub 1/ concentration above 13 ..mu..M resulted in the additional Cu being deposited on the surface of the calcite. A possible explanation for this behavior is the formation of a precipitate of malachite on the calcite surface. The value of K/sub s/ decreased slightly with increasing solid to solution ratios in seawater.

  8. Hydrothermal replacement of calcite by Mg-carbonates

    NASA Astrophysics Data System (ADS)

    Jonas, Laura; Mueller, Thomas; Dohmen, Ralf

    2014-05-01

    The transport of heat and mass through the Earth's crust is coupled to mineral reactions and the exchange of isotopes and elements between different phases. Carbonate minerals are a major constituent of the Earth's crust and play an important role in different physical, chemical and even biological processes. In this experimental study, the element exchange reaction between calcite (CaCO3) and a Mg-rich fluid phase is investigated under hydrothermal conditions. Single crystals of calcite (2x2x2 mm) react with 1 ml of a 1 M MgCl2 solution at 200° C in a Teflon-lined steel autoclave for different times between one day and four weeks. The reaction leads to the formation of a porous reaction front and the pseudomorphic replacement of calcite by dolomite [CaMg(CO3)2] and magnesite (MgCO3). Scanning electron microscopy revealed that the reaction rim consists of small Mg-carbonate rhombs closely attached to each other, suggesting that the replacement reaction takes place by a dissolution-precipitation mechanism. Typically, the observed reaction front can be divided into two different domains. The outer part of the reaction rim, i.e. from the mineral surface in contact to the fluid inwards, consists of magnesite, whereas the inner part of the rim surrounding the unreacted calcite core consists of Ca-rich dolomite. The formation of a porous microstructure that varies in different parts of the reaction rim is a direct result of the large molar volume change induced by the replacement of calcite by magnesite and dolomite. The developing porosity therefore creates fluid pathways that promote the progress of the reaction front towards the unreacted core of the single crystal. Compositional profiles measured perpendicular to the mineral surface across the reactions rims using electron microprobe (EMPA) further revealed a compositional gradient within the reaction rim with regard to the structure-forming elements Mg and Ca. Here, the amount of Mg incorporated in both product

  9. Regulation of Photosynthesis during Abiotic Stress-Induced Photoinhibition.

    PubMed

    Gururani, Mayank Anand; Venkatesh, Jelli; Tran, Lam Son Phan

    2015-09-01

    Plants as sessile organisms are continuously exposed to abiotic stress conditions that impose numerous detrimental effects and cause tremendous loss of yield. Abiotic stresses, including high sunlight, confer serious damage on the photosynthetic machinery of plants. Photosystem II (PSII) is one of the most susceptible components of the photosynthetic machinery that bears the brunt of abiotic stress. In addition to the generation of reactive oxygen species (ROS) by abiotic stress, ROS can also result from the absorption of excessive sunlight by the light-harvesting complex. ROS can damage the photosynthetic apparatus, particularly PSII, resulting in photoinhibition due to an imbalance in the photosynthetic redox signaling pathways and the inhibition of PSII repair. Designing plants with improved abiotic stress tolerance will require a comprehensive understanding of ROS signaling and the regulatory functions of various components, including protein kinases, transcription factors, and phytohormones, in the responses of photosynthetic machinery to abiotic stress. Bioenergetics approaches, such as chlorophyll a transient kinetics analysis, have facilitated our understanding of plant vitality and the assessment of PSII efficiency under adverse environmental conditions. This review discusses the current understanding and indicates potential areas of further studies on the regulation of the photosynthetic machinery under abiotic stress. PMID:25997389

  10. Oxygen isotopes in calcite grown under cave-analogue conditions

    NASA Astrophysics Data System (ADS)

    Day, C. C.; Henderson, G. M.

    2011-07-01

    Speleothem oxygen isotopes and growth rates are valuable proxies for reconstructing climate history. There is debate, however, about the conditions that allow speleothems to grow in oxygen isotope equilibrium, and about the correct equilibrium fractionation factors. We report results from a series of carbonate growth experiments in karst-analogue conditions in the laboratory. The setup closely mimics natural processes (e.g. precipitation driven by CO 2-degassing, low ionic strength solution, thin solution film) but with a tight control on growth conditions (temperature, pCO 2, drip rate, calcite saturation index and the composition of the initial solution). Calcite is dissolved in water in a 20,000 ppmV pCO 2 environment. This solution is dripped onto glass plates (coated with seed-carbonate) in a lower pCO 2 environment (<2500 ppmV), where degassing leads to calcite growth. Experiments were performed at 7, 15, 25 and 35 °C. At each temperature, calcite was grown at three drip rates (2, 6 and 10 drips per minute) on separate plates. The mass of calcite grown in these experiments varies with temperature ( T in K) and drip rate ( d_ r in drips min -1) according to the relationship daily growth mass = 1.254 + 1.478 ∗ 10 -9 ∗ e0.0679 T + ( e0.00248 T - 2) ∗ (-0.779 d_ r2 + 10.05 d_ r + 11.69). This relationship indicates a substantial increase of growth mass with temperature, a smaller influence of drip rate on growth mass at low temperature and a non-linear relationship between drip rate and growth mass at higher temperatures. Low temperature, fast dripping conditions are found to be the most favourable for reducing effects associated with evaporation and rapid depletion of the dissolved inorganic carbon reservoir (rapid DIC-depletion). The impact of evaporation can be large so caves with high relative humidity are also preferable for palaeoclimate reconstruction. Even allowing for the maximum offsets that may have been induced by evaporation and rapid DIC

  11. The sensitized luminescence of manganese-activated calcite

    USGS Publications Warehouse

    Schulman, J.H.; Evans, L.W.; Ginther, R.J.; Murata, K.J.

    1947-01-01

    Synthetic manganese-activated calcites are shown to be practically inert to ultraviolet excitation in the range 2000-3500A, while they are luminescent under cathode-ray excitation. The incorporation of small amounts of an auxiliary impurity along with the manganese produces the strong response to ultraviolet radiation hitherto ascribed to CaCO3:Mn itself. Three such impurities have been studied: lead, thallium, and cerium. The first two induce excitation in the neighborhood of the mercury resonance line, while the cerium introduces a response principally to longer wave ultraviolet. The strong response to 2537A excitation shown by some natural calcites is likewise found to be due to the presence of lead along with the manganese, rather than to the manganese alone. The data do not warrant ascribing the longer wave-length ultraviolet-excited luminescence of all natural calcites to the action of an auxiliary impurity. The essential identity of the cathode-ray excited luminescence spectra of CaCO 3:Mn, CaCO3: (Pb+Mn), CaCO3:(Tl+Mn), and CaCO3:(Ce+Mn) with the 2537A-excited spectra of the latter three is evidence that the luminescent center in all cases is the manganese ion or the MnO6 group. It is shown that a "cascade" mechanism for the action of the auxiliary impurities, lead, thallium, and cerium, is incorrect; and that the phenomenon must be considered as a case of sensitized luminescence. Owing to the nature of cathode-ray excitation, the manganese activator can be excited by this agent even in the absence of a second impurity. For optical excitation, however, an absorption band for the ultraviolet must be established by building into the CaCO3:Mn a second impurity or "sensitizer.".

  12. Principles of Calcite Dissolution in Human and Artificial Otoconia

    PubMed Central

    Walther, Leif Erik; Blödow, Alexander; Buder, Jana; Kniep, Rüdiger

    2014-01-01

    Human otoconia provide mechanical stimuli to deflect hair cells of the vestibular sensory epithelium for purposes of detecting linear acceleration and head tilts. During lifetime, the volume and number of otoconia are gradually reduced. In a process of degeneration morphological changes occur. Structural changes in human otoconia are assumed to cause vertigo and balance disorders such as benign paroxysmal positional vertigo (BPPV). The aim of this study was to investigate the main principles of morphological changes in human otoconia in dissolution experiments by exposure to hydrochloric acid, EDTA, demineralized water and completely purified water respectively. For comparison reasons artificial (biomimetic) otoconia (calcite gelatin nanocomposits) and natural calcite were used. Morphological changes were detected in time steps by the use of environmental scanning electron microscopy (ESEM). Under in vitro conditions three main dissolution mechanisms were identified as causing characteristic morphological changes of the specimen under consideration: pH drops in the acidic range, complex formation with calcium ions and changes of ion concentrations in the vicinity of otoconia. Shifts in pH cause a more uniform reduction of otoconia size (isotropic dissolution) whereas complexation reactions and changes of the ionic concentrations within the surrounding medium bring about preferred attacks at specific areas (anisotropic dissolution) of human and artificial otoconia. Owing to successive reduction of material, all the dissolution mechanisms finally produce fragments and remnants of otoconia. It can be assumed that the organic component of otoconia is not significantly attacked under the given conditions. Artificial otoconia serve as a suitable model system mimicking chemical attacks on biogenic specimens. The underlying principles of calcite dissolution under in vitro conditions may play a role in otoconia degeneration processes such as BPPV. PMID:25048115

  13. Effect of airborne particle on SO 2-calcite reaction

    NASA Astrophysics Data System (ADS)

    Böke, Hasan; Göktürk, E. Hale; Caner-Saltık, Emine N.; Demirci, Şahinde

    1999-02-01

    In modern urban atmosphere, sulphur dioxide (SO 2) attacks calcite (CaCO 3) in calcareous stone-producing gypsum (CaSO 4·2H 2O) which forms crust at rain sheltered surfaces and accelerates erosion at areas exposed to rain. The airborne particles collected on stone surfaces have always been considered to enhance the gypsum crust formation and thus it is believed that they should be removed from the surface to decrease the effects of SO 2. In this study, our aim was to investigate this event by carrying out a series of experiments in laboratory using pure calcium carbonate powder to represent calcareous stone. Sodium montmorillonite, activated carbon, ferric oxide, vanadium pentoxide and cupric chloride were mixed in the pure calcium carbonate powder as substitutes of the airborne particles in the polluted atmosphere. The samples have been exposed at nearly 10 ppmv SO 2 concentrations at 90% relative humidity conditions in a reaction chamber for several days. The mineralogical composition of the exposed samples were determined by X-ray diffraction (XRD) analysis and infrared spectrometer (IR). Sulphation reaction products, calcium sulphite hemihydrate, gypsum and unreacted calcite, were determined quantitatively using IR. Exposed samples have also been investigated morphologically using a scanning electron microscope (SEM). Experimental results reveal that calcium sulphite hemihydrate is the main reaction product of the SO 2-calcite reaction. It turns out that airborne particles play an important catalytic role in the oxidation of calcium sulphite hemihydrate into gypsum, although their presence does not very significantly affect the extent of sulphation reaction. This behaviour of airborne particles is explained by the presence of liquid film on the calcium carbonate surface where a series of reactions in the gas-liquid-solid interfaces takes place.

  14. Bony fish and their contribution to marine inorganic carbon cycling

    NASA Astrophysics Data System (ADS)

    Salter, Michael; Perry, Chris; Wilson, Rod; Harborne, Alistair

    2016-04-01

    Conventional understanding of the marine inorganic carbon cycle holds that CaCO3 (mostly as low Mg-calcite and aragonite) precipitates in the upper reaches of the ocean and sinks to a point where it either dissolves or is deposited as sediment. Thus, it plays a key role controlling the distribution of DIC in the oceans and in regulating their capacity to absorb atmospheric CO2. However, several aspects of this cycle remain poorly understood and have long perplexed oceanographers, such as the positive alkalinity anomaly observed in the upper water column of many of the world's oceans, above the aragonite and calcite saturation horizons. This anomaly would be explained by extensive dissolution of a carbonate phase more soluble than low Mg-calcite or aragonite, but major sources for such phases remain elusive. Here we highlight marine bony fish as a potentially important primary source of this 'missing' high-solubility CaCO3. Precipitation of CaCO3 takes place within the intestines of all marine bony fish as part of their normal physiological functioning, and global production models suggest it could account for up to 45 % of total new marine CaCO3 production. Moreover, high Mg-calcite containing >25 % mol% MgCO3 - a more soluble phase than aragonite - is a major component of these precipitates. Thus, fish CaCO3 may at least partially explain the alkalinity anomaly in the upper water column. However, the issue is complicated by the fact that carbonate mineralogy actually varies among fish species, with high Mg-calcite (HMC), low Mg-calcite (LMC), aragonite, and amorphous calcium carbonate (ACC) all being common products. Using data from 22 Caribbean fish species, we have generated a novel production model that resolves phase proportions. We evaluate the preservation/dissolution potential of these phases and consider potential implications for marine inorganic carbon cycling. In addition, we consider the dramatic changes in fish biomass structure that have resulted

  15. Recent Molecular Advances on Downstream Plant Responses to Abiotic Stress

    PubMed Central

    dos Reis, Sávio Pinho; Lima, Aline Medeiros; de Souza, Cláudia Regina Batista

    2012-01-01

    Abiotic stresses such as extremes of temperature and pH, high salinity and drought, comprise some of the major factors causing extensive losses to crop production worldwide. Understanding how plants respond and adapt at cellular and molecular levels to continuous environmental changes is a pre-requisite for the generation of resistant or tolerant plants to abiotic stresses. In this review we aimed to present the recent advances on mechanisms of downstream plant responses to abiotic stresses and the use of stress-related genes in the development of genetically engineered crops. PMID:22942725

  16. Chemical Priming of Plants Against Multiple Abiotic Stresses: Mission Possible?

    PubMed

    Savvides, Andreas; Ali, Shawkat; Tester, Mark; Fotopoulos, Vasileios

    2016-04-01

    Crop plants are subjected to multiple abiotic stresses during their lifespan that greatly reduce productivity and threaten global food security. Recent research suggests that plants can be primed by chemical compounds to better tolerate different abiotic stresses. Chemical priming is a promising field in plant stress physiology and crop stress management. We review here promising chemical agents such as sodium nitroprusside, hydrogen peroxide, sodium hydrosulfide, melatonin, and polyamines that can potentially confer enhanced tolerance when plants are exposed to multiple abiotic stresses. The challenges and opportunities of chemical priming are addressed, with the aim to boost future research towards effective application in crop stress management. PMID:26704665

  17. Relating Mechanical Behavior and Microstructural Observations in Calcite Fault Gouge

    NASA Astrophysics Data System (ADS)

    Carpenter, B. M.; Di Stefano, G.; Viti, C.; Collettini, C.

    2013-12-01

    Many important earthquakes, magnitude 5-7, nucleate and/or propagate through carbonate-dominated lithologies. Additionally, the presence of precipitated calcite in (cement) and near (vein fill) faults indicates that the mechanical behavior of carbonate-dominated material likely plays an important role in shallow- and mid-crustal faulting. We report on laboratory experiments designed to explore the mechanical behavior of calcite and relate that behavior to post experiment microstructural observations. We sheared powdered gouge of Carrara Marble, >98% CaCO3, at constant normal stresses between 1 and 50 MPa under saturated conditions at room temperature. We performed velocity-stepping tests, 0.1-1000 μm/s, to evaluate frictional stability, and slide-hold-slide tests, 1-10,000 seconds, to measure the amount of frictional healing. Small subsets of experiments were performed under different environmental conditions and shearing velocities to better elucidate physicochemical processes and their role in the mechanical behavior of calcite fault gouge. All experimental samples were collected for SEM analysis. We find that the frictional healing rate is 7X higher under saturated conditions than under nominally dry conditions. We also observe a divergence between the rates of creep relaxation (increasing) and frictional healing (decreasing) as shear velocity is increased from 1 to 3000 μm/s. Our highest healing rates are observed at our lowest normal stresses. We observe a frictional strength of μ = 0.64, consistent with previous data under similar conditions. Furthermore, although we observe velocity-weakening frictional behavior in both the saturated and dry cases, rate- and-state friction parameters are distinctly different for each case. Our combined observations of rapid healing and of velocity-weakening frictional behavior indicate that faults where calcite-dominated gouge is present are likely to be seismic and have the ability to regain their strength quickly

  18. Calcite dissolution: an in situ study in the Panama Basin

    SciTech Connect

    Thunell, R.C.; Keir, R.S.; Honjo, S.

    1981-05-08

    The results of an in situ study of calcite dissolution in the Panama Basin indicate that the rate of dissolution in the water column increases suddenly below a water depth of about 2800 meters. This coincides with the depth at which the calcium carbonate content of surface sediments begins to decrease rapidly or the sedimentary lysocline. Since this level of increased dissolution both in the water column and on the sea floor does not appear to be related to the transition from supersaturation to undersaturation with respect to carbonate, there may be a kinetic origin for the lysocline in this region.

  19. Simulating Succinate-Promoted Dissolution at Calcite {104} Steps

    NASA Astrophysics Data System (ADS)

    Mkhonto, D.; Sahai, N.

    2008-12-01

    Organic molecules of a wide range of molecular weights from small organic acids, amino-acids, acidic peptides and acidic proteins to humic and fulvic acids play a key role in modulating nucleation, crystal growth and dissolution of calcium carbonate polymorphs. In general, these acidic molecules inhibit calcite growth and, promote dissolution preferentially along specific crystallographic directions, in the process, regulating crystal shape and size, and even whether a metastable polymorph (e.g., vaterite or aragonite) is nucleated first. For example, chiral faces of calcite are selected by chiral amino-acids and the unusual {hk0} faces are expressed in the presence of amino-acids [Orme et al., 2001], and unusual heptagonal dissolution etch-pit are seen in the presence of succinate compared to the normal rhombohedral pits in water alone [Teng et al., 2006]. Thus, the presence of unusual crystal morphologies may indicate organic-mediated growth, thus serving as a biosignature. We have conducted the Molecular Dynamics (MD) simulations using the Consistent Valence Force Field (CVFF) as implemented in the FORCITE© module of the Materials Studio © software package (Accelrys, Inc. TM) to model the adsorption of succinate, a dicarboxylic acid, and charge- balancing Na+ ions on dry and hydrated steps in different directions on the {104} cleavage face of calcite [Mkhonto and Sahai, in prep.]. At the site of succinate adsorption, we find elongation of the interatomic distances (Ca-OCO3,i) between surface Ca2+ cation and the oxygen of the underlying inorganic CO32- anion the first surface layer of calcite, compared to the corresponding distances in the presence of water alone, suggesting greater ease of surface Ca2+ detachment. This result is consistent with the empirically observed increase in overall dissolution rate with succinate [Teng et al., 2006]. Furthermore, succinate adsorption lowers the step energies, which explains the appearance of steps in the unsusual [42

  20. Abiotic uptake of gases by organic soils

    NASA Astrophysics Data System (ADS)

    Smagin, A. V.

    2007-12-01

    Methodological and experimental studies of the abiotic uptake of gaseous substances by organic soils were performed. The static adsorption method of closed vessels for assessing the interaction of gases with the solid and liquid soil phases and the dynamic method of determining the sorption isotherms of gases by soils were analyzed. The theoretical substantiation of the methods and their practical implementations on the basis of a PGA-7 portable gas analyzer (Russia) were considered. Good agreement between the equilibrium sorption isotherms of the gases and the Langmuir model was revealed; for the real ranges of natural gas concentrations, this model can be reduced to the linear Henry equation. The limit values of the gas sorption (Langmuir monolayer capacity) are typical for dry samples; they vary from 670 4000 g/m3 for methane and oxygen to 20 000 25 000 g/m3 for carbon dioxide. The linear distribution coefficients of gases between the solid and gas phases of organic soils (Henry constants) are 8 18 units for poorly sorbed gases (O2, CH4) and 40 60 units for CO2. The kinetics of the chemicophysical uptake of gases by the soil studied is linear in character and obeys the relaxation kinetic model of the first order with the corresponding relaxation constants, which vary from 1 h -1 in wet samples to 10 h -1 in dry samples.

  1. Polyamines and abiotic stress tolerance in plants

    PubMed Central

    Gill, Sarvajeet Singh

    2010-01-01

    Environmental stresses including climate change, especially global warming, are severely affecting plant growth and productivity worldwide. It has been estimated that two-thirds of the yield potential of major crops are routinely lost due to the unfavorable environmental factors. On the other hand, the world population is estimated to reach about 10 billion by 2050, which will witness serious food shortages. Therefore, crops with enhanced vigour and high tolerance to various environmental factors should be developed to feed the increasing world population. Maintaining crop yields under adverse environmental stresses is probably the major challenge facing modern agriculture where polyamines can play important role. Polyamines (PAs)(putrescine, spermidine and spermine) are group of phytohormone-like aliphatic amine natural compounds with aliphatic nitrogen structure and present in almost all living organisms including plants. Evidences showed that polyamines are involved in many physiological processes, such as cell growth and development and respond to stress tolerance to various environmental factors. In many cases the relationship of plant stress tolerance was noted with the production of conjugated and bound polyamines as well as stimulation of polyamine oxidation. Therefore, genetic manipulation of crop plants with genes encoding enzymes of polyamine biosynthetic pathways may provide better stress tolerance to crop plants. Furthermore, the exogenous application of PAs is also another option for increasing the stress tolerance potential in plants. Here, we have described the synthesis and role of various polyamines in abiotic stress tolerance in plants. PMID:20592804

  2. Paleoenvironment of Jawa basalt plateau, Jordan, inferred from calcite speleothems from a lava tube

    NASA Astrophysics Data System (ADS)

    Frumkin, Amos; Bar-Matthews, Miryam; Vaks, Anton

    2008-11-01

    This paper explores the environmental conditions that faced the people of ancient Jawa during the Holocene, as well as previous prehistoric periods of the mid-late Pleistocene. Calcite speleothems in a lava tube are dated using the U-Th method, to marine oxygen isotope stage 7 from ˜ 250 to 240 ka and from ˜ 230 to ˜ 220 ka; and the stage 5/4 transition between ˜ 80 and 70 ka. The available evidence indicates general aridity of the Black Desert during most of the mid-late Quaternary, punctuated by short wetter periods, when the Mediterranean cyclonic systems intensified and penetrated the north Arabian Desert. These Mediterranean systems had a longer and more intense effect on the desert fringe closer to the Mediterranean and only rarely penetrated the Black Desert of Jawa. The results do not exclude some increase of rainfall which did not change water availability dramatically during the warm Holocene. The ancient Jawa city appears to have depended on technological ability to build elaborate runoff-collection systems, which became the prime condition for success.

  3. Olivine Weathering: Abiotic Versus Biotic Processes as Possible Biosignatures

    NASA Technical Reports Server (NTRS)

    Longazo, T. G.; Wentworth, S. J.; McKay, D. S.; Southam, G.; Clemett, S. J.

    2001-01-01

    A preliminary study to determine how abiotic versus biotic processes affect the weathering of olivine crystals. Perhaps the differences between these weathering processes could be used as biosignatures. Additional information is contained in the original extended abstract.

  4. Abiotic stress responses in plant roots: a proteomics perspective

    PubMed Central

    Ghosh, Dipanjana; Xu, Jian

    2014-01-01

    Abiotic stress conditions adversely affect plant growth, resulting in significant decline in crop productivity. To mitigate and recover from the damaging effects of such adverse environmental conditions, plants have evolved various adaptive strategies at cellular and metabolic levels. Most of these strategies involve dynamic changes in protein abundance that can be best explored through proteomics. This review summarizes comparative proteomic studies conducted with roots of various plant species subjected to different abiotic stresses especially drought, salinity, flood, and cold. The main purpose of this article is to highlight and classify the protein level changes in abiotic stress response pathways specifically in plant roots. Shared as well as stressor-specific proteome signatures and adaptive mechanism(s) are simultaneously described. Such a comprehensive account will facilitate the design of genetic engineering strategies that enable the development of broad-spectrum abiotic stress-tolerant crops. PMID:24478786

  5. Circadian regulation of abiotic stress tolerance in plants

    PubMed Central

    Grundy, Jack; Stoker, Claire; Carré, Isabelle A.

    2015-01-01

    Extremes of temperatures, drought and salinity cause widespread crop losses throughout the world and impose severe limitations on the amount of land that can be used for agricultural purposes. Hence, there is an urgent need to develop crops that perform better under such abiotic stress conditions. Here, we discuss intriguing, recent evidence that circadian clock contributes to plants’ ability to tolerate different types of environmental stress, and to acclimate to them. The clock controls expression of a large fraction of abiotic stress-responsive genes, as well as biosynthesis and signaling downstream of stress response hormones. Conversely, abiotic stress results in altered expression and differential splicing of the clock genes, leading to altered oscillations of downstream stress-response pathways. We propose a range of mechanisms by which this intimate coupling between the circadian clock and environmental stress-response pathways may contribute to plant growth and survival under abiotic stress. PMID:26379680

  6. Roles of melatonin in abiotic stress resistance in plants.

    PubMed

    Zhang, Na; Sun, Qianqian; Zhang, Haijun; Cao, Yunyun; Weeda, Sarah; Ren, Shuxin; Guo, Yang-Dong

    2015-02-01

    In recent years melatonin has emerged as a research highlight in plant studies. Melatonin has different functions in many aspects of plant growth and development. The most frequently mentioned functions of melatonin are related to abiotic stresses such as drought, radiation, extreme temperature, and chemical stresses. This review mainly focuses on the regulatory effects of melatonin when plants face harsh environmental conditions. Evidence indicates that environmental stress can increase the level of endogenous melatonin in plants. Overexpression of the melatonin biosynthetic genes elevates melatonin levels in transgenic plants. The transgenic plants show enhanced tolerance to abiotic stresses. Exogenously applied melatonin can also improve the ability of plants to tolerate abiotic stresses. The mechanisms by which melatonin alleviates abiotic stresses are discussed. PMID:25124318

  7. Upscaling Calcite Growth Rates From the Mesoscale to the Macroscale

    SciTech Connect

    Bracco, Jacquelyn N; Stack, Andrew G; Steefel, Carl I

    2013-01-01

    Quantitative prediction of mineral reaction rates in the subsurface remains a daunting task partly because a key parameter for macroscopic models, the reactive site density, is poorly constrained. Here we report atomic force microscopy (AFM) measurements on the calcite surface of monomolecular step densities, treated as equivalent to the reactive site density, as a function of aqueous calcium-to-carbonate ratio and saturation index. Data for the obtuse step orientation are combined with existing step velocity measurements to generate a model that predicts overall macroscopic calcite growth rates. The model is quantitatively consistent with several published macroscopic rates under a range of alkaline solution conditions, particularly for two of the most comprehensive data sets without the need for additional fit parameters. The model reproduces peak growth rates and its functional form is simple enough to be incorporated into reactive transport or other macroscopic models designed for predictions in porous media. However, it currently cannot model equilibrium, pH effects, and may overestimate rates at high aqueous calcium-to-carbonate ratios. The discrepancies in rates at high calcium-to-carbonate ratios may be due to differences in pre-treatment, such as exposing the seed material to SI 1.0 to generate/develop growth hillocks, or other factors.

  8. Texture effects on megahertz dielectric properties of calcite rock samples

    NASA Astrophysics Data System (ADS)

    Kenyon, W. E.

    1984-04-01

    Dielectric measurements have been made from 0.5 to 1300 MHz on Whitestone, a quarried calcite rock, saturated with salty water. Whitestone shows a large increase in dielectric permittivity (dispersion) at the low end of this frequency range. When the conductivity of the water is varied, the dielectric permittivity of Whitestone is found to scale as water conductivity/frequency, i.e., as the complex dielectric constant of water. This is believed to be unique in measurements on insulator-conductor mixtures, and establishes that the dispersion is primarily caused by the geometry of the sample. Two other calcite samples show much lower dielectric dispersion. Micrographs indicate that the variation in dispersion among the three samples is in rough proportion to grain platiness. This is consistent with the platey grain mechanism, one of three mechanisms proposed by Sen to explain dielectric dispersion in water-saturated rocks. A model consisting of water containing insulating spheroids of identical aspect ratio, isotropically distributed in orientation, predicts that increased grain platiness reduces both low-frequency conductivity and high-frequency dielectric permittivity in a closely related way; this is observed experimentally. However, this model does not fit simultaneously all electrical properties of Whitestone; evidently a more complex geometrical model is needed. Dielectric dispersion caused by texture is of practical importance in estimating water content of subsurface rocks from borehole measurements of dielectric permittivity, particularly at high water salinities.

  9. [Removal of Phosphate by Calcite in Open-System].

    PubMed

    Li, Zhen-xuan; Diao, Jia-yong; Huang, Li-dong; Chen, Yan-fan; Liu, Da-gang; Xu, Zheng-wen

    2015-12-01

    Batch methods were deployed to study the removal of phosphate by calcite in an open-system. Results showed that: (1) The pre-equilibrium process of calcite in open system could be achieved within 24 hours (2) The kinetic results showed that, at initial concentration of 0.5 mg · L⁻¹, the phosphate removal was almost completed within 10 hours of the first phase. The observation may be attributed to surface adsorption. At initial concentration of 2.5 mg · L⁻¹, the phosphate removal was mainly carried out by the precipitation of phosphate at later stage of the process; (3) At initial concentration of ≤ 2.5 mg · L⁻¹ setting 10 h as reaction time, the phosphate removal process was described well by the Langmuir model. It is hypothesized that surface adsorption was the principal removal way of phosphate; (4) With the addition of phthalate, at initial concentration of < 2.5 mg · L⁻¹, the phosphate removal rate experienced a small decrease. That was because phosphate was mainly removed by surface adsorption, and thus, phthalate was a competitor to phosphate for the same adsorption site. The phosphate removal rate increased a little at initial concentration of > 2.5 mg · L⁻¹, this was because the phosphate precipitation was reinforced by the increase of calcium concentration, which was caused by phthalate addition. PMID:27011989

  10. Anisotropic Transverse Stress in Calcite and Sapphire Measured Using Birefringence

    NASA Astrophysics Data System (ADS)

    Tear, Gareth R.; Chapman, David J.; Eakins, Daniel E.; Proud, William G.

    2015-06-01

    Many significant geological minerals have anisotropic crystal structures leading to material properties that are anisotropic, including compressive elastic behaviour. A non-invasive approach to investigate the directional dependence of transverse stress in these materials during shock compression would supplement current understanding. As many geological minerals are transparent and hence optically anisotropic, measuring the change in birefringence induced by transverse stress in the material offers the possibility of a fast, non-invasive approach to probe transverse behaviour. Shock compression experiments have been performed on a-cut calcite and a-cut sapphire for strain rates of order 105 s-1 and up to longitudinal stresses of 2 GPa for calcite and 12 GPa for sapphire. We present measured changes in birefringence for these materials under shock compression, comparing with current and past literature as well as an in house optical model. The authors would like to thank Mr Steve Johnson and Mr David Pittman for technical support. The Institute of Shock Physics acknowledges the continued support of AWE and Imperial College London.

  11. Acceleration of calcite kinetics by abalone nacre proteins

    SciTech Connect

    Fu, G; Qiu, S R; Orme, C A; Morse, D E; De Yoreo, J J

    2005-06-09

    The fascinating shapes and hierarchical designs of biomineralized structures have long been an inspiration to materials scientists because of the potential they suggest for biomolecular control over synthesis of crystalline materials. One prevailing view is that mineral-associated macromolecules are responsible for initiating and stabilizing non-equilibrium crystal polymorphs and morphologies through interactions between anionic moieties and cations in solution or at mineral surfaces. Indeed, numerous studies have demonstrated that bio-organic additives can dramatically alter crystal shapes and growth-rates in vitro. However, previous molecular-scale studies revealing mechanisms of growth modification focused on small molecules such as amino acids or peptides and always observed growth inhibition. In contrast, studies using full proteins were non-quantitative and underlying sources of growth modification were ill-defined. Here we investigate interactions between proteins isolated from abalone shell nacre and growing surfaces of calcite. We find that these proteins significantly accelerate the molecular-scale kinetics and, though much larger than atomic steps, alter growth morphology through step-specific interactions that lower their free energies. We propose that these proteins act as surfactants to promote ion attachment at calcite surfaces.

  12. The coordination and distribution of B in foraminiferal calcite

    NASA Astrophysics Data System (ADS)

    Branson, Oscar; Kaczmarek, Karina; Redfern, Simon A. T.; Misra, Sambuddha; Langer, Gerald; Tyliszczak, Tolek; Bijma, Jelle; Elderfield, Henry

    2015-04-01

    The isotopic ratio and concentration of B in foraminiferal calcite appear to reflect the pH and bicarbonate concentration of seawater. The use of B as a chemical proxy tracer has the potential to transform our understanding of the global carbon cycle, and ocean acidification processes. However, discrepancies between the theory underpinning the B proxies, and mineralogical observations of B coordination in biomineral carbonates call the basis of these proxies into question. Here, we use synchrotron X-ray spectromicroscopy to show that B is hosted solely as trigonal BO3 in the calcite test of Amphistegina lessonii, and that B concentration exhibits banding at the micron length scale. In contrast to previous results, our observation of trigonal B agrees with the predictions of the theoretical mechanism behind B palaeoproxies. These data strengthen the use of B for producing palaeo-pH records. The observation of systematic B heterogeneity, however, highlights the complexity of foraminiferal biomineralisation, implying that B incorporation is modulated by biological or crystal growth processes.

  13. Crystallographic orientation inhomogeneity and crystal splitting in biogenic calcite

    PubMed Central

    Checa, Antonio G.; Bonarski, Jan T.; Willinger, Marc G.; Faryna, Marek; Berent, Katarzyna; Kania, Bogusz; González-Segura, Alicia; Pina, Carlos M.; Pospiech, Jan; Morawiec, Adam

    2013-01-01

    The calcitic prismatic units forming the outer shell of the bivalve Pinctada margaritifera have been analysed using scanning electron microscopy–electron back-scatter diffraction, transmission electron microscopy and atomic force microscopy. In the initial stages of growth, the individual prismatic units are single crystals. Their crystalline orientation is not consistent but rather changes gradually during growth. The gradients in crystallographic orientation occur mainly in a direction parallel to the long axis of the prism, i.e. perpendicular to the shell surface and do not show preferential tilting along any of the calcite lattice axes. At a certain growth stage, gradients begin to spread and diverge, implying that the prismatic units split into several crystalline domains. In this way, a branched crystal, in which the ends of the branches are independent crystalline domains, is formed. At the nanometre scale, the material is composed of slightly misoriented domains, which are separated by planes approximately perpendicular to the c-axis. Orientational gradients and splitting processes are described in biocrystals for the first time and are undoubtedly related to the high content of intracrystalline organic molecules, although the way in which these act to induce the observed crystalline patterns is a matter of future research. PMID:23804442

  14. Calcite sealing in a fractured geothermal reservoir: Insights from combined EBSD and chemistry mapping

    NASA Astrophysics Data System (ADS)

    McNamara, David D.; Lister, Aaron; Prior, Dave J.

    2016-09-01

    Fractures play an important role as fluid flow pathways in geothermal resources hosted in indurated greywacke basement of the Taupo Volcanic Zone, New Zealand, including the Kawerau Geothermal Field. Over time, the permeability of such geothermal reservoirs can be degraded by fracture sealing as minerals deposit out of transported geothermal fluids. Calcite is one such fracture sealing mineral. This study, for the first time, utilises combined data from electron backscatter diffraction and chemical mapping to characterise calcite vein fill morphologies, and gain insight into the mechanisms of calcite fracture sealing in the Kawerau Geothermal Field. Two calcite sealing mechanisms are identified 1) asymmetrical syntaxial growth of calcite, inferred by the presence of single, twinned, calcite crystals spanning the entire fracture width, and 2) 3D, interlocking growth of bladed vein calcite into free space as determined from chemical and crystallographic orientation mapping. This study also identifies other potential uses of combined EBSD and chemical mapping to understand geothermal field evolution including, potentially informing on levels of fluid supersaturation from the study of calcite lattice distortion, and providing information on a reservoir's history of stress, strain, and deformation through investigation of calcite crystal deformation and twinning patterns.

  15. Anisotropic parallel self-diffusion coefficients near the calcite surface: A molecular dynamics study.

    PubMed

    Franco, Luís F M; Castier, Marcelo; Economou, Ioannis G

    2016-08-28

    Applying classical molecular dynamics simulations, we calculate the parallel self-diffusion coefficients of different fluids (methane, nitrogen, and carbon dioxide) confined between two {101̄4} calcite crystal planes. We have observed that the molecules close to the calcite surface diffuse differently in distinct directions. This anisotropic behavior of the self-diffusion coefficient is investigated for different temperatures and pore sizes. The ion arrangement in the calcite crystal and the strong interactions between the fluid particles and the calcite surface may explain the anisotropy in this transport property. PMID:27586936

  16. Utilization of calcite and waste glass for preparing construction materials with a low environmental load.

    PubMed

    Maeda, Hirotaka; Imaizumi, Haruki; Ishida, Emile Hideki

    2011-11-01

    In this study, porous calcite materials are hydrothermally treated at 200 °C using powder compacts consisting of calcite and glasses composed of silica-rich soda-lime. After treatment, the glasses are converted into calcium aluminosilicate hydrates, such as zeolite phases, which increase their strength. The porosity and morphology of new deposits of hydrothermally solidified materials depend up on the chemical composition of glass. The use of calcite and glass in the hydrothermal treatment plays an important role in the solidification of calcite without thermal decomposition. PMID:21794973

  17. Crystal growth of calcite from calcium bicarbonate solutions at constant PCO2 and 25°C: a test of a calcite dissolution model

    USGS Publications Warehouse

    Reddy, Michael M.; Plummer, L. Neil; Busenberg, E.

    1981-01-01

    A highly reproducible seeded growth technique was used to study calcite crystallization from calcium bicarbonate solutions at 25°C and fixed carbon dioxide partial pressures between 0.03 and 0.3 atm. The results are not consistent with empirical crystallization models that have successfully described calcite growth at low PCO2 (< 10−3 atm). Good agreement was found between observed crystallization rates and those calculated from the calcite dissolution rate law and mechanism proposed by Plummer et al. (1978).

  18. Marine pollution

    SciTech Connect

    Albaiges, J. )

    1989-01-01

    This book covers the following topics: Transport of marine pollutants; Transformation of pollutants in the marine environment; Biological effects of marine pollutants; Sources and transport of oil pollutants in the Persian Gulf; Trace metals and hydrocarbons in Syrian coastal waters; and Techniques for analysis of trace pollutants.

  19. Interactions of arsenic with calcite surfaces revealed by in-situ nanoscale imaging

    NASA Astrophysics Data System (ADS)

    Renard, Francois; Putnis, Christine; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hövelmann, Jörn; Sarret, Géraldine

    2015-04-01

    Arsenic dissolved in water represents a key environmental and health challenge because several million people are under the threat of contamination. In calcareous environments calcite may play an important role in arsenic solubility and transfer in water. Arsenic-calcite interactions remain controversial, especially for As(III) which was proposed to be either incorporated as such, or as As(V) after oxidation. Here, we provide the first time-lapse in-situ study of calcite dissolution and growth in the presence of solutions with various amounts of As(III) or As(V). This was performed at room temperature and pH range 6-9 using a flow through cell connected to an atomic force microscope (AFM), to study the evolution of the (10-14) calcite cleavage surface morphology. Reaction products were then characterized by Raman spectroscopy. In parallel, co-precipitation experiments with either As(III) or As(V) were performed in batch reactors, and the speciation of arsenic in the resulting solids was studied by X-ray absorption spectroscopy (XAS). For As(V), AFM results showed that it interacts strongly with the calcite surface, and XAS results showed that As(V) was mostly incorporated in the calcite structure. For As(III), AFM results showed much less impact on calcite growth and dissolution and less incorporation was observed. This was confirmed by XAS results that indicate that As(III) was partly oxidized into As(V) before being incorporated into calcite and the resulting calcite contained 36% As(III) and 64% As(V). All these experimental results confirm that As(V) has a much stronger interaction with calcite than As(III) and that calcite may represent an important reservoir for arsenic in various geological environments.

  20. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    SciTech Connect

    Gorman, Brian P

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  1. A model of early calcite cementation in alluvial fans: Evidence from the Burdigalian sandstones and limestones of the Vallès-Penedès half-graben (NE Spain)

    NASA Astrophysics Data System (ADS)

    Parcerisa, D.; Gómez-Gras, D.; Travé, A.

    2005-07-01

    The Vallès-Penedès half-graben developed during a Neogene extensive period as part of the Catalan Coastal Ranges in the northwestern edge of the Valencia Trough. The Neogene deposits of the Vallès-Penedès half-graben consist of, from base to top, three lithostratigraphic complexes: i) a lower continental complex of Aquitanian?-early Langhian age; ii) a continental to marine complex with reefal carbonate platforms of Langhian age and; iii) an upper continental complex of middle Serravallian-Tortonian age. This study focuses on the calcite cements of the lower continental complex consisting of red beds (mudstones, sandstones and conglomerates) and lacustrine limestones deposited in alluvial fan environments. The studied materials are cemented by calcite precipitated from meteoric waters that circulated through the sediments during the early diagenesis at shallow burial depths. The calcite cement was studied by means of petrographic, cathodoluminescence, microprobe and δ 18O and δ 13C isotopic analysis. The petrographic and geochemical results show that these cements vary according to the sedimentary environment: (i) sandstones deposited in proximal alluvial fan environments cemented by calcite with low contents of Mg, Fe, Mn, Sr and Na, δ 13C values of - 7,4‰ PDB and δ 18O values from - 6.5 to - 6.2‰ PDB; (ii) sandstones sedimented in medium to distal alluvial fan environments cemented by Mn-rich and Mg, Fe, Sr and Na-poor calcite with δ 13C values from - 7.9 to - 6.9‰ PDB and δ 18O values from - 10.5 to - 8.6‰ PDB; and (iii) lacustrine limestones of distal alluvial fan environments cemented by Fe-rich calcite with variable contents of Mn and low contents of Mg, Sr and Na. The distribution of these calcite cements allows us to propose a model of fluid circulation and early calcite cementation within an alluvial fan indicating spatial and temporal variations in chemical composition of meteoric water during migration from proximal to distal alluvial

  2. Significance of aragonite cements around Cretaceous marine methane seeps

    SciTech Connect

    Savard, M.M.; Beauchamp, B.; Veizer, J.

    1996-05-01

    Detailed petrography and geochemistry of carbonate precipitates in Cretaceous cold seep mounds from the Canadian Arctic show spectacular early diagenetic products: some still-preserved splays and isopachous layers of fine, acicular aragonite, and large botryoids and crusts of low-magnesium calcite showing unusual entanglement of former fibrous calcite and aragonite. The latter mineralogy is suggested by clear, flat-terminated cathodoluminescence patterns interpreted as ancient crystal growth steps, and the former by rhombohedral terminations. The early cement phases very likely precipitated in cold Arctic water dominated by bicarbonates derived from bacterially oxidized methane: these cements have {delta}{sup 13}C values around {minus}44.0% and {delta}{sup 18}O values of 1.8 to 0.1% PDB. Coexistence of calcite and aragonite early cements in the Cretaceous seep mounds is unusual, because precipitation occurred in high-latitude, cold-water settings, and during a so-called calcite sea mode. As in modern marine hydrocarbon seeps, the chemistry of the Cretaceous system was apparently controlled by chemosynthetic bacterial activity, resulting in high a{sub HCO{sub 3}{sup {minus}}} that promoted precipitation of carbonates. The authors suggest that, locally, fluctuations in a{sub HCO{sub 3}{sup {minus}}}/a{sub SO{sub 4}{sup 2{minus}}} resulted in oscillating aragonite or calcite supersaturation, and hence, controlled the mineralogy of the early precipitates.

  3. Nanoscale observations of the effect of citrate on calcium oxalate precipitation on calcite surfaces.

    NASA Astrophysics Data System (ADS)

    Burgos-Cara, Alejandro; Ruiz-Agudo, Encarnacion; Putnis, Christine V.

    2016-04-01

    Calcium oxalate (CaC2O4ṡxH2O) minerals are naturally occurring minerals found in fossils, plants, kidney stones and is a by-product in some processes such as paper, food and beverage production [1,2]. In particular, calcium oxalate monohydrate phase (COM) also known as whewellite (CaC2O4ṡH2O), is the most frequently reported mineral phase found in urinary and kidney stones together with phosphates. Organic additives are well known to play a key role in the formation of minerals in both biotic and abiotic systems, either facilitating their precipitation or hindering it. In this regard, recent studies have provided direct evidence demonstrating that citrate species could enhance dissolution of COM and inhibit their precipitation. [3,4] The present work aims at evauate the influence of pH, citrate and oxalic acid concentrations in calcium oxalate precipitation on calcite surfaces (Island Spar, Chihuahua, Mexico) through in-situ nanoscale observation using in situ atomic force microscopy (AFM, Multimode, Bruker) in flow-through experiments. Changes in calcium oxalate morphologies and precipitated phases were observed, as well as the inhibitory effect of citrate on calcium oxalate precipitation, which also lead to stabilization an the amorphous calcium oxalate phase. [1] K.D. Demadis, M. Öner, Inhibitory effects of "green"additives on the crystal growth of sparingly soluble salts, in: J.T. Pearlman (Ed.), Green Chemistry Research Trends, Nova Science Publishers Inc., New York, 2009, pp. 265-287. [2] M. Masár, M. Zuborová, D. Kaniansky, B. Stanislawski, Determination of oxalate in beer by zone electrophoresis on a chip with conductivity detection, J. Sep. Sci. 26 (2003) 647-652. [3] Chutipongtanate S, Chaiyarit S, Thongboonkerd V. Citrate, not phosphate, can dissolve calcium oxalate monohydrate crystals and detach these crystals from renal tubular cells. Eur J Pharmacol 2012;689:219-25. [4] Weaver ML, Qiu SR, Hoyer JR, Casey WH, Nancollas GH, De Yoreo JJ

  4. Understanding control of calcitic biomineralization-proteomics to the rescue.

    PubMed

    Hincke, Maxwell T

    2013-12-01

    The avian eggshell is one of the fastest calcifying processes known and represents a unique model for studying biomineralization. Eggshell strength is a crucial economic trait for table egg production, and ensures that a safe egg reaches the consumer kitchen. However, a common toolkit for eggshell mineralization has not yet been defined. In this issue, label-free MS-based protein quantification technology has been used by Sun et al. (Proteomics 2013, 13, 3523-3536) to detect differences in protein abundance between eggshell matrix from strong and weak eggs and between the corresponding uterine fluids bathing strong and weak eggs. Proteins associated with the formation of strong eggshells are identified, which are now candidates for further investigations to define the regulatory relationship between specific eggshell matrix proteins and calcite crystal texture. PMID:24307661

  5. Shock-induced effects in calcite from Cactus Crater

    NASA Technical Reports Server (NTRS)

    Vizgirda, J.; Ahrens, T. J.; Tsay, F.-D.

    1980-01-01

    The paper discusses shock metamorphism of calcite from coralline limestone samples retrieved from a borehole drilled into rocks beneath Cactus Crater, a nuclear explosion crater at Eniwetok Atoll. The metamorphism was detected and quantified using electron spin resonance (ESR); the ESR spectra of Mn(+) present as a trace constituent in the coral samples, show a consistent decrease in hyperfine peak splitting with decreasing depth of sample. It is suggested that the decrease in hyperfine peak splitting reflects a decrease in crystal field splitting, and therefore, small increases on cation-anion distances produced by mechanical energy input during the shock process. Two alternative crater models suggested by the ESR results are a depiction of a steady decay of the shock wave, and a delineation of a breccia lens with a breccia-bedrock interface at 20 plus or minus 5 m.

  6. Calcite and dolomite in intrusive carbonatites. I. Textural variations

    NASA Astrophysics Data System (ADS)

    Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Zaitsev, Anatoly N.

    2016-04-01

    Carbonatites are nominally igneous rocks, whose evolution commonly involves also a variety of postmagmatic processes, including exsolution, subsolidus re-equilibration of igneous mineral assemblages with fluids of different provenance, hydrothermal crystallization, recrystallization and tectonic mobilization. Petrogenetic interpretation of carbonatites and assessment of their mineral potential are impossible without understanding the textural and compositional effects of both magmatic and postmagmatic processes on the principal constituents of these rocks. In the present work, we describe the major (micro)textural characteristics of carbonatitic calcite and dolomite in the context of magma evolution, fluid-rock interaction, or deformation, and provide information on the compositional variation of these minerals and its relation to specific evolutionary processes.

  7. Age constraints on fluid inclusions in calcite at Yucca Mountain

    SciTech Connect

    Neymark, Leonid A.; Amelin, Yuri V.; Paces, James B.; Peterman, Zell E.; Whelan, Joseph F.

    2001-04-29

    The {sup 207}Pb/{sup 235}U ages for 14 subsamples of opal or chalcedony layers younger than calcite formed at elevated temperature range between 1.88 {+-} 0.05 and 9.7 {+-} 1.5 Ma with most values older than 6-8 Ma. These data indicate that fluids with elevated temperatures have not been present in the unsaturated zone at Yucca Mountain since about 1.9 Ma and most likely since 6-8 Ma. Discordant U-Pb isotope data for chalcedony subsamples representing the massive silica stage in the formation of the coatings are interpreted using a model of the diffusive loss of U decay products. The model gives an age estimate for the time of chalcedony formation around 10-11 Ma, which overlaps ages of clay minerals formed in tuffs below the water table at Yucca Mountain during the Timber Mountain thermal event.

  8. On the origin of fiber calcite crystals in moonmilk deposits.

    PubMed

    Cañaveras, Juan Carlos; Cuezva, Soledad; Sanchez-Moral, Sergio; Lario, Javier; Laiz, Leonila; Gonzalez, Juan Miguel; Saiz-Jimenez, Cesareo

    2006-01-01

    In this study, we show that moonmilk subaerial speleothems in Altamira Cave (Spain) consist of a network of fiber calcite crystals and active microbial structures. In Altamira moonmilks, the study of the typology and distribution of fiber crystals, extracellular polymeric substances, and microorganisms allowed us to define the initial stages of fiber crystal formation in recent samples as well as the variations in the microstructural arrangement in more evolved stages. Thus, we have been able to show the existence of a relationship among the different types of fiber crystals and their origins. This allowed us to outline a model that illustrates the different stages of formation of the moonmilk, developed on different substrata, concluding that microbes influence physicochemical precipitation, resulting in a variety of fiber crystal morphologies and sizes. PMID:16240102

  9. Structural evolution of calcite at high temperatures: Phase V unveiled

    PubMed Central

    Ishizawa, Nobuo; Setoguchi, Hayato; Yanagisawa, Kazumichi

    2013-01-01

    The calcite form of calcium carbonate CaCO3 undergoes a reversible phase transition between Rc and Rm at ~1240 K under a CO2 atmosphere of ~0.4 MPa. The joint probability density function obtained from the single-crystal X-ray diffraction data revealed that the oxygen triangles of the CO3 group in the high temperature form (Phase V) do not sit still at specified positions in the space group Rm, but migrate along the undulated circular orbital about carbon. The present study also shows how the room temperature form (Phase I) develops into Phase V through an intermediate form (Phase IV) in the temperature range between ~985 K and ~1240 K. PMID:24084871

  10. Calcite orientations and composition ranges within teeth across Echinoidea

    PubMed Central

    Stock, Stuart R.; Ignatiev, Konstantin; Lee, Peter L.; Almer, Jonathan D.

    2016-01-01

    Sea urchin’s teeth from four families of order Echinoida and from orders Temnopleuroida, Arbacioida and Cidaroida were studied with synchrotron x-ray diffraction. The high and very high Mg calcite phases of the teeth, i.e. the first and second stage mineral constituents, respectively, have the same crystallographic orientations. The co-orientation of first and second stage mineral, which the authors attribute to epitaxy, extends across the phylogenic width of the extant regular sea urchins and demonstrates that this is a primitive character of this group. The range of compositions Δx for the two phases of Ca1−xMgxCO3 is about 0.20 or greater and is consistent with a common biomineralization process. PMID:25158180

  11. Polyamines and abiotic stress in plants: a complex relationship.

    PubMed

    Minocha, Rakesh; Majumdar, Rajtilak; Minocha, Subhash C

    2014-01-01

    The physiological relationship between abiotic stress in plants and polyamines was reported more than 40 years ago. Ever since there has been a debate as to whether increased polyamines protect plants against abiotic stress (e.g., due to their ability to deal with oxidative radicals) or cause damage to them (perhaps due to hydrogen peroxide produced by their catabolism). The observation that cellular polyamines are typically elevated in plants under both short-term as well as long-term abiotic stress conditions is consistent with the possibility of their dual effects, i.e., being protectors from as well as perpetrators of stress damage to the cells. The observed increase in tolerance of plants to abiotic stress when their cellular contents are elevated by either exogenous treatment with polyamines or through genetic engineering with genes encoding polyamine biosynthetic enzymes is indicative of a protective role for them. However, through their catabolic production of hydrogen peroxide and acrolein, both strong oxidizers, they can potentially be the cause of cellular harm during stress. In fact, somewhat enigmatic but strong positive relationship between abiotic stress and foliar polyamines has been proposed as a potential biochemical marker of persistent environmental stress in forest trees in which phenotypic symptoms of stress are not yet visible. Such markers may help forewarn forest managers to undertake amelioration strategies before the appearance of visual symptoms of stress and damage at which stage it is often too late for implementing strategies for stress remediation and reversal of damage. This review provides a comprehensive and critical evaluation of the published literature on interactions between abiotic stress and polyamines in plants, and examines the experimental strategies used to understand the functional significance of this relationship with the aim of improving plant productivity, especially under conditions of abiotic stress. PMID:24847338

  12. Polyamines and abiotic stress in plants: a complex relationship1

    PubMed Central

    Minocha, Rakesh; Majumdar, Rajtilak; Minocha, Subhash C.

    2014-01-01

    The physiological relationship between abiotic stress in plants and polyamines was reported more than 40 years ago. Ever since there has been a debate as to whether increased polyamines protect plants against abiotic stress (e.g., due to their ability to deal with oxidative radicals) or cause damage to them (perhaps due to hydrogen peroxide produced by their catabolism). The observation that cellular polyamines are typically elevated in plants under both short-term as well as long-term abiotic stress conditions is consistent with the possibility of their dual effects, i.e., being protectors from as well as perpetrators of stress damage to the cells. The observed increase in tolerance of plants to abiotic stress when their cellular contents are elevated by either exogenous treatment with polyamines or through genetic engineering with genes encoding polyamine biosynthetic enzymes is indicative of a protective role for them. However, through their catabolic production of hydrogen peroxide and acrolein, both strong oxidizers, they can potentially be the cause of cellular harm during stress. In fact, somewhat enigmatic but strong positive relationship between abiotic stress and foliar polyamines has been proposed as a potential biochemical marker of persistent environmental stress in forest trees in which phenotypic symptoms of stress are not yet visible. Such markers may help forewarn forest managers to undertake amelioration strategies before the appearance of visual symptoms of stress and damage at which stage it is often too late for implementing strategies for stress remediation and reversal of damage. This review provides a comprehensive and critical evaluation of the published literature on interactions between abiotic stress and polyamines in plants, and examines the experimental strategies used to understand the functional significance of this relationship with the aim of improving plant productivity, especially under conditions of abiotic stress. PMID:24847338

  13. Nyerereite from calcite carbonatite at the Kerimasi Volcano, Northern Tanzania

    NASA Astrophysics Data System (ADS)

    Zaitsev, A. N.

    2010-12-01

    The extinct Quaternary Kerimasi volcano located in the southern part of the Gregory Rift, northern Tanzania, contains both intrusive and extrusive calciocarbonatites. One carbonate mineral with a high content of Na and Ca has been found in a sample of volcanic carbonatite, which is probably a cumulate rock. On the basis of Raman spectroscopy and SEM/EDS, this mineral was identified as nyerereite, ideally Na2Ca(CO3)2. It occurs as solid inclusions up to 300 × 200 μm in size in magnetite and contains (wt. %) 25.4-27.4 Na2O, 26.0-26.8 CaO, 1.6-1.9 K2O, 0.6-1.8 FeO, 0.3-0.6 SrO, <0.4 BaO, 1.4-2.3 SO3, and 0.6-0.9 P2O5. The average mineral formula is (Na1.84K0.08)Σ1.92(Ca1.00Fe0.03Sr0.01)Σ1.04[(CO3)1.91(SO4)0.05(PO4)0.02]Σ1.98. A few inclusions in magnetite also contain calcite, which is considered here to be a late-stage, subsolidus mineral. The occurrence of nyerereite in carbonatite supports Hay's (1983) idea that some of the extrusive carbonatites at the Kerimasi volcano were originally alkaline rich and contained both calcite and nyerereite as primary minerals.

  14. Kinetic model of impurity poisoning during growth of calcite

    SciTech Connect

    DeYoreo, J; Wasylenki, L; Dove, P; Wilson, D; Han, N

    2004-05-18

    The central role of the organic component in biologically controlled mineralization is widely recognized. These proteins are characterized by a high proportion of acidic amino acid residues, especially aspartate, Asp. At the same time, biomineralization takes place in the presence of a number of naturally-occurring, inorganic impurities, particularly Mg and Sr. In an attempt to decipher the controls on calcite growth imposed by both classes of modifiers, we have used in situ AFM to investigate the dependence of growth morphology and step kinetics on calcite in the presence of Sr{sup 2+}, as well as a wide suite of Aspartic acid-bearing polypeptides. In each case, we observe a distinct and step-specific modification. Most importantly, we find that the step speed exhibits a characteristic dependence on impurity concentration not predicted by existing crystal growth models. While all of the impurities clearly induce appearance of a 'dead zone,' neither the width of that dead zone nor the dependence of step speed on activity or impurity content can be explained by invoking the Gibbs-Thomson effect, which is the basis for the Cabrera-Vermilyea model of impurity poisoning. Common kink-blocking models also fail to explain the observed dependencies. Here we propose a kinetic model of inhibition based on a 'cooperative' effect of impurity adsorption at adjacent kink sites. The model is in qualitative agreement with the experimental results in that it predicts a non-linear dependence of dead zone width on impurity concentration, as well as a sharp drop in step speed above a certain impurity content. However, a detailed model of impurity adsorption kinetics that give quantitative agreement with the data has yet to be developed.

  15. A global deglacial negative carbon isotope excursion in speleothem calcite

    NASA Astrophysics Data System (ADS)

    Breecker, D.

    2015-12-01

    δ13C values of speleothem calcite decreased globally during the last deglaciation defining a carbon isotope excursion (CIE) despite relatively constant δ13C values of carbon in the ocean-atmosphere system. The magnitude of the CIE varied with latitude, increasing poleward from ~2‰ in the tropics to as much as 7‰ at high latitudes. This recent CIE provides an interesting comparison with CIEs observed in deep time. A substantial portion of this CIE can be explained by the increase in atmospheric pCO2 that accompanied deglaciation. The dependence of C3 plant δ13C values on atmospheric pCO2 predicts a 2‰ δ13C decrease driven by the deglacial pCO2 increase. I propose that this signal was transferred to caves and thus explains nearly 100% of the CIE magnitude observed in the tropics and no less than 30% at the highest latitudes in the compilation. An atmospheric pCO2 control on speleothem δ13C values, if real, will need to be corrected for using ice core data before δ13C records can be interpreted in a paleoclimate context. The decrease in the magnitude of the equilibrium calcite-CO2 carbon isotope fractionation factor explains a maximum of 1‰ of the CIE at the highest northern latitude in the compilation, which experienced the largest deglacial warming. Much of the residual extratropical CIE was likely driven by increasing belowground respiration rates, which were presumably pronounced at high latitudes as glacial retreat exposed fresh surfaces and/or vegetation density increased. The largest increases in belowground respiration would have therefore occurred at the highest latitudes, explaining the meridional trend. This work supports the notion that increases in atmospheric pCO2 and belowground respiration rates can result in large CIEs recorded in terrestrial carbonates, which, as previously suggested, may explain the magnitude of the PETM CIE as recorded by paleosol carbonates.

  16. Carbon and oxygen isotopes in apatite CO/sub 2/ and co-existing calcite

    SciTech Connect

    Kolodny, Y.; Kaplan, I. R.

    1981-04-01

    Carbon and oxygen isotopes were analyzed in carbonate apatite CO/sub 2/ and in co-existing calcite. Both C and O in apatite CO/sub 2/ are enriched in the respective light isotopes relative to calcite. These results confirm the proposition that carbonate is part of the apatite structure.

  17. Evidence of a stable uranyl site in ancient organic-rich calcite.

    PubMed

    Kelly, Shelly D; Rasbury, E Troy; Chattopadhyay, Soma; Kropf, A Jeremy; Kemner, Kenneth M

    2006-04-01

    The mechanism of uranium (U) incorporation into calcite (calcium carbonate) is of fundamental importance to the fate and transport of U at the surface and in the shallow subsurface and has implications for (a) the accuracy of U-Pb and U-series isotope ratio methods used to determine the ages of ancient deposits and (b) potential remediation strategies based on sequestration of U in the subsurface. Extended X-ray absorption fine structure (EXAFS) spectroscopy is uniquely suited to the study of U-calcite systems. The sensitivity of the EXAFS spectrum to the local atomic Ca coordination about U(VI) in the calcite structure results in an increase in the number and amplitude of Ca signals as the U(VI) becomes more ordered within the crystal structure. Our X-ray microprobe (10-microm) measurements of an ancient 298 million-year-old organic-rich calcite (calcrete) clearly revealed three coordination shells of Ca atoms, defining a well-ordered calcite structure about uranyl to a distance of approximately 6.5 angstroms. These results indicate that uranyl is incorporated at the Ca2+ site in calcite and that the uranyl environment may evolve over long time scales, becoming more calcite-like and more stable for long-term sequestration of uranium. These results therefore validate U-related dating methods and show that calcite can be effective at sequestering U in vadose zone sediments. PMID:16646462

  18. Biotic Control of Skeletal Growth by Scleractinian Corals in Aragonite–Calcite Seas

    PubMed Central

    Higuchi, Tomihiko; Fujimura, Hiroyuki; Yuyama, Ikuko; Harii, Saki; Agostini, Sylvain; Oomori, Tamotsu

    2014-01-01

    Modern scleractinian coral skeletons are commonly composed of aragonite, the orthorhombic form of CaCO3. Under certain conditions, modern corals produce calcite as a secondary precipitate to fill pore space. However, coral construction of primary skeletons from calcite has yet to be demonstrated. We report a calcitic primary skeleton produced by the modern scleractinian coral Acropora tenuis. When uncalcified juveniles were incubated from the larval stage in seawater with low mMg/Ca levels, the juveniles constructed calcitic crystals in parts of the primary skeleton such as the septa; the deposits were observable under Raman microscopy. Using scanning electron microscopy, we observed different crystal morphologies of aragonite and calcite in a single juvenile skeleton. Quantitative analysis using X-ray diffraction showed that the majority of the skeleton was composed of aragonite even though we had exposed the juveniles to manipulated seawater before their initial crystal nucleation and growth processes. Our results indicate that the modern scleractinian coral Acropora mainly produces aragonite skeletons in both aragonite and calcite seas, but also has the ability to use calcite for part of its skeletal growth when incubated in calcite seas. PMID:24609012

  19. Low limit of Mn 2+-activated cathodoluminescence of calcite: state of the art

    NASA Astrophysics Data System (ADS)

    Habermann, Dirk; Neuser, Rolf D.; Richter, Detlev K.

    1998-02-01

    In the literature, the lower limit for Mn 2+-activated cathodoluminescence (CL) of calcite is variously reputed to over a very wide range of values above 10 ppm Mn. Our spectroscopic investigations of the CL response in natural calcite reveal that below 10 ppm manganese content Mn 2+-activation is also present. Using the Quantitative High Resolution Spectral analysis of CL (QHRS-CL) an activation by Mn 2+ in the range of 700 ppb is proved, which cannot be determined visually. So, if not quenched, the minimum Mn 2+ content for Mn 2+-activation is one atom in the irradiated calcite crystal lattice volume. As the intrinsic (background blue) luminescence is used to determine non-altered biogenic calcite, the limit of Mn 2+-activation plays an important role in the interpretation of diagenetic processes. Our results of spectroscopic analyses require a revision of current opinions about the diagenesis of calcite as revealed by CL investigation.

  20. Influence of calcite on uranium(VI) reactive transport in the groundwater–river mixing zone

    SciTech Connect

    Ma, Rui; Liu, Chongxuan; Greskowiak, Janek; Prommer, Henning; Zachara, John M.; Zheng, Chunmiao

    2014-01-23

    Calcite is an important mineral that can affect uranyl reactive transport in subsurface sediments. This study investigated the distribution of calcite and its influence on uranyl adsorption and reactive transport in the groundwater-river mixing zone at US Hanford 300A, Washington State. Simulations using a 2D reactive transport model under field-relevant hydrogeochemical conditions revealed a complex distribution of calcite concentration as a result of dynamic groundwater-river interactions. The calcite concentration distribution in turn affected the spatial and temporal changes in aqueous carbonate, calcium, and pH, which subsequently influenced U(VI) mobility and discharge rates into the river. The results implied that calcite distribution and its concentration dynamics is an important consideration for field characterization, monitoring, and reactive transport prediction.

  1. Formation of pristane from α-tocopherol under simulated anoxic sedimentary conditions: A combination of biotic and abiotic degradative processes

    NASA Astrophysics Data System (ADS)

    Rontani, Jean-François; Nassiry, Mina; Michotey, Valérie; Guasco, Sophie; Bonin, Patricia

    2010-01-01

    Incubation of intact and oxidized α-tocopherol (vitamin E) in anaerobic sediment slurries allowed us to demonstrate that, as previously suggested by Goossens et al. (1984), the degradation of α-tocopherol in anoxic sediments results in the formation of pristane. The conversion of α-tocopherol to this isoprenoid alkane involves a combination of biotic and abiotic degradative processes, i.e. the anaerobic biodegradation (which seems to be mainly induced by denitrifying bacteria) of trimeric structures resulting from the abiotic oxidation of α-tocopherol. On the basis of the results obtained, it is proposed that in the marine environment most of the α-tocopherol present in phytoplanktonic cells should be quickly degraded within the water column and the oxic zone of sediments by way of aerobic biodegradation, photo- and autoxidation processes. Abiotic transformation of this compound mainly results in the production of trimeric oxidation products, sufficiently stable to be incorporated into anoxic sediments and whose subsequent anaerobic bacterial degradation affords pristane. These results confirm that the ratio pristane to phytane cannot be used as an indicator of the oxicity of the environment of deposition; in contrast, they support the use of PFI (Pristane Formation Index) as a proxy for the state of diagenesis of sedimentary organic matter.

  2. ROS Regulation During Abiotic Stress Responses in Crop Plants

    PubMed Central

    You, Jun; Chan, Zhulong

    2015-01-01

    Abiotic stresses such as drought, cold, salt and heat cause reduction of plant growth and loss of crop yield worldwide. Reactive oxygen species (ROS) including hydrogen peroxide (H2O2), superoxide anions (O2•-), hydroxyl radical (OH•) and singlet oxygen (1O2) are by-products of physiological metabolisms, and are precisely controlled by enzymatic and non-enzymatic antioxidant defense systems. ROS are significantly accumulated under abiotic stress conditions, which cause oxidative damage and eventually resulting in cell death. Recently, ROS have been also recognized as key players in the complex signaling network of plants stress responses. The involvement of ROS in signal transduction implies that there must be coordinated function of regulation networks to maintain ROS at non-toxic levels in a delicate balancing act between ROS production, involving ROS generating enzymes and the unavoidable production of ROS during basic cellular metabolism, and ROS-scavenging pathways. Increasing evidence showed that ROS play crucial roles in abiotic stress responses of crop plants for the activation of stress-response and defense pathways. More importantly, manipulating ROS levels provides an opportunity to enhance stress tolerances of crop plants under a variety of unfavorable environmental conditions. This review presents an overview of current knowledge about homeostasis regulation of ROS in crop plants. In particular, we summarize the essential proteins that are involved in abiotic stress tolerance of crop plants through ROS regulation. Finally, the challenges toward the improvement of abiotic stress tolerance through ROS regulation in crops are discussed. PMID:26697045

  3. Diel cycles in calcite production and dissolution in a eutrophic basin

    SciTech Connect

    Cicerone, D.S.; Stewart, A.J.; Roh, Y.

    1999-10-01

    Calcite production is understood largely as a longer-term phenomenon (e.g., seasonal whitings) that can occur in hardwater lakes, and is significant ecologically because it can slow the rate of eutrophication by reducing, through adsorption, the availability of nutrients to primary producers. In this study the authors show that rapid changes in concentration of dissolved CO{sub 2} by photosynthesis and respiration within a eutrophic basin generated strong day-to-night cycles in calcite production and dissolution. Diel cycles in calcite production and dissolution were large enough that they could drive secondary diel cycles in the availability of metals that strongly sorb to the surfaces of calcite particles. They explored the possibility of the secondary diel cycling of metals by intensive 7-d in situ monitoring of water-quality conditions in a shallow, eutrophic spill-control basin near an industrial facility in eastern Tennessee; inspecting data from a 7-year record of water-quality parameters for this basin; analyzing physicochemical characteristics and mineralogic composition of sediments in the basin; and conducting laboratory experiments to characterize the interaction of calcite with Cd, under solid-liquid nonequilibrium conditions. The authors found that the basin accumulated and stored calcite. In situ monitoring showed that calcite was produced during daylight, and tended to dissolve again at night; the calcite production and dissolution processes seemed to be modulated by dissolved-phase CO{sub 2} dynamics, in concert with large diel fluctuations in pCa, pH, and Po{sub 2}. Laboratory experiments showed a rapid interaction ({lt}6 h) of Cd with calcite, in response to dissolved CO{sub 2} changes. Thus, concentrations of dissolved Cd can vary over daily cycles, mediated by diel changes in calcite production and dissolution. Thermodynamic considerations suggest that other metals, such as Zn, Sr, Ni, and Ba, may demonstrate this behavior as well.

  4. The mechanical and microstructural behaviour of calcite-dolomite composites: An experimental investigation

    NASA Astrophysics Data System (ADS)

    Kushnir, Alexandra R. L.; Kennedy, L. A.; Misra, Santanu; Benson, Philip; White, J. C.

    2015-01-01

    The styles and mechanisms of deformation associated with many variably dolomitized limestone shear systems are strongly controlled by strain partitioning between dolomite and calcite. Here, we present experimental results from the deformation of four composite materials designed to address the role of dolomite on the strength of limestone. Composites were synthesized by hot isostatic pressing mixtures of dolomite (Dm) and calcite powders (% Dm: 25%-Dm, 35%-Dm, 51%-Dm, and 75%-Dm). In all composites, calcite is finer grained than dolomite. The synthesized materials were deformed in torsion at constant strain rate (3 × 10-4 and 1 × 10-4 s-1), high effective pressure (262 MPa), and high temperature (750 °C) to variable finite shear strains. Mechanical data show an increase in yield strength with increasing dolomite content. Composites with <75% dolomite (the remaining being calcite), accommodate significant shear strain at much lower shear stresses than pure dolomite but have significantly higher yield strengths than anticipated for 100% calcite. The microstructure of the fine-grained calcite suggests grain boundary sliding, accommodated by diffusion creep and dislocation glide. At low dolomite concentrations (i.e. 25%), the presence of coarse-grained dolomite in a micritic calcite matrix has a profound effect on the strength of composite materials as dolomite grains inhibit the superplastic flow of calcite aggregates. In high (>50%) dolomite content samples, the addition of 25% fine-grained calcite significantly weakens dolomite, such that strain can be partially localized along narrow ribbons of fine-grained calcite. Deformation of dolomite grains by shear fracture is observed; there is no intracrystalline deformation in dolomite irrespective of its relative abundance and finite shear strain.

  5. Interactions of arsenic with calcite surfaces revealed by in situ nanoscale imaging

    NASA Astrophysics Data System (ADS)

    Renard, François; Putnis, Christine V.; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hovelmann, Jörn; Sarret, Géraldine

    2015-06-01

    Arsenic dissolved in water represents a key environmental and health challenge because several million people are under the threat of contamination. In calcareous environments calcite may play an important role in arsenic solubility and transfer in water. Arsenic-calcite interactions remain controversial, especially for As(III) which was proposed to be either incorporated as such, or as As(V) after oxidation. Here, we provide the first time-lapse in situ study of the evolution of the (10-14) calcite cleavage surface morphology during dissolution and growth in the presence of solutions with various amounts of As(III) or As(V) at room temperature and pH range 6-11 using a flow-through cell connected to an atomic force microscope (AFM). Reaction products were then characterized by Raman spectroscopy. In parallel, co-precipitation experiments with either As(III) or As(V) were performed in batch reactors, and the speciation of arsenic in the resulting solids was studied by X-ray absorption spectroscopy (XAS). For As(V), AFM results showed that it interacts strongly with the calcite surface, and XAS results showed that As(V) was mostly incorporated in the calcite structure. For As(III), AFM results showed much less impact on calcite growth and dissolution and less incorporation was observed. This was confirmed by XAS results that indicate that As(III) was partly oxidized into As(V) before being incorporated into calcite and the resulting calcite contained 36% As(III) and 64% As(V). All these experimental results confirm that As(V) has a much stronger interaction with calcite than As(III) and that calcite may represent an important reservoir for arsenic in various geological environments.

  6. Diverse roles of jasmonates and ethylene in abiotic stress tolerance.

    PubMed

    Kazan, Kemal

    2015-04-01

    Jasmonates (JAs) and ethylene (ET), often acting cooperatively, play essential roles in regulating plant defense against pests and pathogens. Recent research reviewed here has revealed mechanistic new insights into the mode of action of these hormones in plant abiotic stress tolerance. During cold stress, JAs and ET differentially regulate the C-repeat binding factor (CBF) pathway. Major JA and ET signaling hubs such as JAZ proteins, CTR1, MYC2, components of the mediator complex, EIN2, EIN3, and several members of the AP2/ERF transcription factor gene family all have complex regulatory roles during abiotic stress adaptation. Better understanding the roles of these phytohormones in plant abiotic stress tolerance will contribute to the development of crop plants tolerant to a wide range of stressful environments. PMID:25731753

  7. Current perspectives in proteomic analysis of abiotic stress in Grapevines

    PubMed Central

    George, Iniga S.; Haynes, Paul A.

    2014-01-01

    Grapes are an important crop plant which forms the basis of a globally important industry. Grape and wine production is particularly vulnerable to environmental and climatic fluctuations, which makes it essential for us to develop a greater understanding of the molecular level responses of grape plants to various abiotic stresses. The completion of the initial grape genome sequence in 2007 has led to a significant increase in research on grapes using proteomics approaches. In this article, we discuss some of the current research on abiotic stress in grapevines, in the context of abiotic stress research in other plant species. We also highlight some of the current limitations in grapevine proteomics and identify areas with promising scope for potential future research. PMID:25538720

  8. STRONTIUM ISOTOPE EVOLUTION OF PORE WATER AND CALCITE IN THE TOPOPAH SPRING TUFF, YUCCA MOUNTAIN , NEVADA

    SciTech Connect

    B.D. Marshall; K. Futa

    2001-02-07

    Yucca Mountain, a ridge of Miocene volcanic rocks in southwest Nevada, is being characterized as a site for a potential high-level radioactive waste repository. One issue of concern for the future performance of the potential repository is the movement of water in and around the potential repository horizon. Past water movement in this unsaturated zone is indicated by fluid inclusions trapped in calcite coatings on fracture footwall surfaces and in some lithophysal cavities. Some of the fluid inclusions have homogenization temperatures above the present-day geotherm (J.F. Whelan, written communication), so determining the ages of the calcite associated with those fluid inclusions is important in understanding the thermal history of the potential repository site. Calcite ages have been constrained by uranium-lead dating of silica polymorphs (opal and chalcedony) that are present in most coatings. The opal and chalcedony ages indicate that deposition of the calcite and opal coatings in the welded part of the Topopah Spring Tuff (TSw hydrogeologic unit) spanned nearly the entire history of the 12.8-million-year-old rock mass at fairly uniform overall long-term rates of deposition (within a factor of five). Constraining the age of a layer of calcite associated with specific fluid inclusions is complicated. Calcite is commonly bladed with complex textural relations, and datable opal or chalcedony may be millions of years older or younger than the calcite layer or may be absent from the coating entirely. Therefore, a more direct method of dating the calcite is presented in this paper by developing a model for strontium evolution in pore water in the TSw as recorded by the strontium coprecipitated with calcium in the calcite. Although the water that precipitated the calcite in fractures and cavities may not have been in local isotopic equilibrium with the pore water, the strontium isotope composition of all water in the TSw is primarily controlled by water

  9. Marine biology

    SciTech Connect

    Thurman, H.V.; Webber, H.H.

    1984-01-01

    This book discusses both taxonomic and ecological topics on marine biology. Full coverage of marine organisms of all five kingdoms is provided, along with interesting and thorough discussion of all major marine habitats. Organization into six major parts allows flexibility. It also provides insight into important topics such as disposal of nuclear waste at sea, the idea that life began on the ocean floor, and how whales, krill, and people interact. A full-color photo chapter reviews questions, and exercises. The contents are: an overview marine biology: fundamental concepts/investigating life in the ocean; the physical ocean, the ocean floor, the nature of water, the nature and motion of ocean water; general ecology, conditions for life in the sea, biological productivity and energy transfer; marine organisms; monera, protista, mycota and metaphyta; the smaller marine animals, the large animals marine habitats, the intertidal zone/benthos of the continental shelf, the photic zone, the deep ocean, the ocean under stress, marine pollution, appendix a: the metric system and conversion factors/ appendix b: prefixes and suffixes/ appendix c: taxonomic classification of common marine organisms, and glossary, and index.

  10. Abiotic Dissolved Organic Matter-Mineral Interaction in the Karstic Floridan Aquifer

    NASA Astrophysics Data System (ADS)

    Jin, J.; Zimmerman, A.

    2007-12-01

    Dissolved organic matter (DOM)-mineral interaction (e.g. adsorption, desorption, mineral dissolution) in groundwater is a significant factor controlling geochemical, environmental and microbial processes and may be helpful in efforts to track groundwater sources or contaminant fate. Despite its importance, the dynamics and consequences of these abiotic interactions remain poorly understood, largely due to the inaccessibility and heterogeneity of the subsurface, as well as the chemical complexity of DOM. This study models the OM-mineral interactions that takes place in the Floridan aquifer through laboratory adsorption-desorption experiments using DOM (groundwater, river water, soil extracts) and carbonate minerals (calcite, dolomite) collected in north Florida. High performance liquid chromatography-size exclusion chromatography (HPLC-SEC) and UV-fluorescence excitation-emission matrix (EEM) spectrophotometry was used to examine the organic compound types exhibiting preferential affinity for carbonate minerals. Our results show that the DOM-carbonate adsorption/desorption isotherms are well described by the Freundlich model. Freundlich exponents (average value: 0.6488) less than one indicated a filling of adsorption sites. Minerals from Ocala tend to have higher adsorption affinity as well as adsorption capacity than those from Suwannee River Basin; however, both were found to have mineral dissolution. Two fluorescent signals, indicative of a fulvic-like (at excitation wavelength 295-310 nm, emission 400-420 nm) and a protein-like (275/345nm) moiety, were detected in DOM. A reduction in the fulvic-like peak intensity occurred following carbonate adsorption while the protein-like peaks remain almost unchanged indicating the preferential adsorption of fulvic acids. HPLC-SEC results (DOM properties as a function of molecular weight) will be discussed. The chemical properties of DOM in environmental groundwater samples will also be presented and evaluated in light of

  11. Influence of surface conductivity on the apparent zeta potential of calcite.

    PubMed

    Li, Shuai; Leroy, Philippe; Heberling, Frank; Devau, Nicolas; Jougnot, Damien; Chiaberge, Christophe

    2016-04-15

    Zeta potential is a physicochemical parameter of particular importance in describing the surface electrical properties of charged porous media. However, the zeta potential of calcite is still poorly known because of the difficulty to interpret streaming potential experiments. The Helmholtz-Smoluchowski (HS) equation is widely used to estimate the apparent zeta potential from these experiments. However, this equation neglects the influence of surface conductivity on streaming potential. We present streaming potential and electrical conductivity measurements on a calcite powder in contact with an aqueous NaCl electrolyte. Our streaming potential model corrects the apparent zeta potential of calcite by accounting for the influence of surface conductivity and flow regime. We show that the HS equation seriously underestimates the zeta potential of calcite, particularly when the electrolyte is diluted (ionic strength ⩽ 0.01 M) because of calcite surface conductivity. The basic Stern model successfully predicted the corrected zeta potential by assuming that the zeta potential is located at the outer Helmholtz plane, i.e. without considering a stagnant diffuse layer at the calcite-water interface. The surface conductivity of calcite crystals was inferred from electrical conductivity measurements and computed using our basic Stern model. Surface conductivity was also successfully predicted by our surface complexation model. PMID:26852350

  12. U-Th dating of calcitic corals from the Red Sea

    NASA Astrophysics Data System (ADS)

    Stein, M.; Yehudai, M.; Kohn, N.; Shaked, Y.; Agnon, A.; Lazar, B.

    2013-12-01

    Pristine aragonite skeletons of reef building corals can be rapidly recrystallized to calcite by the interaction of the corals with freshwater in coastal aquifers. The aragonite/calcite transformation is accompanied by opening the coral's U-Th isotope system in which uranium is partly lost while Th remains adsorbed and reincorporates into the newly formed calcite. Depending on the geological setting of the reef, the corals may incorporate secondary aragonite with higher U and 234U/238U isotope ratio, while still submerged, before the recrystallization process. Recrystallization to calcite occurs during sea level drop or coast tectonic uplift and later may follow a subaerial closed system decay scheme. In this study we examine the behavior of the U and Th in calcitic corals from the last interglacial reefs at the northern Gulf of Aqaba. We analyzed several subsamples from selected reef coral skeletons in an attempt to follow the recrystallization scheme of the corals and find a reliable method to estimate the age of these heavily altered corals. The main assumptions were that all subsamples from the same coral have identical deposition age and the sub-samples Th (and hence 230Th) was fully preserved during recrystallization to calcite (increasing the 230Th/238U isotope ratio). Diagenesis to calcite occurred several thousand years after the initial precipitation of the aragonitic skeleton. This calls for wetter (than present) conditions during the last interglacial in the currently hyperarid northern Red Sea.

  13. Controls of carbonate mineralogy and solid-solution of Mg in calcite: evidence from spelean systems

    SciTech Connect

    Gonzalez, L.A.; Lohmann, K.C.

    1985-01-01

    Precipitation of carbonate minerals in spelean systems occurs under a wide range of fluid chemistry, Mg-Ca ratios, alkalinities, pH and temperatures; thus, spelean systems provide ideal settings to determine factors controlling the mineralogy of precipitated carbonates and solid-solution of Mg in calcite. Cave waters and actively-precipitating carbonate speleothems were collected from Carlsbad Caverns National Park, New Mexico and the Mammoth-Flint Cave System, Kentucky. Carbonate mineralogy of precipitated phases was determined by x-ray diffraction, and major and minor element composition of waters and accompanying minerals were determined by Atomic Absorption Spectrophotometry. Results demonstrate that at a constant CO3 concentration the precipitation threshold for calcite to aragonite is controlled dominantly by the Mg/Ca ratio of the ambient fluid. Aragonite precipitation is favored by high Mg/Ca ratios. Conversely, with increasing CO3 concentration at constant fluid Mg/Ca ratios, calcite is preferentially precipitated. Solid-solution of Mg in calcite is positively correlated with both increased Mg/Ca ratios and CO3 concentrations. These data suggest that Mg contents of calcite can not be defined solely in terms of a homogeneous distribution coefficient. Rather, Mg concentrations can be also be affected by the CO3 concentration and degree of calcite saturation, suggesting that the rate of crystal growth also plays and important role in Mg solid-solution in calcites.

  14. Fabrication of porous calcite using chopped nylon fiber and its evaluation using rats.

    PubMed

    Ishikawa, Kunio; Tram, Nguyen Xuan Thanh; Tsuru, Kanji; Toita, Riki

    2015-02-01

    Although porous calcite has attracted attention as bone substitutes, limited studies have been made so far. In the present study, porous calcite block was fabricated by introducing chopped nylon fiber as porogen. Ca(OH)2 powder containing 10 wt% chopped nylon fiber was compacted at 150 MPa, and sintered to burn out the fiber and to carbonate the Ca(OH)2 under stream of 1:2 O2-CO2. Sintering of Ca(OH)2 at 750 °C or lower temperature resulted in incomplete burning out of the fiber whereas sintering at 800 °C or higher temperature resulted in the formation of CaO due to the thermal decomposition of Ca(OH)2. However, sintering at 770 °C resulted in complete burning out of the fiber and complete carbonation of Ca(OH)2 to calcite without forming CaO. Macro- and micro-porosities of the porous calcite were approximately 23 and 16%, respectively. Diameter of the macropores was approximately 100 μm which is suitable for bone tissue penetration. Porous calcite block fabricated by this method exhibited good tissue response when implanted in the bone defect in femur of 12-weeks-old rat. Four weeks after implantation, bone bonded on the surface of calcite. Furthermore, bone tissue penetrated interior to the macropore at 8 weeks. These results demonstrated the good potential value of porous calcite as artificial bone substitutes. PMID:25649514

  15. Direct nanoscale observations of the coupled dissolution of calcite and dolomite and the precipitation of gypsum

    PubMed Central

    Cama, Jordi; Soler, Josep Maria; Putnis, Christine V

    2014-01-01

    Summary In-situ atomic force microscopy (AFM) experiments were performed to study the overall process of dissolution of common carbonate minerals (calcite and dolomite) and precipitation of gypsum in Na2SO4 and CaSO4 solutions with pH values ranging from 2 to 6 at room temperature (23 ± 1 °C). The dissolution of the carbonate minerals took place at the (104) cleavage surfaces in sulfate-rich solutions undersaturated with respect to gypsum, by the formation of characteristic rhombohedral-shaped etch pits. Rounding of the etch pit corners was observed as solutions approached close-to-equilibrium conditions with respect to calcite. The calculated dissolution rates of calcite at pH 4.8 and 5.6 agreed with the values reported in the literature. When using solutions previously equilibrated with respect to gypsum, gypsum precipitation coupled with calcite dissolution showed short gypsum nucleation induction times. The gypsum precipitate quickly coated the calcite surface, forming arrow-like forms parallel to the crystallographic orientations of the calcite etch pits. Gypsum precipitation coupled with dolomite dissolution was slower than that of calcite, indicating the dissolution rate to be the rate-controlling step. The resulting gypsum coating partially covered the surface during the experimental duration of a few hours. PMID:25161860

  16. Low-magnesium uranium-calcite with high degree of crystallinity and gigantic luminescence emission.

    PubMed

    Valle-Fuentes, Francisco-Jose; Garcia-Guinea, Javier; Cremades, Ana; Correcher, Virgilio; Sanchez-Moral, Sergio; Gonzalez-Martin, Rafael; Sanchez-Muñoz, Luis; Lopez-Arce, Paula

    2007-01-01

    Cabrera (Madrid) low-Mg calcites exhibit: (i) an unusual twofold elevation in X-ray diffraction pattern intensity; (ii) a 60-fold elevation of luminescence emission, compared to six common natural calcites selected for comparison purposes; (iii) a natural relatively high radiation level of circa 200 nSvh(-1) not detected in 1300 other calcites from the Natural History Museum of Madrid. Calcites were analysed by the X-ray diffraction powder method (XRD), cathodo-luminescence spectroscopy in scanning electron microscopy (CL-SEM), thermoluminescence (TL), differential thermal analysis (DTA), X-ray fluorescence spectrometry (XRF) and particle size distribution (PSD). The Cabrera calcite study shows: (i) helicoidally distributed steps along the (0001) orientation; (ii) protuberance defects onto the (0001) surface, observed by SEM; (iii) XRF chemical contents of 0.03% MgO, 0.013% of Y(2)O(3), and 0.022% of U(3)O(8), with accessory amounts of rare earth elements (REE); (iv) DTA dissociation temperature of 879 degrees C; (v) TL maxima peaks at 233 and 297 degrees C whose areas are 60 times compared to other calcites; (vi) spectra CL-SEM bands at 2.0 and 3.4 eV in the classic structure of Mn(2+) activators; (vii) a twofold XRD pattern explained given that sample is a low-Mg calcite. The huge TL and CL emissions of the Cabrera calcite sample must be linked with the uranyl group presence. This intense XRD pattern in low-Mg calcites could bring into being analytical errors. PMID:17011199

  17. Isotopic evidence for the source of Ca and S in soil gypsum, anhydrite and calcite in the Atacama Desert, Chile

    NASA Astrophysics Data System (ADS)

    Rech, Jason A.; Quade, Jay; Hart, William S.

    The origin of pedogenic salts in the Atacama Desert has long been debated. Possible salt sources include in situ weathering at the soil site, local sources such as aerosols from the adjacent Pacific Ocean or salt-encrusted playas (salars), and extra-local atmospheric dust. To identify the origin of Ca and S in Atacama soil salts, we determined δ 34S and 87Sr/ 86Sr values of soil gypsum/anhydrite and 87Sr/ 86Sr values of soil calcite along three east-west trending transects. Our results demonstrate the strong influence of marine aerosols on soil gypsum/anhydrite development in areas where marine fog penetrates inland. Results from an east-west transect located along a breach in the Coastal Cordillera show that most soils within 90 km of the coast, and below 1300 m in elevation, are influenced by marine aerosols and that soils within 50 km, and below 800 m in elevation, receive >50% of Ca and S from marine aerosols (δ 34S values > 14‰ and 87Sr/ 86Sr values >0.7083). In areas where the Coastal Cordillera is >1200 m in elevation, however, coastal fog cannot penetrate inland and the contribution of marine aerosols to soils is greatly reduced. Most pedogenic salts from inland soils have δ 34S values between +5.0 to +8.0‰ and 87Sr/ 86Sr ratios between 0.7070 and 0.7076. These values are similar to average δ 34S and 87Sr/ 86Sr values of salts from local streams, lakes, and salars (+5.4 ±2‰ δ 34S and 0.70749 ± 0.00045 87Sr/ 86Sr) in the Andes and Atacama, suggesting extensive eolian reworking of salar salts onto the surrounding landscape. Ultimately, salar salts are precipitated from evaporated ground water, which has acquired its dissolved solutes from water-rock interactions (both high and low-temperature) along flowpaths from recharge areas in the Andes. Therefore, the main source for Ca and S in gypsum/anhydrite in non-coastal soils is indirect and involves bedrock alteration, not surficially on the hyperarid landscape, but in the subsurface by ground water

  18. Abiotic Formation of Valine Peptides Under Conditions of High Temperature and High Pressure

    NASA Astrophysics Data System (ADS)

    Furukawa, Yoshihiro; Otake, Tsubasa; Ishiguro, Takato; Nakazawa, Hiromoto; Kakegawa, Takeshi

    2012-12-01

    We investigated the oligomerization of solid valine and the stabilities of valine and valine peptides under conditions of high temperature (150-200 °C) and high pressure (50-150 MPa). Experiments were performed under non-aqueous condition in order to promote dehydration reaction. After prolonged exposure of monomeric valine to elevated temperatures and pressures, the products were analyzed by liquid chromatography mass spectrometry comparing their retention times and masses. We identified linear peptides that ranged in size from dimer to hexamer, as well as a cyclic dimer. Previous studies that attempted abiotic oligomerization of valine in the absence of a catalyst have never reported valine peptides larger than a dimer. Increased reaction temperature increased the dissociative decomposition of valine and valine peptides to products such as glycine, β-alanine, ammonia, and amines by processes such as deamination, decarboxylation, and cracking. The amount of residual valine and peptide yields was greater at higher pressures at a given temperature, pressure, and reaction time. This suggests that dissociative decomposition of valine and valine peptides is reduced by pressure. Our findings are relevant to the investigation of diagenetic processes in prebiotic marine sediments where similar pressures occur under water-poor conditions. These findings also suggest that amino acids, such as valine, could have been polymerized to peptides in deep prebiotic marine sediments within a few hundred million years.

  19. Recurrent Pure Calcite Urolithiasis Confirmed by Endoscopic Removal and Infrared Spectroscopy in a Malnourished Anorectic Female.

    PubMed

    Christiansen, Frederikke Eichner; Andreassen, Kim Hovgaard; Sloth Osther, Palle Jörn

    2016-01-01

    Often when calcite is found as a component of urinary calculi, they are considered false calculi or artifacts. We present a case of true calcite urolithiasis. The stone material was removed percutaneously from a severely malnourished anorectic woman and analyzed by infrared spectroscopy (IRS). In addition, calcite urolithiasis was confirmed in several recurrent stone events by IRS. Laxative abuse with magnesium oxide was believed to be the underlying cause of stone formation, and ammonium chloride given as one weekly dose turned out to be effective for stone prevention. PMID:27579419

  20. Activators of photoluminescence in calcite: evidence from high-resolution, laser-excited luminescence spectroscopy

    USGS Publications Warehouse

    Pedone, V.A.; Cercone, K.R.; Burruss, R.C.

    1990-01-01

    Laser-excited luminescence spectroscopy of a red-algal, biogenic calcite and a synthetic Mn-calcite can make the distinction between organic and trace-element activators of photoluminescence. Organic-activated photoluminescence in biogenic calcite is characterized by significant peak shifts and increasing intensity with shorter-wavelength excitation and by significant decreases in intensity after heating to ??? 400??C. In contrast, Mn-activated photoluminescence shows no peak shift, greatest intensity under green excitation and limited changes after heating. Examination of samples with a high-sensitivity spectrometer using several wavelengths of exciting light is necessary for identification of photoluminescence activators. ?? 1990.

  1. Distribution of Minor Elements in Calcite From the Unsaturated Zone at Yucca Mountain, Nevada

    NASA Astrophysics Data System (ADS)

    Marshall, B. D.; Whelan, J. F.

    2001-12-01

    Calcite is sporadically distributed in fractures and cavities in the volcanic rocks that form the 500- to 700-m-thick unsaturated zone at Yucca Mountain. Previous work has shown that the calcite precipitated from water moving downward through the unsaturated zone since the volcanic rocks were emplaced approximately 13 Ma. Calcite thus serves as a proxy for the chemistry and amounts of past percolation, two parameters that are important in predictions of the future behavior of the potential radioactive waste repository at Yucca Mountain. Latest calcite, which began forming between approximately 5 and 2 Ma, typically displays fine-scale growth zoning defined by distributions of Mn (inferred from cathodoluminescence), Mg, and Sr. Electron microprobe (EPMA) mapping of outermost calcite reveals Mg growth zoning1 and higher overall concentrations of Mg in late calcite than in older calcite. Micro X-ray fluorescence (micro-XRF) maps were obtained by slow rastering of the samples over a 100-watt X-ray source collimated through a final aperture of 100 μ m. Although the spatial resolution of the micro-XRF mapping is much less than that of EPMA, this technique reveals distributions of some elements to which EPMA is less sensitive. Micro-XRF maps show that Sr is spatially correlated with Mg; Sr concentrations range to 500 μ g/g at the resolution of the 100-μ m collimator. Because both Mg and Sr have similar calcite-water distribution coefficients much less than one, the Mg/Sr in calcite reflects the Mg/Sr of the water that precipitated the calcite. The distribution coefficient for Mn is greater than one and variations in Mn are not correlated with Mg and Sr. Covariation of Mg and Sr in the percolating water may be explained by reactions that affect the rate of uptake of chemical constituents from the overlying rock and soil, and/or evaporation. Late calcite has lower δ 13C values, probably due to a regional change from wetter to drier climate conditions. The higher Mg and

  2. Recurrent Pure Calcite Urolithiasis Confirmed by Endoscopic Removal and Infrared Spectroscopy in a Malnourished Anorectic Female

    PubMed Central

    Andreassen, Kim Hovgaard; Sloth Osther, Palle Jörn

    2016-01-01

    Abstract Often when calcite is found as a component of urinary calculi, they are considered false calculi or artifacts. We present a case of true calcite urolithiasis. The stone material was removed percutaneously from a severely malnourished anorectic woman and analyzed by infrared spectroscopy (IRS). In addition, calcite urolithiasis was confirmed in several recurrent stone events by IRS. Laxative abuse with magnesium oxide was believed to be the underlying cause of stone formation, and ammonium chloride given as one weekly dose turned out to be effective for stone prevention. PMID:27579419

  3. The influence of impurities on the growth rate of calcite

    NASA Astrophysics Data System (ADS)

    Meyer, H. J.

    1984-05-01

    The effects of 34 different additives on the growth rate of calcite were investigated. An initial growth rate of about one crystal monolayer (3 × 10 -8 cm) per minute was adjusted at a constant supersaturation which was maintained by a control circuit. Then the impurity was added step by step and the reduction of the growth rate was measured. The impurity concentration necessary to reduce the initial growth rate by a certain percentage increased in the order Fe 2+, ATP, P 3O 5-10, P 2O 4-7, (PO 3) 6-6, Zn 2+, ADP, Ce 3+, Pb 2+, carbamyl phosphate, Fe 3+, PO 3-4, Co 2+, Mn 2+, Be 2+, β-glycerophosphate, Ni 2+, Cd 2+, "Tris", phenylphosphate, chondroitine sulphate, Ba 2+, citrate, AMP, Sr 2+, tricarballylate, taurine, SO 2-4, Mg 2+ by 4 orders of magnitude. The most effective additives halved the initial growth rate in concentrations of 2 × 10 -8 mol/1. For Fe 2+ the halving concentration was nearly proportional to the initial rate. The mechanism of inhibition by adsorption of the impurities at growth sites (kinks) is discussed.

  4. Microbiologically Induced Calcite Precipitation Mediated by Sporosarcina pasteurii.

    PubMed

    Bhaduri, Swayamdipta; Debnath, Nandini; Mitra, Sushanta; Liu, Yang; Kumar, Aloke

    2016-01-01

    The particular bacterium under investigation here (S. pasteurii) is unique in its ability, under the right conditions, to induce the hydrolysis of urea (ureolysis) in naturally occurring environments through secretion of an enzyme urease. This process of ureolysis, through a chain of chemical reactions, leads to the formation of calcium carbonate precipitates. This is known as Microbiologically Induced Calcite Precipitation (MICP). The proper culture protocols for MICP are detailed here. Finally, visualization experiments under different modes of microscopy were performed to understand various aspects of the precipitation process. Techniques like optical microscopy, Scanning Electron Microscopy (SEM) and X-Ray Photo-electron Spectroscopy (XPS) were employed to chemically characterize the end-product. Further, the ability of these precipitates to clog pores inside a natural porous medium was demonstrated through a qualitative experiment where sponge bars were used to mimic a pore-network with a range of length scales. A sponge bar dipped in the culture medium containing the bacterial cells hardens due to the clogging of its pores resulting from the continuous process of chemical precipitation. This hardened sponge bar exhibits superior strength when compared to a control sponge bar which becomes compressed and squeezed under the action of an applied external load, while the hardened bar is able to support the same weight with little deformation. PMID:27167458

  5. Effect of fluid salinity on subcritical crack propagation in calcite

    NASA Astrophysics Data System (ADS)

    Rostom, Fatma; Røyne, Anja; Dysthe, Dag Kristian; Renard, François

    2013-01-01

    The slow propagation of cracks, also called subcritical crack growth, is a mechanism of fracturing responsible for a ductile deformation of rocks under crustal conditions. In the present study, the double-torsion technique was used to measure the effect of fluid chemistry on the slow propagation of cracks in calcite single crystals at room temperature. Time-lapse images and measurements of force and load-point displacement allowed accurate characterization of crack velocities in a range of 10- 8 to 10- 4 m/s. Velocity curves as a function of energy-release rates were obtained for different fluid compositions, varying NH4Cl and NaCl concentrations. Our results show the presence of a threshold in fluid composition, separating two regimes: weakening conditions where the crack propagation is favored, and strengthening conditions where crack propagation slows down. We suggest that electrostatic surface forces that modify the repulsion forces between the two surfaces of the crack may be responsible for this behavior.

  6. Stress remagnetization in pyrrhotite-calcite synthetic aggregates

    NASA Astrophysics Data System (ADS)

    Robion, Philippe; Borradaile, Graham J.

    2001-01-01

    Stress-induced remagnetization has been applied to multidomain pyrrhotite-calcite synthetic aggregates in a triaxial rig. Experimental deformation used 150MPa confining pressure, a constant strain rate of 10-5 s-1 and applied differential stresses of up to 70MPa. New components of magnetization, parallel to the direction of the pressure vessel field, were added to the pre-deformational magnetization. The intensity of remagnetization (M'-M0) increases with the intensity of the applied differential stress and affects the coercivity fraction below 15mT. Bulk shortening is less than 8 per cent, thus grain rotation cannot explain selective remagnetization of the low-coercivity fraction. Remagnetization is thus attributed to deformational viscous remanent magnetization (DVRM). It is observed that high-coercivity (>15mT) grains do not remagnetize. There is, however, slight progressive rotation of pre-deformational magnetization with increasing strain up to 8 per cent of bulk shortening. The lack of piezoremanent magnetization in the high-coercivity range may be due to defects introduced in pyrrhotite during sample preparation. Experiments using synthetic pyrrhotite, expected to show low dislocation densities, would be necessary to test this effect.

  7. Thin-film-induced morphological instabilities over calcite surfaces

    PubMed Central

    Vesipa, R.; Camporeale, C.; Ridolfi, L.

    2015-01-01

    Precipitation of calcium carbonate from water films generates fascinating calcite morphologies that have attracted scientific interest over past centuries. Nowadays, speleothems are no longer known only for their beauty but they are also recognized to be precious records of past climatic conditions, and research aims to unveil and understand the mechanisms responsible for their morphological evolution. In this paper, we focus on crenulations, a widely observed ripple-like instability of the the calcite–water interface that develops orthogonally to the film flow. We expand a previous work providing new insights about the chemical and physical mechanisms that drive the formation of crenulations. In particular, we demonstrate the marginal role played by carbon dioxide transport in generating crenulation patterns, which are indeed induced by the hydrodynamic response of the free surface of the water film. Furthermore, we investigate the role of different environmental parameters, such as temperature, concentration of dissolved ions and wall slope. We also assess the convective/absolute nature of the crenulation instability. Finally, the possibility of using crenulation wavelength as a proxy of past flows is briefly discussed from a theoretical point of view. PMID:27547086

  8. Marine Biomedicine

    ERIC Educational Resources Information Center

    Bang, Frederik B.

    1977-01-01

    Describes early scientific research involving marine invertebrate pathologic processes that may have led to new insights into human disease. Discussed are inquiries of Metchnikoff, Loeb, and Cantacuzene (immunolgic responses in sea stars, horseshoe crabs, and marine worms, respectively). Describes current research stemming from these early…

  9. Marine Biology

    ERIC Educational Resources Information Center

    Dewees, Christopher M.; Hooper, Jon K.

    1976-01-01

    A variety of informational material for a course in marine biology or oceanology at the secondary level is presented. Among the topics discussed are: food webs and pyramids, planktonic blooms, marine life, plankton nets, food chains, phytoplankton, zooplankton, larval plankton and filter feeders. (BT)

  10. Marine Diagenesis of Shallow Marine Lime-Mud Sediments: Insights from dgrO18 and dgrC13 Data.

    PubMed

    Choquette, P W

    1968-09-13

    Shallow marine lime-mud sediments of the Ste. Genevieve Formation (Mississippian), in part of the Illinois Basin, underwent at least three diagenetic changes: (i) local dolomitization in seawater or a brine, producing dolostone having average deltaC(13) of +2.5 per mille and deltaO(18) of +1.9 per mille (versus PDB-1); (ii) more usually cementation of unreplaced CaCO(3), in intrasediment seawater, yielding isotopically marine lime mudstone mainly composed of calcite, 4-micron or finer, with deltaO(18) of from -1 to +1 per mille; (iii) later partial alteration of CaCO(3), in permeable dolomitic rocks, by isotopically "lighter" waters, to calcite with an estimated deltaO(18) of -10 per mille or less. Isotope data appraised by petrographic analysis thus suggest "submarine" cementation of these carbonates in shallow marine conditions. PMID:17812283

  11. Geochemistry of metastable carbonate minerals from the Brush Creek marine interval (Missourian), Indiana County, Pennsylvania

    SciTech Connect

    Cercone, K.R.; Kime, A.; Mutchler, S.; Rittle, K. )

    1991-08-01

    Many marine fossils from the Missourian Brush Creek interval of western Pennsylvania display partial preservation of metastable aragonite and high-magnesium calcite shell material. Bivalve mollusks have been shown by x-ray diffraction to contain as much as 96% aragonite, with lesser amounts of both high-magnesium and low-magnesium calcite. Stable carbon and oxygen isotopic ratios from these bivalves suggest they precipitated in equilibrium with Pennsylvanian ocean water. The bellerophontid Pharkidonotus, which exhibits partial recrystallization textures under scanning electron microscopy, consists of 45% aragonite and 55% low-magnesium calcite, and has slightly more depleted isotopic values than bivalves. Crinoids also appear to have been partially recrystallized, resulting in a mixture of primary high-magnesium calcite and secondary low-magnesium calcite and microdolomite, with much of the original shell structure still preserved. The degree of preservation of metastable carbonate minerals varies both stratigraphically and spatially within the Brush Creek interval. Maximum preservation occurs in organic-rich shales deposited in low-lying areas of the Brush Creek sea floor. The preservation of aragonite and high-magnesium calcite in such units may have resulted from a lack of circulating porewater during early diagenesis.

  12. ABIOTIC DEGRADATION OF TRICHLOROETHYLENE UNDER THERMAL REMEDIATION CONDITIONS

    EPA Science Inventory

    The degradation of TCE (C2HCl3) to carbon dioxide (CO2) and chloride (Cl-) has been reported to occur during thermal remediation of subsurface environments. The overall goal of this study was to evaluate abiotic degradation of TCE at el...

  13. ABIOTIC REDUCTION OF NITRO AROMATIC PESTICIDES IN ANAEROBIC LABORATORY SYSTEMS

    EPA Science Inventory

    Rapid abiotic reduction of nitro aromatic pesticides occurs in homogeneous solutions of quinone redox couples, which were selected to model the redox-labile functianal groups in natural organic matter. he kinetics of methyl parathion disappearance are first order in methyl parath...

  14. Recent advances in polyamine metabolism and abiotic stress tolerance.

    PubMed

    Rangan, Parimalan; Subramani, Rajkumar; Kumar, Rajesh; Singh, Amit Kumar; Singh, Rakesh

    2014-01-01

    Global warming is an alarming problem in agriculture and its effect on yield loss has been estimated to be five per cent for every degree centigrade rise in temperature. Plants exhibit multiple mechanisms like optimizing signaling pathway, involvement of secondary messengers, production of biomolecules specifically in response to stress, modulation of various metabolic networks in accordance with stress, and so forth, in order to overcome abiotic stress factors. Many structural genes and networks of pathway were identified and reported in plant systems for abiotic stress tolerance. One such crucial metabolic pathway that is involved in normal physiological function and also gets modulated during stress to impart tolerance is polyamine metabolic pathway. Besides the role of structural genes, it is also important to know the mechanism by which these structural genes are regulated during stress. Present review highlights polyamine biosynthesis, catabolism, and its role in abiotic stress tolerance with special reference to plant systems. Additionally, a system based approach is discussed as a potential strategy to dissect the existing variation in crop species in unraveling the interacting regulatory components/genetic determinants related to PAs mediated abiotic stress tolerance. PMID:25136565

  15. Genetic Diversity In Abiotic Stress Tolerances Among Wheat Species

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Landraces and close related species of hexaploid wheat (Triticum aestivum L.) offer a vast reservoir of genetic resources for wheat improvement to production on abiotic stressed soils. In order to utilize the wheat landrace and close relative gene pools, the evaluation of wheat landrace and close r...

  16. Are karrikins involved in plant abiotic stress responses?

    PubMed

    Li, Weiqiang; Tran, Lam-Son Phan

    2015-09-01

    Recent reports have shown that strigolactones play a positive role in plant responses to drought and salt stress through MAX2 (More Axillary Growth 2). Increasing evidence suggests that MAX2 is also involved in karrikin signaling, raising the question whether karrikins play any role in plant adaptation to abiotic stresses. PMID:26255855

  17. ABIOTIC TRANSFORMATION PATHWAYS OF ORGANIC CHEMICALS IN AQUATIC ECOSYSTEMS

    EPA Science Inventory

    Information is presented for assessing the potential of an organic chemical to undergo abiotic transformation in aquatic ecosystems. hen predicting the environmental fate of an organic chemical, two primary questions must be addressed. irst, what are the reaction kinetics for the...

  18. A membraneless single compartment abiotic glucose fuel cell

    NASA Astrophysics Data System (ADS)

    Slaughter, Gymama; Sunday, Joshua

    2014-09-01

    A simple energy harvesting strategy has been developed to selectively catalyze glucose in the presence of oxygen in a glucose/O2 fuel cell. The anode consists of an abiotic catalyst Al/Au/ZnO, in which ZnO seed layer was deposited on the surface of Al/Au substrate using hydrothermal method. The cathode is constructed from a single rod of platinum with an outer diameter of 500 μm. The abiotic glucose fuel cell was studied in phosphate buffer solution (pH 7.4) containing 5 mM glucose at a temperature of 22 °C. The cell is characterized according to its open-circuit voltage, polarization profile, and power density plot. Under these conditions, the abiotic glucose fuel cell possesses an open-circuit voltage of 840 mV and delivered a maximum power density of 16.2 μW cm-2 at a cell voltage of 495 mV. These characteristics are comparable to biofuel cell utilizing a much more complex system design. Such low-cost lightweight abiotic catalyzed glucose fuel cells have a great promise to be optimized, miniaturized to power bio-implantable devices.

  19. Weighing Abiotic and Biotic Influences on Weed Seed Predation Rates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Weed seed predation is an important ecosystem service supporting weed management in low-external-input agroecosystems. Current knowledge of weed seed predation focuses on biotic mechanisms, with less understood about the relative impact of abiotic variables. In order to quantify relative contributio...

  20. Weighing Abiotic and Biotic Influences on Weed Seed Predation Rates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Weed seed predation is an important ecosystem service supporting weed management in low-external-input agroecosystems. Current knowledge of weed seed predation in arable systems focuses on biotic mechanisms, with less understood about the relative impact of abiotic variables on this process. In orde...

  1. Genetic mapping of abiotic stress responses in sorghum

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Due to rich genetic diversity for tolerance to various abiotic stress conditions, sorghum is an ideal system for genetic mapping and elucidation of genome regions that confer such response among cereal crops. Coupled with the development of DNA marker technologies and most recently the sequencing o...

  2. Plastid transformation for abiotic stress tolerance in plants.

    PubMed

    Bansal, K C; Singh, A K; Wani, S H

    2012-01-01

    Abiotic stresses such as drought, salinity, and extreme temperatures are major limiting factors in plant growth and development and pose serious threat to global agricultural production. Here we describe a procedure, using a tobacco plastid transformation vector, to generate transplastomic plants with an enhanced ability to tolerate abiotic stresses such as salinity, drought, or cold stress. The procedure involves biolistic delivery of a plastid transformation vector into explants, antibiotic selection procedures, and -identification of transplastomic lines. The plastid transformation vector contains an aadA gene that encodes resistance to spectinomycin as a selectable marker along with the gene of interest for developing transplastomic plants that are tolerant to abiotic stresses. Shoot buds appear over the surface of bombarded explants following spectinomycin selection. Transplastomic shoots are multiplied following several rounds of -spectinomycin selection. Homoplasmic transplastomic lines are confirmed by spectinomycin and streptomycin double selection over a period of 4-5 weeks. The available reports suggest that transplastomic technology is a useful tool for expressing genes in plastids or chloroplasts for enhancing abiotic stress tolerance in plants. PMID:22895771

  3. Recent Advances in Polyamine Metabolism and Abiotic Stress Tolerance

    PubMed Central

    Rangan, Parimalan; Subramani, Rajkumar; Singh, Amit Kumar

    2014-01-01

    Global warming is an alarming problem in agriculture and its effect on yield loss has been estimated to be five per cent for every degree centigrade rise in temperature. Plants exhibit multiple mechanisms like optimizing signaling pathway, involvement of secondary messengers, production of biomolecules specifically in response to stress, modulation of various metabolic networks in accordance with stress, and so forth, in order to overcome abiotic stress factors. Many structural genes and networks of pathway were identified and reported in plant systems for abiotic stress tolerance. One such crucial metabolic pathway that is involved in normal physiological function and also gets modulated during stress to impart tolerance is polyamine metabolic pathway. Besides the role of structural genes, it is also important to know the mechanism by which these structural genes are regulated during stress. Present review highlights polyamine biosynthesis, catabolism, and its role in abiotic stress tolerance with special reference to plant systems. Additionally, a system based approach is discussed as a potential strategy to dissect the existing variation in crop species in unraveling the interacting regulatory components/genetic determinants related to PAs mediated abiotic stress tolerance. PMID:25136565

  4. Kinetic Effects on B/Ca in Synthetic Calcite: Implications for B(OH)4- and B(OH)3 Incorporation.

    NASA Astrophysics Data System (ADS)

    Uchikawa, J.; Penman, D. E.; Zachos, J. C.; Zeebe, R. E.

    2014-12-01

    In this experimental study, we investigated the influence of solution chemistry on the boron abundance in synthetic calcite using a pH-stat system. We systematically varied solution pH as well as the concentration of total dissolved boron (BT), inorganic carbon (DIC) and calcium ion. We found robust positive correlations between boron abundance in calcite (measured as the boron to calcium ratio, B/Ca) and solution pH, [BT], [DIC] as well as [Ca2+], when a given parameter was solely manipulated while keeping the others constant. Except for [BT], raising these parameters also caused simultaneous increase in calcite saturation and precipitation rate. We found that much of the B/Ca variability as a results of the chemical manipulations tested here can be essentially explained by just precipitation rate and the [BT]/[DIC] ratio in the solution, which was particularly the case for relatively rapidly precipitated calcite samples. On the contrary, for relatively slowly precipitated samples, the [B(OH)4-]/[DIC] and [BT]/[DIC] ratios are equally effective in explaining the B/Ca variability (along with precipitation rate). This observation suggests the possibility of a hitherto unrecognized and apparently kinetically-controlled mechanism that promotes B(OH)3 incorporation for rapidly forming calcite. In recent years both the abundance and isotopic composition of boron in marine biogenic CaCO3 (B/Ca and δ11B, respectively) has been increasingly utilized to constrain past ocean carbonate chemistry. But these boron-based proxies crucially rely on the first order assumption that B(OH)4- is predominantly incorporated. Thus, the possibility of kinetically-controlled B(OH)3 incorporation presented here raises a concern for the reliability of the B/Ca and δ11B proxy. If it is similarly applicable to foraminifers, shell B/Ca and δ11B may be prone to significant uncertainties due to long-term changes in seawater chemistry. Our results further suggest that future calibrations of

  5. TRANSFORMATIONS OF HALOGENATED ALIPHATIC COMPOUNDS: OXIDATION, REDUCTION, SUBSTITUTION, AND DEHYDROHALOGENATION REACTIONS OCCUR ABIOTICALLY OR IN MICROBIAL AND MAMMALIAN SYSTEMS

    EPA Science Inventory

    The current understanding of abiotic and biotic chemistry of halogenated aliphatic compounds is systematized and summarized. Knowledge of abiotic transformations can provide a conceptual framework for understanding biologically mediated transformations. Most abiotic transformatio...

  6. Influence of abiotic stress, flower morphology, and pollen dehydration sensitivity on cotton out-crossing potential

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Genetic diversity in reproductive abiotic stress tolerance has been reported for cotton [Gossypium hirsutum (L.)] based upon the percentage of anther dehiscence of mature pollen in adverse environments. This study investigated the abiotic stress tolerance of mature pollen and identified ...

  7. Integrating omic approaches for abiotic stress tolerance in soybean

    PubMed Central

    Deshmukh, Rupesh; Sonah, Humira; Patil, Gunvant; Chen, Wei; Prince, Silvas; Mutava, Raymond; Vuong, Tri; Valliyodan, Babu; Nguyen, Henry T.

    2014-01-01

    Soybean production is greatly influenced by abiotic stresses imposed by environmental factors such as drought, water submergence, salt, and heavy metals. A thorough understanding of plant response to abiotic stress at the molecular level is a prerequisite for its effective management. The molecular mechanism of stress tolerance is complex and requires information at the omic level to understand it effectively. In this regard, enormous progress has been made in the omics field in the areas of genomics, transcriptomics, and proteomics. The emerging field of ionomics is also being employed for investigating abiotic stress tolerance in soybean. Omic approaches generate a huge amount of data, and adequate advancements in computational tools have been achieved for effective analysis. However, the integration of omic-scale information to address complex genetics and physiological questions is still a challenge. In this review, we have described advances in omic tools in the view of conventional and modern approaches being used to dissect abiotic stress tolerance in soybean. Emphasis was given to approaches such as quantitative trait loci (QTL) mapping, genome-wide association studies (GWAS), and genomic selection (GS). Comparative genomics and candidate gene approaches are also discussed considering identification of potential genomic loci, genes, and biochemical pathways involved in stress tolerance mechanism in soybean. This review also provides a comprehensive catalog of available online omic resources for soybean and its effective utilization. We have also addressed the significance of phenomics in the integrated approaches and recognized high-throughput multi-dimensional phenotyping as a major limiting factor for the improvement of abiotic stress tolerance in soybean. PMID:24917870

  8. Abiotic ozone and oxygen in atmospheres similar to prebiotic Earth

    SciTech Connect

    Domagal-Goldman, Shawn D.; Segura, Antígona; Claire, Mark W.; Robinson, Tyler D.; Meadows, Victoria S.

    2014-09-10

    The search for life on planets outside our solar system will use spectroscopic identification of atmospheric biosignatures. The most robust remotely detectable potential biosignature is considered to be the detection of oxygen (O{sub 2}) or ozone (O{sub 3}) simultaneous to methane (CH{sub 4}) at levels indicating fluxes from the planetary surface in excess of those that could be produced abiotically. Here we use an altitude-dependent photochemical model with the enhanced lower boundary conditions necessary to carefully explore abiotic O{sub 2} and O{sub 3} production on lifeless planets with a wide variety of volcanic gas fluxes and stellar energy distributions. On some of these worlds, we predict limited O{sub 2} and O{sub 3} buildup, caused by fast chemical production of these gases. This results in detectable abiotic O{sub 3} and CH{sub 4} features in the UV-visible, but no detectable abiotic O{sub 2} features. Thus, simultaneous detection of O{sub 3} and CH{sub 4} by a UV-visible mission is not a strong biosignature without proper contextual information. Discrimination between biological and abiotic sources of O{sub 2} and O{sub 3} is possible through analysis of the stellar and atmospheric context—particularly redox state and O atom inventory—of the planet in question. Specifically, understanding the spectral characteristics of the star and obtaining a broad wavelength range for planetary spectra should allow more robust identification of false positives for life. This highlights the importance of wide spectral coverage for future exoplanet characterization missions. Specifically, discrimination between true and false positives may require spectral observations that extend into infrared wavelengths and provide contextual information on the planet's atmospheric chemistry.

  9. High School Forum: "Invitations to Enquiry": The Calcite/Acid Reaction.

    ERIC Educational Resources Information Center

    Herron, J. Dudley, Ed.; Driscoll, D. R.

    1979-01-01

    Describes a high school chemistry experiment which involves the reaction between calcite and hydrochloric and sulfuric acids. This reaction can be carried out as a projected demonstration and on an individual basis. (HM)

  10. Simulation of calcite dissolution and porosity changes in saltwater mixing zones in coastal aquifers

    USGS Publications Warehouse

    Sanford, W.E.; Konikow, L.F.

    1989-01-01

    Thermodynamic models of aqueous solutions have indicated that the mixing of seawater and calcite-saturated fresh groundwater can produce a water that is undersaturated with respect to calcite. Mixing of such waters in coastal carbonate aquifers could lead to significant amounts of limestone dissolution. The potential for such dissolution in coastal saltwater mixing zones is analyzed by coupling the results from a reaction simulation model (PHREEQE) with a variable density groundwater flow and solute transport model. Idealized cross sections of coastal carbonate aquifers are simulated to estimate the potential for calcite dissolution under a variety of hydrologic and geochemical conditions. Results show that limestone dissolution in mixing zones is strongly dependent on groundwater flux and nearly independent of the dissolution kinetics of calcite. -from Authors

  11. Calcium sulfoaluminate (Ye'elimite) hydration in the presence of gypsum, calcite, and vaterite

    SciTech Connect

    Hargis, Craig W.; Telesca, Antonio; Monteiro, Paulo J.M.

    2014-11-15

    Six calcium sulfoaluminate-based cementitious systems composed of calcium sulfoaluminate, calcite, vaterite, and gypsum were cured as pastes and mortars for 1, 7, 28 and 84 days. Pastes were analyzed with X-ray diffraction, thermogravimetric and differential thermal analyses. Mortars were tested for compressive strength, dimensional stability and setting time. Furthermore, pastes with a water/cementitious material mass ratio of 0.80 were tested for heat evolution during the first 48 h by means of isothermal conduction calorimetry. It has been found that: (1) both calcite and vaterite reacted with monosulfoaluminate to give monocarboaluminate and ettringite, with vaterite being more reactive; (2) gypsum lowered the reactivity of both carbonates; (3) expansion was reduced by calcite and vaterite, irrespective of the presence of gypsum; and (4) both carbonates increased compressive strength in the absence of gypsum and decreased compressive strength less in the presence of gypsum, with vaterite's action more effective than that of calcite.

  12. Enhancing mechanical properties of calcite by Mg substitutions: An ab initio study

    NASA Astrophysics Data System (ADS)

    Elstnerova, Pavlina; Friak, Martin; Hickel, Tilmann; Fabritius, Helge Otto; Lymperakis, Liverios; Petrov, Michal; Raabe, Dierk; Neugebauer, Joerg; Nikolov, Svetoslav; Zigler, Andreas; Hild, Sabine

    2011-03-01

    Arthropoda representing a majority of all known animal species are protected by an exoskeleton formed by their cuticle. The cuticle represents a hierarchically structured multifunctional bio-composite based on chitin and proteins. Some groups like Crustacea reinforce the load-bearing parts of their cuticle with calcite. As the calcite sometimes contains Mg it was speculated that Mg may have a stiffening impact on the mechanical properties of the cuticle. We present a theoretical parameter-free quantum-mechanical study of thermodynamic, structural and elastic properties of Mg-substituted calcite. Our results show that substituting Ca by Mg causes an almost linear decrease in the crystal volume with Mg concentration and of substituted crystals. As a consequence the calcite crystals become stiffer giving rise e.g. to substantially increased bulk moduli.

  13. The Influence of Exotic Calcite on the Mechanical Behavior of Quartz Bearing Fault Gouge

    NASA Astrophysics Data System (ADS)

    Carpenter, B. M.; Di Stefano, G.; Collettini, C.

    2014-12-01

    The interseismic recovery of frictional strength is a fundamental part of the seismic cycle. This restrengthening, and related phenomena, plays a key role in determining the stability and mode of tectonic faulting. Recent experimental data has shown that gouge mineralogy has a strong influence on the rate of frictional healing, with calcite-dominated gouges showing the highest rates. Combining these data with widespread observations of calcite as cement or veins in non-carbonate hosted faults, indicates that the presence of calcite within a fault gouge could play an important role in shallow- and mid-crustal earthquakes. We report on laboratory experiments designed to explore the mechanical behavior of quartz/calcite mixtures as a means to better understand the evolution of fault behavior in faults where carbonate materials are present. We sheared mixtures of powdered Carrara marble (>98% CaCO3) and disaggregated Ottawa sand (99.8% SiO2) at constant normal stress of 5 MPa under saturated conditions at room temperature. We performed slide-hold-slide tests, 1-3,000 seconds, and velocity stepping tests, 0.1-1000 μm/s, to measure the amount of frictional healing and velocity dependence of friction respectively. Small subsets of experiments were conducted at different boundary conditions. Preliminary results show that the presence of calcite in quartz-based fault gouge has a hardening effect, both in overall frictional strength, where the strength of our mixtures increases with increasing calcite content, and in single experiments, where mixtures with low percentages of calcite show a consistent strain-hardening trend. We also observe that the rates of frictional healing and creep relaxation increase with increasing calcite content. Finally, our results show that the addition of as little as 2.5% calcite within a fault gouge results in a 30% increase in the rate of frictional healing, with further increases in calcite content resulting in larger increases in the rate

  14. The Influence of Calcite on The Mechanical Behavior of Quartz-Bearing Gouge

    NASA Astrophysics Data System (ADS)

    Carpenter, Brett; Di Stefano, Giuseppe; Collettini, Cristiano

    2015-04-01

    Mechanical heterogeneities along faults can result in diverse and complex fault slip. These heterogeneities can vary spatially and temporally and may result from changes in fault structure or frictional properties. The accumulation of calcite in non-carbonate faults, via cementation or entrainment, is likely to alter the frictional properties of that fault gouge. Furthermore, widespread observations of calcite as cement, veins, or cataclasites in non-carbonate hosted faults indicates that calcite is readily available and could play an important role during fault reactivation at shallow- and mid-crustal earthquakes. We report on laboratory experiments designed to explore the mechanical behavior of quartz/calcite mixtures as a means to better understand the evolution in behavior of quartz-bearing gouge in the presence of exotic calcite. We sheared mixtures of powdered Carrara marble (>98% CaCO3) and disaggregated Ottawa sand (99.8% SiO2) at constant normal stresses of 5 and 50 MPa under saturated conditions at room temperature. We performed slide-hold-slide tests, 1-3,000 seconds, and velocity stepping tests, 0.1-1000 µm/s, to measure the amount of frictional healing and velocity dependence of friction respectively. At low normal stress, the addition of calcite to quartz-based synthetic fault gouge results in increases in the steady-state frictional strength, and rates of frictional healing and creep relaxation of the gouge. In particular, with the addition of as little as 2.5 wt% calcite, the frictional healing rate increases by 30%. Microstructural observations indicate that shear is accommodated by distributed deformation throughout the gouge layer and that calcite undergoes significantly more comminution compared to quartz. Large quartz grains frequently show minor rounding of angular edges with fine-grained calcite often penetrating fractures. The in-situ addition of calcite to fault gouge, by either the circulation of fluids or the involvement of carbonate

  15. The potential for phosphorus pollution remediation by calcite precipitation in UK freshwaters

    NASA Astrophysics Data System (ADS)

    Neal, Colin

    This paper examines the potential for calcium carbonate to reduce phosphate pollution in freshwaters by co-precipitation, a process known as a "self cleansing mechanism". Calcium carbonate saturation levels and phosphate concentrations (SRP - soluble reactive phosphate) across the major eastern UK river basins are examined to test for solubility controls. The study shows that calcite saturation varies for each catchment as a function of flow and biological activity rather than by direct regulation by SRP. Indeed, there is no evidence, for any of the rivers studied, that calcite solubility controls hold. However, for groundwater and groundwater-fed springs in the Chalk of the Thames basin, calcite saturation is observed with associated low SRP levels. A self-cleansing mechanism may well be operative within the Chalk due to two factors. Firstly, there is a high potential for nucleation on the calcite micro-crystals in the aquifer. Secondly, there are within aquifer reactions that remove the calcite nucleating inhibitors (SRP and dissolved organic carbon, DOC) to levels lower than those occurring within the rivers do. These inhibitors enter the catchment at very high concentrations in association with agricultural pollution (fertilizer application and animal slurry) and household contamination (e.g. sewage sources from septic tanks). Under low flow conditions, when the saturation index for calcite is at its highest, so too is the concentration of the nucleation inhibitor SRP. Companion work shows that calcite precipitation can occur at the water-sediment interface of the river and this may involve SRP removal. The data, as a whole, define an apparent bound for calcite solubility control where in the presence of nucleating centres, SRP must be less than 4 mM-P l-1 and DOC must be less than 150 mM-C l-1: a condition that does not seem to pertain within most UK rivers.

  16. Coprecipitation of Uranium (VI) with Calcite: XAFS, Micro-XAS,and Luminescence Characterization

    SciTech Connect

    Reeder, Richard J; Nugent, Melissa; Tait, C DREW; Morris, David E; Heald, Steve M; Beck, Kenneth M; Hess, Wayne P; Lanzirotti, Anthony

    2001-04-06

    X-ray absorption and luminescence spectroscopies have been used to characterize the local structure and coordination of uranium (VI) species coprecipitated with calcite (CaCO3) in room-temperature aqueous solutions. Different solution chemistries and pHs are found to result in defferences in the equatorial coordination of the uranyl species (UO2/2+) in the calcite, with multiple coordination environments of uranyl evident in one sample.

  17. The calcite → aragonite transformation in low-Mg marble: Equilibrium relations, transformations mechanisms, and rates

    USGS Publications Warehouse

    Hacker, Bradley R.; Rubie, David C.; Kirby, Stephen H.; Bohlen, Steven R.

    2005-01-01

    Experimental transformation of a rather pure natural calcite marble to aragonite marble did not proceed via the expected straightforward polymorphic replacement. Instead, the small amount of Mg in the starting material (0.36 wt %) was excluded from the growing aragonite and diffused preferentially into the remaining calcite grains, producing Mg-rich calcite rods that persisted as relicts. Nucleation of aragonite occurred exclusively on grain boundaries, with aragonite [001] oriented subparallel to calcite [0001]. The aragonite crystals preferentially consumed the calcite crystal on which they nucleated, and the reaction fronts developed preferentially along the {010} and {110} planes of aragonite. Each aragonite neoblast that grew was nearly free of Mg (typically <0.1 wt %). The excess Mg was taken up by the calcite grains in between, stabilizing them and causing a few volume percent rodlike relicts of Mg-enriched calcite (up to 10 wt % MgO) to be left behind by the advancing reaction front. The aragonite growth rates are approximately linear and range from ∼3 × 10−11 m s−1 at 600°C to ∼9 × 10−9 m s−1 at 850°C, with an apparent activation enthalpy of 166 ± 91 kJ mol−1. This reaction mechanism and the resultant texture are akin to cellular precipitation reactions in metals. Similar transformation textures have been reported from high-Mg marbles in Japan and China that disproportionated to low-Mg calcite and dolomite.

  18. Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes?

    NASA Astrophysics Data System (ADS)

    Bindschedler, S.; Cailleau, G.; Braissant, O.; Millière, L.; Job, D.; Verrecchia, E. P.

    2014-01-01

    Calcitic nanofibres are ubiquitous habits of secondary calcium carbonate (CaCO3) accumulations observed in calcareous vadose environments. Despite their widespread occurrence, the origin of these nanofeatures remains enigmatic. Three possible mechanisms fuel the debate: (i) purely physicochemical processes, (ii) mineralization of rod-shaped bacteria, and (iii) crystal precipitation on organic templates. Nanofibres can be either mineral (calcitic) or organic in nature. They are very often observed in association with Needle Fibre Calcite (NFC), another typical secondary CaCO3 habit in terrestrial environments. This association has contributed to some confusion between both habits, however they are truly two distinct calcitic features and their recurrent association is likely to be an important fact to help understanding the origin of nanofibres. In this manuscript the different hypotheses that currently exist to explain the origin of calcitic nanofibres are critically reviewed. In addition to this, a new hypothesis for the origin of nanofibres is proposed based on the fact that current knowledge attributes a fungal origin to NFC. As this feature and nanofibres are recurrently observed together, a possible fungal origin for nanofibres which are associated with NFC is investigated. Sequential enzymatic digestion of the fungal cell wall of selected fungal species demonstrates that the fungal cell wall can be a source of organic nanofibres. The obtained organic nanofibres show a striking morphological resemblance when compared to their natural counterparts, emphasizing a fungal origin for part of the organic nanofibres observed in association with NFC. It is further hypothesized that these organic nanofibres may act as templates for calcite nucleation in a biologically-influenced mineralization process, generating calcitic nanofibres. This highlights the possible involvement of Fungi in CaCO3 biomineralization processes, a role still poorly documented at present

  19. Unravelling the enigmatic origin of calcitic nanofibres in soils and caves: purely physicochemical or biogenic processes?

    NASA Astrophysics Data System (ADS)

    Bindschedler, S.; Cailleau, G.; Braissant, O.; Millière, L.; Job, D.; Verrecchia, E. P.

    2014-05-01

    Calcitic nanofibres are ubiquitous habits of secondary calcium carbonate (CaCO3) accumulations observed in calcareous vadose environments. Despite their widespread occurrence, the origin of these nanofeatures remains enigmatic. Three possible mechanisms fuel the debate: (i) purely physicochemical processes, (ii) mineralization of rod-shaped bacteria, and (iii) crystal precipitation on organic templates. Nanofibres can be either mineral (calcitic) or organic in nature. They are very often observed in association with needle fibre calcite (NFC), another typical secondary CaCO3 habit in terrestrial environments. This association has contributed to some confusion between both habits, however they are truly two distinct calcitic features and their recurrent association is likely to be an important fact to help understanding the origin of nanofibres. In this paper the different hypotheses that currently exist to explain the origin of calcitic nanofibres are critically reviewed. In addition to this, a new hypothesis for the origin of nanofibres is proposed based on the fact that current knowledge attributes a fungal origin to NFC. As this feature and nanofibres are recurrently observed together, a possible fungal origin for nanofibres which are associated with NFC is investigated. Sequential enzymatic digestion of the fungal cell wall of selected fungal species demonstrates that the fungal cell wall can be a source of organic nanofibres. The obtained organic nanofibres show a striking morphological resemblance when compared to their natural counterparts, emphasizing a fungal origin for part of the organic nanofibres observed in association with NFC. It is further hypothesized that these organic nanofibres may act as templates for calcite nucleation in a biologically influenced mineralization process, generating calcitic nanofibres. This highlights the possible involvement of fungi in CaCO3 biomineralization processes, a role still poorly documented. Moreover, on a global

  20. The inhibition of calcite dissolution/precipitation: Mg[sup 2+] cations

    SciTech Connect

    Compton, R.G.; Brown, C.A. . Physical Chemistry Lab.)

    1994-07-01

    The dissolution of calcite under conditions of high pH (8.0--9.0) is shown to be strongly inhibited by the presence of magnesium (Mg[sup 2+]) cations. Channel flow cell measurements are used to deduce the appropriate rate law for dissolution and it is demonstrated that the inhibition arises from competitive Langmuirian adsorption of Mg[sup 2+] and Ca[sup 2+] ions on the calcite surface.

  1. Auger spectroscopy analysis of magnesian calcite overgrowths precipitated from seawater and solutions of similar composition

    SciTech Connect

    Mucci, A.; Morse, J.W.; Kaminsky, M.S.

    1985-04-01

    Novel procedures were developed to determine the composition of magnesian calcite overgrowths precipitated on calcite crystals from seawater solutions. A surface sensitive analytical technique, Scanning Auger Microanalysis (SAM), was used to determine the composition of very thin overgrowths (< 0.5 ..mu..m) which could not be analyzed by more conventional techniques. Thin magnesian calcite overgrowths were precipitated by exposing Iceland spar calcite crystals to slightly supersaturated (Omega similarly ordered 1.2) synthetic seawater solutions of various Mg to Ca ratios, at 25/sup 0/C, for various lengths of time. The SAM analysis of these thin overgrowths (30-300 A) reveals that their composition is identical to the composition of much thicker overgrowths (approx. = 4000 A) which were precipitated from highly supersaturated solutions (3 less than or equal to Omega less than or equal to 17) on reagent grade calcite powder. These results strongly suggest that the magnesian calcite overgrowth is in exchange equilibrium with the solution from which it precipitates and that it is representative of the solubility controlling phase. A magnesian calcite overgrowth containing 8 +/- 1 mol percent magnesium carbonate will precipitate from standard composition seawater ((Mg/sup 2 +/)/(Ca/sup 2 +/) = 5.13) under their experimental conditions. The SAM analysis of the surface-most adsorbed layer (approx. = 10 A) on the overgrowths precipitated from seawater solutions of various magnesium-to-calcium concentration ratios reveals that the magnesium-to-calcium concentration ratio in the surface-most region follows a typical Langmuir adsorption isotherm profile. Since it appears that the composition of the surface-most adsorbed layer of a magnesian calcite does not play an active role in determining the composition of the precipitating solid, they speculate that the adsorbed layers on the overgrowth may be viewed as a porous region within which the growth process takes place.

  2. Origin of sulfate in barite and calcite cements in the Jebel Madar salt dome (Oman)

    NASA Astrophysics Data System (ADS)

    Vandeginste, V.; John, C. M.; Gilhooly, W. P.

    2012-12-01

    Jebel Madar is a 500-m high mountain rising in the desert at the Oman Foothills. The Jebel consists of Triassic to Cretaceous carbonate host rocks forming the carapace of a salt dome. Halokinesis caused major fracturing and faulting at Jebel Madar, and the resulting structures acted as the main pathways for fluids that generated diagenetic cements composed of both barite and calcite. The spatial distribution of calcite and barite occurrences shows that calcite is formed in large abundance along the three main faults, whereas barite is more concentrated along faults further away from the three main ones. The stable carbon and oxygen isotope composition of calcite and fluid inclusion data from both calcite and barite show a distinct evolution of the fluid with a highly saline component towards more mixing with meteoric water. This is in agreement with clumped isotopes data on calcite cements indicating an evolution towards lower temperatures, consistent with doming of the Jebel and greater input of lower-temperature descending meteoric fluids. Here, we present sulphur and oxygen isotopic data on barite that suggest a link between the barite formation and the Precambrian salt underlying Jebel Madar. The average δ34S measured in barite is 33‰ CDT (1σ = 5‰; n = 33), which falls at the lower end of the δ34S range reported for the Ara Group anhydrite. The average δ18O in the same barite samples is 23‰ VSMOW (1σ = 2‰; n = 33). Data from the barite will be compared with sulphur isotopes from the carbonate-associate sulfate in the calcite cements. The overall goal of our research is to gain a better insight in the formation process of barite and calcite in Jebel Madar and its link with salt tectonics. We would like to acknowledge the financial support of QCCSRC (funded jointly by Qatar Petroleum, Shell and the Qatar Science & Technology Park) and the GSA Laubach fund for this study.

  3. Effects of chitosan on the alignment, morphology and shape of calcite crystals nucleating under Langmuir monolayers

    SciTech Connect

    Kim, Kyungil; Uysal, Ahmet; Kewalramani, Sumit; Stripe, Benjamin; Dutta, Pulak

    2009-04-22

    The growth of calcium carbonate crystals under Langmuir monolayers was investigated in the presence of chitosan, a soluble derivative of chitin added to the subphase to better simulate the polyelectrolyte-containing in vivo environment. Chitosan causes distinct concentration-dependent changes in the orientation, shape and morphology of the calcite crystals nucleating under acid and sulfate monolayers. Our results suggest that polyelectrolytes may play essential roles in controlling the growth of biogenic calcite crystals.

  4. Effects of Chitosan on the Morphology and Alignment of Calcite Crystals Nucleating Under Langmuir Monolayers

    SciTech Connect

    Kim, K.; Uysal, A; Kewalramani, S; Stripe, B; Dutta, P

    2009-01-01

    The growth of calcium carbonate crystals under Langmuir monolayers was investigated in the presence of chitosan, a soluble derivative of chitin added to the subphase to better simulate the polyelectrolyte-containing in vivo environment. Chitosan causes distinct concentration-dependent changes in the orientation, shape and morphology of the calcite crystals nucleating under acid and sulfate monolayers. Our results suggest that polyelectrolytes may play essential roles in controlling the growth of biogenic calcite crystals.

  5. Catalytic Biomineralization of Fluorescent Calcite by the Thermophilic Bacterium Geobacillus thermoglucosidasius▿

    PubMed Central

    Yoshida, Naoto; Higashimura, Eiji; Saeki, Yuichi

    2010-01-01

    The thermophilic Geobacillus bacterium catalyzed the formation of 100-μm hexagonal crystals at 60°C in a hydrogel containing sodium acetate, calcium chloride, and magnesium sulfate. Under fluorescence microscopy, crystals fluoresced upon excitation at 365 ± 5, 480 ± 20, or 545 ± 15 nm. X-ray diffraction indicated that the crystals were magnesium-calcite in calcite-type calcium carbonate. PMID:20851984

  6. Effects of abiotic stressors on lutein production in the green microalga Dunaliella salina

    PubMed Central

    2014-01-01

    Background Recent years have witnessed a rising trend in exploring microalgae for valuable carotenoid products as the demand for lutein and many other carotenoids in global markets has increased significantly. In green microalgae lutein is a major carotenoid protecting cellular components from damage incurred by reactive oxygen species under stress conditions. In this study, we investigated the effects of abiotic stressors on lutein accumulation in a strain of the marine microalga D. salina which had been selected for growth under stress conditions of combined blue and red lights by adaptive laboratory evolution. Results Nitrate concentration, salinity and light quality were selected as three representative influencing factors and their impact on lutein production in batch cultures of D. salina was evaluated using response surface analysis. D. salina was found to be more tolerant to hyper-osmotic stress than to hypo-osmotic stress which caused serious cell damage and death in a high proportion of cells while hyper-osmotic stress increased the average cell size of D. salina only slightly. Two models were developed to explain how lutein productivity depends on the stress factors and for predicting the optimal conditions for lutein productivity. Among the three stress variables for lutein production, stronger interactions were found between nitrate concentration and salinity than between light quality and the other two. The predicted optimal conditions for lutein production were close to the original conditions used for adaptive evolution of D. salina. This suggests that the conditions imposed during adaptive evolution may have selected for the growth optima arrived at. Conclusions This study shows that systematic evaluation of the relationship between abiotic environmental stresses and lutein biosynthesis can help to decipher the key parameters in obtaining high levels of lutein productivity in D. salina. This study may benefit future stress-driven adaptive

  7. Exploring biotic vs. abiotic controls on syngenetic carbonate and clay mineral precipitation

    NASA Astrophysics Data System (ADS)

    Nascimento, Gabriela S.; McKenzie, Judith A.; Martinez Ruiz, Francisca; Bontognali, Tomaso R. R.; Vasconcelos, Crisogono

    2016-04-01

    A possible syngenetic relationship between carbonate and clay mineral precipitation has been reported for sedimentary rocks deposited in both lacustrine and marine sedimentary environments throughout the geological record. In particular, the mineral dolomite is often found associated with Mg-rich clays, such as stevensite. It is notable that this carbonate/clay association has been recorded in numerous samples taken from modern dolomite precipitating environments; for example, the Coorong lakes, South Australia, coastal sabkhas, Abu Dhabi, UAE and coastal hypersaline lagoons (Lagoa Vermelha and Brejo do Espinho) east of Rio de Janeiro, Brazil. An HRTEM study of samples from these three locations indicates a possible physical/chemical association between the Ca-dolomite and Mg-rich clays, demonstrating a probable co-precipitation. To test this hypothesis, we have conducted a series of biotic and abiotic laboratory experiments. If this syngenesis actually occurs in nature, what, if any, are the biogeochemical processes controlling these precipitation reactions? Our experiments were designed to determine the extent of the biotic versus abiotic component influencing the mineral precipitation and, in the case of a biotic influence, to understand the mechanism through which microorganisms might mediate the formation of clay minerals. The experiments were carried out in the Geomicrobiology Laboratory of ETH Zürich using cultures of living microbes and artificial organic compounds that simulate functional groups present in natural biofilms formed under both aerobic and anaerobic conditions. In addition, pure inorganic experiments were designed to understand possible physico-chemical conditions for diagenetic processes that could induce dissolution of Mg-carbonates and precipitation of Mg-rich clays. Our results show a remarkable biotic influence during the formation of clay minerals. Specifically, extracellular polymeric substances (EPS), released by microbes in their

  8. Initial formation of calcite crystals in the thin prismatic layer with the periostracum of Pinctada fucata.

    PubMed

    Suzuki, Michio; Nakayama, Seiji; Nagasawa, Hiromichi; Kogure, Toshihiro

    2013-02-01

    Although the formation mechanism of calcite crystals in the prismatic layer has been studied well in many previous works, the initial state of calcite formation has not been observed in detail using electron microscopes. In this study, we report that the soft prismatic layer with transparent color (the thin prismatic layer) in the tip of the fresh shell of Pinctada fucata was picked up to observe the early calcification phase. A scanning electron microscope (SEM) image showed that the growth tip of the thin prismatic layer was covered by the periostracum, which was also where the initial formation of calcite crystals began. A cross-section containing the thin calcite crystals in the thin prismatic layer with the periostracum was made using a focused ion beam (FIB) system. In a transmission electron microscope (TEM) observation, the thin calcite crystal (thickness is about 1μm) on the periostracum was found to be a single crystal with the c-axis oriented perpendicular to the shell surface. On the other hand, many aggregated small particles consisting of bassanite crystals were observed in the periostracum suggesting the possibility that not only organic sulfate but also inorganic sulfates exist in the prismatic layer. These discoveries in the early calcification phase of the thin prismatic layer may help to clarify the mechanism of regulating the nucleation and orientation of the calcite crystal in the shell. PMID:23176816

  9. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    SciTech Connect

    Bevilaqua, Rochele C. A.; Miranda, Caetano R.; Rigo, Vagner A.; Veríssimo-Alves, Marcos

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca{sup 2+}. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO{sub 3} (101{sup ¯}4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for {sup 43}Ca, {sup 13}C, and {sup 17}O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  10. NMR characterization of hydrocarbon adsorption on calcite surfaces: a first principles study.

    PubMed

    Bevilaqua, Rochele C A; Rigo, Vagner A; Veríssimo-Alves, Marcos; Miranda, Caetano R

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca(2+). Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for (43)Ca, (13)C, and (17)O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated. PMID:25429955

  11. Estimation of past seepage volumes from calcite distribution in the Topopah Spring Tuff, Yucca Mountain, Nevada.

    PubMed

    Marshall, Brian D; Neymark, Leonid A; Peterman, Zell E

    2003-01-01

    Low-temperature calcite and opal record the past seepage of water into open fractures and lithophysal cavities in the unsaturated zone at Yucca Mountain, Nevada, site of a proposed high-level radioactive waste repository. Systematic measurements of calcite and opal coatings in the Exploratory Studies Facility (ESF) tunnel at the proposed repository horizon are used to estimate the volume of calcite at each site of calcite and/or opal deposition. By estimating the volume of water required to precipitate the measured volumes of calcite in the unsaturated zone, seepage rates of 0.005 to 5 liters/year (l/year) are calculated at the median and 95th percentile of the measured volumes, respectively. These seepage rates are at the low end of the range of seepage rates from recent performance assessment (PA) calculations, confirming the conservative nature of the performance assessment. However, the distribution of the calcite and opal coatings indicate that a much larger fraction of the potential waste packages would be contacted by this seepage than is calculated in the performance assessment. PMID:12714293

  12. Microstructural control of calcite via incorporation of intracrystalline organic molecules in shells

    NASA Astrophysics Data System (ADS)

    Okumura, Taiga; Suzuki, Michio; Nagasawa, Hiromichi; Kogure, Toshihiro

    2013-10-01

    It is widely accepted that organic substances regulate or influence the structure of biominerals, but its direct evidences are not plenty. Here we show that the crystallographic microstructures in biotic calcites arise from incorporated intracrystalline organic molecules (IOMs), through a comparison between biotic calcites in shells and synthetic ones with the IOMs extracted from the shells. Although the prismatic layers of a pearl oyster (Pinctada fucata) and a pen shell (Atrina pectinata) morphologically resemble each other, the crystallographic features of constituent calcites are considerably different; in Pinctada, the IOMs are distributed inhomogeneously to form small-angle grain boundaries and associated crystal defects, whereas in Atrina, the IOMs are distributed almost homogeneously and defects are rare in the calcite crystals. We conducted in vitro calcite syntheses in the presence of the IOMs in EDTA-soluble extracts from the prisms. The IOMs in the extracts from Pinctada and Atrina were incorporated into synthetic calcites in a different manner, exhibiting defect-rich/free features as observed in the natural shells. With regard to amino acid compositions of the IOMs, the extract from Atrina has a higher proportion of acidic amino acids than that from Pinctada, implying that acidic proteins do not correlate directly to their affinity for calcium carbonate crystals.

  13. Estimation of past seepage volumes from calcite distribution in the Topopah Spring Tuff, Yucca Mountain, Nevada

    USGS Publications Warehouse

    Marshall, B.D.; Neymark, L.A.; Peterman, Z.E.

    2003-01-01

    Low-temperature calcite and opal record the past seepage of water into open fractures and lithophysal cavities in the unsaturated zone at Yucca Mountain, Nevada, site of a proposed high-level radioactive waste repository. Systematic measurements of calcite and opal coatings in the Exploratory Studies Facility (ESF) tunnel at the proposed repository horizon are used to estimate the volume of calcite at each site of calcite and/or opal deposition. By estimating the volume of water required to precipitate the measured volumes of calcite in the unsaturated zone, seepage rates of 0.005 to 5 liters/year (l/year) are calculated at the median and 95th percentile of the measured volumes, respectively. These seepage rates are at the low end of the range of seepage rates from recent performance assessment (PA) calculations, confirming the conservative nature of the performance assessment. However, the distribution of the calcite and opal coatings indicate that a much larger fraction of the potential waste packages would be contacted by this seepage than is calculated in the performance assessment.

  14. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    NASA Astrophysics Data System (ADS)

    Bevilaqua, Rochele C. A.; Rigo, Vagner A.; Veríssimo-Alves, Marcos; Miranda, Caetano R.

    2014-11-01

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca2+. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 ( {10bar 14} )). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for 43Ca, 13C, and 17O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  15. Mixing-induced calcite precipitation and dissolution kinetics in micromodel experiments.

    SciTech Connect

    Valocchi, Albert J.; Dewers, Thomas A.; Dehoff, Karl; Yoon, Hongkyu; Werth, Charles J.

    2010-12-01

    Dissolved CO2 from geological CO2 sequestration may react with dissolved minerals in fractured rocks or confined aquifers and cause mineral precipitation. The overall rate of reaction can be limited by diffusive or dispersive mixing, and mineral precipitation can block pores and further hinder these processes. Mixing-induced calcite precipitation experiments were performed by injecting solutions containing CaCl2 and Na2CO3 through two separate inlets of a micromodel (1-cm x 2-cm x 40-microns); transverse dispersion caused the two solutions to mix along the center of the micromodel, resulting in calcite precipitation. The amount of calcite precipitation initially increased to a maximum and then decreased to a steady state value. Fluorescent microscopy and imaging techniques were used to visualize calcite precipitation, and the corresponding effects on the flow field. Experimental micromodel results were evaluated with pore-scale simulations using a 2-D Lattice-Boltzmann code for water flow and a finite volume code for reactive transport. The reactive transport model included the impact of pH upon carbonate speciation and calcite dissolution. We found that proper estimation of the effective diffusion coefficient and the reaction surface area is necessary to adequately simulate precipitation and dissolution rates. The effective diffusion coefficient was decreased in grid cells where calcite precipitated, and keeping track of reactive surface over time played a significant role in predicting reaction patterns. Our results may improve understanding of the fundamental physicochemical processes during CO2 sequestration in geologic formations.

  16. Sea urchin tooth mineralization: Calcite present early in the aboral plumula

    PubMed Central

    Stock, Stuart R.; Veis, Arthur; Xiao, Xianghui; Almer, Jonathan D.; Dorvee, Jason R.

    2012-01-01

    In both vertebrate bone, containing carbonated hydroxyapatite as the mineral phase, and in invertebrate hard tissue comprised of calcium carbonate, a popular view is that the mineral phase develops from a long-lived amorphous precursor which later transforms into crystal form. Important questions linked to this popular view are: When and where is the crystallized material formed, and is amorphous solid added subsequently to the crystalline substrate? Sea urchin teeth, in which the earliest mineral forms within isolated compartments, in a time and position dependent manner, allow direct investigation of the timing of crystallization of the calcite primary plates. Living teeth of the sea urchin Lytechinus variegatus, in their native coelomic fluid, were examined by high-energy synchrotron x-ray diffraction. The diffraction data show that calcite is present in the most aboral portions of the plumula, representing the very earliest stages of mineralization, and that this calcite has the same crystal orientation as in the more mature adoral portions of the same tooth. Raman spectroscopy of the aboral plumula confirms the initial primary plate mineral material is calcite and does not detect amorphous calcium carbonate; in the more mature adoral incisal flange, it does detect a broader calcite peak, consistent with two or more magnesium compositions. We hypothesize that some portion of each syncytial membrane in the plumula provides the information for nucleation of identically oriented calcite crystals that subsequently develop to form the complex geometry of the single crystal sea urchin tooth. PMID:22940703

  17. (U-Th)/He dating and He diffusion in calcite from veins and breccia

    NASA Astrophysics Data System (ADS)

    Gautheron, C.; Cros, A.; Pagel, M.; Berthet, P.; Tassan-Got, L.; Douville, E.; Pinna-Jamme, R.; Sarda, P.

    2013-12-01

    Knowledge of He retention in crystalline calcite is mandatory to estimate the possibility of (U-Th)/He dating of calcite. To this aim, fault-filling calcite crystals from the Eocene/Oligocene Gondrecourt graben, Paris Basin, Eastern France, have been sampled, based on their relatively old, Eocene-Oligocene, precipitation age and cold thermal history (<40°C since precipitation). The samples were sorted into three main tectonic and morphological groups, including successively (1) micro-fracture calcites, (2) breccia and associated geodic calcites, and (3) vein and associated geodic calcites. (U-Th)/He dating of 63 calcite fragments yields ages dispersed from 0.2×0.02 to 35.8×2.7 Ma, as well as two older dates of 117×10 and 205×28 Ma (1s). These He ages correlate to grain chemistry, such as to Sr and ΣREE concentrations or (La/Yb)N ratios, and these correlations probably reflect the evolution of parent fluid. Only the oldest He ages are in agreement with the He-retentive character of calcite as determined by Copeland et al. (2007), and these ages were obtained for the most recently precipitated crystals. To better understand the large He-age scatter and why calcites precipitated earlier show younger ages, He diffusion experiments have been conducted on 10 Gondrecourt calcite fragments from 3 samples with He ages of 0.2 to 6 Ma. In addition, a crystallographic investigation by X-Ray Diffraction (XRD) performed on similar samples reveals that the crystal structure evolves with increasing temperature, showing with micro-cracks and cleavage opening. These XRD results indicate that, in fault-filling calcite, He retention is controlled by multiple diffusion domains (MDD, Lovera et al., 1991) with various sizes, and therefore, evolves through time with strong consequences on (U-Th)/He age. We thus interpret the Gondrecourt calcite (U-Th)/He age scatter of older samples as a consequence of cleavage opening due to a succession of calcite crystallization phases related to

  18. In situ AFM crystal growth and dissolution study of calcite in the presence of aqueous fluoride

    NASA Astrophysics Data System (ADS)

    Vavouraki, A.; Putnis, C. V.; Putnis, A.; Koutsoukos, P. G.

    2009-04-01

    Fluoride is naturally abundant, encountered in rocks, soil and fresh and ocean water. Calcite crystals, during crystal growth may incorporate fluoride ions into their lattice (Okumura et al., 1983). In situ atomic force microscopy (AFM) has been used to study the growth and dissolution of calcite {104} surfaces in aqueous solutions in the presence of fluoride, using a fluid cell in which the supersaturated and the understaturated solutions respectively, flow over a freshly cleaved calcite crystal. For growth experiments, supersaturation index (S.I.) with respect to calcite was equal to 0.89 and the initial solution pH 10.2. The crystal growth rates were measured from the closure of the rhombohedral etch pits along the [010] direction induced by an initial dissolution step using pure water. The spreading rate of 2-dimensional nuclei was also measured along the same direction. In the presence of low fluoride concentrations (≤0.33 mM), the crystal growth rate of calcite was unaffected. At higher concentrations (up to 5 mM) growth rate decreased substantially to 50% of the rate in the absence of fluoride. Potential fluoride sorption over the calcite surface may ascribe the decrease of growth rates. Dissolution experiments were conducted at pH= 7.2 and dissolution rates of calcite were measured from the spreading of rhombohedral etch pits along both [010] and [42] directions. The presence of low concentrations of fluoride (≤1.1 mM) in the undersaturated solutions enhanced the dissolution rate along the [42] direction by 50% in comparison with pure water. The morphology of rhombohedral etch pits changed to hexagonal in the presence of fluoride in the undersaturated solutions. The AFM dissolution experiments suggested that the fluoride ions adsorbed onto the calcite surface. Further increase of fluoride concentrations (up to 1.6 mM) resulted in the decrease of the calcite dissolution rate by 60% in both [010] and [42] directions. Reference: Okumura, M, Kitano, Y

  19. Strain localization and the onset of dynamic weakening in calcite fault gouge

    NASA Astrophysics Data System (ADS)

    Smith, S. A. F.; Nielsen, S.; Di Toro, G.

    2015-03-01

    To determine the role of strain localization during dynamic weakening of calcite gouge at seismic slip rates, single-slide and slide-hold-slide experiments were conducted on 2-3-mm thick layers of calcite gouge at normal stresses up to 26 MPa and slip rates up to 1 m s-1. Microstructures were analyzed from short displacement (< 35 cm) experiments stopped prior to and during the transition to dynamic weakening. In fresh calcite gouge layers, dynamic weakening occurs after a prolonged strengthening phase that becomes shorter with increasing normal stress and decreasing layer thickness. Strain is initially distributed across the full thickness of the gouge layer, but within a few millimeters displacement the strain becomes localized to a boundary-parallel, high-strain shear band c. 20 μm wide. During the strengthening phase, which lasts between 3 and 30 cm under the investigated conditions, the shear band broadens to become c. 100 μm wide at peak stress. The transition to dynamic weakening in calcite gouges is associated with the nucleation of micro-slip surfaces dispersed throughout the c. 100 μm wide shear band. Each slip surface is surrounded by aggregates of extremely fine grained and tightly packed calcite, interpreted to result from grain welding driven by local frictional heating in the shear band. By the end of dynamic weakening strain is localized to a single 2- 3-μm wide principal slip surface, flanked by layers of recrystallized gouge. Calcite gouge layers re-sheared following a hold period weaken nearly instantaneously, much like solid cylinders of calcite marble deformed under the same experimental conditions. This is due to reactivation of the recrystallized and cohesive principal slip surface that formed during the first slide, reducing the effective gouge layer thickness to a few microns. Our results suggest that formation of a high-strain shear band is a critical precursor to dynamic weakening in calcite gouges. Microstructures are most compatible

  20. Relative growth rates and compositions of aragonite and MG calcite cements in seawater: effects of temperature and sulfate

    SciTech Connect

    Burton, E.A.; Walter, L.M.

    1985-01-01

    Experimental work shows that carbonate cement compositions and relative growth rates are controlled by changes in temperature and chemical composition of seawater. Substrate mineralogy controls cement mineralogy. Low-Mg calcite cements are favored at low temperatures. As temperature rises, aragonite precipitation becomes progressively more favored and the mole % MgCO/sub 3/ in calcite increases. Aragonite and calcite seeds of known surface area were added to natural seawater at 5, 25 and 37/sup 0/C and a p/sub CO/sup 2// of 0.01 atm. Runs were conducted at 10 times calcite saturation. Saturation state was held constant during each run by injection of titrants to replace calcium and carbonate ions lost by precipitation. Overgrowth compositions were analyzed by XRD. In all experiments, aragonite seeds had only aragonite overgrowths. Only calcite cements grew on calcite seeds. Sulfate also effects calcite precipitation rates and cement compositions. Preliminary results at 25/sup 0/C indicate that, at the same saturation state, calcite growth rates are 10 times faster in sulfate-free seawater-like solutions (Mg/Ca=5) than in normal seawater. Cements grown in sulfate-free media were enriched by 2 to 3 mole % over the calcite cements from natural seawater. This suggests that sulfate depletion of seawater should lead to a more rapid precipitation of progressively more Mg-rich calcites.

  1. Calcite Fluid Inclusion, Paragenetic, and Oxygen Isotopic Records of Thermal Event(s) at Yucca Mountain, Nevada

    SciTech Connect

    B. Peterman; R. Moscati

    2000-08-10

    Yucca Mountain, Nevada, is under consideration as a potential high-level radioactive waste repository situated above the water table in 12.7 Ma tuffs. A wealth of textural and geochemical evidence from low-temperature deposits of calcite and silica, indicates that their genesis is related to unsaturated zone (UZ) percolation and that the level of the potential repository has never been saturated. Nonetheless, some scientists contend that thermal waters have periodically risen to the surface depositing calcite and opal in the tuffs and at the surface. This hypothesis received some support in 1996 when two-phase fluid inclusions (FIs) with homogenization temperatures (Th) between 35 and 75 C were reported from UZ calcite. Calcite deposition likely followed closely on the cooling of the tuffs and continues into the present. The paragenetic sequence of calcite and silica in the UZ is early stage calcite followed by chalcedony and quartz, then calcite with local opal during middle and late stages. Four types of FIs are found in calcite assemblages: (1) all-liquid (L); (2) all-vapor (V); (3) 2-phase with large and variable V:L ratios; and (4) a few 2-phase with small and consistent V:L ratios. Late calcite contains no FI assemblages indicating elevated depositional temperatures. In early calcite, the Th of type 4 FIs ranges from {approx} 40 to {approx} 85 C. Such temperatures (sub-boiling) and the assemblage of FIs are consistent with deposition in the UZ. Some delta 18O values < 10 permil in early calcite support such temperatures. Type 4 FIs, however, seem to be restricted to the early calcite stage, during which either cooling of the tuffs or regional volcanism were possible heat sources. Nonetheless, at present there is no compelling evidence of upwelling water as a source for the calcite/opal deposits.

  2. Arbuscular mycorrhizal fungal responses to abiotic stresses: A review.

    PubMed

    Lenoir, Ingrid; Fontaine, Joël; Lounès-Hadj Sahraoui, Anissa

    2016-03-01

    The majority of plants live in close collaboration with a diversity of soil organisms among which arbuscular mycorrhizal fungi (AMF) play an essential role. Mycorrhizal symbioses contribute to plant growth and plant protection against various environmental stresses. Whereas the resistance mechanisms induced in mycorrhizal plants after exposure to abiotic stresses, such as drought, salinity and pollution, are well documented, the knowledge about the stress tolerance mechanisms implemented by the AMF themselves is limited. This review provides an overview of the impacts of various abiotic stresses (pollution, salinity, drought, extreme temperatures, CO2, calcareous, acidity) on biodiversity, abundance and development of AMF and examines the morphological, biochemical and molecular mechanisms implemented by AMF to survive in the presence of these stresses. PMID:26803396

  3. Demonstration of significant abiotic iron isotope fractionation in nature

    USGS Publications Warehouse

    Bullen, T.D.; White, A.F.; Childs, C.W.; Vivit, D.V.; Schultz, M.S.

    2001-01-01

    Field and laboratory studies reveal that the mineral ferrihydrite, formed as a result of abiotic oxidation of aqueous ferrous to ferric Fe, contains Fe that is isotopically heavy relative to coexisting aqueous Fe. Because the electron transfer step of the oxidation process at pH >5 is essentially irreversible and should favor the lighter Fe isotopes in the ferric iron product, this result suggests that relatively heavy Fe isotopes are preferentially partitioned into the readily oxidized Fe(II)(OH)x(aq) species or their transition complexes prior to oxidation. The apparent Fe isotope fractionation factor, ??ferrihydrite-water, depends primarily on the relative abundances of the Fe(II)(aq) species. This study demonstrates that abiotic processes can fractionate the Fe isotopes to the same extent as biotic processes, and thus Fe isotopes on their own do not provide an effective biosignature.

  4. Effects of abiotic stress on plants: a systems biology perspective

    PubMed Central

    2011-01-01

    The natural environment for plants is composed of a complex set of abiotic stresses and biotic stresses. Plant responses to these stresses are equally complex. Systems biology approaches facilitate a multi-targeted approach by allowing one to identify regulatory hubs in complex networks. Systems biology takes the molecular parts (transcripts, proteins and metabolites) of an organism and attempts to fit them into functional networks or models designed to describe and predict the dynamic activities of that organism in different environments. In this review, research progress in plant responses to abiotic stresses is summarized from the physiological level to the molecular level. New insights obtained from the integration of omics datasets are highlighted. Gaps in our knowledge are identified, providing additional focus areas for crop improvement research in the future. PMID:22094046

  5. Abiotic mediation of a mutualism drives herbivore abundance.

    PubMed

    Mooney, Emily H; Phillips, Joseph S; Tillberg, Chadwick V; Sandrow, Cheryl; Nelson, Annika S; Mooney, Kailen A

    2016-01-01

    Species abundance is typically determined by the abiotic environment, but the extent to which such effects occur through the mediation of biotic interactions, including mutualisms, is unknown. We explored how light environment (open meadow vs. shaded understory) mediates the abundance and ant tending of the aphid Aphis helianthi feeding on the herb Ligusticum porteri. Yearly surveys consistently found aphids to be more than 17-fold more abundant on open meadow plants than on shaded understory plants. Manipulations demonstrated that this abundance pattern was not due to the direct effects of light environment on aphid performance, or indirectly through host plant quality or the effects of predators. Instead, open meadows had higher ant abundance and per capita rates of aphid tending and, accordingly, ants increased aphid population growth in meadow but not understory environments. The abiotic environment thus drives the abundance of this herbivore exclusively through the mediation of a protection mutualism. PMID:26563752

  6. Probing the record of seawater carbonate chemistry in coccolithophore calcite

    NASA Astrophysics Data System (ADS)

    Candelier, Yael; Minoletti, Fabrice; Hermoso, Michael

    2013-04-01

    Previous works on the biogeochemistry of the ubiquist coccolithophore Calcidiscus leptoporus quantified an oxygen isotope fractionation of about -2.2 ‰ with respect to equilibrium. New cultures experiments and core top study of this taxon enable the calibration of the temperature dependance recorded in δ18O of this coccolith providing a new tool to decipher surfaces water temperatures through the Cenozoic. These findings, concordant in the two approaches show a reduced range of vital effect (-1.1 ‰ ). Other cultured and isolated species (Gephyrocapsa oceanica, Emiliania huxleyi and C.pelagicus) show similar patterns that raise the question of a possible overestimation of isotopic disequilibria in coccolith calcite. A promising research topic in palaeoceanography consists of exploiting interspecific isotopic fractionation because species respond differently to ambient changes in carbonate system chemistry. While E.huxleyi or G.oceanica are isotopically sensitive to changes in dissolved inorganic carbon speciation or concentration, others such as C.leptoporus remains almost unaffected. This may indicate that in addition to traditional δ18O temperature proxy, coccolith interspecific isotopic offsets can provide an innovative means to constrain the carbonate chemistry of the mixed-layer. We investigated this hypothesis with a study case of the last Pleistocene deglaciation that appears to be a good candidate by his abrupt changes in temperatures, oxygen isotope composition of seawater and atmospheric pCO2. While numerous studies have investigated climate changes at high latitudes, we present here the first coccoliths-based isotopic record of mixed-layer temperature at the border of North Atlantic Subtropical Gyre (southwards of the polar front). From Site DSDP 607 we successfully isolated fractions of coccolithophore species C.leptoporus, G.oceanica, E. huxleyi and C.pelagicus over the last 17 kyr. Oxygen isotope variations from these fractions exhibit a shift of

  7. Ages and Origins of Calcite and Opal in the Exploratory Studies Facility Tunnel, Yucca Mountain, Nevada

    USGS Publications Warehouse

    Paces, James B.; Neymark, Leonid A.; Marshall, Brian D.; Whelan, Joseph F.; Peterman, Zell E.

    2001-01-01

    Deposits of calcite and opal are present as coatings on open fractures and lithophysal cavities in unsaturated-zone tuffs at Yucca Mountain, Nevada, site of a potential high-level radioactive waste repository. Outermost layers of calcite and opal have radiocarbon ages of 16,000 to 44,000 years before present and thorium-230/uranium ages of 28,000 to more than 500,000 years before present. These ages are young relative to the 13-million-year age of the host rocks. Multiple subsamples from the same outer layer typically show a range of ages with youngest ages from the thinnest subsamples. Initial uranium-234/uranium-238 activity ratios between 1 and 9.5 show a distinct negative correlation with thorium-230/uranium age and are greater than 4 for all but one sample younger than 100,000 years before present. These data, along with micrometer-scale layering and distinctive crystal morphologies, are interpreted to indicate that deposits formed very slowly from water films migrating through open cavities. Exchanges of carbon dioxide and water vapor probably took place between downward-migrating liquids and upward-migrating gases at low rates, resulting in oversaturation of mineral constituents at crystal extremities and more or less continuous deposition of very thin layers. Therefore, subsamples represent mixtures of older and younger layers on a scale finer than sampling techniques can resolve. Slow, long-term rates of deposition (less than about 5 millimeters of mineral per million years) are inferred from subsamples of outermost calcite and opal. These growth rates are similar to those calculated assuming that total coating thicknesses of 10 to 40 millimeters accumulated over 12 million years. Calcite has a wide range of delta carbon-13 values from about -8.2 to 8.5 per mil and delta oxygen-18 values from about 10 to 21 per mil. Systematic microsampling across individual mineral coatings indicates basal (older) calcite tends to have the largest delta carbon-13 values

  8. Wheat EST resources for functional genomics of abiotic stress

    PubMed Central

    Houde, Mario; Belcaid, Mahdi; Ouellet, François; Danyluk, Jean; Monroy, Antonio F; Dryanova, Ani; Gulick, Patrick; Bergeron, Anne; Laroche, André; Links, Matthew G; MacCarthy, Luke; Crosby, William L; Sarhan, Fathey

    2006-01-01

    Background Wheat is an excellent species to study freezing tolerance and other abiotic stresses. However, the sequence of the wheat genome has not been completely characterized due to its complexity and large size. To circumvent this obstacle and identify genes involved in cold acclimation and associated stresses, a large scale EST sequencing approach was undertaken by the Functional Genomics of Abiotic Stress (FGAS) project. Results We generated 73,521 quality-filtered ESTs from eleven cDNA libraries constructed from wheat plants exposed to various abiotic stresses and at different developmental stages. In addition, 196,041 ESTs for which tracefiles were available from the National Science Foundation wheat EST sequencing program and DuPont were also quality-filtered and used in the analysis. Clustering of the combined ESTs with d2_cluster and TGICL yielded a few large clusters containing several thousand ESTs that were refractory to routine clustering techniques. To resolve this problem, the sequence proximity and "bridges" were identified by an e-value distance graph to manually break clusters into smaller groups. Assembly of the resolved ESTs generated a 75,488 unique sequence set (31,580 contigs and 43,908 singletons/singlets). Digital expression analyses indicated that the FGAS dataset is enriched in stress-regulated genes compared to the other public datasets. Over 43% of the unique sequence set was annotated and classified into functional categories according to Gene Ontology. Conclusion We have annotated 29,556 different sequences, an almost 5-fold increase in annotated sequences compared to the available wheat public databases. Digital expression analysis combined with gene annotation helped in the identification of several pathways associated with abiotic stress. The genomic resources and knowledge developed by this project will contribute to a better understanding of the different mechanisms that govern stress tolerance in wheat and other cereals. PMID

  9. Quantified biotic and abiotic responses to multiple stress in freshwater, marine and ground waters.

    PubMed

    Nõges, Peeter; Argillier, Christine; Borja, Ángel; Garmendia, Joxe Mikel; Hanganu, Jenică; Kodeš, Vit; Pletterbauer, Florian; Sagouis, Alban; Birk, Sebastian

    2016-01-01

    We reviewed 219 papers and built an inventory of 532 items of ecological evidence on multiple stressor impacts in rivers, lakes, transitional and coastal waters, as well as groundwaters. Our review revealed that, despite the existence of a huge conceptual knowledge base in aquatic ecology, few studies actually provide quantitative evidence on multi-stress effects. Nutrient stress was involved in 71% to 98% of multi-stress situations in the three types of surface water environments, and in 42% of those in groundwaters. However, their impact manifested differently along the groundwater-river-lake-transitional-coastal continuum, mainly determined by the different hydro-morphological features of these ecosystems. The reviewed papers addressed two-stressor combinations most frequently (42%), corresponding with the actual status-quo of pressures acting on European surface waters as reported by the Member States in the WISE WFD Database (EEA, 2015). Across all biological groups analysed, higher explanatory power of the stress-effect models was discernible for lakes under multi-stressor compared to single stressor conditions, but generally lower for coastal and transitional waters. Across all aquatic environments, the explanatory power of stress-effect models for fish increased when multi-stressor conditions were taken into account in the analysis, qualifying this organism group as a useful indicator of multi-stress effects. In contrast, the explanatory power of models using benthic flora decreased under conditions of multiple stress. PMID:26116411

  10. Abiotic carbonate dissolution traps carbon in a semiarid desert

    NASA Astrophysics Data System (ADS)

    Fa, Keyu; Liu, Zhen; Zhang, Yuqing; Qin, Shugao; Wu, Bin; Liu, Jiabin

    2016-03-01

    It is generally considered that desert ecosystems release CO2 to the atmosphere, but recent studies in drylands have shown that the soil can absorb CO2 abiotically. However, the mechanisms and exact location of abiotic carbon absorption remain unclear. Here, we used soil sterilization, 13CO2 addition, and detection methods to trace 13C in the soil of the Mu Us Desert, northern China. After 13CO2 addition, a large amount of 13CO2 was absorbed by the sterilised soil, and 13C was found enriched both in the soil gaseous phase and dissolved inorganic carbon (DIC). Further analysis indicated that about 79.45% of the total 13C absorbed by the soil was trapped in DIC, while the amount of 13C in the soil gaseous phase accounted for only 0.22% of the total absorbed 13C. However, about 20.33% of the total absorbed 13C remained undetected. Our results suggest that carbonate dissolution might occur predominately, and the soil liquid phase might trap the majority of abiotically absorbed carbon. It is possible that the trapped carbon in the soil liquid phase leaches into the groundwater; however, further studies are required to support this hypothesis.

  11. Biotic and abiotic mercury methylation and demethylation in sediments

    SciTech Connect

    Zhang, L.; Planas, D. )

    1994-05-01

    Inorganic mercury (Hg(II)) methylation and methylmercury (MeHg) demethylation may occur in the water column, sediment-water interface and subsurficial sediment of aquatic ecosystems. These transformations involve mainly microbial mechanisms, although abiotic methylation may play a more important role in the water compartment. The relative importance of biotic versus abiotic mechanisms of methylation has not been determined however, and abiotic demethylation remains unknown. Little quantitative information is available on the role of bacterial activity in mercury transformations. It has been reported that at least 16 genera of aerobic and anaerobic microorganisms are able to methylate HG(II), and that a greater number are able to demethylate MeHg. Nevertheless, not all populations of these species are capable of methyl- and demethyl-transformations. The actual concentration of MeHg in the aquatic environment is regulated by the relative production and decomposition rates. This, in turn, depends on the availability of Hg(II), MeHg, and bacteria as well as on the physico-chemical properties of the sample. The objective of this study was to compare mercury methylation and demethylation rates in sediment samples with and without active bacterial populations. We therefore performed experiments to follow bacterial evolution during the course of Hg(II) methylation and MeHg demethylation in sediment slurries containing both sterile and non-sterile sediments.

  12. Abiotic Deposition of Fe Complexes onto Leptothrix Sheaths

    PubMed Central

    Kunoh, Tatsuki; Hashimoto, Hideki; McFarlane, Ian R.; Hayashi, Naoaki; Suzuki, Tomoko; Taketa, Eisuke; Tamura, Katsunori; Takano, Mikio; El-Naggar, Mohamed Y.; Kunoh, Hitoshi; Takada, Jun

    2016-01-01

    Bacteria classified in species of the genus Leptothrix produce extracellular, microtubular, Fe-encrusted sheaths. The encrustation has been previously linked to bacterial Fe oxidases, which oxidize Fe(II) to Fe(III) and/or active groups of bacterial exopolymers within sheaths to attract and bind aqueous-phase inorganics. When L. cholodnii SP-6 cells were cultured in media amended with high Fe(II) concentrations, Fe(III) precipitates visibly formed immediately after addition of Fe(II) to the medium, suggesting prompt abiotic oxidation of Fe(II) to Fe(III). Intriguingly, these precipitates were deposited onto the sheath surface of bacterial cells as the population was actively growing. When Fe(III) was added to the medium, similar precipitates formed in the medium first and were abiotically deposited onto the sheath surfaces. The precipitates in the Fe(II) medium were composed of assemblies of globular, amorphous particles (ca. 50 nm diameter), while those in the Fe(III) medium were composed of large, aggregated particles (≥3 µm diameter) with a similar amorphous structure. These precipitates also adhered to cell-free sheaths. We thus concluded that direct abiotic deposition of Fe complexes onto the sheath surface occurs independently of cellular activity in liquid media containing Fe salts, although it remains unclear how this deposition is associated with the previously proposed mechanisms (oxidation enzyme- and/or active group of organic components-involved) of Fe encrustation of the Leptothrix sheaths. PMID:27271677

  13. Lipid signalling in plant responses to abiotic stress.

    PubMed

    Hou, Quancan; Ufer, Guido; Bartels, Dorothea

    2016-05-01

    Lipids are one of the major components of biological membranes including the plasma membrane, which is the interface between the cell and the environment. It has become clear that membrane lipids also serve as substrates for the generation of numerous signalling lipids such as phosphatidic acid, phosphoinositides, sphingolipids, lysophospholipids, oxylipins, N-acylethanolamines, free fatty acids and others. The enzymatic production and metabolism of these signalling molecules are tightly regulated and can rapidly be activated upon abiotic stress signals. Abiotic stress like water deficit and temperature stress triggers lipid-dependent signalling cascades, which control the expression of gene clusters and activate plant adaptation processes. Signalling lipids are able to recruit protein targets transiently to the membrane and thus affect conformation and activity of intracellular proteins and metabolites. In plants, knowledge is still scarce of lipid signalling targets and their physiological consequences. This review focuses on the generation of signalling lipids and their involvement in response to abiotic stress. We describe lipid-binding proteins in the context of changing environmental conditions and compare different approaches to determine lipid-protein interactions, crucial for deciphering the signalling cascades. PMID:26510494

  14. Abiotic Deposition of Fe Complexes onto Leptothrix Sheaths.

    PubMed

    Kunoh, Tatsuki; Hashimoto, Hideki; McFarlane, Ian R; Hayashi, Naoaki; Suzuki, Tomoko; Taketa, Eisuke; Tamura, Katsunori; Takano, Mikio; El-Naggar, Mohamed Y; Kunoh, Hitoshi; Takada, Jun

    2016-01-01

    Bacteria classified in species of the genus Leptothrix produce extracellular, microtubular, Fe-encrusted sheaths. The encrustation has been previously linked to bacterial Fe oxidases, which oxidize Fe(II) to Fe(III) and/or active groups of bacterial exopolymers within sheaths to attract and bind aqueous-phase inorganics. When L. cholodnii SP-6 cells were cultured in media amended with high Fe(II) concentrations, Fe(III) precipitates visibly formed immediately after addition of Fe(II) to the medium, suggesting prompt abiotic oxidation of Fe(II) to Fe(III). Intriguingly, these precipitates were deposited onto the sheath surface of bacterial cells as the population was actively growing. When Fe(III) was added to the medium, similar precipitates formed in the medium first and were abiotically deposited onto the sheath surfaces. The precipitates in the Fe(II) medium were composed of assemblies of globular, amorphous particles (ca. 50 nm diameter), while those in the Fe(III) medium were composed of large, aggregated particles (≥3 µm diameter) with a similar amorphous structure. These precipitates also adhered to cell-free sheaths. We thus concluded that direct abiotic deposition of Fe complexes onto the sheath surface occurs independently of cellular activity in liquid media containing Fe salts, although it remains unclear how this deposition is associated with the previously proposed mechanisms (oxidation enzyme- and/or active group of organic components-involved) of Fe encrustation of the Leptothrix sheaths. PMID:27271677

  15. Titania may produce abiotic oxygen atmospheres on habitable exoplanets.

    PubMed

    Narita, Norio; Enomoto, Takafumi; Masaoka, Shigeyuki; Kusakabe, Nobuhiko

    2015-01-01

    The search for habitable exoplanets in the Universe is actively ongoing in the field of astronomy. The biggest future milestone is to determine whether life exists on such habitable exoplanets. In that context, oxygen in the atmosphere has been considered strong evidence for the presence of photosynthetic organisms. In this paper, we show that a previously unconsidered photochemical mechanism by titanium (IV) oxide (titania) can produce abiotic oxygen from liquid water under near ultraviolet (NUV) lights on the surface of exoplanets. Titania works as a photocatalyst to dissociate liquid water in this process. This mechanism offers a different source of a possibility of abiotic oxygen in atmospheres of exoplanets from previously considered photodissociation of water vapor in upper atmospheres by extreme ultraviolet (XUV) light. Our order-of-magnitude estimation shows that possible amounts of oxygen produced by this abiotic mechanism can be comparable with or even more than that in the atmosphere of the current Earth, depending on the amount of active surface area for this mechanism. We conclude that titania may act as a potential source of false signs of life on habitable exoplanets. PMID:26354078

  16. Titania may produce abiotic oxygen atmospheres on habitable exoplanets

    PubMed Central

    Narita, Norio; Enomoto, Takafumi; Masaoka, Shigeyuki; Kusakabe, Nobuhiko

    2015-01-01

    The search for habitable exoplanets in the Universe is actively ongoing in the field of astronomy. The biggest future milestone is to determine whether life exists on such habitable exoplanets. In that context, oxygen in the atmosphere has been considered strong evidence for the presence of photosynthetic organisms. In this paper, we show that a previously unconsidered photochemical mechanism by titanium (IV) oxide (titania) can produce abiotic oxygen from liquid water under near ultraviolet (NUV) lights on the surface of exoplanets. Titania works as a photocatalyst to dissociate liquid water in this process. This mechanism offers a different source of a possibility of abiotic oxygen in atmospheres of exoplanets from previously considered photodissociation of water vapor in upper atmospheres by extreme ultraviolet (XUV) light. Our order-of-magnitude estimation shows that possible amounts of oxygen produced by this abiotic mechanism can be comparable with or even more than that in the atmosphere of the current Earth, depending on the amount of active surface area for this mechanism. We conclude that titania may act as a potential source of false signs of life on habitable exoplanets. PMID:26354078

  17. Abiotic carbonate dissolution traps carbon in a semiarid desert

    PubMed Central

    Fa, Keyu; Liu, Zhen; Zhang, Yuqing; Qin, Shugao; Wu, Bin; Liu, Jiabin

    2016-01-01

    It is generally considered that desert ecosystems release CO2 to the atmosphere, but recent studies in drylands have shown that the soil can absorb CO2 abiotically. However, the mechanisms and exact location of abiotic carbon absorption remain unclear. Here, we used soil sterilization, 13CO2 addition, and detection methods to trace 13C in the soil of the Mu Us Desert, northern China. After 13CO2 addition, a large amount of 13CO2 was absorbed by the sterilised soil, and 13C was found enriched both in the soil gaseous phase and dissolved inorganic carbon (DIC). Further analysis indicated that about 79.45% of the total 13C absorbed by the soil was trapped in DIC, while the amount of 13C in the soil gaseous phase accounted for only 0.22% of the total absorbed 13C. However, about 20.33% of the total absorbed 13C remained undetected. Our results suggest that carbonate dissolution might occur predominately, and the soil liquid phase might trap the majority of abiotically absorbed carbon. It is possible that the trapped carbon in the soil liquid phase leaches into the groundwater; however, further studies are required to support this hypothesis. PMID:27020762

  18. Abiotic Reductive Immobilization of U(VI) by Biogenic Mackinawite

    SciTech Connect

    Veeramani, Harish; Scheinost, Andreas; Monsegue, Niven; Qafoku, Nikolla; Kukkadapu, Ravi K.; Newville, Mathew; Lanzirotti, Anthony; Pruden, Amy; Murayama, Mitsuhiro; Hochella, Michael F.

    2013-03-01

    During subsurface bioremediation of uranium-contaminated sites, indigenous metal and sulfate-reducing bacteria may utilize a variety of electron acceptors, including ferric iron and sulfate that could lead to the formation of various biogenic minerals in-situ. Sulfides, as well as structural and adsorbed Fe(II) associated with biogenic Fe(II)-sulfide phases, can potentially catalyze abiotic U6+ reduction via direct electron transfer processes. In the present work, the propensity of biogenic mackinawite (Fe1+xS, x = 0 to 0.11) to reduce U6+ abiotically was investigated. The biogenic mackinawite produced by Shewanella putrefaciens strain CN32 was characterized by employing a suite of analytical techniques including TEM, SEM, XAS and Mössbauer analyses. Nanoscale and bulk analyses (microscopic and spectroscopic techniques, respectively) of biogenic mackinawite after exposure to U6+ indicate the formation of nanoparticulate UO2. This study suggests the relevance of Fe(II) and sulfide bearing biogenic minerals in mediating abiotic U6+ reduction, an alternative pathway in addition to direct enzymatic U6+ reduction.

  19. Abscisic Acid and Abiotic Stress Tolerance in Crop Plants

    PubMed Central

    Sah, Saroj K.; Reddy, Kambham R.; Li, Jiaxu

    2016-01-01

    Abiotic stress is a primary threat to fulfill the demand of agricultural production to feed the world in coming decades. Plants reduce growth and development process during stress conditions, which ultimately affect the yield. In stress conditions, plants develop various stress mechanism to face the magnitude of stress challenges, although that is not enough to protect them. Therefore, many strategies have been used to produce abiotic stress tolerance crop plants, among them, abscisic acid (ABA) phytohormone engineering could be one of the methods of choice. ABA is an isoprenoid phytohormone, which regulates various physiological processes ranging from stomatal opening to protein storage and provides adaptation to many stresses like drought, salt, and cold stresses. ABA is also called an important messenger that acts as the signaling mediator for regulating the adaptive response of plants to different environmental stress conditions. In this review, we will discuss the role of ABA in response to abiotic stress at the molecular level and ABA signaling. The review also deals with the effect of ABA in respect to gene expression. PMID:27200044

  20. Titania may produce abiotic oxygen atmospheres on habitable exoplanets

    NASA Astrophysics Data System (ADS)

    Narita, Norio; Enomoto, Takafumi; Masaoka, Shigeyuki; Kusakabe, Nobuhiko

    2015-12-01

    The search for habitable exoplanets in the Universe is actively ongoing in the field of astronomy. The biggest future milestone is to determine whether life exists on such habitable exoplanets. In that context, oxygen in the atmosphere has been considered strong evidence for the presence of photosynthetic organisms. In this paper, we show that a previously unconsidered photochemical mechanism by titanium (IV) oxide (titania) can produce abiotic oxygen from liquid water under near ultraviolet (NUV) lights on the surface of exoplanets. Titania works as a photocatalyst to dissociate liquid water in this process. This mechanism offers a different source of a possibility of abiotic oxygen in atmospheres of exoplanets from previously considered photodissociation of water vapor in upper atmospheres by extreme ultraviolet (XUV) light. Our order-of-magnitude estimation shows that possible amounts of oxygen produced by this abiotic mechanism can be comparable with or even more than that in the atmosphere of the current Earth, depending on the amount of active surface area for this mechanism. We conclude that titania may act as a potential source of false signs of life on habitable exoplanets.Reference:Narita N. et al.,Scientific Reports 5, Article number: 13977 (2015)http://www.nature.com/articles/srep13977

  1. Cell Wall Metabolism in Response to Abiotic Stress

    PubMed Central

    Gall, Hyacinthe Le; Philippe, Florian; Domon, Jean-Marc; Gillet, Françoise; Pelloux, Jérôme; Rayon, Catherine

    2015-01-01

    This review focuses on the responses of the plant cell wall to several abiotic stresses including drought, flooding, heat, cold, salt, heavy metals, light, and air pollutants. The effects of stress on cell wall metabolism are discussed at the physiological (morphogenic), transcriptomic, proteomic and biochemical levels. The analysis of a large set of data shows that the plant response is highly complex. The overall effects of most abiotic stress are often dependent on the plant species, the genotype, the age of the plant, the timing of the stress application, and the intensity of this stress. This shows the difficulty of identifying a common pattern of stress response in cell wall architecture that could enable adaptation and/or resistance to abiotic stress. However, in most cases, two main mechanisms can be highlighted: (i) an increased level in xyloglucan endotransglucosylase/hydrolase (XTH) and expansin proteins, associated with an increase in the degree of rhamnogalacturonan I branching that maintains cell wall plasticity and (ii) an increased cell wall thickening by reinforcement of the secondary wall with hemicellulose and lignin deposition. Taken together, these results show the need to undertake large-scale analyses, using multidisciplinary approaches, to unravel the consequences of stress on the cell wall. This will help identify the key components that could be targeted to improve biomass production under stress conditions. PMID:27135320

  2. Cell Wall Metabolism in Response to Abiotic Stress.

    PubMed

    Le Gall, Hyacinthe; Philippe, Florian; Domon, Jean-Marc; Gillet, Françoise; Pelloux, Jérôme; Rayon, Catherine

    2015-01-01

    This review focuses on the responses of the plant cell wall to several abiotic stresses including drought, flooding, heat, cold, salt, heavy metals, light, and air pollutants. The effects of stress on cell wall metabolism are discussed at the physiological (morphogenic), transcriptomic, proteomic and biochemical levels. The analysis of a large set of data shows that the plant response is highly complex. The overall effects of most abiotic stress are often dependent on the plant species, the genotype, the age of the plant, the timing of the stress application, and the intensity of this stress. This shows the difficulty of identifying a common pattern of stress response in cell wall architecture that could enable adaptation and/or resistance to abiotic stress. However, in most cases, two main mechanisms can be highlighted: (i) an increased level in xyloglucan endotransglucosylase/hydrolase (XTH) and expansin proteins, associated with an increase in the degree of rhamnogalacturonan I branching that maintains cell wall plasticity and (ii) an increased cell wall thickening by reinforcement of the secondary wall with hemicellulose and lignin deposition. Taken together, these results show the need to undertake large-scale analyses, using multidisciplinary approaches, to unravel the consequences of stress on the cell wall. This will help identify the key components that could be targeted to improve biomass production under stress conditions. PMID:27135320

  3. Origin and paleoenvironmental significance of calcite pseudomorphs after ikaite in the Oligocene Creede Formation, Colorado

    SciTech Connect

    Larsen, D. . Dept. of Earth and Planetary Sciences)

    1994-07-01

    Pseudomorphs of calcite are present in lacustrine strata and travertine of the Oligocene Creede Formation, the sedimentary moat fill of the Creede caldera in the Tertiary San Juan volcanic field. The pseudomorphs, previously thought to have formed after gaylussite (Ca-CO[sub 3]Na[sub 2]CO[sub 3] [center dot] 5H[sub 2]O), are interpreted to have formed after ikaite (CaCO[sub 3] [center dot] 6H[sub 2]O) on the basis of their modes of occurrence, pseudomorph morphology, and textural and chemical aspects of the calcite replacement. The extent of their exposure and degree of preservation in the Creede Formation allow elucidation of the depositional conditions in which the ikaite formed and was subsequently pseudomorphically replaced. The revised paleoenvironmental interpretation of the Creede Formation also has implications for understanding of the late Oligocene climate of the southwestern US. Formation of ikaite requires water temperatures of 0--3 C, supersaturation with respect to calcite, and the presence of a chemical inhibitor, such as dissolved phosphate, to prevent growth of calcite or aragonite (Shearman and Smith 1985). Geochemical calculations and hydrogeologic considerations suggest that waters with dissolved phosphate contents sufficient to inhibit calcite growth and stabilize ikaite could have developed in the Creede moat lake, although a chemical remnant of high phosphate content is not observed in the strata. The granular texture of the Creede pseudomorphs is common to calcite pseudomorphs after ikaite from many localities. A model is proposed in which slow pseudomorphic replacement (over a period of a day or more) results in sand-size calcite grains formed directly from the ikaite. This model has important implications for the interpretation of isotopic and chemical data obtained from pseudomorphs (and thinolitic tufa).

  4. An Investigation Into the use of Calcite Fossils as Alpha Thermochronometers

    NASA Astrophysics Data System (ADS)

    Cox, K. L.; Copeland, P.; Lapen, T. J.; Ausich, W. I.

    2006-12-01

    Diffusion studies of He in calcite suggest a potential to use carbonates as an alpha thermochronometer (Tc ~ 65°C). These results are all from coarse-grained calcite and dolomite but carbonate mud is a common constituent in many limestones. However, coarse calcite can usually be found in even the most micritic limestones in the form of biotic allochems. We have investigated the suitability of using crinoid columnals and shells of the bivalve Inoceramus for alpha thermochronolgy in limestones. After the death of a crinoid, the high-Mg calcite converts to low-Mg calcite with no loss of optical continuity, and the porosity is filled with syntaxial cement thus becoming permineralized. Bivalves undergo typical diagenesis where the high- Mg calcite converts to low-Mg calcite. Two of four crinoid samples yield reasonable alpha ages: A crinoid from the Thrifty Fm. (Pennsylvanian) in Texas gives an age of 120 Ma (0.7-4.0 ppm U) and one from the Edwardsville Fm. of the Borden Group (Lower Mississippian) in Indiana gives an age of 64 Ma (0.9 ppm U). Each of these results are consistent with the tectonic history of the regions. Crinoid pieces from the New Providence Shale Mbr. of the Borden Fm. (Lower Mississippian) in Kentucky have very low [U] (less than 90 ppb) and give Archean ages. Crinoids from the Hughes Creek Shale (Permian) in Kansas have seemingly robust amounts of U (0.7-2.1 ppm) but this sample also seems to be dominated by common He, yielding Proterozoic ages. Inoceramus from the Burditt Fm. of the Austin Gr. (Upper Cretaceous) in Texas gives an age of 0.5 Ma, suggesting that the closure temperature may be much lower than 65°C. Our preliminary conclusion is that crinoid columnals with more than 500 ppb U may be generally suitable for alpha thermochronology but that the closure temperature of He in Inoceramus shells may be too low for geologic application.

  5. Thermal and Evolved Gas Behavior of Calcite Under Mars Phoenix TEGA Operating Conditions

    NASA Technical Reports Server (NTRS)

    Ming, D.W.; Niles, P.B.; Morris, R.V.; Boynton, W.V.; Golden, D.C.; Lauer, H.V.; Sutter, B.

    2009-01-01

    The Mars Phoenix Scout Mission with its diverse instrument suite successfully examined several soils on the Northern plains of Mars. The Thermal and Evolved Gas Analyzer (TEGA) was employed to detect organic and inorganic materials by coupling a differential scanning calorimeter (DSC) with a magnetic-sector mass spectrometer (MS). Martian soil was heated up to 1000 C in the DSC ovens and evolved gases from mineral decomposition products were examined with the MS. TEGA s DSC has the capability to detect endothermic and exothermic reactions during heating that are characteristic of minerals present in the Martian soil. Initial TEGA results indicated the presence of endothermic peaks with onset temperatures that ranged from 675 C to 750 C with corresponding CO2 release. This result suggests the presence of calcite (CaCO3. CaO + CO2). Organic combustion to CO2 is not likely since this mostly occurs at temperatures below 550 C. Fe-carbonate and Mg-carbonate are not likely because their decomposition temperatures are less than 600 C. TEGA enthalpy determinations suggest that calcite, may occur in the Martian soil in concentrations of approx.1 to 5 wt. %. The detection of calcite could be questioned based on previous results that suggest Mars soils are mostly acidic. However, the Phoenix landing site soil pH was measured at pH 8.3 0.5, which is typical of terrestrial soils where pH is controlled by calcite solubility. The range of onset temperatures and calcite concentration as calculated by TEGA is poorly con-strained in part because of limited thermal data of cal-cite at reduced pressures. TEGA operates at <30 mbar while most calcite literature thermal data was obtained at 1000 mbar or higher pressures.

  6. Effect of Mg on the Grain Growth and Dislocation Creep of Calcite

    NASA Astrophysics Data System (ADS)

    Xu, L.

    2004-12-01

    We tested the effect of variations in the amount of the solute impurity (Mg) on grain growth and strength of calcite aggregate. Synthetic marbles were produced by hot isostatic pressing mixtures of powders of calcite and dolomite at 850° C and 300 MPa confining pressure for different intervals (2 to 30 hrs). The HIP treatment resulted in homogeneous aggregates of calcite with Mg content from 0.5 to 17 mol%. Stress stepping tests and constant strain rate tests were used to examine the effect of Mg content on the dislocation creep of calcite. The grain growth rate under static conditions was decreased with Mg content from 7 to 17 mol%, indicating perhaps that grain boundary mobility is suppressed by the solute drag effect. In the diffusion creep at stresses below 40 Mpa, the strength of calcite decreases with increasing Mg content owing to the difference in grain size at 800° C and 300 MPa confining pressure. The contribution of dislocation creep increases with increasing stress, and the transition between diffusion and dislocation creep occurs at higher stresses for the samples with higher magnesium content and smaller grain size. The creep data were fit assuming a composite flow law consisting of a linear combination of diffusion and dislocation creep and a single-valued grain size. The best agreement was obtained by using a dislocation creep law with exponential dependence of strain rate on stress (e.g. Peierls law). More evidence from microstructure is needed to identify the dominant deformation mechanism conclusively. Most of the samples were compressed up to strains of 0.25; small recrystallized grains are formed resulting in a bimodal grain size distribution in some of the deformed samples. Preliminary data shows that the recrystallized grain sizes are smaller for Mg-calcite compared with that of pure calcite. This study will help to understand the effect of impurities on grain-growth kinetics and strain weakening in localized shear zones.

  7. Experimental Study of Sr Partitioning into Calcite at Various Linear Growth Rates and Temperatures: Preliminary Results.

    NASA Astrophysics Data System (ADS)

    Gabitov, R. I.; Watson, B. E.

    2004-05-01

    The surface of a crystal in equilibrium with surrounding fluid can have a composition that differs from the bulk crystal. If growth rate of the crystal exceeds a minimum value at which partitioning-equilibrium can be maintained, then the crystal surface composition may be "captured" by the newly-formed lattice. The degree of this entrapment increases with increasing crystal growth rate. Non-equlibrium partitioning of Sr into calcite probably occurs by this entrapment mechanism. Sr and calcite are geochemically significant in understanding the thermal history of the ocean because the substitution of Sr for Ca in calcite is temperature dependent. To improve our understanding of the partitioning of Sr into calcite, we conducted two different types of experiment: 1) calcite growth from Sr-bearing solution with analysis of the crystal cross-section by electron microprobe (bulk crystal-liquid runs); and 2) treatment of calcite cleavage surfaces with Sr-bearing solutions and examination of the top few nm surface layer by X-ray photoelectron spectroscopy (surface-liquid runs). In the series of bulk-liquid experiments crystals were grown by three different procedures: 1) precipitation on glass slide (pre-coated with calcite), where a steady flow of CaCl2 - SrCl2 and Na2CO3 solutions were mixed just before passage through a tube and allowed to drip onto a slide ("cave"-type experiments, ionic strength I=0.01); 2) growth from a CaCl2 - NH4Cl - SrCl2 solution by diffusion of CO2 from an ammonium carbonate source ("drift" experiments, I=0.52); 3) coarsening of small calcite crystals in the CaCO3-SrCO3-NaCl-H2O system at 800-950° C and 0.5-1 kb in a cold seal apparatus. The growth rate of individual crystals was determined by periodic monitoring of crystal size with time or roughly by comparison of final size with duration of the experiment. Surface-liquid experiments were performed by treatment of cleavage surfaces of natural calcite fragments in a Sr(ClO4)2 solution for 1

  8. Isotopic tracer evidence for the amorphous calcium carbonate to calcite transformation by dissolution-reprecipitation

    NASA Astrophysics Data System (ADS)

    Giuffre, Anthony J.; Gagnon, Alexander C.; De Yoreo, James J.; Dove, Patricia M.

    2015-09-01

    Observations that some biogenic and sedimentary calcites grow from amorphous calcium carbonate (ACC) raise the question of how this mineralization process influences composition. However, the detailed pathway and geochemical consequences of the ACC to calcite transformation are not well constrained. This experimental study investigated the formation of calcite from ACC by using magnesium and calcium stable isotope labeling to directly probe the transformation pathway and controls on composition. Four processes were considered: dissolution-reprecipitation, solid state transformation, and combinations of these end-members. To distinguish between these scenarios, ACC was synthesized from natural isotope abundance solutions and subsequently transferred to spiked solutions that were enriched in 43Ca and 25Mg for the transformation to calcite. Isotope measurements by NanoSIMS determined the 43Ca/40Ca, and 25Mg/24Mg ratios of the resulting calcite crystals. Analysis of the data shows the transformation is best explained by a dissolution-reprecipitation process. We find that when a small amount of ACC is transferred, the isotopic signals in the resulting calcite are largely replaced by the composition of the surrounding spiked solution. When larger amounts of ACC are transferred, calcite compositions reflect a mixture between the ACC and initial solution end-member. Comparisons of the measurements to the predictions of a simple mixing model indicate that calcite compositions (1) are sensitive to relative amounts of ACC and the surrounding solution reservoir and (2) are primarily governed by the conditions at the time of ACC transformation rather than the initial ACC formation. Shifts in calcite composition over the duration of the transformation period reflect the progressive evolution of the local solution conditions. This dependence indicates the extent to which there is water available would change the end point composition on the mixing line. While these findings have

  9. Sorption and catalytic oxidation of Fe(II) at the surface of calcite

    NASA Astrophysics Data System (ADS)

    Mettler, Suzanne; Wolthers, Mariëtte; Charlet, Laurent; Gunten, Urs von

    2009-04-01

    The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds-minutes) was followed by (b) a slower incorporation (hours-weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA57 (1993), 3505; Pokrovsky et al., Langmuir16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO 3Fe + and >CO 3FeCO 3H 0. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system ( t1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite ( t1/2 = 41 ± 1 min and t1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO 3FeCO 3H 0, for which the species specific rate constant was estimated.

  10. The Influence of Kinetic Growth Factors on the Clumped Isotope Composition of Calcite

    NASA Astrophysics Data System (ADS)

    Hunt, J. D.; Watkins, J. M.; Tripati, A.; Ryerson, F. J.; DePaolo, D. J.

    2014-12-01

    Clumped isotope paleothermometry is based on the association of 13C and 18O within carbonate minerals. Although the influence of temperature on equilibrium 13C-18O bond ordering has been studied, recent oxygen isotope studies of inorganic calcite demonstrate that calcite grown in laboratory experiments and in many natural settings does not form in equilibrium with water. It is therefore likely that the carbon and clumped isotope composition of these calcite crystals are not representative of true thermodynamic equilibrium. To isolate kinetic clumped isotope effects that arise at the mineral-solution interface, clumped isotopic equilibrium of DIC species must be maintained. This can be accomplished by dissolving the enzyme carbonic anhydrase (CA) into the solution, thereby reducing the time required for isotopic equilibration of DIC species by approximately two orders of magnitude between pH 7.7 and 9.3. We conduct calcite growth experiments aimed specifically at measuring the pH-dependence of kinetic clumped isotope effects during non-equilibrium precipitation of calcite. We precipitated calcite from aqueous solution at a constant pH and controlled supersaturation over the pH range 7.7-9.3 in the presence of CA. For each experiment, a gas mixture of N2 and CO2 is bubbled through a beaker of solution without seed crystals. As CO2 from the gas dissolves into solution, calcite crystals grow on the beaker walls. The pH of the solution is maintained by use of an autotitrator with NaOH as the titrant. We control the temperature, pH, the pCO2 of the gas inflow, and the gas inflow rate, and monitor the total alkalinity, the pCO2 of the gas outflow, and the amount of NaOH added. A constant crystal growth rate of ~1.6 mmol/m2/hr is maintained over all experiments. Results from these experiments are compared to predictions from a recently-developed isotopic ion-by-ion growth model of calcite. The model describes the rate, temperature and pH dependence of oxygen isotope uptake

  11. Marine Ecomechanics

    NASA Astrophysics Data System (ADS)

    Denny, Mark W.; Gaylord, Brian

    2010-01-01

    The emerging field of marine ecomechanics provides an explicit physical framework for exploring interactions among marine organisms and between these organisms and their environments. It exhibits particular utility through its construction of predictive, mechanistic models, a number of which address responses to changing climatic conditions. Examples include predictions of (a) the change in relative abundance of corals as a function of colony morphology, ocean acidity, and storm intensity; (b) the rate of disturbance and patch formation in beds of mussels, a competitive dominant on many intertidal shores; (c) the dispersal and recruitment patterns of giant kelps, an important nearshore foundation species; (d) the effects of turbulence on external fertilization, a widespread method of reproduction in the sea; and (e) the long-term incidence of extreme ecological events. These diverse examples emphasize the breadth of marine ecomechanics. Indeed, its principles can be applied to any ecological system.

  12. Abiotic Versus Biotic Weathering Of Olivine As Possible Biosignatures

    NASA Technical Reports Server (NTRS)

    Longazo, Teresa G.; Wentworth, Susan J.; Clemett, Simon J.; Southam, Gordon; McKay, David S.

    2001-01-01

    We are investigating the weathering of silicate minerals by both purely inorganic, and biologically mediated processes using field-emission scanning electron microscopy (FESEM) and energy dispersive x-ray spectroscopy (EDS). By resolving surface textures and chemical compositions of weathered surfaces at the sub-micron scale we hope to be able to distinguish abiotic from biotic weathering processes and so establish a new biosignature applicable to the study of astromaterials including but not limited to the Martian meteorites. Sterilized olivine grains (San Carlos, Arizona) no more than 1-2 mm in their longest dimension were optically assayed to be uniform in color and free of inclusions were selected as weathering subjects. Prior to all experiments surface morphologies and Fe/Mg ratios were determined for each grain using FE-SEM and EDS. Experiments were divided into two categories abiotic and biotic and were compared with "naturally" weathered samples. For the preliminary experiments, two trials (open and closed to the ambient laboratory environment) were performed under abiotic conditions, and three trials under biotic conditions (control, day 1 and day 2). The open system abiotic trials used sterile grains heated at 98 C and 200 C for both 24 and 48 hours in 1L double distilled de-ionized water. The closed system abiotic trials were conducted under the same conditions but in a sealed two layer steel/Teflon "bomb" apparatus. The biotic trials used sterile grains mounted in a flow-through device attached to a wellhead on the Columbia River aquifer. Several discolored, altered, grains were selected to document "natural" weathering surface textures for comparison with the experimental samples. Preliminary results indicate there are qualitative differences in weathered surface textures among all the designed experiments. The olivine grains in abiotic trials displayed etching, pitting, denticulate margins, dissolution and clay formation. The scale of the features

  13. Bioleaching of cobalt and zinc from pyrite ore in relation to calcitic gangue content.

    PubMed

    Baldi, F; Bralia, A; Riccobono, F; Sabatini, G

    1991-05-01

    Bioleaching of a pyrite ore containing high concentrations of cobalt (0.1%) and zinc (0.065%) was affected by small amounts of calcitic gangue (from 0.01 to 1.01%). Results from an air-lift percolator and from Erlenmeyer flask experiments show that a small percentage of calcite raises the pH and arrests the growth of the acidophilic bacterium Thiobacillus ferrooxidans. In percolator experiments, when calcite is completely removed by the continuous addition of small quantities of acid, and the pH of the liquor becomes acid, the micro-organism begins to grow and to bio-oxidize the pyrite ore. The growth of T. ferrooxidans shows different lag phase spans (from 13 to 190 days) depending on carbonate dissolution. The metals Fe, Zn and Co are released into the leaching solution together at different rates after a lag-time which depends on calcite concentrations in pyrite gangue. Metal ratios in the mineral bulk are different from those in the liquor, Zn dissolving 5 times more readily than Co. Bioleaching rates for metal removal from pyrite are higher in percolator (for Fe, from 5 to 15 mg/l/h) than in flask experiments (from 0.5 to 2 mg/l/h), but the lag phases are shorter (from 2 to 65 days). The differences between the two systems are related to calcite dissolution and gypsum precipitation. PMID:24425016

  14. Mechanism of Calcite Co-Orientation in the Sea Urchin Tooth

    SciTech Connect

    Killian, Christopher; Metzler, Rebecca; Gong, Y. U. T.; Olson, Ian; Aizenberg, Joanna; Politi, Yael; Wilt, Fred; Scholl, Andreas; Young, Anthony; Doran, Andrew; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan; Gilbert, P. U. P. A.

    2009-12-01

    Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO{sub 3}) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin (Strongylocentrotus purpuratus), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction ({mu}XRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO{sub 3} is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.

  15. Vorticity analysis in calcite tectonites: An example from the Attico-Cycladic massif (Attica, Greece)

    NASA Astrophysics Data System (ADS)

    Spanos, D.; Xypolias, P.; Koukouvelas, I.

    2015-11-01

    Although calcite tectonites are widespread in nature their use to quantify flow vorticity is limited. We use new (micro-)structural, petrofabric and vorticity data to analyse the kinematics of flow in outcrop-scale calcite mylonite zones. These zones are genetically related to a crustal-scale NE-directed ductile thrust (Basal Thrust) that emplaced the Blueschist over the Basal unit during the exhumation of the Attico-Cycladic Massif. Calcite microstructures reveal that the last stage of deformation occurred at temperatures 200-300 °C achieved by mild heating, which is possibly related with the reburial of the Basal Thrust's footwall. Vorticity analyses were based on the degree of asymmetry of calcite c-axis fabrics as well as on the assumption that the orientation of the long axes of calcite neoblasts within an oblique foliation delineates the direction of instantaneous stretching axis. Both methodological approaches provide consistent estimates with a simple shear component between 55% and 82% (Wn = 0.76-0.96). The use of the stress axis (σ1) orientation recorded by twin-c-axis-pairs to quantify vorticity generally gives significantly lower simple shear component. Comparison of our vorticity estimates with previous estimates inferred from quartz fabrics and rigid porphyroclasts reveals that exhumation-related deformation in the nappe pile was steady state.

  16. Towards a Mechanism-Based Understanding of Vital Effects: Biomolecules Influence Mg/Ca in Calcite

    NASA Astrophysics Data System (ADS)

    Stephenson, A. E.; Nelson, E. J.; Wu, K. J.; de Yoreo, J. J.; Dove, P. M.

    2006-12-01

    Recent findings from our group suggest that the chemistry of biomolecules present at sites of mineral formation have a strong influence on the structure of water near calcite surfaces (Elhadj et al., CGD, 2006) and exercise predictable controls on the rate of calcite growth (Elhadj et al., submitted). Observing the extent to which biomolecules can mediate growth processes leads us to hypothesize that they also have measurable influence over impurity (Mg, Sr) contents. If true, this could be a significant contributor to the widely documented 'vital effects' that complicate interpretations of paleoenvironments, largely based on chemical signatures found in the skeletal remains of organisms. We use in situ AFM to measure the growth rate of calcite at the nanoscale under controlled solution compositions and at characterized chemical driving force. The relationship between the presence of carboxyl- rich peptides in solution during growth and the magnesium content in the resulting calcite was quantified using time-of-flight SIMS. This new work with tof-SIMS has validated previous compositional maps of Mg distributions collected by electron microprobe, and has yielded new insights into controls on impurity content. We are using similar methods to also determine factors that influence impurity contents of calcites grown in solutions at seawater ionic strength.

  17. Carbon isotope fractionation between calcite, graphite and CO2: an experimental study

    NASA Astrophysics Data System (ADS)

    Scheele, Norbert; Hoefs, Jochen

    1992-10-01

    The partitioning of stable carbon isotopes between calcite, graphite and CO2 was experimentally determined at temperatures from 500 to 1200 °C and 1 to 15 kbar pressure. Attainment of carbon isotope equilibrium in CO2-calcite runs was proven by achieving the same fractionation from isotopically opposite directions. The resultant CO2-calcite fractionation curve for carbon differs from Bottinga's calculation by 1.2‰ and confirms recent experiments of Chacko et al. and Mattey et al. In CO2-graphite experiments equilibrium fractions were extrapolated by applying the partial-exchange technique of Northrop and Clayton and by optimizing the contribution of surface reaction in graphite. CO2-graphite fractionations at temperatures up to 800 °C are in fair agreement with Bottinga's calculation, but yield a surprisingly high fractionation of ≈5‰ at upper mantle temperatures. The combination of CO2-calcite (carbon) and CO2-graphite fractionation results in a new experimentally determined calcite-grapite fractionation curve, expressed by the equation: 410_2004_Article_BF00310954_TeX2GIFE1.gif begin{gathered} 10^3 {text{ ln }}α _{{text{cc - gr}}} = 7.99 × 10^6 /T^2 - 9.58 × 10^3 / + 5.76 \\ {text{ (873 - 1473 Kelvin)}} \\ Applying the experimentally determined fractionation curve on graphite-bearing metacarbonates yields metamorphic temperatures distinctly higher than those obtained by Valley and O'Neil.

  18. Self-Assembly of Protein Nanofibrils Orchestrates Calcite Step Movement through Selective Nonchiral Interactions.

    PubMed

    So, Christopher R; Liu, Jinny; Fears, Kenan P; Leary, Dagmar H; Golden, Joel P; Wahl, Kathryn J

    2015-06-23

    The recognition of atomically distinct surface features by adsorbed biomolecules is central to the formation of surface-templated peptide or protein nanostructures. On mineral surfaces such as calcite, biomolecular recognition of, and self-assembly on, distinct atomic kinks and steps could additionally orchestrate changes to the overall shape and symmetry of a bulk crystal. In this work, we show through in situ atomic force microscopy (AFM) experiments that an acidic 20 kDa cement protein from the barnacle Megabalanus rosa (MRCP20) binds specifically to step edge atoms on {101̅4} calcite surfaces, remains bound and further assembles over time to form one-dimensional nanofibrils. Protein nanofibrils are continuous and organized at the nanoscale, exhibiting striations with a period of ca. 45 nm. These fibrils, templated by surface steps of a preferred geometry, in turn selectively dissolve underlying calcite features displaying the same atomic arrangement. To demonstrate this, we expose the protein solution to bare and fibril-associated rhombohedral etch pits to reveal that nanofibrils accelerate only the movement of fibril-forming steps when compared to undecorated steps exposed to the same solution conditions. Calcite mineralized in the presence of MRCP20 results in asymmetric crystals defined by frustrated faces with shared mirror symmetry, suggesting a similar step-selective behavior by MRCP20 in crystal growth. As shown here, selective surface interactions with step edge atoms lead to a cooperative regime of calcite modification, where templated long-range protein nanostructures shape crystals. PMID:25970003

  19. Strontium isotope geochemistry of calcite fracture fillings in deep core, Yucca Mountain, Nevada; A progress report

    SciTech Connect

    Peterman, Z.E.; Stuckless, J.S.; Marshall, B.D.; Mahan, S.A.; Futa, K.

    1992-11-01

    This paper reports on the variation of {sup 87}SR/{sup 86}Sr in calcite fracture fillings as a function of depth which has been determined using samples from five boreholes at Yucca Mountain. The data group into three discrete populations. Within 400 m of the present-day land surface, the distribution of {sup 87}Sr/{sup 86}Sr for calcite fracture fillings is similar to that of calcretes and near-surface veins suggesting an origin by infiltrating meteoric water. Veins within a 100-m zone immediately about the modern water table have {sup 87}Sr/{sup 86}Sr values similar to those of ground water from the Cenozoic volcanic aquifer suggesting a past connection between the two through aqueous diffusion or a higher water level. {sup 87}Sr/{sup 86}Sr values for calcite fracture fillings below the water table are low (mean = 0.70909 {plus_minus} 0.00038) and similar to those of the host rocks. The surficial calcites and those in the vadose zone are clearly unrelated to the deep calcite fracture fillings.

  20. Influence of calcite on uranium(VI) reactive transport in the groundwate-river mixing zone

    NASA Astrophysics Data System (ADS)

    Ma, Rui; Liu, Chongxuan; Greskowiak, Janek; Prommer, Henning; Zachara, John; Zheng, Chunmiao

    2014-01-01

    Calcite is an important, relatively soluble mineral phase that can affect uranium reactive transport in subsurface sediments. This study was conducted to investigate the distribution of calcite and its influence on uranium adsorption and reactive transport in the groundwate-river mixing zone of the Hanford 300A site, Washington State. Simulations using a two-dimensional (2D) reactive transport model under field-relevant hydrological and hydrogeochemical conditions revealed the development of a calcite reaction front through the mixing zone as a result of dynamic groundwate-river interactions. The calcite concentration distribution, in turn, affected the concentrations of aqueous carbonate and calcium, and pH through dissolution, as river waters intruded and receded from the site at different velocities in response to stage changes. The composition variations in groundwater subsequently influenced uranium mobility and discharge rates into the river in a complex fashion. The results implied that calcite distribution and concentration are important variables that need to be quantified for accurate reactive transport predictions of uranium, especially in dynamic groundwate-river mixing zones.

  1. Influence of calcite on uranium(VI) reactive transport in the groundwater-river mixing zone.

    PubMed

    Ma, Rui; Liu, Chongxuan; Greskowiak, Janek; Prommer, Henning; Zachara, John; Zheng, Chunmiao

    2014-01-01

    Calcite is an important, relatively soluble mineral phase that can affect uranium reactive transport in subsurface sediments. This study was conducted to investigate the distribution of calcite and its influence on uranium adsorption and reactive transport in the groundwater-river mixing zone of the Hanford 300A site, Washington State. Simulations using a two-dimensional (2D) reactive transport model under field-relevant hydrological and hydrogeochemical conditions revealed the development of a calcite reaction front through the mixing zone as a result of dynamic groundwater-river interactions. The calcite concentration distribution, in turn, affected the concentrations of aqueous carbonate and calcium, and pH through dissolution, as river waters intruded and receded from the site at different velocities in response to stage changes. The composition variations in groundwater subsequently influenced uranium mobility and discharge rates into the river in a complex fashion. The results implied that calcite distribution and concentration are important variables that need to be quantified for accurate reactive transport predictions of uranium, especially in dynamic groundwater-river mixing zones. PMID:24240103

  2. Growth and Dissolution of Calcite in the Presence of Adsorbed Stearic Acid.

    PubMed

    Ricci, Maria; Segura, Juan José; Erickson, Blake W; Fantner, Georg; Stellacci, Francesco; Voïtchovsky, Kislon

    2015-07-14

    The interaction of organic molecules with the surface of calcite plays a central role in many geochemical, petrochemical, and industrial processes and in biomineralization. Adsorbed organics, typically fatty acids, can interfere with the evolution of calcite when immersed in aqueous solutions. Here we use atomic force microscopy in liquid to explore in real-time the evolution of the (1014) surface of calcite covered with various densities of stearic acid and exposed to different saline solutions. Our results show that the stearic acid molecules tend to act as "pinning points" on the calcite's surface and slow down the crystal's restructuring kinetics. Depending on the amount of material adsorbed, the organic molecules can form monolayers or bilayer islands that become embedded into the growing crystal. The growth process can also displaces the organic molecules and actively concentrate them into stacked multilayers. Our results provide molecular-level insights into the interplay between the adsorbed fatty acid molecules and the evolving calcite crystal, highlighting mechanisms that could have important implications for several biochemical and geochemical processes and for the oil industry. PMID:26087312

  3. Dolomite-magnesian calcite relations at elevated temperatures and CO2 pressures

    USGS Publications Warehouse

    Graf, D.L.; Goldsmith, J.R.

    1955-01-01

    The equilibrium thermal decomposition curve of dolomite has been determined up to a CO2 pressure of 20,000 lb/in.2, at which pressure dolomite decomposes at 857??C. Equilibrium was approached from both directions, by the breakdown and by the solid-state synthesis of dolomite. At elevated temperatures and pressures, calcites in equilibrium with periclase as well as those in equilibrium with dolomite contain Mg in solid solution. In the former, the Mg content increases with increasing CO2 pressure, and decreases with increasing temperature. In the latter, it is a function of temperature only. The exsolution curve of dolomite and magnesian calcite has been determined between 500?? and 800??C; at 500?? dolomite is in equilibrium with a magnesian calcite containing ~6 mol per cent MgCO2; at 800??, ~22 mol per cent. There appears to be a small but real deviation from the ideal 1 : 1 Ca : Mg ratio of dolomite, in the direction of excess Ca, for material in equilibrium with magnesian calcite at high temperature. The experimental findings indicate that very little Mg is stable in the calcites of sedimentary environments, but that an appreciable amount is stable under higher-temperature metamorphic conditions, if sufficient CO2 pressure is maintained. ?? 1955.

  4. Stabilities of synthetic magnesian calcites in aqueous solution: comparison with biogenic materials

    SciTech Connect

    Bischoff, W.D.; Mackenzie, F.T.; Bishop, F.C.

    1987-06-01

    Free-drift dissolution data and inverse time plots were used to evaluate the stabilities of synthetic and biogenic magnesian calcites in aqueous solutions at 25/sup 0/C and 1 atm total pressure. Synthetic phases with MgCO/sub 3/ concentrations below 6 mole percent have stoichiometric ion activity products that are less than the value for calcite, whereas the values for phases with higher concentrations are greater than that of calcite. For synthetic phases, stability is a smooth function of composition, and all phases have values of ion activity products less than that for aragonite. Average sea water at 25/sup 0/ and 1 atm total pressure is supersaturated with respect to all synthetic phases in the compositional range studied. The difference in stability between biogenic materials and synthetic phases is due to greater variation in chemical and physical heterogeneities found for the biogenic samples. If it is assumed that the results of the dissolution experiments reflect only differences in Gibbs free energies of formation between synthetic phases and biogenic materials of similar Mg concentration, the biogenic materials are 200-850 j/mol less stable than the synthetic phases. Only the results of synthetic dissolution experiments should be used to model the thermodynamic behavior of the magnesian calcite solid solution. The results for the synthetic phases, however, may not be appropriate to use for interpreting diagenetic reaction pathways for magnesian calcites in modern sediments, except as a basis of comparison with the behavior of natural minerals.

  5. Sea surface temperature contributes to marine crocodylomorph evolution.

    PubMed

    Martin, Jeremy E; Amiot, Romain; Lécuyer, Christophe; Benton, Michael J

    2014-01-01

    During the Mesozoic and Cenozoic, four distinct crocodylomorph lineages colonized the marine environment. They were conspicuously absent from high latitudes, which in the Mesozoic were occupied by warm-blooded ichthyosaurs and plesiosaurs. Despite a relatively well-constrained stratigraphic distribution, the varying diversities of marine crocodylomorphs are poorly understood, because their extinctions neither coincided with any major biological crises nor with the advent of potential competitors. Here we test the potential link between their evolutionary history in terms of taxic diversity and two abiotic factors, sea level variations and sea surface temperatures (SST). Excluding Metriorhynchoidea, which may have had a peculiar ecology, significant correlations obtained between generic diversity and estimated Tethyan SST suggest that water temperature was a driver of marine crocodylomorph diversity. Being most probably ectothermic reptiles, these lineages colonized the marine realm and diversified during warm periods, then declined or became extinct during cold intervals. PMID:25130564

  6. Intracrystalline alteration of low-magnesian calcite cement in the Devonian Pillara Formation, Canning Basin, Western Australia

    SciTech Connect

    Pedone, V.A. . Dept. of Geological Sciences); Dickson, J.A.D. . Dept. of Earth Sciences); Meyers, W.J. . Dept. of Earth and Space Sciences)

    1994-04-01

    Intracrystalline alteration is present in approximately 25% of the low-Mg calcite cement throughout the lowermost 160 m of the Middle to Upper Devonian Pillara Formation in the Emanuel Range, Canning Basin, Western Australia. A younger, luminescently and chemically distinct calcite phase disrupts primary zonation in older cement and results in irregular, mottled cathodoluminescence (CL). The younger calcite is always in optical continuity with host calcite. Continuous records of Mg, Fe, Mn, and Sr abundances were measured across concentrically zoned, non-CL and yellow-CL cement altered by orange-CL calcite using a new microprobe method designed for high spatial resolution and rapid collection of minor-element abundances in calcite cement. Low-Mg calcite traditionally is regarded as a stable carbonate phase with little tendency toward intracrystalline alteration of chemistry or microstructure. Significant elemental variations measured over small-scale intervals within time-equivalent zones in cement VIa indicate that some parts of the crystal have different chemical potential, which could provide the thermodynamic drive for intracrystalline alteration. Alteration could take place either by a one-step, iterative process of recrystallization or by a two-step, dissolution-cementation process. Lack of micro-collapse features in host calcite, in combination with lack of minor-element memory between host and secondary calcite, support alteration by recrystallization at a high water-rock ratio.

  7. Observation of an Organic-Inorganic Lattice Match during Biomimetic Growth of (001)-Oriented Calcite Crystals under Floating Sulfate Monolayers

    SciTech Connect

    Kewalramani, S.; Kim, K; Stripe, B; Evmenenko, G; Dommett, G; Dutta, P

    2008-01-01

    Macromolecular layers rich in amino acids and with some sulfated polysaccharides appear to control oriented calcite growth in living organisms. Calcite crystals nucleating under floating acid monolayers have been found to be unoriented on average. We have now observed directly, using in situ grazing incidence X-ray diffraction, that there is a 1:1 match between the monolayer unit cell and the unit cell of the (001) plane of calcite. Thus, sulfate head groups appear to act as templates for the growth of (001)-oriented calcite crystals, which is the orientation commonly found in biominerals.

  8. Abiotic factors influencing the spatial and temporal variability of juvenile fish in Pamlico Sound, North Carolina

    SciTech Connect

    Pietrafesa, L.J.; Janowitz, G.S.; Miller, J.M.; Noble, E.B.; Ross, S.W.; Epperly, S.P.

    1985-07-01

    A 3-D, time dependent model of the circulation in Pamlico Sound, NC, is used to relate the direction and magnitude of winds to the number of juvenile fish sampled at specified estuarine nursery locations. NC marine sport fishes are known to be spawned in NC continental waters, and then make transit to an through barrier island inlets, into Pamlico Sound. The juveniles then move 40-70 kilometers across the Sound to the nurseries. It is hypothesized that wind driven, pressure gradient induced and topographically steered currents, all abiotic factors, provide the transport mechanisms, during the recruitment period February-April, necessary for the transect. Moreover, the inherent variability in the atmospherically derived physical factors and the influence of topographic irregularities such as a large shoal which laterally bisects the Sound and bifurcates the bottom currents are seen as sources of the temporal and spatial variation observed in the distribution of juvenile fish, while the influence of biological processes is viewed as providing fine-tuned structuring.

  9. Biosequestration of copper by bacteria isolated from an abandoned mine by using microbially induced calcite precipitation.

    PubMed

    Kang, Chang-Ho; Shin, YuJin; Anbu, Periasamy; Nam, In-Hyun; So, Jae-Seong

    2016-09-12

    Abandoned mine sites are frequently polluted with high concentrations of heavy metals. In this study, 25 calcite-forming bacteria were newly isolated from the soil of an abandoned metal mine in Korea. Based on their urease activity, calcite production, and resistance to copper toxicity, four isolates were selected and further identified by 16S rRNA gene sequencing. Among the isolates, Sporosarcina soli B-22 was selected for subsequent copper biosequestration studies, using the sand impermeability test by production of calcite and extracellular polymeric substance. High removal rates (61.8%) of copper were obtained when the sand samples were analyzed using an inductively coupled plasma-optical emission spectrometer following 72 h of incubation. Scanning electron microscopy showed that the copper carbonate precipitates had a diameter of approximately 5-10 μm. X-ray diffraction further confirmed the presence of copper carbonate and calcium carbonate crystals. PMID:27488956

  10. Strontium isotope evolution of pore water and calcite in the Topopah Spring Tuff, Yucca Mountain, Nevada

    SciTech Connect

    Marshall, Brian D.; Futa, Kiyoto

    2001-04-29

    Pore water in the Topopah Spring Tuff has a narrow range of {delta}{sup 87}Sr values that can be calculated from the {delta}{sup 87}Sr values of the rock considering advection through and reaction with the overlying nonwelded tuffs of the PTn. This model can be extended to estimate the variation of {delta}{sup 87}Sr in the pore water through time; this approximates the variation of {delta}{sup 87}Sr measured in calcite fracture coatings. In samples of calcite where no silica can be dated by other methods, strontium isotope data may be the only method to determine ages. In addition, other Sr-bearing minerals in the calcite and opal coatings, such as fluorite, may be dated using the same model.

  11. A U Th calcite isochron age from an active geothermal field in New Zealand

    NASA Astrophysics Data System (ADS)

    Grimes, Stephen; Rickard, David; Hawkesworth, Chris; van Calsteren, Peter; Browne, Patrick

    1998-05-01

    We report here the first U-Th disequilibrium age for a hydrothermal mineral from an active geothermal system in New Zealand. Vein calcite recovered from a depth of 389 m in Well Thm-1 at the Tauhara geothermal field has an age of 99±44 ka BP. This age was determined using a leachate-leachate isochron technique on four silicate containing sub-samples of calcite from a single vein. Although the error on this isochron age is considerable, it is significantly younger than the earlier estimated age of ˜200 ka BP for the onset of activity at the Tauhara system and probably records the date of brecciation and veining, which may be associated with volcanic activity at the adjacent dacitic Tauhara Volcanic Complex. These results demonstrate that hydrothermal vein calcite can now be dated directly, and opens the way for more detailed studies of the evolution of the New Zealand geothermal systems.

  12. Structure of the (1014) Surfaces of Calcite, Dolomite, and Magnesite under Wet and Dry Conditions

    SciTech Connect

    WRIGHT,KATE; CYGAN,RANDALL T.; SLATER,BEN

    2000-06-12

    Atomistic computer simulation methods have been employed to model the structure of the (10{bar 1}4) surfaces of calcite, dolomite and magnesite. The authors calculations show that under vacuum conditions, calcite undergoes the greatest degree of surface relaxation with rotation and distortion of the carbonate group accompanied by movement of the calcium ion. The magnesite surface is the least distorted of the three carbonates, with dolomite being intermediate to the two end members. When water molecules are placed on the surface to produce complete monolayer coverage, the calcite surface is stabilized and the amount of relaxation is substantially reduced. In contrast, the dolomite and magnesite surfaces are destabilized by hydration as indicated by a significant increase in the surface energies relative to the dry surface.

  13. Swift heavy ion irradiation induced phase transformation in calcite single crystals

    NASA Astrophysics Data System (ADS)

    Nagabhushana, H.; Nagabhushana, B. M.; Lakshminarasappa, B. N.; Singh, Fouran; Chakradhar, R. P. S.

    2009-11-01

    Ion irradiation induced phase transformation in calcite single crystals have been studied by means of Raman and infrared spectroscopy using 120 MeV Au 9+ ions. The observed bands have been assigned according to group theory analysis. For higher fluence of 5×10 12 ion/cm 2, an extra peak on either side of the 713 cm -1 peak and an increase in the intensity of 1085 cm -1 peak were observed in Raman studies. FTIR spectra exhibit extra absorption bands at 674, 1589 cm -1 and enhancement in bands at 2340 and 2374 cm -1 was observed. This might be due to the phase transformation from calcite to vaterite. The damage cross section ( σ) for all the Raman and FTIR active modes was determined. The increase of FWHM, shift in peak positions and appearance of new peaks indicated that calcite phase is converted into vaterite.

  14. Heterogeneous distribution of dye-labelled biomineralizaiton proteins in calcite crystals

    NASA Astrophysics Data System (ADS)

    Liu, Chuang; Xie, Liping; Zhang, Rongqing

    2015-12-01

    Biominerals are highly ordered crystals mediated by organic matters especially proteins in organisms. However, how specific proteins are distributed inside biominerals are not well understood. In the present study, we use fluorescein isothiocyanate (FITC) to label extracted proteins from the shells of bivalve Pinctada fucata. By confocal laser scanning microscopy (CLSM), we observe a heterogeneous distribution of dye-labelled proteins inside synthetic calcite at the microscale. Proteins from the prismatic calcite layers accumulate at the edge of crystals while proteins from the nacreous aragonite layers accumulate at the center of crystals. Raman and X-ray powder diffraction show that both the proteins cannot alter the crystal phase. Scanning electron microscope demonstrates both proteins are able to affect the crystal morphology. This study may provide a direct approach for the visualization of protein distributions in crystals by small-molecule dye-labelled proteins as the additives in the crystallization process and improve our understanding of intracrystalline proteins distribution in biogenic calcites.

  15. Marine Resources

    NASA Technical Reports Server (NTRS)

    Sherman, J. W., III

    1975-01-01

    The papers presented in the marine session may be broadly grouped into several classes: microwave region instruments compared to infrared and visible region sensors, satellite techniques compared to aircraft techniques, open ocean applications compared to coastal region applications, and basic research and understanding of ocean phenomena compared to research techniques that offer immediate applications.

  16. Marine Mammals.

    ERIC Educational Resources Information Center

    Meith, Nikki

    Marine mammals have not only fascinated and inspired human beings for thousands of years, but they also support a big business by providing flesh for sea-borne factories, sustaining Arctic lifestyles and traditions, and attracting tourists to ocean aquaria. While they are being harpooned, bludgeoned, shot, netted, and trained to jump through…

  17. Marine Trades.

    ERIC Educational Resources Information Center

    Abbott, Alan

    This curriculum guide provides materials for a competency-based course in marine trades at the secondary level. The curriculum design uses the curriculum infused model for the teaching of basic skills as part of vocational education and demonstrates the relationship of vocationally related skills to communication, mathematics, and science…

  18. Heterogeneous growth of cadmium and cobalt carbonate phases at the (101¯4) calcite surface

    SciTech Connect

    Xu, Man; Ilton, Eugene S.; Engelhard, Mark H.; Qafoku, Odeta; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien N.

    2015-03-01

    The ability of surface precipitates to form heteroepitaxially is an important factor that controls the extent of heterogeneous growth. In this work, the growth of cadmium and cobalt carbonate phases on (10-14) calcite surfaces is compared for a range of initial saturation states with respect to otavite (CdCO3) and sphaerocobaltite (CoCO3), two isostructural metal carbonates that exhibit different lattice misfits with respect to calcite. Calcite single crystals were reacted in static conditions for 16 hours with CdCl2 and CoCl2 aqueous solutions with initial concentrations 0.3 ≤ [Cd2+]0 ≤ 100 μM and 25 ≤ [Co2+]0 ≤ 200 μM. The reacted crystals were imaged in situ with atomic force microscopy (AFM) and analyzed ex situ with X-ray photoelectron spectroscopy (XPS). AFM images of Cd-reacted crystals showed the formation of large islands elongated along the direction, clear evidence of heteroepitaxial growth, whereas surface precipitates on Co-reacted crystals were small round islands. Deformation of calcite etch pits in both cases indicated the incorporation of Cd and Co at step edges. XPS analysis pointed to the formation of a Cd-rich (Ca,Cd)CO3 solid solution coating atop the calcite substrate. In contrast, XPS measurements of the Co-reacted crystals provided evidence for the formation of a mixed hydroxy-carbonate cobalt phase. The combined AFM and XPS results suggest that the lattice misfit between CoCO3 and CaCO3 ( 15% based on surface areas) is too large to allow for heteroepitaxial growth of a pure cobalt carbonate phase on calcite surfaces in aqueous solutions and at ambient conditions. The use of the satellite structure of the Co 2p3/2 photoelectron line as a tool for determining the nature of cobalt surface precipitates is also discussed.

  19. The effect of fluid composition, salinity, and acidity on subcritical crack growth in calcite crystals

    NASA Astrophysics Data System (ADS)

    Bergsaker, Anne Schad; Røyne, Anja; Ougier-Simonin, Audrey; Aubry, Jérôme; Renard, François

    2016-03-01

    Chemically activated processes of subcritical cracking in calcite control the time-dependent strength of this mineral, which is a major constituent of the Earth's brittle upper crust. Here experimental data on subcritical crack growth are acquired with a double torsion apparatus to characterize the influence of fluid pH (range 5-7.5) and ionic strength and species (Na2SO4, NaCl, MgSO4, and MgCl2) on the propagation of microcracks in calcite single crystals. The effect of different ions on crack healing has also been investigated by decreasing the load on the crack for durations up to 30 min and allowing it to relax and close. All solutions were saturated with CaCO3. The crack velocities reached during the experiments are in the range 10-9-10-2 m/s and cover the range of subcritical to close to dynamic rupture propagation velocities. Results show that for calcite saturated solutions, the energy necessary to fracture calcite is independent of pH. As a consequence, the effects of fluid salinity, measured through its ionic strength, or the variation of water activity have stronger effects on subcritical crack propagation in calcite than pH. Consequently, when considering the geological sequestration of CO2 into carbonate reservoirs, the decrease of pH within the range of 5-7.5 due to CO2 dissolution into water should not significantly alter the rate of fracturing of calcite. Increase in salinity caused by drying may lead to further reduction in cracking and consequently a decrease in brittle creep. The healing of cracks is found to vary with the specific ions present.

  20. Determination of aragonite trace element partition coefficients from speleothem calcite-aragonite transitions

    NASA Astrophysics Data System (ADS)

    Wassenburg, Jasper A.; Scholz, Denis; Jochum, Klaus Peter; Cheng, Hai; Oster, Jessica; Immenhauser, Adrian; Richter, Detlev K.; Haeger, Tobias; Hoffmann, Dirk; Breitenbach, Sebastian F. M.

    2016-04-01

    Speleothem trace element variability has often been linked to environmental changes. While research has focused on element incorporation into speleothem calcite, our current knowledge of trace element variability in speleothem aragonite is limited to a few studies only. Here we present, to our knowledge, for the first time quantitative estimates of distribution coefficients for speleothem aragonite (DMg, DBa, DSr, and DU). These were derived from ten calcite-to-aragonite transitions from seven speleothems from Morocco, Germany, Spain, France and India. Our calculations indicate the following distribution coefficients: DMg = 1.01E-04 ± 9.0E-05, DBa(Ar) = 0.91 ± 0.53, DSr(Ar) = 1.38 ± 0.53, and DU(Ar) = 6.26 ± 4.53. These results are discussed in the context of speleothem growth rates, Rayleigh distillation effects, temperature, drip water elemental composition and drip water pH. We conclude that speleothem aragonite DMg(Ar) is below one, DSr(Ar) is close to unity, and DU(Ar) is above one. For DBa(Ar), such a conclusion is difficult. Speleothem growth rate may affect aragonite DSr in samples forming at a growth rate lower than 20 μm/a. Our results also indicate that calcite DSr and calcite DBa are affected by the Mg content of calcite. This has important implications for studies attempting to quantify processes like prior calcite precipitation. In particular, DSr and DBa cannot be transferred from caves developed within a limestone host rock to caves developed within a dolostone host rock.

  1. Fatty acids in sparry calcite fracture fills and microsparite cement of septarian diagenetic concretions

    NASA Astrophysics Data System (ADS)

    Pearson, M. J.; Hendry, J. P.; Taylor, C. W.; Russell, M. A.

    2005-04-01

    Sparry calcite fracture fills and concretion body cements in concretions from the Flodigarry Shale Member of the Staffin Shale Formation, Isle of Skye, Scotland, entrap and preserve mineral and organic materials of sedimentary and diagenetic origin. Fatty acids are a major component of the lipids recovered by decarbonation and comprise mainly n-alkanoic and α-ω dicarboxylic acids. Two generations of fracture-fill calcite (early brown and later yellow) and the concretion body microspar yield significantly different fatty acid profiles. Early brown calcites yield mainly medium-chain n-alkanoic acids with strong even predominance; later yellow calcites are dominated by α-ω dicarboxylic acids with no even predominance. Both fracture fills lack the long-chain n-alkanoic and α-ω dicarboxylic acids additionally recovered from the concretion bodies. The absence of longer chain acids in the calcite spar fracture fills is inferred to result from the transport of fatty acids by septarian mineralising fluids whereby low-aqueous solubility of longer chain acids or their salts accounts for their relative immobility. Comparative experiments have been carried out using conventional solvent extraction on the concretion body and associated shales, both decarbonated and untreated. Extracted lipid yields are higher, but the fatty acids probably derive from mixed locations in the rock including both kerogen- and carbonate-associated lipid pools. Only experiments involving decarbonation yielded α-ω dicarboxylic acids in molecular distributions probably controlled mainly by fluid transport. Alkane biomarker ratios indicate very low thermal maturity has been experienced by the concretions and their host sediments. Septarian cracks lined by brown calcite formed during early burial. Microbial CO 2 from sulphate-reducing bacteria was probably the main source of mineralising carbonate. Emplacement of the later septarian fills probably involved at least one episode of fluid invasion.

  2. Burial Diagenesis Effects on Clumped Isotope Signatures of Coexisting Dolomites and Calcites

    NASA Astrophysics Data System (ADS)

    Winkelstern, I. Z.; Lohmann, K. C.

    2014-12-01

    Carbonate clumped isotope paleothermometry is a promising method for diagenetic and deep time paleoclimate studies, but original clumped isotope (Δ47) compositions can be altered by fluid and thermal diagenetic processes. Previous work shows Δ47 resetting of calcite occurs at temperatures exceeding 100°C over time periods of millions of years, but such thermally-driven effects have not been considered for dolomite. Differences between calcite and dolomite temperature calibrations are also largely unquantified, and the effect of burial diagenesis on dolomite Δ47 has not been measured. Coexisting calcites and dolomites in a ~4500 meter core from Andros Island, Bahamas, offer a unique opportunity to address these questions. These dolomites and calcites formed over a time span from the Cretaceous to Pleistocene under near-surface temperature conditions. Clumped isotope analysis of this material reveals that where these carbonate phases are buried to depths greater than ~3000 meters, realistic surface temperatures (~25 °C) are not preserved. Moreover, these phases do not record reasonable geothermal conditions (> 80 °C), but rather record temperatures between 40 and 60°C. Here we evaluate whether this Δ47 "error" is due to solid-state resetting of clumped isotopes, emplacement of minor burial cements, fabric retentive recrystallization, or some combination thereof. Our results show that clumped isotope compositions of both calcite and dolomite respond similarly to diagenetic resetting of primary values under conditions of burial. These data further emphasize the need to constrain the diagenetic history of samples used for clumped isotope work. The similar Δ47 temperatures recorded by each carbonate type suggest that dolomites and calcites are equally viable temperature proxy sources under shallow burial conditions, yet both seem equally susceptible to "resetting" of their primary clumped isotope abundances.

  3. U and Sr Isotopes in ground water and calcite, Yucca Mountain, Nevada: Evidence against upwelling water

    USGS Publications Warehouse

    Stuckless, J.S.; Peterman, Z.E.; Muhs, D.R.

    1991-01-01

    Hydrogenic calcite and opaline silica deposits in fault zones at Yucca Mountain, Nevada, have created considerable public and scientific controversy because of the possible development of a high-level nuclear waste repository at this location. Strontium and uranium isotopic compositions of hydrogenic materials were used to test whether the veins could have formed by upwelling of deep-seated waters. The vein deposits are isotopically distinct from ground water in the two aquifers that underlie Yucca Mountain, indicating that the calcite could not have precipitated from ground water. The data are consistent with a surficial origin for the hydrogenic deposits.

  4. Controls on trace-element partitioning in cave-analogue calcite

    NASA Astrophysics Data System (ADS)

    Day, Christopher C.; Henderson, Gideon M.

    2013-11-01

    We report trace-element data from a series of carbonate growth experiments in cave-analogue conditions in the laboratory with the goal of better understanding environmental controls on trace-element incorporation in stalagmites. The experimental setup closely mimics natural processes (e.g. precipitation driven by CO2-degassing, low ionic strength solution, thin solution-film) but with a tight control on growth conditions (temperature, pCO2, drip rate, calcite saturation index and the composition of the initial solution). Calcite is dissolved in deionized water in a 20,000 ppmV pCO2 environment, with trace-elements (Li, Na, Mg, Co, Sr, Cd, Ba, U) at appropriate concentrations to mimic natural cave drip-waters. This solution is dripped onto glass plates (coated with seed-calcite) in a lower pCO2 environment at 7, 15, 25 and 35 °C and drip rates of 2, 6 and 10 drips per minute. D(Sr) was shown to be statistically invariant over the full range of temperature and growth rate studied. No relationship between Sr/Ca and growth rate is therefore expected in stalagmite samples over comparable growth rates. D(Mg) has a relationship with temperature defined by D(Mg) = 0.01e0.02[±0.006]T, but temperature is not expected to be the dominant control on Mg/Ca in cave calcite due to the larger impact of calcite precipitation on Mg/Ca. Over short timescales, in conditions where temperature is well buffered, the fraction of calcium remaining in solution (f) is likely to be the dominant control on Mg/Ca and other trace-element ratios. But differences in the response of trace-elements to f and T may allow their combined use to assess past cave conditions. High Cd/Castalagmite is particularly indicative of low amounts of prior calcite precipitation and Cd/Ca would be a useful addition to trace-element studies of natural stalagmites. Significant scatter is observed in trace-element ratios during the laboratory experiments, which cannot be explained by simple Rayleigh distillation. This

  5. Galacturonomannan and Golgi-derived membrane linked to growth and shaping of biogenic calcite

    NASA Technical Reports Server (NTRS)

    Marsh, M. E.; Ridall, A. L.; Azadi, P.; Duke, P. J.

    2002-01-01

    The coccolithophores are valuable models for the design and synthesis of composite materials, because the cellular machinery controlling the nucleation, growth, and patterning of their calcitic scales (coccoliths) can be examined genetically. The coccoliths are formed within the Golgi complex and are the major CaCO(3) component in limestone sediments-particularly those of the Cretaceous period. In this study, we describe mutants lacking a sulfated galacturonomannan and show that this polysaccharide in conjunction with the Golgi-derived membrane is directly linked to the growth and shaping of coccolith calcite but not to the initial orientated nucleation of the mineral phase.

  6. Arsenate Uptake by Calcite: Macroscopic and Spectroscopic Characterization of Adsorption and Incorporation Mechanisms

    SciTech Connect

    Alexandratos,V.; Elzinga, E.; Reeder, R.

    2007-01-01

    Batch uptake experiments and X-ray element mapping and spectroscopic techniques were used to investigate As(V) (arsenate) uptake mechanisms by calcite, including adsorption and coprecipitation. Batch sorption experiments in calcite-equilibrated suspensions (pH 8.3; PCO{sub 2} = 10{sup -3.5} atm) reveal rapid initial sorption to calcite, with sorption rate gradually decreasing with time as available sorption sites decrease. An As(V)-calcite sorption isotherm determined after 24 h equilibration exhibits Langmuir-like behavior up to As concentrations of 300 {mu}M. Maximum distribution coefficient values (K{sub d}), derived from a best fit to a Langmuir model, are {approx}190 L kg{sup -1}. Calcite single crystals grown in the presence of As(V) show well-developed rhombohedral morphology with characteristic growth hillocks on (10{bar 1}4) surfaces at low As(V) concentrations ({<=}5 {mu}M), but habit modification is evident at As(V) concentrations {>=}30 {mu}M in the form of macrostep development preferentially on the - vicinal surfaces of growth hillocks. Micro-X-ray fluorescence element mapping of (10{bar 1}4) surfaces shows preferential incorporation of As in the - vicinal faces relative to + vicinals. EXAFS fit results for both adsorption and coprecipitation samples confirm that As occurs in the 5+ oxidation state in tetrahedral coordination with oxygen, i.e., as arsenate. For adsorption samples, As(V) forms inner-sphere surface complexes via corner-sharing with Ca octahedra. As(V) coprecipitated with calcite substitutes in carbonate sites but with As off-centered, as indicated by two Ca shells, and with likely disruption of local structure. The results indicate that As(V) interacts strongly with the calcite surface, similar to often-cited analog phosphate, and uptake can occur via both adsorption and coprecipitation reactions. Therefore, calcite may be effective for partial removal of dissolved arsenate from aquatic and soil systems.

  7. Pathways for abiotic organic synthesis at submarine hydrothermal fields

    PubMed Central

    McDermott, Jill M.; Seewald, Jeffrey S.; German, Christopher R.; Sylva, Sean P.

    2015-01-01

    Arguments for an abiotic origin of low-molecular weight organic compounds in deep-sea hot springs are compelling owing to implications for the sustenance of deep biosphere microbial communities and their potential role in the origin of life. Theory predicts that warm H2-rich fluids, like those emanating from serpentinizing hydrothermal systems, create a favorable thermodynamic drive for the abiotic generation of organic compounds from inorganic precursors. Here, we constrain two distinct reaction pathways for abiotic organic synthesis in the natural environment at the Von Damm hydrothermal field and delineate spatially where inorganic carbon is converted into bioavailable reduced carbon. We reveal that carbon transformation reactions in a single system can progress over hours, days, and up to thousands of years. Previous studies have suggested that CH4 and higher hydrocarbons in ultramafic hydrothermal systems were dependent on H2 generation during active serpentinization. Rather, our results indicate that CH4 found in vent fluids is formed in H2-rich fluid inclusions, and higher n-alkanes may likely be derived from the same source. This finding implies that, in contrast with current paradigms, these compounds may form independently of actively circulating serpentinizing fluids in ultramafic-influenced systems. Conversely, widespread production of formate by ΣCO2 reduction at Von Damm occurs rapidly during shallow subsurface mixing of the same fluids, which may support anaerobic methanogenesis. Our finding of abiogenic formate in deep-sea hot springs has significant implications for microbial life strategies in the present-day deep biosphere as well as early life on Earth and beyond. PMID:26056279

  8. Pathways for abiotic organic synthesis at submarine hydrothermal fields.

    PubMed

    McDermott, Jill M; Seewald, Jeffrey S; German, Christopher R; Sylva, Sean P

    2015-06-23

    Arguments for an abiotic origin of low-molecular weight organic compounds in deep-sea hot springs are compelling owing to implications for the sustenance of deep biosphere microbial communities and their potential role in the origin of life. Theory predicts that warm H2-rich fluids, like those emanating from serpentinizing hydrothermal systems, create a favorable thermodynamic drive for the abiotic generation of organic compounds from inorganic precursors. Here, we constrain two distinct reaction pathways for abiotic organic synthesis in the natural environment at the Von Damm hydrothermal field and delineate spatially where inorganic carbon is converted into bioavailable reduced carbon. We reveal that carbon transformation reactions in a single system can progress over hours, days, and up to thousands of years. Previous studies have suggested that CH4 and higher hydrocarbons in ultramafic hydrothermal systems were dependent on H2 generation during active serpentinization. Rather, our results indicate that CH4 found in vent fluids is formed in H2-rich fluid inclusions, and higher n-alkanes may likely be derived from the same source. This finding implies that, in contrast with current paradigms, these compounds may form independently of actively circulating serpentinizing fluids in ultramafic-influenced systems. Conversely, widespread production of formate by ΣCO2 reduction at Von Damm occurs rapidly during shallow subsurface mixing of the same fluids, which may support anaerobic methanogenesis. Our finding of abiogenic formate in deep-sea hot springs has significant implications for microbial life strategies in the present-day deep biosphere as well as early life on Earth and beyond. PMID:26056279

  9. Distinguishing Biotic from Abiotic Phosphate Oxygen Isotopic Signatures

    NASA Astrophysics Data System (ADS)

    Blake, R.; Moyer, C.; Colman, A.; Liang, Y.; Dogru, D.

    2006-05-01

    On earth, phosphate has a strong biological oxygen isotope signature due to its concentration and intense cycling by living organisms as an essential nutrient. Phosphate does not undergo oxygen isotope exchange with water at low temperature without enzymatic catalysis, making the oxygen isotope ratio (18O/16O) of phosphate, δ18OP, an attractive biosignature in the search for early and extraterrestrial life. Recent laboratory and field studies have demonstrated that the δ18OP value of dissolved inorganic phosphate (PO4) records specific microbial activity and enzymatic reaction pathways in both laboratory cultures and natural waters/sediments (Blake et al., 2005; Colman et al 2005; Liang and Blake, 2005). Phosphate oxygen isotope biosignatures may be distinguished from abiotic signatures by: (1) evaluating the degree of temperature-dependent PO4-water oxygen isotope exchange in aqueous systems and deviation from equilibrium; and (2) evolution from an abiotic P reservoir signature towards a biotic P reservoir signature. Important abiotic processes potentially affecting phosphate δ18OP values include dissolution/precipitation, adsorption/desorption, recrystallization of PO4 mineral phases, diagenesis and metamorphism. For most of these processes, the recording, retention and alteration of δ18OP biosignatures have not been evaluated. Deep-sea hydrothermal vent fields are an ideal system in which to study the preservation and alteration of δ18OP biosignatures, as well as potential look-alikes produced by heat-promoted PO4 -water oxygen isotope exchange. Results from recent studies of δ18OP biosignatures in hydrothermal deposits near 9 and 21 degrees N. EPR and at Loihi seamount will be presented.

  10. Marine microbial genomics in Europe: current status and perspectives

    PubMed Central

    Glöckner, Frank Oliver; Joint, Ian

    2010-01-01

    Summary The oceans are the Earth's largest ecosystem, covering 70% of our planet and providing goods and services for the majority of the world's population. Understanding the complex abiotic and biotic processes on the micro‐ to macroscale is the key to protect and sustain the marine ecosystem. Marine microorganisms are the ‘gatekeepers’ of the biotic processes that control the global cycles of energy and organic matter. A multinational, multidisciplinary approach, bringing together research on oceanography, biodiversity and genomics, is now needed to understand and finally predict the complex responses of the marine ecosystem to ongoing global changes. Such an integrative approach will not only bring better understanding of the complex interplay of the organisms with their environment, but will reveal a wealth of new metabolic processes and functions, which have a high potential for biotechnological applications. This potential has already been recognized by the European commission which funded a series of workshops and projects on marine genomics in the sixth and seventh framework programme. Nevertheless, there remain many obstacles to achieving the goal – such as a lack of bioinformatics tailored for the marine field, consistent data acquisition and exchange, as well as continuous monitoring programmes and a lack of relevant marine bacterial models. Marine ecosystems research is complex and challenging, but it also harbours the opportunity to cross the borders between disciplines and countries to finally create a rewarding marine research era that is more than the sum of its parts. PMID:20953416

  11. Marine microbial genomics in Europe: current status and perspectives.

    PubMed

    Glöckner, Frank Oliver; Joint, Ian

    2010-09-01

    The oceans are the Earth's largest ecosystem, covering 70% of our planet and providing goods and services for the majority of the world's population. Understanding the complex abiotic and biotic processes on the micro- to macroscale is the key to protect and sustain the marine ecosystem. Marine microorganisms are the 'gatekeepers' of the biotic processes that control the global cycles of energy and organic matter. A multinational, multidisciplinary approach, bringing together research on oceanography, biodiversity and genomics, is now needed to understand and finally predict the complex responses of the marine ecosystem to ongoing global changes. Such an integrative approach will not only bring better understanding of the complex interplay of the organisms with their environment, but will reveal a wealth of new metabolic processes and functions, which have a high potential for biotechnological applications. This potential has already been recognized by the European commission which funded a series of workshops and projects on marine genomics in the sixth and seventh framework programme. Nevertheless, there remain many obstacles to achieving the goal – such as a lack of bioinformatics tailored for the marine field, consistent data acquisition and exchange, as well as continuous monitoring programmes and a lack of relevant marine bacterial models. Marine ecosystems research is complex and challenging, but it also harbours the opportunity to cross the borders between disciplines and countries to finally create a rewarding marine research era that is more than the sum of its parts. PMID:20953416

  12. Intra-skeletal calcite in a live-collected Porites sp.: Impact on environmental proxies and potential formation process

    NASA Astrophysics Data System (ADS)

    Lazareth, Claire E.; Soares-Pereira, Caroline; Douville, Eric; Brahmi, Chloé; Dissard, Delphine; Le Cornec, Florence; Thil, François; Gonzalez-Roubaud, Cécile; Caquineau, Sandrine; Cabioch, Guy

    2016-03-01

    Geochemical proxies measured in the carbonate skeleton of tropical coral Porites sp. have commonly been used to reconstruct sea surface temperature (SST) and more recently seawater pH. Nevertheless, both reconstructed SST and pH depend on the preservation state of the skeleton, here made of aragonite; i.e., diagenetic processes and its related effects should be limited. In this study, we report on the impact of the presence of intra-skeletal calcite on the skeleton geochemistry of a live-collected Porites sp. The Porites skeleton preservation state was analyzed using X-ray diffraction and scanning electron microscopy. Sr/Ca, Mg/Ca, U/Ca, Ba/Ca, Li/Mg, and B/Ca ratios were measured at a monthly and yearly resolution using quadrupole ICP-MS and multi-collector ICP-MS. The δ11B signatures and the calcite percentages were acquired at a yearly timescale. The coral colony presents two parts, one with less than 3% calcite (referred to as "no-calcite" skeleton), the other one, corresponding to the skeleton formed during the last 4 years of growth, with calcite percentages varying from 13% to 32% (referred to as "with calcite" skeleton). This intra-skeletal calcite replaces partly or completely numerous centers of calcification (COCs). All investigated geochemical tracers are significantly impacted by the presence of calcite. The reconstructed SST decreases by about 0.1 °C per calcite-percent as inferred from the Sr/Ca ratio. Such impact reaches up to 0.26 °C per calcite-percent for temperature deduced from the Li/Mg ratio. So, less than 5% of such intra-skeletal calcite does not prevent SST reconstructions using Sr/Ca ratio, but the percentage and type of calcite have to be determined before fine SST interpretation. Seawater pH reconstruction inferred from boron isotopes drop by about -0.011 pH-unit per calcite-percent. Such sensitivity to calcite presence is particularly dramatic for fine paleo-pH reconstructions. Here we suggest that after being brought to shallow

  13. Model Comparison for Abiotic versus Biotic Pollen Dispersal.

    PubMed

    Foster, Erich L; Chan, David M; Dyer, Rodney J

    2016-10-01

    An agent-based model with a correlated random walk is used to explore pollination within a forest. For abiotic dispersal, say via the wind, we use a purely random walk where there is no correlation between consecutive steps and for biotic dispersal, say via insect, we use a moderate or highly correlated random walk. In particular, we examine the differences in a number of biological measurement between a purely random walk and a correlated random walk in terms of gene dispersal in low and high plant densities. PMID:27550704

  14. Coupled Abiotic-Biotic Degradation of Bisphenol A

    NASA Astrophysics Data System (ADS)

    Im, J.; Prevatte, C.; Campagna, S. R.; Loeffler, F.

    2014-12-01

    Bisphenol A (BPA) is a ubiquitous environmental contaminant with weak estrogenic activity. BPA is readily biodegradable with oxygen available, but is recalcitrant to microbial degradation under anoxic conditions. However, BPA is susceptible to abiotic transformation under anoxic conditions. To better understand the fate of BPA in anoxic environments, the kinetics of BPA transformation by manganese oxide (d-MnO2) were investigated. BPA was rapidly transformed by MnO2 with a pseudo-first-order rate constant of 0.413 min-1. NMR and LC-MS analyses identified 4-hydroxycumyl alcohol (HCA) as a major intermediate. Up to 64% of the initial amount of BPA was recovered as HCA within 5 min, but the conversion efficiency decreased with time, suggesting that HCA was further degraded by MnO2. Further experiments confirmed that HCA was also susceptible to transformation by MnO2, albeit at 5-fold lower rates than BPA transformation. Mass balance approaches suggested that HCA was the major BPA transformation intermediate, but other compounds may also be formed. The abiotic transformation of BPA by MnO2 was affected by pH, and 10-fold higher transformation rates were observed at pH 4.5 than at pH 10. Compared to BPA, HCA has a lower octanol-water partitioning coefficient (Log Kow) of 0.76 vs 2.76 for BPA and a higher aqueous solubility of 2.65 g L-1 vs 0.31 g L-1 for BPA, suggesting higher mobility of HCA in the environment. Microcosms established with freshwater sediment materials collected from four geographically distinct locations and amended with HCA demonstrated rapid HCA biodegradation under oxic, but not under anoxic conditions. These findings suggest that BPA is not inert under anoxic conditions and abiotic reactions with MnO2 generate HCA, which has increased mobility and is susceptible to aerobic degradation. Therefore, coupled abiotic-biotic processes can affect the fate and longevity of BPA in terrestrial environments.

  15. May Cyclic Nucleotides Be a Source for Abiotic RNA Synthesis?

    NASA Astrophysics Data System (ADS)

    Costanzo, Giovanna; Pino, Samanta; Botta, Giorgia; Saladino, Raffaele; di Mauro, Ernesto

    2011-12-01

    Nucleic bases are obtained by heating formamide in the presence of various catalysts. Formamide chemistry also allows the formation of acyclonucleosides and the phosphorylation of nucleosides in every possible position, also affording 2',3' and 3',5' cyclic forms. We have reported that 3',5' cyclic GMP and 3',5' cyclic AMP polymerize in abiotic conditions yielding short oligonucleotides. The characterization of this reaction is being pursued, several of its parameters have been determined and experimental caveats are reported. The yield of non-enzymatic polymerization of cyclic purine nucleotides is very low. Polymerization is strongly enhanced by the presence of base-complementary RNA sequences.

  16. Abiotic gas formation drives nitrogen loss from a desert ecosystem.

    PubMed

    McCalley, Carmody K; Sparks, Jed P

    2009-11-01

    In arid environments such as deserts, nitrogen is often the most limiting nutrient for biological activity. The majority of the ecosystem nitrogen flux is typically thought to be driven by production and loss of reactive nitrogen species by microorganisms in the soil. We found that high soil-surface temperatures (greater than 50 degrees C), driven by solar radiation, are the primary cause of nitrogen loss in Mojave Desert soils. This abiotic pathway not only enables the balancing of arid ecosystem nitrogen budgets, but also changes our view of global nitrogen cycling and the predicted impact of climate change and increased temperatures on nitrogen bioavailability. PMID:19892980

  17. Experimental fractionation of stable carbon isotopes during degassing of carbon dioxide and precipitation of calcite from aqueous solutions

    NASA Astrophysics Data System (ADS)

    Müller, K.; Winde, V.; Escher, P.; von Geldern, R.; Böttcher, M. E.

    2012-04-01

    Processes in the carbonate system of surface waters are in particular sensitive to variations of boundary conditions as, for instance, the partial pressure of carbon dioxide in the atmosphere and the aqueous solution. Examples range from streams, rivers, to coastal marine waters. The flux of carbon dioxide from continental flowing waters was recently included into calculations of the global carbon budget (Butman & Raymond, 2011, Nature Geo.). These solutions, are often supersaturated in carbon dioxide with respect to the atmosphere. The degassing of carbon dioxide is associated with a kinetically controlled fractionation of the stable carbon isotopes, which has to be considered in balancing water-air carbon dioxide fluxes. The degassing process additionally leads to the super-saturation of the aqueous solution with respect to calcium carbonate. Stable isotope fractionation is of particular value to identify and quantify processes at the water-gas phase interface and link these non-equilibrium processes to the formation mechanisms of calcite and the hydrodynamics of surface waters. Experiments were carried out with or without inert N2 gas flow to degas carbon dioxide from initially supersaturated solutions. Natural solutions used are from different stations of the Elbe estuary, the Jade Bay, the backbarrier tidal area of Spiekeroog Island, carbonate springs of Rügen Island, and the Baltic Sea coastline. Results are compared experiments using bottled mineral waters. By following the (physico) chemical changes in the solutions (pH, TA, Ca PHREEQC modeling) it was found, that two evolutionary stages can be differentiated. Reaction progress led to the preferential liberation of carbon dioxide containing the light carbon isotope, following a Rayleigh-type process. After an induction period, where only degassing of carbon dioxide took place, a second stage was observed where calcite began to form from the highly supersaturated solutions. In this stage the carbonate

  18. Linking Species Traits to the Abiotic Template of Flowing Waters: Contrasting Eco physiologies Underlie Displacement of Zebra Mussels by Quagga Mussels in a Large River-Estuary

    NASA Astrophysics Data System (ADS)

    Casper, A. F.

    2005-05-01

    The St. Lawrence River-Estuary was the gateway of entry for dreissenids to North America and holds some of the oldest populations. The St. Lawrence also has four distinct physical-chemical water masses (a regional scale abiotic template) that both species inhabit. Despite their ecological similarities, quagga mussels are supplanting zebra mussels in much of their shared range. In order to try to better understand the changing distributions of these two species we compared glycogen, shell mass and tissue biomass in each of the water masses. This comparative physiological combined with experimental approaches (estuarine salinity experiments and reciprocal transplants) showed that while quagga mussels should dominate in most habitats, that abiotic/bioenergetic constraints in two regions (the Ottawa River plume and the freshwater-marine transition zone) might prevent them from dominating these locations. These findings are an example of how the interaction of landscape scale abiotic heterogeneity and a species-specific physiology can have strong impacts of distribution of biota large rivers.

  19. Expression of the tetrahydrofolate-dependent nitric oxide synthase from the green alga Ostreococcus tauri increases tolerance to abiotic stresses and influences stomatal development in Arabidopsis.

    PubMed

    Foresi, Noelia; Mayta, Martín L; Lodeyro, Anabella F; Scuffi, Denise; Correa-Aragunde, Natalia; García-Mata, Carlos; Casalongué, Claudia; Carrillo, Néstor; Lamattina, Lorenzo

    2015-06-01

    Nitric oxide (NO) is a signaling molecule with diverse biological functions in plants. NO plays a crucial role in growth and development, from germination to senescence, and is also involved in plant responses to biotic and abiotic stresses. In animals, NO is synthesized by well-described nitric oxide synthase (NOS) enzymes. NOS activity has also been detected in higher plants, but no gene encoding an NOS protein, or the enzymes required for synthesis of tetrahydrobiopterin, an essential cofactor of mammalian NOS activity, have been identified so far. Recently, an NOS gene from the unicellular marine alga Ostreococcus tauri (OtNOS) has been discovered and characterized. Arabidopsis thaliana plants were transformed with OtNOS under the control of the inducible short promoter fragment (SPF) of the sunflower (Helianthus annuus) Hahb-4 gene, which responds to abiotic stresses and abscisic acid. Transgenic plants expressing OtNOS accumulated higher NO concentrations compared with siblings transformed with the empty vector, and displayed enhanced salt, drought and oxidative stress tolerance. Moreover, transgenic OtNOS lines exhibited increased stomatal development compared with plants transformed with the empty vector. Both in vitro and in vivo experiments indicate that OtNOS, unlike mammalian NOS, efficiently uses tetrahydrofolate as a cofactor in Arabidopsis plants. The modulation of NO production to alleviate abiotic stress disturbances in higher plants highlights the potential of genetic manipulation to influence NO metabolism as a tool to improve plant fitness under adverse growth conditions. PMID:25880454

  20. Small RNAs in Plant Responses to Abiotic Stresses: Regulatory Roles and Study Methods

    PubMed Central

    Ku, Yee-Shan; Wong, Johanna Wing-Hang; Mui, Zeta; Liu, Xuan; Hui, Jerome Ho-Lam; Chan, Ting-Fung; Lam, Hon-Ming

    2015-01-01

    To survive under abiotic stresses in the environment, plants trigger a reprogramming of gene expression, by transcriptional regulation or translational regulation, to turn on protective mechanisms. The current focus of research on how plants cope with abiotic stresses has transitioned from transcriptomic analyses to small RNA investigations. In this review, we have summarized and evaluated the current methodologies used in the identification and validation of small RNAs and their targets, in the context of plant responses to abiotic stresses. PMID:26501263

  1. Origin, timing, and temperature of secondary calcite-silica mineral formation at Yucca Mountain, Nevada

    NASA Astrophysics Data System (ADS)

    Wilson, Nicholas S. F.; Cline, Jean S.; Amelin, Yuri V.

    2003-03-01

    The origin of secondary calcite-silica minerals in primary and secondary porosity of the host Miocene tuffs at Yucca Mountain has been hotly debated during the last decade. Proponents of a high-level nuclear waste repository beneath Yucca Mountain have interpreted the secondary minerals to have formed from cool, descending meteoric fluids in the vadose zone; critics, citing the presence of two-phase fluid inclusions, argued that the minerals could only have formed in the phreatic zone from ascending hydrothermal fluids. Understanding the origin, temperature, and timing of these minerals is critical in characterizing geologically recent fluid flux at the site, and has significant implications to whether waste should be stored at Yucca Mountain. Petrographic and paragenetic studies of 155 samples collected from the Exploratory Studies Facility (ESF) and repository block cross drift (ECRB) tunnels indicate that heterogeneously distributed calcite with lesser chalcedony, quartz, opal, and fluorite comprise the oldest secondary minerals. These are typically overgrown by intermediate-aged calcite, often exhibiting distinctive bladed habits. The youngest event recorded across the site is the deposition of Mg-enriched (up to ˜1 wt%) and depleted, growth-zoned calcite intergrown with U-enriched opal. The cyclical variation in Mg enrichment and depletion is probably related to climate changes that have occurred during the last few million years. The distribution of secondary minerals is consistent with precipitation in the vadose zone. Fluid inclusion petrography of sections from the 155 samples determined that 96% of the fluid inclusion assemblages (FIAs) contained liquid-only inclusions that formed at ambient temperatures (<35°C). However, 50% of the samples (n = 78) contained relatively rare FIA that contain both liquid-only and liquid plus vapor inclusions (herein termed two-phase FIAs) that formed at temperatures above 35°C. Virtually all of these two-phase FIAs

  2. Marine Education: Progress and Promise.

    ERIC Educational Resources Information Center

    Fortner, Rosanne; Wildman, Terry M.

    1980-01-01

    Examined are the scope and status of precollege marine education, including history of marine education, present interdisciplinary marine education, informal approaches to marine education, marine awareness studies, and some implications of marine education. (Author/DS)

  3. Petrography and geochemistry of vein-filling calcites, balcones fault zone, upper cretaceous strata, north-central Texas

    SciTech Connect

    Dawson, W.C.; Szymczyk, H.M.; Reaser, D.F.

    1994-12-31

    The Austin Chalk and the underlying Eagle Ford Shale are transected by en echelon faults and fractures, associated with the Balcones Fault Zone, along an outcrop trend that extends from Dallas to Austin, Texas. These faults and fractures strike generally northeastward, and many are cemented by sparry calcite. Slickensides, preserved on outer surfaces of calcite cements, record fault movement. Early calcite cements are nonferroan, and later cements are ferroan calcite. Petrographic analyses indicate the occurrence of fir-tree zoning and fluorescent inclusions within calcite cements. Vein-filling cements have stable isotopic signatures {delta}{sup 18}O -5.7 to -9.8% PDB; {delta}{sup 13}C +1.6 to +2.7% PDB that are markedly depleted in {delta}{sup 18}O relative to the chalk matrix, inoceramid shells, and the estimated value for Cretaceous seawater. The depleted {delta}{sup 18}O signatures of the vein-filling calcites are suggestive of precipitation from warm basinal fluids. {delta}{sup 13}C analyses reveal that the Austin Chalk buffered the carbon incorporated into the calcite cements. These veins probably formed by a {open_quotes}crack-seal mechanism{close_quotes}, whereby episodic increases in hydropressure caused fracturing. Precipitation of calcite cements within fractures is induced by subsequent decreases in pore pressure. Tectonic and diagenetic features in these outcrops provide analogs for fractured Austin Chalk reservoirs.

  4. Marine Jet

    NASA Technical Reports Server (NTRS)

    1978-01-01

    The marine turbine pump pictured is the Jacuzzi 12YJ, a jet propulsion system for pleasure or commercial boating. Its development was aided by a NASA computer program made available by the Computer Software Management and Information Center (COSMIC) at the University of Georgia. The manufacturer, Jacuzzi Brothers, Incorporated, Little Rock, Arkansas, used COSMIC'S Computer Program for Predicting Turbopump Inducer Loading, which enabled substantial savings in development time and money through reduction of repetitive testing.

  5. Calcium-Mediated Abiotic Stress Signaling in Roots

    PubMed Central

    Wilkins, Katie A.; Matthus, Elsa; Swarbreck, Stéphanie M.; Davies, Julia M.

    2016-01-01

    Roots are subjected to a range of abiotic stresses as they forage for water and nutrients. Cytosolic free calcium is a common second messenger in the signaling of abiotic stress. In addition, roots take up calcium both as a nutrient and to stimulate exocytosis in growth. For calcium to fulfill its multiple roles must require strict spatio-temporal regulation of its uptake and efflux across the plasma membrane, its buffering in the cytosol and its sequestration or release from internal stores. This prompts the question of how specificity of signaling output can be achieved against the background of calcium’s other uses. Threats to agriculture such as salinity, water availability and hypoxia are signaled through calcium. Nutrient deficiency is also emerging as a stress that is signaled through cytosolic free calcium, with progress in potassium, nitrate and boron deficiency signaling now being made. Heavy metals have the capacity to trigger or modulate root calcium signaling depending on their dose and their capacity to catalyze production of hydroxyl radicals. Mechanical stress and cold stress can both trigger an increase in root cytosolic free calcium, with the possibility of membrane deformation playing a part in initiating the calcium signal. This review addresses progress in identifying the calcium transporting proteins (particularly channels such as annexins and cyclic nucleotide-gated channels) that effect stress-induced calcium increases in roots and explores links to reactive oxygen species, lipid signaling, and the unfolded protein response. PMID:27621742

  6. Ion Transporters and Abiotic Stress Tolerance in Plants

    PubMed Central

    Brini, Faïçal; Masmoudi, Khaled

    2012-01-01

    Adaptation of plants to salt stress requires cellular ion homeostasis involving net intracellular Na+ and Cl− uptake and subsequent vacuolar compartmentalization without toxic ion accumulation in the cytosol. Sodium ions can enter the cell through several low- and high-affinity K+ carriers. Some members of the HKT family function as sodium transporter and contribute to Na+ removal from the ascending xylem sap and recirculation from the leaves to the roots via the phloem vasculature. Na+ sequestration into the vacuole depends on expression and activity of Na+/H+ antiporter that is driven by electrochemical gradient of protons generated by the vacuolar H+-ATPase and the H+-pyrophosphatase. Sodium extrusion at the root-soil interface is presumed to be of critical importance for the salt tolerance. Thus, a very rapid efflux of Na+ from roots must occur to control net rates of influx. The Na+/H+ antiporter SOS1 localized to the plasma membrane is the only Na+ efflux protein from plants characterized so far. In this paper, we analyze available data related to ion transporters and plant abiotic stress responses in order to enhance our understanding about how salinity and other abiotic stresses affect the most fundamental processes of cellular function which have a substantial impact on plant growth development. PMID:27398240

  7. Reductive transformation of carbamazepine by abiotic and biotic processes.

    PubMed

    König, Anne; Weidauer, Cindy; Seiwert, Bettina; Reemtsma, Thorsten; Unger, Tina; Jekel, Martin

    2016-09-15

    The antiepileptic drug carbamazepine (CBZ) is ubiquitously present in the anthropogenic water cycle and is therefore of concern regarding the potable water supply. Despite of its persistent behavior in the aquatic environment, a redox dependent removal at bank filtration sites with anaerobic aquifer passage was reported repeatedly but not elucidated in detail yet. The reductive transformation of CBZ was studied, using abiotic systems (catalytic hydrogenation, electrochemistry) as well as biologically active systems (column systems, batch degradation tests). In catalytic hydrogenation CBZ is gradually hydrogenated and nine transformation products (TPs) were detected by liquid chromatography high-resolution mass spectrometry. 10,11-Dihydro-CBZ ((2H)-CBZ) was the major stable product in these abiotic, surface catalyzed reduction processes and turned out to be not a precursor of the more hydrogenated TPs. In the biotic reduction processes the formation of (2H)-CBZ alone could not explain the observed CBZ decline. There, also traces of (6H)-CBZ and (8H)-CBZ were formed by microbes under anaerobic conditions and four phase-II metabolites of reduced CBZ could be detected and tentatively identified. Thus, the spectrum of reduction products of CBZ is more diverse than previously thought. In environmental samples CBZ removal along an anaerobic soil passage was confirmed and (2H)-CBZ was determined at one of the sites. PMID:27267475

  8. Abiotic transformation of dinitrophenols under sulfate-reducing conditions

    SciTech Connect

    Gui, L.; Bouwer, E.J.

    1996-10-01

    Dinitrophenols are hazardous chemicals commonly detected in the environment. Little is known about their fate under sulfate-reducing conditions (SRC) where H{sub 2}S level is elevated due to microbial activity. Dinitrophenols are susceptible to both biotic and abiotic transformation under SRC. The objectives of this research are to investigate dinitrophenol transformation using hydrogen sulfide as a reductant, and to determine factors that affect the abiotic transformation kinetics under SRC. Dinitrophenols studied were 2,4-dinitrophenol (DNP), 4,6-dinitro-o-cresol (DNOC), and 2-sec-butyl-4,6-dinitrophenol (dinoseb). All three dinitrophenols were transformed through an ortho-nitroreduction pathway. In the presence of H{sub 2}S as the bulk reductant and a small amount of trace metals (10{sup -6} to 10{sup -7} M), pseudo-first-order kinetics was observed. Addition of yeast extract (YE, 0.02%) enhanced dinoseb transformation rate significantly. An increase in HS concentration resulted in Michaelis-Menton type kinetics for dinoseb in the presence of trace metals and YE, suggesting that trace metals and YE functioned as electron mediators.

  9. Hexagonal Lyotropic Liquid Crystal from Simple "Abiotic" Foldamers.

    PubMed

    Chen, Yu; Zhao, Zhiqiang; Bian, Zheng; Jin, Rizhe; Kang, Chuanqing; Qiu, Xuepeng; Guo, Haiquan; Du, Zhijun; Gao, Lianxun

    2016-08-01

    The motivation of foldamer chemistry is to identify novel building blocks that have the potential to imitate natural species. Peptides and peptide mimetics can form stable helical conformations and further self-assemble into diverse aggregates in water, where it is difficult to isolate a single helix. In contrast, most "abiotic" foldamers may fold into helical structures in solution, but are difficult to assemble into tertiary ones. It remains a challenge to obtain "abiotic" species similar to peptides. In this paper, a novel foldamer scaffold, in which p-phenyleneethynylene units are linked by chiral carbon atoms, was designed and prepared. In very dilute solutions, these oligomers were random coils. The hexamer and octamers could form a hexagonal lyotropic liquid crystal (LC) in CH2Cl2 when the concentrations reached the critical values. The microscopic observations indicated that they could assemble into the nanofibers in the LC. Interestingly, after some LC phases were diluted at room temperature, the nanofibers could be preserved. The good stabilities of the assemblies are possibly attributed to a more compact backbone and more rigid side chains. PMID:27547649

  10. Influence of abiotic stress signals on secondary metabolites in plants

    PubMed Central

    Ramakrishna, Akula; Ravishankar, Gokare Aswathanarayana

    2011-01-01

    Plant secondary metabolites are unique sources for pharmaceuticals, food additives, flavors, and industrially important biochemicals. Accumulation of such metabolites often occurs in plants subjected to stresses including various elicitors or signal molecules. Secondary metabolites play a major role in the adaptation of plants to the environment and in overcoming stress conditions. Environmental factors viz. temperature, humidity, light intensity, the supply of water, minerals, and CO2 influence the growth of a plant and secondary metabolite production. Drought, high salinity, and freezing temperatures are environmental conditions that cause adverse effects on the growth of plants and the productivity of crops. Plant cell culture technologies have been effective tools for both studying and producing plant secondary metabolites under in vitro conditions and for plant improvement. This brief review summarizes the influence of different abiotic factors include salt, drought, light, heavy metals, frost etc. on secondary metabolites in plants. The focus of the present review is the influence of abiotic factors on secondary metabolite production and some of important plant pharmaceuticals. Also, we describe the results of in vitro cultures and production of some important secondary metabolites obtained in our laboratory. PMID:22041989

  11. Abiotic factors influence plant storage lipid accumulation and composition.

    PubMed

    Singer, Stacy D; Zou, Jitao; Weselake, Randall J

    2016-02-01

    The demand for plant-derived oils has increased substantially over the last decade, and is sure to keep growing. While there has been a surge in research efforts to produce plants with improved oil content and quality, in most cases the enhancements have been small. To add further complexity to this situation, substantial differences in seed oil traits among years and field locations have indicated that plant lipid biosynthesis is also influenced to a large extent by multiple environmental factors such as temperature, drought, light availability and soil nutrients. On the molecular and biochemical levels, the expression and/or activities of fatty acid desaturases, as well as diacylglycerol acyltransferase 1, have been found to be affected by abiotic factors, suggesting that they play a role in the lipid content and compositional changes seen under abiotic stress conditions. Unfortunately, while only a very small number of strategies have been developed as of yet to minimize these environmental effects on the production of storage lipids, it is clear that this feat will be of the utmost importance for developing superior oil crops with the capability to perform in a consistent manner in field conditions in the future. PMID:26795146

  12. Calcium-Mediated Abiotic Stress Signaling in Roots.

    PubMed

    Wilkins, Katie A; Matthus, Elsa; Swarbreck, Stéphanie M; Davies, Julia M

    2016-01-01

    Roots are subjected to a range of abiotic stresses as they forage for water and nutrients. Cytosolic free calcium is a common second messenger in the signaling of abiotic stress. In addition, roots take up calcium both as a nutrient and to stimulate exocytosis in growth. For calcium to fulfill its multiple roles must require strict spatio-temporal regulation of its uptake and efflux across the plasma membrane, its buffering in the cytosol and its sequestration or release from internal stores. This prompts the question of how specificity of signaling output can be achieved against the background of calcium's other uses. Threats to agriculture such as salinity, water availability and hypoxia are signaled through calcium. Nutrient deficiency is also emerging as a stress that is signaled through cytosolic free calcium, with progress in potassium, nitrate and boron deficiency signaling now being made. Heavy metals have the capacity to trigger or modulate root calcium signaling depending on their dose and their capacity to catalyze production of hydroxyl radicals. Mechanical stress and cold stress can both trigger an increase in root cytosolic free calcium, with the possibility of membrane deformation playing a part in initiating the calcium signal. This review addresses progress in identifying the calcium transporting proteins (particularly channels such as annexins and cyclic nucleotide-gated channels) that effect stress-induced calcium increases in roots and explores links to reactive oxygen species, lipid signaling, and the unfolded protein response. PMID:27621742

  13. Unusual biogenic calcite structures in two shallow lakes, James Ross Island, Antarctica

    NASA Astrophysics Data System (ADS)

    Elster, J.; Nedbalová, L.; Vodrážka, R.; Láska, K.; Haloda, J.; Komárek, J.

    2016-01-01

    The floors of two shallow endorheic lakes, located on volcanic surfaces on James Ross Island, are covered with calcareous organosedimentary structures. Their biological and chemical composition, lake water characteristics, and seasonal variability of the thermal regime are introduced. The lakes are frozen down to the bottom for 8-9 months a year and their water chemistry is characterised by low conductivity and neutral to slightly alkaline pH. The photosynthetic microbial mat is composed of filamentous cyanobacteria and microalgae that are considered to be Antarctic endemic species. The mucilaginous black biofilm is covered by green spots formed by a green microalga and the macroscopic structures are packed together with fine material. Thin sections consist of rock substrate, soft biofilm, calcite spicules and mineral grains originating from different sources. The morphology of the spicules is typical of calcium carbonate monocrystals having a layered structure and specific surface texture, which reflect growth and degradation processes. The spicules' chemical composition and structure correspond to pure calcite. The lakes' age, altitude, morphometry, geomorphological and hydrological stability, including low sedimentation rates, together with thermal regime predispose the existence of this community. We hypothesise that the precipitation of calcite is connected with the photosynthetic activity of the green microalgae that were not recorded in any other lake in the region. This study has shown that the unique community producing biogenic calcite spicules is quite different to any yet described.

  14. Impact of seawater [Ca2+] on the calcification and calciteMg / Ca of Amphistegina lessonii

    NASA Astrophysics Data System (ADS)

    Mewes, A.; Langer, G.; Thoms, S.; Nehrke, G.; Reichart, G.-J.; de Nooijer, L. J.; Bijma, J.

    2015-04-01

    Mg / Ca ratios in foraminiferal tests are routinely used as paleotemperature proxies, but on long timescales, they also hold the potential to reconstruct past seawater Mg / Ca. The impact of both temperature and seawater Mg / Ca on Mg incorporation in Foraminifera has been quantified by a number of studies. The underlying mechanism responsible for Mg incorporation in foraminiferal calcite and its sensitivity to environmental conditions, however, has not been fully identified. A recently published biomineralization model (Nehrke et al., 2013) proposes a combination of transmembrane transport and seawater leakage or vacuolization to link calcite Mg / Ca to seawater Mg / Ca and explains inter-species variability in Mg / Ca ratios. To test the assumptions of this model, we conducted a culture study in which seawater Mg / Ca was manipulated by varying [Ca2+] and keeping [Mg2+] constant. Foraminiferal growth rates, test thickness and calcite Mg / Ca of newly formed chambers were analyzed. Results showed optimum growth rates and test thickness at Mg / Ca closest to that of ambient seawater. Calcite Mg / Ca is positively correlated to seawater Mg / Ca, indicating that it is not absolute seawater [Ca2+] and [Mg2+] but their ratio that controls Mg / Ca in tests. These results demonstrate that the calcification process cannot be based only on seawater vacuolization, supporting the mixing model proposed by Nehrke et al. (2013). Here, however, we suggest transmembrane transport fractionation that is not as strong as suggested by Nehrke et al. (2013).

  15. Noncrystallographic calcite dendrites from hot-spring deposits at Lake Bogoria, Kenya

    SciTech Connect

    Jones, B.; Renaut, R.W.

    1995-01-02

    Complex calcite crystals are an integral component of precipitates that form around the orifices of the Loburu and Mawe Moto hot springs on the shores of Lake bogoria, Kenya. Two types of large (up to 4 cm long) noncrystallographic dendrites are important components of these deposits. Feather dendrites are characterized by multiple levels of branching with individual branches developed through crystal splitting and spherulitic growth. Scandulitic (from Latin meaning shingle) dendrites are formed of stacked calcite crystals and are generally more compact than feather dendrites. These developed through the incremental stacking of rectangular-shaped calcite crystals that initially grew as skeletal crystals. Feather and scandulitic dendrites precipitated from the same waters in the same springs. The difference in morphology is therefore related to microenvironments in which they grew. Feather dendrites grew in any direction in pools of free-standing water provided that they were in constant contact with the solute. Conversely, scandulitic dendrites grew on rims of dams where water flowed over the surface in concert with the pulses of spring water. Thus, each calcite crystal in these dendrites represents one episode of crystal growth. The orientation of the component crystals in scandulitic dendrites is controlled by the topography of the dam or surface, not crystallographic criteria. The noncrystallographic dendrites formed from spring waters with initial temperatures of 90--99 C. Surficial water cooling, loss of CO{sub 2}, and presence of other elements that can interfere with crystal growth contributed to the formation of these unusual crystals.

  16. Modelling how incorporation of divalent cations affects calcite wettability–implications for biomineralisation and oil recovery

    NASA Astrophysics Data System (ADS)

    Andersson, M. P.; Dideriksen, K.; Sakuma, H.; Stipp, S. L. S.

    2016-06-01

    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase.

  17. Impact of seawater Ca2+ on the calcification and calcite Mg/Ca of Amphistegina lessonii

    NASA Astrophysics Data System (ADS)

    Mewes, A.; Langer, G.; Thoms, S.; Nehrke, G.; Reichart, G.-J.; de Nooijer, L. J.; Bijma, J.

    2014-12-01

    Mg/Ca ratios in foraminiferal tests are routinely used as paleo temperature proxy, but on long timescales, also hold the potential to reconstruct past seawater Mg/Ca. Impact of both temperature and seawater Mg/Ca on Mg incorporation in foraminifera have been quantified by a number of studies. The underlying mechanism responsible for Mg incorporation in foraminiferal calcite and its sensitivity to environmental conditions, however, is not fully identified. A recently published biomineralization model (Nehrke et al., 2013) proposes a combination of transmembrane transport and seawater leakage or vacuolization to link calcite Mg/Ca to seawater Mg/Ca and explains inter-species variability in Mg/Ca ratios. To test the assumptions of this model, we conducted a culture study in which seawater Mg/Ca was manipulated by varying [Ca2+] and keeping [Mg2+] constant. Foraminiferal growth rates, test thickness and calcite Mg/Ca of newly formed chambers were analyzed. Results showed optimum growth rates and test thickness at Mg/Ca closest to that of ambient seawater. Calcite Mg/Ca is positively correlated to seawater Mg/Ca, indicating that not absolute seawater [Ca2+] and [Mg2+], but the telative ratio controls Mg/Ca in tests. These results demonstrate that the calcification process cannot be based only on seawater vacuolization, supporting the mixing model proposed by Nehrke et al. (2013). Here we, however, suggest a transmembrane transport fractionation that is not as strong as suggested by Nehrke et al. (2013).

  18. Altered former alkalic carbonatite lava from Oldoinyo Lengai, Tanzania: Inferences for calcite carbonatite lavas

    NASA Astrophysics Data System (ADS)

    Dawson, J. B.; Garson, M. S.; Roberts, B.

    1987-08-01

    The active volcano Oldoinyo Lengai, Tanzania, is well known for its extrusions of alkalic carbonatite lava, first witnessed in 1960. An older carbonatite flow from the volcano was originally also rich in Na and K, but replacement of nyerereite by pirssonite as a result of leaching of these elements (together with soluble components such as SO3, Cl, and Rb) and addition of Ca has resulted in a rock intermediate in bulk composition between the unique 1960 Lengai lavas and calcite-rich carbonatite flows reported from other localities. Further replacement of Na by Ca could theoretically result in a pure calcite rock, and we suggest that the partially altered alkalic lava described here is the “missing link” between lavas that are now calcitic but which had a high alkali content when originally extruded. The suggested link between alkali carbonate precursors and present-day calcium carbonate “lavas” explains the apparent paradox between the existence of calcite-rich “flows” and the experimental evidence that denies the possibility of hot, liquid calcium carbonate.

  19. Kinetics and mechanisms of cadmium carbonate heteroepitaxial growth at the calcite (10 1bar 4) surface

    NASA Astrophysics Data System (ADS)

    Xu, Man; Kovarik, Libor; Arey, Bruce W.; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien

    2014-06-01

    Elucidating the kinetics and mechanisms of heteroepitaxial nucleation and growth at mineral-water interfaces is essential to understanding surface reactivity in geochemical systems. In the present work, the formation of heteroepitaxial cadmium carbonate coatings at calcite-water interfaces was investigated by exposing calcite (10 1bar 4) surfaces to Cd-bearing aqueous solutions. In situ atomic force microscopy (AFM) was employed as the primary technique. The AFM results indicate that the heteroepitaxial growth of cadmium carbonate proceeds via three different mechanisms depending on the initial supersaturation of the aqueous solution: advancement of existing steps, nucleation and growth of three-dimensional (3D) islands, and nucleation and spread of two-dimensional (2D) nuclei. The 3D islands and 2D nuclei exhibit different morphologies and growth kinetics. The effects of supersaturation on heteroepitaxial growth mechanisms can be interpreted in terms of the free energy barrier for nucleation. At low initial supersaturation, where 3D nucleation dominates, it is hypothesized, from the growth rate and morphology of the 3D islands observed with AFM, that the crystallization of the overgrowth follows a non-classical pathway involving the formation of a surface precursor that is not fully crystalline, whereas high supersaturation favors the formation of crystalline 2D nuclei whose morphology is based on the atomic structure of the calcite substrate. Cross-sectional transmission electron microscopy (TEM) images reveal that the atomic structure of the interface between the cadmium carbonate coating and calcite shows perfect, dislocation-free epitaxy.

  20. Inferences of paleoenvironment from petrographic, chemical and stable-isotope studies of calcretes and fracture calcites

    SciTech Connect

    Vaniman, D.T.; Whelan, J.F.

    1994-03-01

    Past research has indicated a genetic connection between calcite formed in calcretes at the surface of Yucca Mountain, Nevada, and calcites deposited in underlying fractures of the unsaturated zone. This common genesis suggests that paleoenvironmental information, as well as the timing and pathways of past recharge episodes, might be obtained from studies of the deposits in both the calcretes and the unsaturated fractures. Chemical and isotopic modification of calcite-precipitating fluids appears to begin at the surface, largely under the influence of plant roots and their decay products. Chemical characteristics of the deeper calcites are either initiated or largely defined within the first few meters of fluid migration into the unsaturated tuffs beneath the calcretes. However, petrographic and isotopic data indicate a very unique low-{delta}{sup 13}C microenvironment that is localized at the upper surfaces of the calcretes. These surfaces form an interface in the soil horizon where infiltration may pond above the underlying carbonate ``plug.`` In order to decipher the chemistry and petrology of past recharge events, it is important to first understand microenvironments such as this that contribute to mineral precipitation/dissolution events in the pedogenic environment.

  1. Calcite fracture fillings as indicators of paleohydrology at the Aspo Hard Rock Laboratory, Sweden

    SciTech Connect

    Wallin, B.; Peterman, Z.

    1995-12-01

    Isotopic compositions of carbon ({delta}{sup 13}C), oxygen ({delta}{sup 16}O) strontium ({delta}{sup 87}Sr) in calcite fracture fillings are being used to reconstruct the source and evolution of the groundwater at Aespoe and Laxemar, at the Aespoe Hard Rock Laboratory (AEHRL), south-eastern Sweden. These calcites precipitated from groundwater in the fractured crystalline rocks at some time in the past, and {delta}{sup 13}C, {delta}{sup 18}O and {delta}{sup 87}Sr values of the calcites reflect those of the source waters. The fracture fillings mark the pathways of past fluid movement so an understanding of their genesis is particularly important for understanding the paleohydrology in the area. The utility in applying the multiple-isotope approach to groundwater and fracture minerals derives from the fact that the different systems represent different processes. Studies of the groundwater chemistry suggest a very complicated history, however, the isotope data demonstrate that it is possible to postulate mixing of different groundwater members to explain the isotopic systematics of the calcite fracture fillings at Aespoe and Laxemar.

  2. NMR surface relaxivity of calcite with adsorbed Mn{sup 2+}

    SciTech Connect

    Kenyon, W.E.; Kolleeny, J.A.

    1995-03-15

    Calcite particles were exposed to Mn{sup 2+} in aqueous solution to allow adsorption. The calcite particles were then packed, and the NMR longitudinal relaxation time T{sub 1} of water saturating the interparticle pores was measured. NMR surface relaxivity was then computed as 1/(T{sub 1}{times}S{sub p}/V{sub p}), where S{sub p}/V{sub p} is the ratio of surface area to pore volume. Adsorbed manganese increases the NMR surface relaxivity to approximately 2.4 {times} 10{sup {minus}3} cm/s, roughly 50 times the surface relaxivity of very pure calcite. Flowing water with 4 {mu}M Mn{sup 2+} through a porous limestone plug decreased its T{sub 1} by a factor of 6. Iron as adsorbate produced relatively small increases in surface relaxivity. These results suggest that manganese dominates the surface relaxivity, of limestone rocks in situ, which is important in the interpretation of NMR borehole logs. Observations suggest that some adsorbed manganese eventually becomes buried by freshly precipitated calcite. In particular, the surface relaxivity increased with initial adsorption, but gradually decreased at long reaction times, even as the aqueous manganese concentration continued to decrease. NMR evidently senses only the manganese in the outermost atomic layer, and thus might prove useful in more detailed studies of adsorption.

  3. Visualising the molecular alteration of the calcite (104) - water interface by sodium nitrate.

    PubMed

    Hofmann, Sascha; Voïtchovsky, Kislon; Spijker, Peter; Schmidt, Moritz; Stumpf, Thorsten

    2016-01-01

    The reactivity of calcite, one of the most abundant minerals in the earth's crust, is determined by the molecular details of its interface with the contacting solution. Recently, it has been found that trace concentrations of NaNO3 severely affect calcite's (104) surface and its reactivity. Here we combine molecular dynamics (MD) simulations, X-ray reflectivity (XR) and in situ atomic force microscopy (AFM) to probe the calcite (104) - water interface in the presence of NaNO3. Simulations reveal density profiles of different ions near calcite's surface, with NO3(-) able to reach closer to the surface than CO3(2-) and in higher concentrations. Reflectivity measurements show a structural destabilisation of the (104) surfaces' topmost atomic layers in NaNO3 bearing solution, with distorted rotation angles of the carbonate groups and substantial displacement of the lattice ions. Nanoscale AFM results confirm the alteration of crystallographic characteristics, and the ability of dissolved NaNO3 to modify the structure of interfacial water was observed by AFM force spectroscopy. Our experiments and simulations consistently evidence a dramatic deterioration of the crystals' surface, with potentially important implications for geological and industrial processes. PMID:26877225

  4. Modelling how incorporation of divalent cations affects calcite wettability-implications for biomineralisation and oil recovery.

    PubMed

    Andersson, M P; Dideriksen, K; Sakuma, H; Stipp, S L S

    2016-01-01

    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase. PMID:27352933

  5. Inhibition of calcite precipitation by natural organic material: Kinetics, mechanism, and thermodynamics

    USGS Publications Warehouse

    Lin, Y.-P.; Singer, P.C.; Aiken, G.R.

    2005-01-01

    The inhibition of calcite precipitation by natural organic material (NOM) in solutions seeded with calcite was investigated using a pH-stat system. Experiments were carried out using three NOMs with different physical/chemical properties. For each of the materials, inhibition was found to be more effective at lower carbonate/calcium ratios and lower pH values. The reduction in the precipitation rate could be explained by a Langmuir adsorption model using a conditional equilibrium constant. By identification of the type of site on the NOM molecules that is involved in the adsorption reaction, the "conditional" equilibrium constants obtained at different solution compositions converged to a single "nonconditional" value. The thermodynamic data determined at 25??C and 1 atm suggest that the interaction between NOM molecules and the calcite surface is chemisorptive in nature and that adsorption is an endothermic reaction driven by the entropy change. The greatest degree of inhibition was observed for the NOM with the highest molecular weight and aromatic carbon content. For a given type of NOM, the degree of inhibition of calcite precipitation was dictated by the balance between the enthalpy change and the entropy change of the adsorption reaction. ?? 2005 American Chemical Society.

  6. Comparison of solidification/stabilization effects of calcite between Australian and South Korean cements

    SciTech Connect

    Lee, Dongjin; Waite, T. David . E-mail: d.waite@unsw.edu.au; Swarbrick, Gareth; Lee, Sookoo

    2005-11-15

    The differences in the effect of calcite on the strength and stability of Pb-rich wastes solidified and stabilized using Australian and South Korean ordinary Portland cements are examined in this study. Pb-rich waste stabilized using Australian OPC has been shown to possess both substantially higher unconfined compressive strength and lead immobilization ability than South Korean OPC as a result of its higher C{sub 3}S content and the associated enhanced degree of precipitation of lead on the surfaces of silicate phases present. Calcite addition is observed to have an accelerating effect on the OPC-induced solidification/stabilization of Pb-rich wastes as gauged by the unconfined compressive strength and leachability of the solids formed. This effect is observed to be far more dramatic for South Korean OPC than for Australian OPC. Using scanning electron microscopy, waste stabilized with cement and calcite was observed to develop significantly greater proportions of hydrated crystals than wastes stabilized with cement alone. The results of X-ray diffraction studies have shown that the presence of calcite in South Korean OPC results in greater acceleration in the formation of portlandite than is the case for Australian OPC.

  7. Intercalation of sea urchin proteins in calcite: Study of a crystalline composite material

    SciTech Connect

    Berman, A.; Addadi, L.; Leiserowitz, L.; Weiner, S. ); Kvick, A.; Nelson, M. )

    1990-11-02

    Sea urchin skeletal elements are composed of single crystals of calcite. Unlike their synthetic counterparts, these crystals do not have well-developed cleavage and are consequently much more resistant to fracture. This phenomenon is due in part to the presence of acidic glycoproteins occluded within the crystals. By means of x-ray diffraction with synchrotron radiation, it is shown that the presence of the protein in synthetic calcite only slightly decreases the coherence length but significantly increases the angular spread of perfect domains of the crystals. In biogenic calcite, the coherence length is 1/3 to 1/4 as much as that in synthetic calcite and the angular spread is 20 to 50 times as wide. It is proposed that the presence of macromolecules concentrated at mosaic boundaries that are oblique to cleavage planes is responsible for the change in fracture properties. These results may be important in the material sciences, because of the unusual nature of this material, namely, a composite based on the controlled intercalation of macromolecules inside single-crystal lattices. 20 refs., 3 figs.

  8. Control of macromolecule distribution within synthetic and biogenic single calcite crystals

    SciTech Connect

    Aizenberg, J.; Weiner, S.; Addadi, L.; Hanson, J.; Koetzle, T.F.

    1997-02-05

    The ability of organisms to exercise control over crystal growth is wonderfully exemplified by skeleton formation in echinoderms. A sea urchin spine is a unique composite of a single crystal of calcite and glycoproteins intercalated inside the crystal during its growth. Here we performed a detailed morphological and high-resolution synchrotron X-ray diffraction study of the textures of synthetic and biogenic calcite crystals. We show that the intracrystalline macromolecules from sea urchin spines, when allowed to interact with growing calcite crystals in vitro, selectively reduce the coherence lengths and degrees of alignment of the perfect domains in specific crystallographic directions. These directions also correspond to the newly-developed stable faces. In contrast, the defect distribution of young sea urchin spines composed entirely of spongy stereomic structure is much more isotropic. In mature spines containing secondarily filled-in wedges of calcite, the degree of anisotropy is intermediate between that of the synthetic crystals and the young spines. The macromolecules extracted from young and mature spines are, however, very similar. These observations demonstrate the inherent capability of occluded matrix macromolecules to finely differentiate between crystal planes by stereochemical recognition processes. 20 refs., 5 figs., 2 tabs.

  9. Kinetics and Mechanisms of Cadmium Carbonate Heteroepitaxial Growth at the Calcite (101¯4) Surface

    SciTech Connect

    Xu, Man; Kovarik, Libor; Arey, Bruce W.; Felmy, Andrew R.; Rosso, Kevin M.; Kerisit, Sebastien N.

    2014-06-01

    Elucidating the kinetics and mechanisms of heteroepitaxial nucleation and growth at mineral-water interfaces is essential to understanding surface reactivity in geochemical systems. In the present work, the formation of heteroepitaxial cadmium carbonate coatings at calcite-water interfaces was investigated by exposing calcite (10-14) surfaces to Cd-bearing aqueous solutions. In situ atomic force microscopy (AFM) was employed as the primary technique. The AFM results indicate that the heteroepitaxial growth of cadmium carbonate proceeds via three different mechanisms depending on the initial supersaturation of the aqueous solution: advancement of existing steps, nucleation and growth of three-dimensional (3D) islands, and nucleation and spread of two-dimensional (2D) nuclei. The 3D islands and 2D nuclei exhibit different morphologies and growth kinetics. The effects of supersaturation on heteroepitaxial growth mechanisms can be interpreted in terms of the free energy barrier for nucleation. At low initial supersaturation, where 3D nucleation dominates, it is hypothesized, from the growth rate and morphology of the 3D islands observed with AFM, that the crystallization of the overgrowth follows a non-classical pathway involving the formation of a surface precursor that is not fully crystalline, whereas high supersaturation favors the formation of crystalline 2D nuclei whose morphology is based on the atomic structure of the calcite substrate. Cross-sectional transmission electron microscopy (TEM) images reveal that the atomic structure of the interface between the cadmium carbonate coating and calcite shows perfect, dislocation-free epitaxy.

  10. STIMULATION OF MICROBIAL UREA HYDROLYSIS IN GROUNDWATER TO ENHANCE CALCITE PRECIPITATION

    SciTech Connect

    Yoshiko Fujita; Joanna L. Taylor; Tina L. Gresham; Mark E. Delwiche; Frederick S. Colwell; Travis McLing; Lynn Petzke; Robert W. Smith

    2008-04-01

    Sequential addition of molasses and urea was tested as a means of stimulating microbial urea hydrolysis in the Eastern Snake River Plain Aquifer in Idaho. Ureolysis is an integral component of a novel remediation approach for divalent trace metal and radionuclide contaminants in groundwater and associated geomedia, where the contaminants are immobilized by coprecipitation in calcite. The generation of carbonate alkalinity from ureolysis promotes calcite precipitation. In calcite-saturated aquifers, this represents a potential long-term contaminant sequestration mechanism. In a single well experiment, dilute molasses was injected three times over two weeks to promote overall microbial growth, followed by one urea injection. With molasses addition, total cell numbers in the groundwater increased one to two orders of magnitude. Estimated ureolysis rates in recovered groundwater samples increased from <0.1 nmol L-1 hr-1 to >25 nmol L-1 hr-1. A quantitative PCR assay for the bacterial ureC gene indicated that urease gene numbers increased up to 170 times above pre-injection levels. Following urea injection, calcite precipitates were recovered. Estimated values for an in situ first order ureolysis rate constant ranged from 0.016 to 0.057 day-1. The results are promising with respect to the potential to manipulate in situ biogeochemical processes to promote contaminant sequestration.

  11. Probing the energetics of organic-nanoparticle interactions of ethanol on calcite.

    PubMed

    Wu, Di; Navrotsky, Alexandra

    2015-04-28

    Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. Herein, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic-NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. These thermochemical observations directly support a structure where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. These differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces. PMID:25870281

  12. QUANTUM-STATE RESOLVED PRODUCTS VIA VACUUM ULTRAVIOLET PHOTOSTIMULATED DESORPTION FROM GEOLOIC CALCITE

    EPA Science Inventory

    We report the results of a photostimulated desorption (PSD) study of neutral CO products from room temperature geologic calcite utilizing fluences <300 microJ/cm2 of 157-nm excimer laser radiation. At this wavelength, we are coincident with an intense absorption peak such that m...

  13. Unusual biogenic calcite structures in two shallow lakes, James Ross Island, Antarctica

    NASA Astrophysics Data System (ADS)

    Elster, J.; Nedbalová, L.; Vodrážka, R.; Láska, K.; Haloda, J.; Komárek, J.

    2015-08-01

    The floors of two shallow endorheic lakes, located on volcanic surfaces on James Ross Island, are covered with calcareous organosedimentary structures. Their biological and chemical composition, lake water characteristics, and seasonal variability of the thermal regime are introduced. The lakes are frozen down to the bottom eight-nine months per year and their water chemistry is characterized by low conductivity and neutral to slightly alkaline pH. The photosynthetic microbial mat is composed of filamentous cyanobacteria and microalgae that are considered to be Antarctic endemic species. The mucilaginous black biofilm is covered by green spots formed by a green microalga and the macroscopic structures are packed together with fine material. Thin sections consist of rock substrate, soft biofilm, calcite spicules and mineral grains originating from different sources. The morphology of the spicules is typical of calcium carbonate monocrystals having a layered structure and worn surface, which reflect growth and degradation processes. The spicules chemical composition and structure correspond to pure calcite. Lakes age, altitude, morphometry, geomorphological and hydrological stability, including low sedimentation rates, together with thermal regime predispose the existence of this community. We hypothesize that the precipitation of calcite is connected with the photosynthetic activity of the green microalgae that were not recorded in any other lake in the region. This study has shown that the unique community producing biogenic calcite spicules is quite different to any yet described.

  14. Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

    PubMed Central

    Wu, Di; Navrotsky, Alexandra

    2015-01-01

    Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. Herein, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic–NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. These thermochemical observations directly support a structure where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. These differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces. PMID:25870281

  15. Amelogenin processing by MMP-20 prevents protein occlusion inside calcite crystals

    PubMed Central

    Bromley, Keith M.; Lakshminarayanan, Rajamani; Thompson, Mitchell; Lokappa, Sowmya B.; Gallon, Victoria A.; Cho, Kang R.; Qiu, S. Roger; Moradian-Oldak, Janet

    2012-01-01

    Calcite crystals were grown in the presence of full-length amelogenin and during its proteolysis by recombinant human matrix metalloproteinase 20 (rhMMP-20). Recombinant porcine amelogenin (rP172) altered the shape of calcite crystals by inhibiting the growth of steps on the {104} faces and became occluded inside the crystals. Upon co-addition of rhMMP-20, the majority of the protein was digested resulting in a truncated amelogenin lacking the C-terminal segment. In rP172-rhMMP-20 samples, the occlusion of amelogenin into the calcite crystals was drastically decreased. Truncated amelogenin (rP147) and the 25-residue C-terminal domain produced crystals with regular shape and less occluded organic material. Removal of the C-terminal diminished the affinity of amelogenin to the crystals and therefore prevented occlusion. We hypothesize that HAP and calcite interact with amelogenin in a similar manner. In the case of each material, full-length amelogenin binds most strongly, truncated amelogenin binds weakly and the C-terminus alone has the weakest interaction. Regarding enamel crystal growth, the prevention of occlusion into maturing enamel crystals might be a major benefit resulting from the selective cleavage of amelogenin at the C-terminus by MMP-20. Our data have important implications for understanding the hypomineralized enamel phenotype in cases of amelogenesis imperfecta resulting from MMP-20 mutations and will contribute to the design of enamel inspired biomaterials. PMID:23226976

  16. Modelling how incorporation of divalent cations affects calcite wettability–implications for biomineralisation and oil recovery

    PubMed Central

    Andersson, M. P.; Dideriksen, K.; Sakuma, H.; Stipp, S. L. S.

    2016-01-01

    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase. PMID:27352933

  17. [Comparative analysis of seven marine biological source of mineral drugs].

    PubMed

    Si, Wei; A, Ru-na; Li, Shang-rong; Zhang, Jing-Xian; Wu, Wan-ying; Cui, Ya-jun

    2014-09-01

    The marine biological source of mineral drugs recorded in Chinese Pharmacopoeia (2010 version) mainly including pearl, nacre, clam shell, common oyster shell, ark shell, cuttle bone, and sea-ear shell are widely used in clinical. Calcium carbonate and a small amount of protein are the main components in this type of drugs. In this paper, a systematical and comparable study were carried out by determination of calcium carbonate by EDTA titration method, the crystal of calcium carbonate by X-Ray powder diffraction and the total amino acids (TAAs) of the hydrolyzed samples by ultraviolet spectrophotometry method. As a result, the crystal structure is calcite for common oyster shell, mixture of calcite and aragonite for nacre and sea-ear shell, aragonite for the other drugs. The content of calcium carbonate ranged from 86% to 96%. Cuttle bone has the highest amount of TAAs among the seven drugs which reached 1.7% while clam shell has the lowest content of 0.16% on average. In conclusion, an effective method was developed for the quality control of marine mineral drugs by comprehensive analysis of calcium carbonate and TAAs in the seven marine mineral drugs. PMID:25522620

  18. Tracing formation and durability of calcite in a Punic-Roman cistern mortar (Pantelleria Island, Italy).

    PubMed

    Dietzel, Martin; Schön, Frerich; Heinrichs, Jens; Deditius, Artur P; Leis, Albrecht

    2016-01-01

    Ancient hydraulic lime mortar preserves chemical and isotopic signatures that provide important information about historical processing and its durability. The distribution and isotopic composition of calcite in a mortar of a well-preserved Punic-Roman cistern at Pantelleria Island (Italy) was used to trace the formation conditions, durability, and individual processing periods of the cistern mortar. The analyses of stable carbon and oxygen isotopes of calcite revealed four individual horizons, D, E, B-1 and B-2, of mortar from the top to the bottom of the cistern floor. Volcanic and ceramic aggregates were used for the production of the mortar of horizons E/D and B-1/B-2, respectively. All horizons comprise hydraulic lime mortar characterized by a mean cementation index of 1.5 ± 1, and a constant binder to aggregate ratio of 0.31 ± 0.01. This suggests standardized and highly effective processing of the cistern. The high durability of calcite formed during carbonation of slaked lime within the matrix of the ancient mortar, and thus the excellent resistance of the hydraulic lime mortar against water, was documented by (i) a distinct positive correlation of δ(18)Ocalcite and δ(13)Ccalcite; typical for carbonation through a mortar horizon, (ii) a characteristic evolution of δ(18)Ocalcite and δ(13)Ccalcite through each of the four mortar horizons; lighter follow heavier isotopic values from upper to lower part of the cistern floor, and (iii) δ(18)Ocalcite varying from -10 to -5 ‰ Vienna Pee Dee belemnite (VPDB). The range of δ(18)Ocalcite values rule out recrystallization and/or neoformation of calcite through chemical attack of water stored in cistern. The combined studies of the chemical composition of the binder and the isotopic composition of the calcite in an ancient mortar provide powerful tools for elucidating the ancient techniques and processing periods. This approach helps to evaluate the durability of primary calcite and demonstrates the

  19. The kinetics of clumped-isotope reactions in calcite and apatite from natural and experimental samples

    NASA Astrophysics Data System (ADS)

    Stolper, D. A.; Eiler, J. M.

    2014-12-01

    Measurements of clumped isotopes of carbonate-bearing minerals are a powerful tool for reconstructing past surface temperatures and thermal histories of shallow crustal rocks. Because the clumped-isotope thermometer is based on homogenous-phase equilibrium, a sample's clumped-isotope temperature is susceptible to resetting through, for example, intracrystalline diffusion and redistribution of C and O isotopes during (re)heating or slow cooling. Quantitative knowledge of the kinetics of this resetting have received increasing attention (1-3) and is critical for understanding the meaning of clumped-isotope temperatures of samples with complex burial histories. To better constrain these kinetics and complement previous work (1-3) we performed heating experiments (400-700°C) on optical calcites and carbonate-bearing apatites. As previously observed (2-3), calcites exhibit non-first-order kinetics. The data were fit using a model that incorporates both diffusion and isotope-exchange reactions (4). The kinetics derived with this model using the optical-calcite heating experiments of (2) and those measured here are indistinguishable. The model predicts that subtle changes (>10°C) in measured calcite clumped-isotope temperatures can occur at burial temperatures between 60-100°C on million-year timescales. Though small, such changes may have an impact on clumped-isotope-based reconstructions of past surface temperatures and thermal histories. The derived kinetics were compared to clumped-isotope measurements of cogenetic calcites and apatites from slowly cooled carbonatite intrusions. Apparent temperatures are 70-140°C for apatites and 120-190°C for calcites. Measured temperatures for calcites match modeled temperatures using reasonable geological cooling rates. Natural apatite samples yield lower apparent temperatures than predicted based on the model. We propose that this difference is the result of annealment of structural damage in apatites (e.g., generated by

  20. Carbonates in thrust faults: High temperature investigations into deformation processes in calcite-dolomite systems

    NASA Astrophysics Data System (ADS)

    Kushnir, A.; Kennedy, L.; Misra, S.; Benson, P.

    2012-04-01

    The role of dolomite on the strength and evolution of calcite-dolomite fold and thrust belts and nappes (as observed in the Canadian Rockies, the Swiss Alps, the Italian Apennines, and the Naukluft Nappe Complex) is largely unknown. Field investigations indicate that strain in natural systems is localized in calcite, resulting in a ductile response, while dolomite deforms in a dominantly brittle manner. To date, experimental studies on polymineralic carbonate systems are limited to homogeneous, fine-grained, calcite-dolomite composites of relatively low dolomite content. The effect of dolomite on limestone rheology, the onset of crystal-plastic deformation in dolomite in composites, and the potential for strain localization in composites have not yet been fully quantified. Constant displacement rate (3x10-4 s-1and 10-4 s-1), high confining pressure (300 MPa) and high temperature (750° C and 800° C) torsion experiments were conducted to address the role of dolomite on the strength of calcite-dolomite composites. Experiments were performed on samples produced by hot isostatic pressing (HIP) amalgams of a natural, pure dolomite and a reagent, pure calcite. We performed experiments on the following mixtures (given as dolomite%): 25%, 35%, 50%, and 75%. These synthetic HIP products eliminated concerns of mineralogical impurities and textural anomalies due to porosity, structural fabrics (e.g., foliation) and fossil content. The samples were deformed up to a maximum finite shear strain of 5.0 and the experimental set up was unvented to inhibit sample decarbonation. Mechanical data shows a considerable increase in sample yield strength with increasing dolomite content. Experimental products with low starting dolomite content (dol%: 25% and 35%) display macroscopic strain localization along compositionally defined foliation. Experimental products with high dolomite content (dol%: 50% and 75%) demonstrate no macroscopic foliation. Post-deformation microstructure analysis

  1. Experimental study of the effect of mica on pressure solution of single crystal calcite

    NASA Astrophysics Data System (ADS)

    Karcz, Z.; Laronne, L.; Polizzotti, R. S.; Ertas, D.; Aharonov, E.

    2007-12-01

    Field and experimental studies suggest that clays and micas accelerate the rate of pressure solution in various geomaterials. It is not clear however whether the "clay effect" is purely mechanical (i.e., maintaining a thick conduit for fluids at the contact) or whether its surface chemistry plays a critical role. A case in point is the insoluble clay filling of stylolites, which are thought by some to be merely an inert byproduct of dissolution, or by others to be a necessary feature for the propagation of the seam. To study the effect of mica on carbonate pressure solution, the corner of a cleaved calcite single crystal rhomb was polished into a triangular face (edge length ~ 200micron) and pressed against either muscovite or quartz discs to yield a nominal stress of 10-20MPa. Immersing the contact in pre-saturated (with respect to microcrystalline calcite) solutions of distilled water or 0.25M NH4Cl caused axial shortening of the crystal. This axial strain was measured with a capacitance sensor (<0.5nm/h resolution) while the contact morphology was imaged in situ with a confocal microscope (3micron spatial resolution). In pre-saturated water solution the axial shortening of calcite loaded against muscovite is ~1nm/h, and no significant changes in contact morphology are detected. In pre-saturated NH4Cl solution however, both calcite- quartz and calcite-muscovite contacts evolve in two stages: the first stage is characterized by low axial strain rates (<5nm/h) during which the original contact area inside the triangle (as determined by interference fringes) shrinks and its perimeter roughens. The second stage is distinguished by high axial strain rates (~40nm/h) and changes in the size and spatial position of isolated contacts (diameter< 10 microns) in a dynamic channel-island morphology covering the entire triangular region. Post-experiment SEM analysis suggests dissolution in this region and precipitation on the free faces adjacent to it. At this point we see no

  2. Experimental study of the effect of mica on pressure solution of single crystal calcite

    NASA Astrophysics Data System (ADS)

    Karcz, Z.; Laronne, L.; Polizzotti, R. S.; Ertas, D.; Aharonov, E.

    2004-12-01

    Field and experimental studies suggest that clays and micas accelerate the rate of pressure solution in various geomaterials. It is not clear however whether the "clay effect" is purely mechanical (i.e., maintaining a thick conduit for fluids at the contact) or whether its surface chemistry plays a critical role. A case in point is the insoluble clay filling of stylolites, which are thought by some to be merely an inert byproduct of dissolution, or by others to be a necessary feature for the propagation of the seam. To study the effect of mica on carbonate pressure solution, the corner of a cleaved calcite single crystal rhomb was polished into a triangular face (edge length ~ 200micron) and pressed against either muscovite or quartz discs to yield a nominal stress of 10-20MPa. Immersing the contact in pre-saturated (with respect to microcrystalline calcite) solutions of distilled water or 0.25M NH4Cl caused axial shortening of the crystal. This axial strain was measured with a capacitance sensor (<0.5nm/h resolution) while the contact morphology was imaged in situ with a confocal microscope (3micron spatial resolution). In pre-saturated water solution the axial shortening of calcite loaded against muscovite is ~1nm/h, and no significant changes in contact morphology are detected. In pre-saturated NH4Cl solution however, both calcite- quartz and calcite-muscovite contacts evolve in two stages: the first stage is characterized by low axial strain rates (<5nm/h) during which the original contact area inside the triangle (as determined by interference fringes) shrinks and its perimeter roughens. The second stage is distinguished by high axial strain rates (~40nm/h) and changes in the size and spatial position of isolated contacts (diameter< 10 microns) in a dynamic channel-island morphology covering the entire triangular region. Post-experiment SEM analysis suggests dissolution in this region and precipitation on the free faces adjacent to it. At this point we see no

  3. Factors controlling the growth rate, carbon and oxygen isotope variation in modern calcite precipitation in a subtropical cave, Southwest China

    NASA Astrophysics Data System (ADS)

    Pu, Junbing; Wang, Aoyu; Shen, Licheng; Yin, Jianjun; Yuan, Daoxian; Zhao, Heping

    2016-04-01

    A prerequisite for using cave speleothems to reconstruct palaeoenvironmental conditions is an accurate understanding of specific factors controlling calcite growth, in particular the isotopic partitioning of oxygen (δ18O) and carbon (δ13C) which are the most commonly used proxies. An in situ monitoring study from April 2008 to September 2009 at Xueyu Cave, Chongqing, SW China, provides insight into the controls on calcite growth rates, drip water composition, cave air parameters and δ18O and δ13C isotopic values of modern calcite precipitation. Both cave air PCO2 and drip water hydrochemical characteristics show obvious seasonality driven by seasonal changes in the external environment. Calcite growth rates also display clear intra-annual variation, with the lowest values occurring during wet season and peak values during the dry season. Seasonal variations of calcite growth rate are primarily controlled by variations of cave air PCO2 and drip water rate. Seasonal δ18O-VPDB and δ13C-VPDB in modern calcite precipitates vary, with more negative values in the wet season than in the dry season. Strong positive correlation of δ18O-VPDB vs. δ13C-VPDB is due to simultaneous enrichment of both isotopes in the calcite. This correlation indicates that kinetic fractionation occurs between parent drip water and depositing calcite, likely caused by the variations of cave air PCO2 and drip rate influenced by seasonal cave ventilation. Kinetic fractionation amplifies the equilibrium fractionation value of calcite δ18O (by ∼1.5‰) and δ13C (by ∼1.7‰), which quantitatively reflects surface conditions during the cave ventilation season. These results indicate that the cave monitoring of growth rate and δ18O and δ13C of modern calcite precipitation are necessary in order to use a speleothem to reconstruct palaeoenvironment.

  4. Vein-filling calcites (petrography and geochemistry): Balcones fault zone, Upper Cretaceous outcrops, north-central Texas

    SciTech Connect

    Dawson, W.C.; Szymczyk, H.M.; Reaser, D.F.

    1994-09-01

    The Austin Chalk and the underlying Eagle Ford Shale are transacted by en echelon faults and fractures, associated with the Balcones fault zone, along an outcrop trend that extends from Dallas to Austin, Texas. These faults and fractures strike northeastward (N35{degrees} to 40{degrees}E) and are cemented by multiple generations of sparry calcite. Vein widths range from 0.1 to 45 cm. Slickensides, preserved on outer surfaces of calcite cements, record fault movement. Inclusions of country rock are present within calcite-filled veins, and rarely, open fracture porosity is observed in outcrop. Early calcite cements are nonferroan and later cements are ferroan calcite. Petrographic analyses indicate the occurrence of {open_quotes}fir-tree{close_quotes} zoning and fluorescent inclusions within calcite cements. Vein-filling cements have stable isotopic signatures ({delta}{sup 18}O-6.3 to -9.8{per_thousand} PDB; {delta}{sup 13}C +1.6 to +2.5{per_thousand} PDB) that are markedly depleted in {delta}{sup 13}O relative to the chalk matrix, inoceramid shells, and the estimated value for Cretaceous seawater. Trace element analyses indicate the presence of strontium (980-1600 ppm), manganese (750-1975 ppm), zinc (10-20 ppm), and copper (5-10 ppm) in the calcite cements. The negative {delta}{sup 18}O signatures of the vein-filling calcites are suggestive of precipitation from warm fluids. {delta}{sup 13}C analyses reveal that the Austin Chalk buffered the carbon incorporated into the calcite cements. These veins probably formed by a {open_quotes}crack-seat mechanism{close_quotes} whereby episodic increases in hydropressure caused fracturing. Precipitation of calcite cements within fractures is induced by subsequent decreases in pore pressure. Tectonic and diagenetic features in these outcrops provide analogs for fractured Austin Chalk reservoirs.

  5. Eu3+ uptake by calcite: preliminary results from coprecipitation experiments and observations with surface-sensitive techniques.

    PubMed

    Stipp, S L S; Lakshtanov, L Z; Jensen, J T; Baker, J A

    2003-03-01

    A lack of information in databases for contamination risk assessment about the transport behaviour of the trivalent f-orbital elements in groundwater systems where calcite is at equilibrium motivated this study of Eu(3+) uptake. The free drift technique was used to examine the effects of Eu(3+) concentration, presence of Na(+) or K(+) and temperature, as well as calcite nucleation and precipitation kinetics, on the partitioning of calcite. Changes in surface composition and morphology resulting from exposure of single crystals of Iceland spar to Eu(3+)-bearing solutions were observed with X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). First results confirm that calcite has high affinity for Eu(3+). Rates of nucleation and precipitation strongly affect the extent of uptake but the presence of Na(+) and K(+) has no effect, suggesting formation of solid solution as CaCO(3)-EuOHCO(3). Surface-sensitive techniques prove that Eu(3+) is adsorbed to calcite even when the surface is dissolving and adsorption is not accompanied by precipitation of a separate Eu(3+)-solid phase. Adsorbed Eu modifies calcite's dissolution behaviour, roughening terraces and rounding step edges, and producing surface morphology where some surface sites appear blocked. Results imply that Eu(3+) concentrations in natural calcites are limited by Eu(3+) availability rather than by a lack of ability to fit into calcite's atomic structure. This behaviour can probably be expected for other trivalent rare Earth elements (REE), actinides and fission products whose behaviour is similar to that of Eu(3+). These elements are likely to be incorporated within the calcite bulk in systems where it is precipitating and the demonstrated strong partitioning ensures some uptake even where calcite is at or under saturation. PMID:12598092

  6. Evolution of calcite growth morphology in the presence of magnesium: Implications for the dolomite problem

    NASA Astrophysics Data System (ADS)

    Hong, Mina; Xu, Jie; Teng, Henry H.

    2016-01-01

    The effect of magnesium on calcite growth morphology was known to occur as step rounding in some cases and surface segmentation in others. What remains unknown are the conditions for and the relations between the different effects, suggesting a lack of comprehensive understanding of the fundamental cause. Here we investigated the evolution of spiral hillock morphology on calcite cleavage surfaces in solutions with increasing Ca to Mg ratios and supersaturation levels using in situ atomic force microscopy. We isolated the effects of Mg and saturation by conducting experiments under conditions of constant pH, ionic strength, and Ca2+/CO32-. Our results revealed three types of morphological variations, ranging from step rounding in one direction (type I), to all directions (type II), and finally to a mosaic-like surface segmentation associated with monolayer buckling and step bunching (type III). These results suggest that the effect of magnesium on calcite growth depends upon multiple parameters including the concentration of Mg in solution, the step speed, as well as the extensiveness of Mg for Ca substitution in calcite lattice. We propose that the morphological variation may be understood by a model taken into consideration of (1) the lifespan and flux size of Mg ions at kinks in comparison to step kinetics, and (2) the diffusion and alignment of point defects created by the substitution of Mg for Ca in the crystal lattice. Stress calculations show that the maximum amount of Mg which calcite lattice can sustain before plastic deformation is ∼40%, suggesting that lattice stress due to the mismatch between MgCO3 and CaCO3 is likely the ultimate cause for the difficulty of ambient condition dolomite crystallization.

  7. Calcite solubility in supercritical CO 2H 2O fluids

    NASA Astrophysics Data System (ADS)

    Fein, Jeremy B.; Walther, John V.

    1987-06-01

    An extraction-quench apparatus was used to measure calcite solubilities in supercritical CO 2H 2O mixtures. Experiments were conducted at 1 kbar and 2 kbar, between 240°C and 620°C and from XCO 2 = .02 toXCO 2 = .15 in order to determine the solubility behavior as a function of pressure, temperature and CO 2 content. The results indicate that calcite solubilities under these conditions behave similarly to previously investigated calcite solubilities at lower pressures and temperatures (SHARP and Kennedy, 1965). At constant XCO 2, the solubility increases with increasing pressure, but it decreases with increasing temperature. When the temperature and pressure are constant, the calcite solubility rises with increasing XCO 2 to a maximum value at XCO 2 between 0.02 and 0.05. For higher CO 2 contents, up to XCO 2 = .15, the calcite solubility decreases, probably due to the decrease of H 2O activities to values significantly below unity. The solubility behavior can be successfully modeled by making the assumption that Ca ++ is the dominant calcium species and that the carbon-bearing species are CO 2(aq) and HCO -3. Since for these dilute H 2OCO 2 fluids, all activity coefficients can be assumed to not differ significantly from unity, ionization constants for the reaction H 2O + CO 2(aq) H + + HCO -3 can be calculated at 1 and 2 kbar between 250°C and 550°C. These calculated values are in good agreement with the low temperature determinations of the ionization constants for this reaction determined by Read (1975). Values of the molal Gibbs free energy of CO 2(aq) obtained in our study exhibit a much greater positive departure from ideality than those calculated with the modified Redlich-Kwong equations of either Flowers (1979) or Kerrick and Jacobs (1981) for dilute CO 2 aqueous solutions.

  8. Influence of calcite and dissolved calcium on uranium(VI) sorption to a hanford subsurface sediment.

    PubMed

    Dong, Wenming; Ball, William P; Liu, Chongxuan; Wang, Zheming; Stone, Alan T; Bai, Jing; Zachara, John M

    2005-10-15

    The influence of calcite and dissolved calcium on U(VI) adsorption was investigated using a calcite-containing sandy silt/clay sediment from the U. S. Department of Energy Hanford site. U(VI) adsorption to sediment, treated sediment, and sediment size fractions was studied in solutions that both had and had not been preequilibrated with calcite, at initial [U(VI)] = 10(-7)-10(-5) mol/L and final pH = 6.0-10.0. Kinetic and reversibility studies (pH 8.4) showed rapid sorption (30 min), with reasonable reversibility in the 3-day reaction time. Sorption from solutions equilibrated with calcite showed maximum U(VI) adsorption at pH 8.4 +/- 0.1. In contrast, calcium-free systems showed the greatest adsorption at pH 6.0-7.2. At pH > 8.4, U(VI) adsorption was identical from calcium-free and calcium-containing solutions. For calcite-presaturated systems, both speciation calculations and laser-induced fluorescence spectroscopic analyses indicated that aqueous U(VI) was increasingly dominated by Ca2UO2(CO3)3(0)(aq) at pH < 8.4 and thatformation of Ca2UO2(CO3)3(0)(aq) is what suppresses U(VI) adsorption. Above pH 8.4, aqueous U(VI) speciation was dominated by UO2(CO3)3(4-) in all solutions. Finally, results also showed that U(VI) adsorption was additive in regard to size fraction but not in regard to mineral mass: Carbonate minerals may have blocked U(VI) access to surfaces of higher sorption affinity. PMID:16295860

  9. Visualizing Organophosphate Precipitation at the Calcite-Water Interface by in Situ Atomic-Force Microscopy.

    PubMed

    Wang, Lijun; Qin, Lihong; Putnis, Christine V; Ruiz-Agudo, Encarnación; King, Helen E; Putnis, Andrew

    2016-01-01

    Esters of phosphoric acid constitute a large fraction of the total organic phosphorus (OP) in the soil environment and, thus, play an important role in the global phosphorus cycle. These esters, such as glucose-6-phosphate (G6P), exhibit unusual reactivity toward various mineral particles in soils, especially those containing calcite. Many important processes of OP transformation, including adsorption, hydrolysis, and precipitation, occur primarily at mineral-fluid interfaces, which ultimately governs the fate of organophosphates in the environment. However, little is known about the kinetics of specific mineral-surface-induced adsorption and precipitation of organophosphates. Here, by using in situ atomic-force microscopy (AFM) to visualize the dissolution of calcite (1014) faces, we show that the presence of G6P results in morphology changes of etch pits from the typical rhombohedral to a fan-shaped form. This can be explained by a site-selective mechanism of G6P-calcite surface interactions that stabilize the energetically unfavorable (0001) or (0112) faces through step-specific adsorption of G6P. Continuous dissolution at calcite (1014)-water interfaces caused a boundary layer at the calcite-water interface to become supersaturated with respect to a G6P-Ca phase that then drives the nucleation and growth of a G6P-Ca precipitate. Furthermore, after the introduction of the enzyme alkaline phosphatase (AP), the precipitates were observed to contain a mixture of components associated with G6P-Ca, amorphous calcium phosphate (ACP)-hydroxyapatite (HAP) and dicalcium phosphate dihydrate (DCPD). These direct dynamic observations of the transformation of adsorption- and complexation-surface precipitation and enzyme-mediated pathways may improve the mechanistic understanding of the mineral-interface-induced organophosphate sequestration in the soil environment. PMID:26636475

  10. Fault evolution in the North Peloponnese inferred from calcite dating and syntectonic sedimentary characteristics

    NASA Astrophysics Data System (ADS)

    Causse, C.; Moretti, I.; Eschard, R.; Micarelli, L.

    2003-04-01

    The evolution of the Gulf of Corinth is often described as a two phases process with a slow first phase and a second fast one from Late Pliocene to now. Other authors propose a simple tectonic history of Corinth Rift as a continuous sequence from 900 ka and present time with a progressive migration of the tectonic activity from South to North. New field observations and dating of calcite cements collected from various faults allow us to present a more complex scenario. Calcite cements were precisely selected in order to date only true cement, related to the current opening. Fragments of calcite breccia or host rocks have been rejected. Th/U dating was obtained by TIMS measurements on calcite containing at least 50 ppb of uranium in order to limit the sample size (2 to 4 grams) and insure the true selection of pure cement. Precise sedimentary logs have been done close to the faults in order to decipher between post and syntectonic deposit related to each fault. Some outcrops are older than 1 Ma, showing 230Th/234U and 234U/238U ratios equilibrated, other are older than 600 ka and younger than 1 Ma, with 230Th/234U ratios equilibrated and 234U/238U ratios presenting excess of 234U. Two sites have delivered younger ages around 120 ka. A particular emphasis will be put on Doumena Fault, located south of Pirgaki Fault, which appears, from sedimentological data, post-sedimentation. A calcite cement has been dated at 125 ka by Th/U disequilibrium, assessing a tectonic phase practically contemporaneous. It means that this fault is clearly younger than the Pirgaki and hence out-of-sequence in a classical model that implies a progressive migration from south to north.

  11. Influence of Calcite and Dissolved Calcium on Uranium(VI) Sorption to a Hanford Subsurface Sediment

    SciTech Connect

    Dong, Wenming; Ball, William P.; Liu, Chongxuan; Wang, Zheming; Stone, Alan T.; Bai, Jing; Zachara, John M.

    2005-10-15

    The influence of calcite and dissolved calcium on U(VI) adsorption was investigated using a calcite-containing sandy silt/clay sediment from the U. S. Department of Energy Hanford site. U(VI) adsorption to sediment, treated sediment, and sediment size fractions was studied in solutions that both had and had not been preequilibrated with calcite, at initial [U(VI)] - 10-7-10-5 mol/L and final pH - 6.0-10.0. Kinetic and reversibility studies (pH 8.4) showed rapid sorption (30 min), with reasonable reversibility in the 3-day reaction time. Sorption from solutions equilibrated with calcite showed maximum U(VI) adsorption at pH 8.4-0.1. In contrast, calcium-free systems showed the greatest adsorption at pH 6.0-7.2. At pH > 8.4, U(VI) adsorption was identical from calcium-free and calcium-containing solutions. For calcite-presaturated systems, both speciation calculations and laser-induced fluorescence spectroscopic analyses indicated that aqueous U(VI) was increasingly dominated by Ca2UO2(CO3)3 0(aq) at pH<8.4 and that formation of Ca2UO2(CO3)3 0(aq) is what suppresses U(VI) adsorption. Above pH 8.4, aqueous U(VI) speciation was dominated by UO2(CO3)3 4- in all solutions. Finally, results also showed that U(VI) adsorption was additive in regard to size fraction but not in regard to mineral mass: Carbonate minerals may have blocked U(VI) access to surfaces of higher sorption affinity.

  12. Crystallization of ikaite and its pseudomorphic transformation into calcite: Raman spectroscopy evidence

    NASA Astrophysics Data System (ADS)

    Sánchez-Pastor, N.; Oehlerich, Markus; Astilleros, José Manuel; Kaliwoda, Melanie; Mayr, Christoph C.; Fernández-Díaz, Lurdes; Schmahl, Wolfgang W.

    2016-02-01

    Ikaite (CaCO3·6H2O) is a metastable phase that crystallizes in nature from alkaline waters with high phosphate concentrations at temperatures close to 0 °C. This mineral transforms into anhydrous calcium carbonate polymorphs when temperatures rise or when exposed to atmospheric conditions. During the transformation in some cases the shape of the original ikaite crystal is preserved as a pseudomorph. Pseudomorphs after ikaite are considered as a valuable paleoclimatic indicator. In this work we conducted ikaite crystal growth experiments at near-freezing temperatures using the single diffusion silica gel technique, prepared with a natural aqueous solution from the polymictic lake Laguna Potrok Aike (51°57‧S, 70°23‧W) in Patagonia, Argentina. The ikaite crystals were recovered from the gels and the transformation reactions were monitored by in situ Raman spectroscopy at two different temperatures. The first spectra collected showed the characteristic features of ikaite. In successive spectra new bands at 1072, 1081 and 1086 cm-1 and changes in the intensity of bands corresponding to the OH modes were observed. These changes in the Raman spectra were interpreted as corresponding to intermediate stages of the transformation of ikaite into calcite and/or vaterite. After a few hours, the characteristics of the Raman spectrum were consistent with those of calcite. While ikaite directly transforms into calcite at 10 °C in contact with air, at 20 °C this transformation involves the formation of intermediate, metastable vaterite. During the whole process the external shape of ikaite crystals was preserved. Therefore, this transformation showed the typical characteristics of a pseudomorphic mineral replacement, involving the generation of a large amount of porosity to account for the large difference in molar volumes between ikaite and calcite. A mechanism involving the coupled dissolution of ikaite and crystallization of calcite/vaterite is proposed for this

  13. Impact of trace metals on the water structure at the calcite surface

    NASA Astrophysics Data System (ADS)

    Wolthers, Mariette; Di Tommaso, Devis; De Leeuw, Nora

    2014-05-01

    Carbonate minerals play an important role in regulating the chemistry of aquatic environments, including the oceans, aquifers, hydrothermal systems, soils and sediments. Through mineral surface processes such as dissolution, precipitation and sorption, carbonate minerals affect the biogeochemical cycles of not only the constituent elements of carbonates, such as Ca, Mg, Fe and C, but also H, P and trace elements. Surface charging of the calcite mineral-water interface, and its reactivity towards foreign ions can be quantified using a surface structural model that includes, among others, the water structure at the interface (i.e. hydrogen bridging) [1,2] in accordance with the CD-MUSIC formalism [3]. Here we will show the impact of foreign metals such as Mg and Sr on the water structure around different surface sites present in etch pits and on growth terraces at the calcite (10-14) surface. We have performed Molecular Dynamics simulations of metal-doped calcite surfaces, using different interatomic water potentials. Results show that the local environment around the structurally distinct sites differs depending on metal presence, suggesting that metal substitutions in calcite affect its reactivity. The information obtained in this study will help in improving existing macroscopic surface model for the reactivity of calcite [2] and give more general insight in mineral surface reactivity in relation to crystal composition. [1] Wolthers, Charlet, & Van Cappellen (2008). Am. J. Sci., 308, 905-941. [2] Wolthers, Di Tommaso, Du, & de Leeuw (2012). Phys. Chem. Chem. Phys. 14, 15145-15157. [3] Hiemstra and Van Riemsdijk (1996) J. Colloid Interf. Sci. 179, 488-508.

  14. Atomistic Molecular Dynamics Simulations of Crude Oil/Brine Displacement in Calcite Mesopores.

    PubMed

    Sedghi, Mohammad; Piri, Mohammad; Goual, Lamia

    2016-04-12

    Unconventional reservoirs such as hydrocarbon-bearing shale formations and ultratight carbonates generate a large fraction of oil and gas production in North America. The characteristic feature of these reservoirs is their nanoscale porosity that provides significant surface areas between the pore walls and the occupying fluids. To better assess hydrocarbon recovery from these formations, it is crucial to develop an improved insight into the effects of wall-fluid interactions on the interfacial phenomena in these nanoscale confinements. One of the important properties that controls the displacement of fluids inside the pores is the threshold capillary pressure. In this study, we present the results of an integrated series of large-scale molecular dynamics (MD) simulations performed to investigate the effects of wall-fluid interactions on the threshold capillary pressures of oil-water/brine displacements in a calcite nanopore with a square cross section. Fully atomistic models are utilized to represent crude oil, brine, and calcite in order to accommodate electrostatic interactions and H-bonding between the polar molecules and the calcite surface. To this end, we create mixtures of various polar and nonpolar organic molecules to better represent the crude oil. The interfacial tension between oil and water/brine and their contact angle on calcite surface are simulated. We study the effects of oil composition, water salinity, and temperature and pressure conditions on these properties. The threshold capillary pressure values are also obtained from the MD simulations for the calcite nanopore. We then compare the MD results against those generated using the Mayer-Stowe-Princen (MSP) method and explain the differences. PMID:27010399

  15. Modern marine dolomite cement in a north Jamaican fringing reef

    SciTech Connect

    Mitchell, J.T.; Land, L.S.; Miser, D.E.

    1987-06-01

    Minor quantities of ordered dolomite (..delta../sup 18/O = +2.0 per thousand PDB; composition = Ca/sub 1.22/Mg/sub 0.78/ (CO/sub 3/)/sub 2/) have formed from near-normal seawater in a subtidal hardground as part of a modern fringing coral reef. Crystals 5 ..mu..m in diameter precipitated within the past 1.8 ka in the form of syntaxial fringes on Mg-calcite marine cements and skeletal allochems. The crystals have a fine modulated microstructure and c reflections, both apparently formed during crystal growth

  16. Abiotic Formation of Methyl Halides in the Terrestrial Environment

    NASA Astrophysics Data System (ADS)

    Keppler, F.

    2011-12-01

    Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

  17. Nitrogen isotopic fractionation during abiotic synthesis of organic solid particles

    NASA Astrophysics Data System (ADS)

    Kuga, Maïa; Carrasco, Nathalie; Marty, Bernard; Marrocchi, Yves; Bernard, Sylvain; Rigaudier, Thomas; Fleury, Benjamin; Tissandier, Laurent

    2014-05-01

    The formation of organic compounds is generally assumed to result from abiotic processes in the Solar System, with the exception of biogenic organics on Earth. Nitrogen-bearing organics are of particular interest, notably for prebiotic perspectives but also for overall comprehension of organic formation in the young Solar System and in planetary atmospheres. We have investigated abiotic synthesis of organics upon plasma discharge, with special attention to N isotope fractionation. Organic aerosols were synthesized from N2-CH4 and N2-CO gaseous mixtures using low-pressure plasma discharge experiments, aimed at simulating chemistry occurring in Titan's atmosphere and in the protosolar nebula, respectively. The nitrogen content, the N speciation and the N isotopic composition were analyzed in the resulting organic aerosols. Nitrogen is efficiently incorporated into the synthesized solids, independently of the oxidation degree, of the N2 content of the starting gas mixture, and of the nitrogen speciation in the aerosols. The aerosols are depleted in 15N by 15-25‰ relative to the initial N2 gas, whatever the experimental setup is. Such an isotopic fractionation is attributed to mass-dependent kinetic effect(s). Nitrogen isotope fractionation upon electric discharge cannot account for the large N isotope variations observed among Solar System objects and reservoirs. Extreme N isotope signatures in the Solar System are more likely the result of self-shielding during N2 photodissociation, exotic effect during photodissociation of N2 and/or low temperature ion-molecule isotope exchange. Kinetic N isotope fractionation may play a significant role in the Titan's atmosphere. On the Titan's night side, 15N-depletion resulting from electron driven reactions may counterbalance photo-induced 15N enrichments occurring on the day's side. We also suggest that the low δ15N values of Archaean organic matter (Beaumont and Robert, 1999) are partly the result of abiotic synthesis of

  18. Combined effects of Corexit EC 9500A with secondary abiotic and biotic factors in the rotifer Brachionus plicatilis.

    PubMed

    Williams, Michael B; Powell, Mickie L; Watts, Stephen A

    2016-10-01

    We examined lethality and behavioral effects of Corexit EC 9500A (C-9500A) exposure on the model marine zooplankton Brachionus plicatilis singularly and in combination with abiotic and biotic factors. C-9500A exposure at standard husbandry conditions (17.5ppt, 24°C, 200 rotifer*mL(-1) density) identified the 24h median lethal concentration, by Probit analysis, to be 107ppm for cultured B. plicatilis. Rotifers surviving exposure to higher concentrations (100 and 150ppm) exhibited a decreased swimming velocity and a reduced net to gross movement ratio. Significant interaction between C-9500A exposure and temperature or salinity was observed. Upper thermal range was reduced and maximal salinity stress was seen as ca. 25ppt. Increased or decreased nutritional availability over the exposure period did not significantly alter mortality of B. plicatilis populations at the concentrations tested. Results from this study may be useful for predicting possible outcomes on marine zooplankton following dispersant application under diverse natural conditions. PMID:27327395

  19. A bacteria-based bead for possible self-healing marine concrete applications

    NASA Astrophysics Data System (ADS)

    Palin, D.; Wiktor, V.; Jonkers, H. M.

    2016-08-01

    This work presents a bacteria-based bead for potential self-healing concrete applications in low-temperature marine environments. The bead consisting of calcium alginate encapsulated bacterial spores and mineral precursor compounds was assessed for: oxygen consumption, swelling, and its ability to form a biocomposite in a simulative marine concrete crack solution (SMCCS) at 8 °C. After six days immersion in the SMCCS the bacteria-based beads formed a calcite crust on their surface and calcite inclusions in their network, resulting in a calcite–alginate biocomposite. Beads swelled by 300% to a maximum diameter of 3 mm, while theoretical calculations estimate that 0.112 g of the beads were able to produce ∼1 mm3 of calcite after 14 days immersion; providing the bead with considerable crack healing potential. The bacteria-based bead shows great potential for the development of self-healing concrete in low-temperature marine environments, while the formation of a biocomposite healing material represents an exciting avenue for self-healing concrete research.

  20. An Abiotic Glass-Bead Collector Exhibiting Active Transport

    NASA Astrophysics Data System (ADS)

    Goto, Youhei; Kanda, Masato; Yamamoto, Daigo; Shioi, Akihisa

    2015-09-01

    Animals relocate objects as needed by active motion. Active transport is ubiquitous in living organisms but has been difficult to realize in abiotic systems. Here we show that a self-propelled droplet can gather scattered beads toward one place on a floor and sweep it clean. This is a biomimetic active transport with loadings and unloadings, because the transport was performed by a carrier and the motion of the carrier was maintained by the energy of the chemical reaction. The oil droplet produced fluctuation of the local number density of the beads on the floor, followed by its autocatalytic growth. This mechanism may inspire the technologies based on active transport wherein chemical and physical substances migrate as in living organisms.

  1. Temporal dynamics of biotic and abiotic drivers of litter decomposition.

    PubMed

    García-Palacios, Pablo; Shaw, E Ashley; Wall, Diana H; Hättenschwiler, Stephan

    2016-05-01

    Climate, litter quality and decomposers drive litter decomposition. However, little is known about whether their relative contribution changes at different decomposition stages. To fill this gap, we evaluated the relative importance of leaf litter polyphenols, decomposer communities and soil moisture for litter C and N loss at different stages throughout the decomposition process. Although both microbial and nematode communities regulated litter C and N loss in the early decomposition stages, soil moisture and legacy effects of initial differences in litter quality played a major role in the late stages of the process. Our results provide strong evidence for substantial shifts in how biotic and abiotic factors control litter C and N dynamics during decomposition. Taking into account such temporal dynamics will increase the predictive power of decomposition models that are currently limited by a single-pool approach applying control variables uniformly to the entire decay process. PMID:26947573

  2. Carbon isotope fractionation during abiotic reductive dehalogenation of trichloroethene (TCE).

    PubMed

    Bill, M; Schüth, C; Barth, J A; Kalin, R M

    2001-08-01

    Dehalogenation of trichloroethene (TCE) in the aqueous phase, either on palladium catalysts with hydrogen as the reductant or on metallic iron, was associated with strong changes in delta13C. In general, the delta13C of product phases were more negative than those of the parent compound and were enriched with time and fraction of TCE remaining. For dehalogenation with iron, the delta13C of TCE and products varied from -42/1000 to +5/1000. For the palladium experiments, the final product, ethane, reached the initial delta13C of TCE at completion of the dehalogenation reaction. During dehalogenation, the carbon isotope fractionation between TCE and product phases was not constant. The variation in delta13C of TCE and products offers a new monitoring tool that operates independently of the initial concentration of pollutants for abiotic degradation processes of TCE in the subsurface, and may be useful for evaluation of remediation efficiency. PMID:11513419

  3. Spectral induced polarization signatures of abiotic FeS precipitation

    SciTech Connect

    Ntarlagiannis, D.; Doherty, R.; Williams, K. H.

    2010-01-15

    In recent years, geophysical methods have been shown to be sensitive to microbial induced mineralization processes. The spectral induced polarization (SIP) method appears to be very promising for monitoring mineralization and microbial processes. With this work, we study the links of mineralization and SIP signals, in the absence of microbial activity. We recorded the SIP response during abiotic FeS precipitation. We show that the SIP signals are diagnostic of FeS mineralization and can be differentiated from SIP signals from bio-mineralization processes. More specifically the imaginary conductivity shows almost linear dependence on the amount of FeS precipitating out of solution, above the threshold value 0.006 gr under our experimental conditions. This research has direct implications for the use of the SIP method as a monitoring, and decision making, tool for sustainable remediation of metals in contaminated soils and groundwater.

  4. Endophytic fungi: resource for gibberellins and crop abiotic stress resistance.

    PubMed

    Khan, Abdul Latif; Hussain, Javid; Al-Harrasi, Ahmed; Al-Rawahi, Ahmed; Lee, In-Jung

    2015-03-01

    The beneficial effects of endophytes on plant growth are important for agricultural ecosystems because they reduce the need for fertilizers and decrease soil and water pollution while compensating for environmental perturbations. Endophytic fungi are a novel source of bioactive secondary metabolites; moreover, recently they have been found to produce physiologically active gibberellins as well. The symbiosis of gibberellins producing endophytic fungi with crops can be a promising strategy to overcome the adverse effects of abiotic stresses. The association of such endophytes has not only increased plant biomass but also ameliorated plant-growth during extreme environmental conditions. Endophytic fungi represent a trove of unexplored biodiversity and a frequently overlooked component of crop ecology. The present review describes the role of gibberellins producing endophytic fungi, suggests putative mechanisms involved in plant endophyte stress interactions and discusses future prospects in this field. PMID:23984800

  5. Oxidation of Black Carbon by Biotic and Abiotic Processes

    SciTech Connect

    Cheng, Chih-hsin; Lehmann, Johannes C.; Thies, Janice E.; Burton, Sarah D.; Engelhard, Mark H.

    2006-11-01

    The objectives of this study were to quantify the relative importance of either biotic or abiotic oxidation of biomass-derived black carbon (BC) and to characterize the surface properties and charge characteristics of oxidized particulate BC. We incubated BC and BC-soil mixtures at two different temperatures (30 C and 70 C) with and without microbial inoculation, nutrient additions, or manure amendments for four months. Abiotic processes were more important for oxidation of BC than biotic processes during this short-term incubation, as inoculation with microorganisms did not change any of the measured parameters. Black C incubated at both 30 C and 70 C without microbial activity showed dramatic decreases in pH (in water) from 5.4 to 5.2 and 3.4, as well as increases in cation exchange capacity (CEC at pH 7) by 53% and 538% and in oxygen (O) contents by 4% and 38%, respectively. Boehm titration and Fourier transform infrared (FTIR) spectroscopy suggested that the formation of carboxylic functional groups was the reason for the enhanced CEC during oxidation. The analyses of BC surface properties by X-ray photoelectron spectroscopy (XPS) indicated that the oxidation of BC particles initiated on the surface. Incubation at 30 C only enhanced oxidation on particle surfaces, while oxidation during incubation at 70 C penetrated into the interior of particles. Such short-term oxidation of BC has great significance for the stability of BC in soils as well as for its effects on soil fertility and biogeochemistry.

  6. Kinetics of Abiotic Uranium(VI) Reduction by Sulfide

    NASA Astrophysics Data System (ADS)

    Hyun, S.; Davis, J. A.; Hayes, K. F.

    2010-12-01

    Uranium(VI) reduction is an important process affecting the radionuclide’s fate under sulfate reducing conditions. In this work, kinetics of abiotic U(VI) reduction by dissolved sulfide was studied using a batch reactor. The effects of solution pH, dissolved carbonate, Ca(II), U(VI), and S(-II) concentration on the reduction kinetics were tested. The ranges of these experimental variables were designed to cover the variation in groundwater chemistry observed at the Old Rifle uranium mill tailings site (Colorado, USA). Dissolved U concentration was monitored as a function of time using inductively coupled plasma-mass spectrometry to measure the rate of U(VI) reduction. Solid phase reduction products were identified using X-ray diffraction, transmission electron microscopy, and X-ray absorption spectroscopy. The results showed that changes in the experimental variables significantly affected U(VI) reduction kinetics by dissolved sulfide. U(VI) reduction occurred under circumneutral pH while no reduction was observed under alkaline conditions. The reduction rate was slowed by increased dissolved carbonate concentration. One solid phase reduction product was identified as nanoscale uraninite (UO2+x(s)). Thermodynamic modeling showed that the dissolved U(VI) aqueous species changed as a function of solution conditions correlated with the change in the reduction rate. These results show that U(VI) aqueous speciation is important in determining abiotic U(VI) reduction kinetics by dissolved sulfide. This study also illustrates the potential importance of dissolved sulfide in field-scale modeling of U reactive transport, and is expected to contribute to the understanding of long-term effects of biostimulation on U transport at the Rifle site.

  7. Formation of Intermediate Carbon Phases in Hydrothermal Abiotic Organic Synthesis

    NASA Astrophysics Data System (ADS)

    Fu, Q.; Foustoukos, D. I.; Seyfried, W. E.

    2005-12-01

    With high dissolved concentrations of methane and other hydrocarbon species revealed at the Rainbow and Logatchev vent systems on the Mid-Atlantic Ridge, it is essential to better understand reaction pathways of abiotic organic synthesis in hydrothermal systems. Thus, we performed a hydrothermal carbon reduction experiment with 13C labeled carbon source at temperature and pressure conditions that approximate those inferred for ultramafic-hosted hydrothermal systems. Pentlandite, a common alteration mineral phase in subseafloor reaction zones, acted as a potential catalyst. Surface analysis techniques (XPS and ToF-SIMS) were used to characterize intermediate carbon species within this process. Time series dissolved H2 and H2S concentrations indicated thermodynamic equilibrium. Dissolved H2 and H2S concentrations of 13 and 2 mmol/kg, respectively, are approximately equivalent to measured values in Rainbow and Logatchev hydrothermal systems. Isotopically pure 13C methane and other alkane species (C2H6 and C3H8) were observed throughout the experiment, and attained steady state conditions. XPS analysis on mineral product surface indicated carbon enrichment on mineral surface following reaction. The majority of surface carbon involves species containing C-C or C-H bonds, such as alkyl or methylene groups. Alcohol and carboxyl groups in fewer amounts were also observed. ToF-SIMS analysis, which can offer isotope identification with high mass resolution, showed that most of these carbon species were 13C-labeled. Unlike gas phase Fischer-Tropsch synthesis, no carbide was observed on mineral product surface during the experiment. Therefore, a reaction pathway is proposed for formation of dissolved linear alkane species in hydrothermal abiotic organic synthesis, where oxygen-bearing organic compounds are expected to form in aqueous products by way of alcohol and carboxyl groups on mineral catalyst surface.

  8. Vital effects in coccolith calcite: Cenozoic climate-pCO2 drove the diversity of carbon acquisition strategies in coccolithophores?

    NASA Astrophysics Data System (ADS)

    Bolton, Clara T.; Stoll, Heather M.; Mendez-Vicente, Ana

    2012-12-01

    Coccoliths, calcite plates produced by the marine phytoplankton coccolithophores, have previously shown a large array of carbon and oxygen stable isotope fractionations (termed "vital effects"), correlated to cell size and hypothesized to reflect the varying importance of active carbon acquisition strategies. Culture studies show a reduced range of vital effects between large and small coccolithophores under high CO2, consistent with previous observations of a smaller range of interspecific vital effects in Paleocene coccoliths. We present new fossil data examining coccolithophore vital effects over three key Cenozoic intervals reflecting changing climate and atmospheric partial pressure of CO2 (pCO2). Oxygen and carbon stable isotopes of size-separated coccolith fractions dominated by different species from well preserved Paleocene-Eocene thermal maximum (PETM, ˜56 Ma) samples show reduced interspecific differences within the greenhouse boundary conditions of the PETM. Conversely, isotope data from the Plio-Pleistocene transition (PPT; 3.5-2 Ma) and the last glacial maximum (LGM; ˜22 ka) show persistent vital effects of ˜2‰. PPT and LGM data show a clear positive trend between coccolith (cell) size and isotopic enrichment in coccolith carbonate, as seen in laboratory cultures. On geological timescales, the degree of expression of vital effects in coccoliths appears to be insensitive topCO2 changes over the range ˜350 ppm (Pliocene) to ˜180 ppm (LGM). The modern array of coccolith vital effects arose after the PETM but before the late Pliocene and may reflect the operation of more diverse carbon acquisition strategies in coccolithophores in response to decreasing Cenozoic pCO2.

  9. Marine Lubricants

    NASA Astrophysics Data System (ADS)

    Carter, B. H.; Green, D.

    Marine diesel engines are classified by speed, either large (medium speed) or very large (slow speed) with high efficiencies and burning low-quality fuel. Slow-speed engines, up to 200 rpm, are two-stroke with separate combustion chamber and sump connected by a crosshead, with trunk and system oil lubricants for each. Medium-speed diesels, 300-1500 rpm, are of conventional automotive design with one lubricant. Slow-speed engines use heavy fuel oil of much lower quality than conventional diesel with problems of deposit cleanliness, acidity production and oxidation. Lubricants are mainly SAE 30/40/50 monogrades using paraffinic basestocks. The main types of additives are detergents/dispersants, antioxidants, corrosion inhibitors, anti-wear/load-carrying/ep, pour-point depressants and anti-foam compounds. There are no simple systems for classifying marine lubricants, as for automotive, because of the wide range of engine design, ratings and service applications they serve. There are no standard tests; lubricant suppliers use their own tests or the Bolnes 3DNL, with final proof from field tests. Frequent lubricant analyses safeguard engines and require standard sampling procedures before determination of density, viscosity, flash point, insolubles, base number, water and wear metal content.

  10. Timing and mechanism of late-Pleistocene calcite vein formation across the Dead Sea Fault Zone, northern Israel

    NASA Astrophysics Data System (ADS)

    Nuriel, Perach; Weinberger, Ram; Rosenbaum, Gideon; Golding, Suzanne D.; Zhao, Jian-xin; Tonguc Uysal, I.; Bar-Matthews, Miryam; Gross, Michael R.

    2012-03-01

    The emplacement of calcite-filled veins perpendicular to the Dead Sea Fault Zone in northern Israel reflects strain partitioning during transpression. We present structural, geochemical, and U-Th geochronological data that constrain the mechanism, conditions and timing of vein formation. Vein walls are strongly brecciated and commonly cemented with coarsely crystalline calcite, whereas calcite-filled veins are composed of wall-parallel bands of calcite crystals. Elongated blocky and fibrous calcite crystals grew perpendicular to the vein walls and are characterised by a truncate sealing-hiatus morphology, indicating episodes of partial or complete sealing of the fractures during calcite precipitation. Stable isotope and rare-earth element and yttrium (REY) analyses indicate that calcite-filled veins precipitated by karst processes, involving meteoric water and limited fluid-rock interactions. U-Th dating results show a prolonged history of vein growth. While some veins initiated prior to 500 ka, the majority of the veins were active between 358 and 17 ka. Age constraints on vein activity correspond to an ˜E-W regional shortening phase in this sector of the Dead Sea Fault Zone, associated with an increased component of convergence during the late-Pleistocene.

  11. A Modified Method for Saline Lake Calcite Isotope Analysis: Application to a Study of Climate Change over 200,000 Years in Death Valley, California.

    NASA Astrophysics Data System (ADS)

    Yang, W.; Lowenstein, T. K.; Krouse, R. H.; Spencer, R. J.; Ku, T.

    2004-12-01

    sediments. For a continuous 200,000-year δ 18O record of lacustrine calcite from a 186-meter sediment core from Badwater Basin, Death Valley, California, a two-level climatic fluctuation model is suggested.. This record provides new insight to the debate on the timing and driving forces of late Quaternary paleoclimatic changes. Excursions in calcite δ 18O are similar to those of δ 18O in sulfate in the Death Valley core, as well as to those in marine carbonate (SPECMAP) and polar ice in the Summit ice core (GRIP), Greenland. The Death Valley record shows periodicities of 96000, 39000, 21000, 14000 and 8000 years. The longer-term (96000, 39000 & 21000 years) fluctuations match Milankovitch orbital forcing, and are thus likely to be global in origin; the shorter-term (14000 and 8000 years) fluctuations probably reflect regional climatic and/or hydrologic forcing.

  12. Trace Metals in Groundwater and Vadose Zone Calcite: In Situ Containment and Stabilization of Stronthium-90 and Other Divalent Metals and Radionuclides at Arid Western DOE Sites: Final Report for Award Number DE-FG07-02ER63486 to the University of Idaho (RW Smith) Environmental Management Science Program Project Number 87016

    SciTech Connect

    Smith, Robert W.; Fujita, Yoshiko

    2007-11-07

    Radionuclide and metal contaminants are present in the vadose zone and groundwater throughout the U.S. Department of Energy (DOE) energy research and weapons complex. In situ containment and stabilization of these contaminants represents a cost-effective treatment strategy that minimizes workers’ exposure to hazardous substances, does not require removal or transport of contaminants, and generally does not generate a secondary waste stream. We have investigated an in situ bioremediation approach that immobilizes radionuclides or contaminant metals (e.g., strontium-90) by their microbially facilitated co-precipitation with calcium carbonate in groundwater and vadose zone systems. Calcite, a common mineral in many aquifers and vadose zones in the arid west, can incorporate divalent metals such as strontium, cadmium, lead, and cobalt into its crystal structure by the formation of a solid solution. Collaborative research undertaken by the Idaho National Laboratory (INL), University of Idaho, and University of Toronto as part of this Environmental Management Science Program project has focused on in situ microbially-catalyzed urea hydrolysis, which results in an increase in pH, carbonate alkalinity, ammonium, calcite precipitation, and co-precipitation of divalent cations. In calcite-saturated aquifers, microbially facilitated co-precipitation with calcium carbonate represents a potential long-term contaminant sequestration mechanism. Key results of the project include: **Demonstrating the linkage between urea hydrolysis and calcite precipitation in field and laboratory experiments **Observing strontium incorporation into calcite precipitate by urea hydrolyzers with higher distribution coefficient than in abiotic **Developing and applying molecular methods for characterizing microbial urease activity in groundwater including a quantitative PCR method for enumerating ureolytic bacteria **Applying the suite of developed molecular methods to assess the feasibility of the

  13. [In situ experimental study of phase transition of calcite by Raman spectroscopy at high temperature and high pressure].

    PubMed

    Liu, Chuan-jiang; Zheng, Hai-fei

    2012-02-01

    The phase transitions of calcite at high temperature and high pressure were investigated by using hydrothermal diamond anvil cell combined with Raman spectroscopy. The result showed that the Raman peak of 155 cm(-1) disappeared, the peak of 1 087 cm(-1) splited into 1083 and 1 090 cm(-1) peaks and the peak of 282 cm(-1) abruptly reduced to 231 cm(-1) at ambient temperature when the system pressure increased to 1 666 and 2 127 MPa respectively, which proved that calcite transformed to calcite-II and calcite-III. In the heating process at the initial pressure of 2 761 MPa and below 171 degrees C, there was no change in Raman characteristic peaks of calcite-III. As the temperature increased to 171 degrees C, the color of calcite crystal became opaque completely and the symmetric stretching vibration peak of 1 087 cm(-1), in-plane bending vibration peak of 713 cm(-1) and lattice vibration peaks of 155 and 282 cm(-1) began to mutate, showing that the calcite-III transformed to a new phase of calcium carbonate at the moment. When the temperature dropped to room temperature, this new phase remained stable all along. It also indicated that the process of phase transformation from calcite to the new phase of calcium carbonate was irreversible. The equation of phase transition between calcite-III and new phase of calcium carbonate can be determined by P(MPa) = 9.09T x (degrees C) +1 880. The slopes of the Raman peak (v1 087) of symmetrical stretching vibration depending on pressure and temperature are dv/dP = 5.1 (cm(-1) x GPa(-1)) and dv/dT = -0.055 3(cm(-1) x degrees C(-1)), respectively. PMID:22512172

  14. A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock.