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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. 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

  5. Abiotic racemization kinetics of amino acids in marine sediments.

    PubMed

    Steen, Andrew D; Jørgensen, Bo Barker; Lomstein, Bente Aa

    2013-01-01

    The ratios of d- versus l-amino acids can be used to infer the sources and composition of sedimentary organic matter. Such inferences, however, rely on knowing the rates at which amino acids in sedimentary organic matter racemize abiotically between the d- and the l-forms. Based on a heating experiment, we report kinetic parameters for racemization of aspartic acid, glutamic acid, serine, and alanine in bulk sediment from Aarhus Bay, Denmark, taken from the surface, 30 cm, and 340 cm depth below seafloor. Extrapolation to a typical cold deep sea sediment temperature of 3°C suggests racemization rate constants of 0.50×10(-5)-11×10(-5) yr(-1). These results can be used in conjunction with measurements of sediment age to predict the ratio of d:l amino acids due solely to abiotic racemization of the source material, deviations from which can indicate the abundance and turnover of active microbial populations.

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. 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.

  11. 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

  12. Origin and timing of siderite and calcite concretions in late Palaeogene non- to marginal-marine facies of the Te Kuiti Group, New Zealand

    NASA Astrophysics Data System (ADS)

    Middleton, Heather A.; Nelson, Campbell S.

    1996-05-01

    The Late Eocene-earliest Miocene Te Kuiti Group represents an overall transgressive sequence of formations ranging upwards from non-marine coal measure facies through marginal-marine low-energy shoreline siliciclastic sediments to fully-marine mixed siliciclastic-carbonate deposits. Concretionary structures are common in the lowest formations of the group, being dominantly sideritic in the non-marine to brackish sediment facies (Waikato Coal Measures and Glen Afton Claystone) and calcitic in the more marine-influenced sediments (Rotowaro Siltstone). The geochemistry of the carbonate cements within these early diagenetic concretions records the change from carbonate precipitation from purely meteoric fluids to precipitation from marine fluids, and a shifting source of carbonate carbon across this transition. Siderite precipitation in the Waikato Coal Measures concretions and hardpans was initiated and often largely completed in the methanogenic zone, within the upper 20 m of the sediment pile over a period possibly lasting 100-300 ka. Precipitation continued at a reduced rate to burial depths of 300 m or more when septarian cracking occurred in some siderite concretions and was healed by calcite vein cements that probably derived carbonate from the oxidation of methane ascending from the maturing coal seams directly below. Siderite precipitation in the concretions and hardpans of the overlying brackish-marine Glen Afton Claystone was completed in the topmost few metres of sediment, possibly a few 10 ka. Stable-isotope values near zero support a marine carbonate carbon source, suggested to be from remobilised shell material as evidenced by the common occurrence of shell casts in the formation and the high degree of Mg and Ca substitution in the siderites. The overlying marginal-marine to low-energy marine Rotowaro Siltstone contains calcite concretions precipitated from pore waters enriched in bicarbonate derived from the sulphate-reduction zone, largely within the

  13. 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.

  14. 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

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. 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).

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. 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

  17. Microbial dissolution of calcite at T = 28 °C and ambient pCO 2

    NASA Astrophysics Data System (ADS)

    Jacobson, Andrew D.; Wu, Lingling

    2009-04-01

    This study used batch reactors to quantify the mechanisms and rates of calcite dissolution in the presence and absence of a single heterotrophic bacterial species ( Burkholderia fungorum). Experiments were conducted at T = 28°C and ambient pCO 2 over time periods spanning either 21 or 35 days. Bacteria were supplied with minimal growth media containing either glucose or lactate as a C source, NH 4+ as an N source, and H 2PO 4- as a P source. Combining stoichiometric equations for microbial growth with an equilibrium mass-balance model of the H 2O-CO 2-CaCO 3 system demonstrates that B. fungorum affected calcite dissolution by modifying pH and alkalinity during utilization of ionic N and C species. Uptake of NH 4+ decreased pH and alkalinity, whereas utilization of lactate, a negatively charged organic anion, increased pH and alkalinity. Calcite in biotic glucose-bearing reactors dissolved by simultaneous reaction with H 2CO 3 generated by dissolution of atmospheric CO 2 (H 2CO 3 + CaCO 3 → Ca 2+ + 2HCO 3-) and H + released during NH 4+ uptake (H + + CaCO 3 → Ca 2+ + HCO 3-). Reaction with H 2CO 3 and H + supplied ˜45% and 55% of the total Ca 2+ and ˜60% and 40% of the total HCO 3-, respectively. The net rate of microbial calcite dissolution in the presence of glucose and NH 4+ was ˜2-fold higher than that observed for abiotic control experiments where calcite dissolved only by reaction with H 2CO 3. In lactate bearing reactors, most H + generated by NH 4+ uptake reacted with HCO 3- produced by lactate oxidation to yield CO 2 and H 2O. Hence, calcite in biotic lactate-bearing reactors dissolved by reaction with H 2CO 3 at a net rate equivalent to that calculated for abiotic control experiments. This study suggests that conventional carbonate equilibria models can satisfactorily predict the bulk fluid chemistry resulting from microbe-calcite interactions, provided that the ionic forms and extent of utilization of N and C sources can be constrained. Because

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Crystal lattice tilting in prismatic calcite.

    PubMed

    Olson, Ian C; Metzler, Rebecca A; Tamura, Nobumichi; Kunz, Martin; Killian, Christopher E; Gilbert, Pupa U P A

    2013-08-01

    We analyzed the calcitic prismatic layers in Atrina rigida (Ar), Haliotis iris (Hi), Haliotis laevigata (HL), Haliotis rufescens (Hrf), Mytilus californianus (Mc), Pinctada fucata (Pf), Pinctada margaritifera (Pm) shells, and the aragonitic prismatic layer in the Nautilus pompilius (Np) shell. Dramatic structural differences were observed across species, with 100-μm wide single-crystalline prisms in Hi, HL and Hrf, 1-μm wide needle-shaped calcite prisms in Mc, 1-μm wide spherulitic aragonite prisms in Np, 20-μm wide single-crystalline calcite prisms in Ar, and 20-μm wide polycrystalline calcite prisms in Pf and Pm. The calcite prisms in Pf and Pm are subdivided into sub-prismatic domains of orientations, and within each of these domains the calcite crystal lattice tilts gradually over long distances, on the order of 100 μm, with an angle spread of crystal orientation of 10-20°. Furthermore, prisms in Pf and Pm are harder than in any other calcite prisms analyzed, their nanoparticles are smaller, and the angle spread is strongly correlated with hardness in all shells that form calcitic prismatic layers. One can hypothesize a causal relationship of these correlated parameters: greater angle spread may confer greater hardness and resistance to wear, thus providing Pf and Pm with a structural advantage in their environment. This is the first structure-property relationship thus far hypothesized in mollusk shell prisms.

  8. 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)

  9. 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.

  10. 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.

  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. 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.

  13. 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.

  14. Controlled calcite nucleation on polarized calcite single crystal substrates in the presence of polyacrylic acid

    NASA Astrophysics Data System (ADS)

    Wada, Norio; Horiuchi, Naohiro; Nakamura, Miho; Nozaki, Kosuke; Hiyama, Tetsuo; Nagai, Akiko; Yamashita, Kimihiro

    2015-04-01

    We studied theoretically and experimentally the effects of the surface electric field generated by polarization and polyacrylic acid (PAA) additives on the heterogeneous nucleation of calcite on the calcite single crystal substrates with (10.4), (10.0) and (00.1) orientations. A set of "in-situ" experiments with optical microscopy was performed to determine the waiting time of CaCO3 nucleation, defined as the time interval between the onset of the diffusion of CO2 and the appearance of the first visible precipitation. Calcite was nucleated on the oriented calcite substrates through diffusion of NH3 and CO2 gas from a solid ammonium carbonate into calcium chloride solutions. A theoretical analysis showed that the surface electric field of the polarized calcite substrate decrease the activation energy for nucleation and consequently promotes nucleation. Experimentally, the surface electric field and PAA addition were found to decrease both contact angles and waiting times, and as a result, promote the heterogeneous nucleation. Combined effect of PAA and surface electric field further reduced contact angles and waiting times regardless of orientation differences of the calcite substrates. The cooperation acts remarkably on N-surface of the respective calcite substrates. The results were explained by the Cassie's equation, a classical heterogeneous nucleation theory under a surface electric field, and matching of the charged sites on the PAA chain with the ion arrangement on the calcite substrate.

  15. 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.

  16. Abiotic self-replication.

    PubMed

    Meyer, Adam J; Ellefson, Jared W; Ellington, Andrew D

    2012-12-18

    functions (including the replication of nucleic acids) to more competent protein enzymes would complete the journey from an abiotic world to the molecular biology we see today. PMID:22891822

  17. Abiotic self-replication.

    PubMed

    Meyer, Adam J; Ellefson, Jared W; Ellington, Andrew D

    2012-12-18

    functions (including the replication of nucleic acids) to more competent protein enzymes would complete the journey from an abiotic world to the molecular biology we see today.

  18. 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.

  19. 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…

  20. 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

  1. Coccolithophore responses to environmental variability in the South China Sea: species composition and calcite content

    NASA Astrophysics Data System (ADS)

    Jin, Xiaobo; Liu, Chuanlian; Poulton, Alex J.; Dai, Minhan; Guo, Xianghui

    2016-08-01

    Coccolithophore contributions to the global marine carbon cycle are regulated by the calcite content of their scales (coccoliths) and the relative cellular levels of photosynthesis and calcification rates. All three of these factors vary between coccolithophore species and with response to the growth environment. Here, water samples were collected in the northern basin of the South China Sea (SCS) during summer 2014 in order to examine how environmental variability influenced species composition and cellular levels of calcite content. Average coccolithophore abundance and their calcite concentration in the water column were 11.82 cells mL-1 and 1508.3 pg C mL-1, respectively, during the cruise. Water samples can be divided into three floral groups according to their distinct coccolithophore communities. The vertical structure of the coccolithophore community in the water column was controlled by the trophic conditions, which were regulated by mesoscale eddies across the SCS basin. The evaluation of coccolithophore-based calcite in the surface ocean also showed that three key species in the SCS (Emiliania huxleyi, Gephyrocapsa oceanica, Florisphaera profunda) and other larger, numerically rare species made almost equal contributions to total coccolith-based calcite in the water column. For Emiliania huxleyi biometry measurements, coccolith size positively correlated with nutrients (nitrate, phosphate), and it is suggested that coccolith length is influenced by light and nutrients through the regulation of growth rates. Larger-sized coccoliths were also linked statistically to low pH and calcite saturation states; however, it is not a simple cause and effect relationship, as carbonate chemistry was strongly co-correlated with the other key environmental factors (nutrients, light).

  2. 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

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

    PubMed

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

    2015-11-01

    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 (>7.5mM). Zeta potential measurements suggest that brucite precipitation caused flocculation by charge neutralization. When calcium concentration was 12.5mM, flocculation was also observed at a pH of 10. Zeta potential remained negative up to pH 11.5, suggesting that precipitated calcite caused flocculation by a sweeping coagulation mechanism.

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

    DOE PAGES

    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

  5. Origin of zoning within dedolomite and calcitized gypsum of the Mississippian Arroyo Penasco Group

    SciTech Connect

    Ulmer, D.S.

    1985-01-01

    The Mississippian Arroyo Penasco Group carbonates are the oldest Paleozoic rocks present in north-central New Mexico. These supratidal to shallow,subtidal sediments exhibit complex diagenetic fabrics produced by periods of pre-Pennsylvanian subaerial exposure. Both extensive recrystallization of the Espiritu Santo carbonates and brecciation of the overlying Macho Member of the Tererro Formation resulted from an extended period of Mississippian subaerial exposure of broad, low-relief tidal flats. Cathodoluminescent petrography indicates that the recrystallized limestones consist of calcite pseudomorphs of dolomite and gypsum. Dedolomite and calcitized gypsum crystals, with /sup 13/C//sup 12/C ratios of -2 to +1.5% PDB, range from highly zoned to uniformly luminescent. Electron microprobe analyses reveals variable Mn and Fe contents across the pseudomorphs which are responsible for differences in observed luminosity. These features are interpreted to reflect a period of subaerial exposure after deposition of Macho Member sediments, which caused dissolution of gypsum and dolomite by sulfate and Mg depleted meteoric fluids and produced the collapse breccia. Preservation of zoning within some pseudomorphs required simultaneous dissolution of gypsum and dolomite and precipitation of calcite. C-isotope data indicates a meteoric to mixed phreatic origin for pore fluids which precipitated calcite; repetitive zoning within dolomite and gypsum pseudomorphs is indicative of interactions between marine and meteoric phreatic fluids in the intertidal environment.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Bendable, free-standing calcite thin films.

    PubMed

    Nakamura, Shiho; Naka, Kensuke

    2015-02-17

    Since the hardness and toughness of natural nacre are determined by hierarchical microstructures with organic matters, it is of great importance to control the microstructures of artificial free-standing CaCO3 thin films. However, the fabrication of such films has so far been quite limited, to the extent that their mechanical properties have not been reported. To address this, free-standing calcite thin films were prepared through repeated cycles of layer-by-layer deposition of vaterite precursor composite particles with organic polymers, followed by a phase transition to calcite. In this way, two distinct calcite thin film types were produced based on either 3.2 or 1.0 wt % organic material, with subsequent three-point bending tests revealing that both exhibit elastic bending prior to fracture. More importantly, by increasing the organic content from 1.0 to 3.2 wt %, the bending strength increased from 0.95 ± 0.26 MPa to 1.90 ± 0.21 MPa. PMID:25621634

  13. 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

  14. 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.

  15. 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

  16. 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.

  17. 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.

  18. 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

  19. Calcite-seeded crystallization of calcium phosphate for phosphorus recovery.

    PubMed

    Song, Yonghui; Weidler, Peter G; Berg, Ute; Nüesch, Rolf; Donnert, Dietfried

    2006-04-01

    For phosphorus recovery from wastewater, the present paper aims at understanding the crystallization of calcium phosphate by using calcites (Juraperle and Coccolith) as seeds from hard water. Synthetic hard water with 60 mgCl(-1) carbonate and 10 mgPl(-1) phosphate was prepared and used in the batch experiments of calcite-seeded crystallization. The solution composition was measured throughout the batch crystallization process, and the corresponding saturation indices with respect to the minerals were calculated with PHREEQC Program. The surface of the calcite seeds was observed and measured with environmental scanning electron microscopy (ESEM), Fourier transform infrared (FTIR) and BET method. The studies show that both calcites are effective seeds for the crystallization of calcium phosphate from hard water; the used calcites are more efficient than the original ones because newly formed crystals with calcium phosphate have covered their surfaces. The studies show that the calcite seeds can be used for phosphorus recovery from hard waters.

  20. Global calcite cycling constrained by sediment preservation controls

    NASA Astrophysics Data System (ADS)

    Dunne, John P.; Hales, Burke; Toggweiler, J. R.

    2012-09-01

    We assess the global balance of calcite export through the water column and burial in sediments as it varies regionally. We first drive a comprehensive 1-D model for sediment calcite preservation with globally gridded field observations and satellite-based syntheses. We then reformulate this model into a simpler five-parameter box model, and combine it with algorithms for surface calcite export and water column dissolution for a single expression for the vertical calcite balance. The resulting metamodel is optimized to fit the observed distributions of calcite burial flux. We quantify the degree to which calcite export, saturation state, organic carbon respiration, and lithogenic sedimentation modulate the burial of calcite. We find that 46% of burial and 88% of dissolution occurs in sediments overlain by undersaturated bottom water with sediment calcite burial strongly modulated by surface export. Relative to organic carbon export, we find surface calcite export skewed geographically toward relatively warm, oligotrophic areas dominated by small, prokaryotic phytoplankton. We assess century-scale projected impacts of warming and acidification on calcite export, finding high sensitive to inferred saturation state controls. With respect to long-term glacial cycling, our analysis supports the hypothesis that strong glacial abyssal stratification drives the lysocline toward much closer correspondence with the saturation horizon. Our analysis suggests that, over the transition from interglacial to glacial ocean, a resulting ˜0.029 PgC a-1decrease in deep Atlantic, Indian and Southern Ocean calcite burial leads to slow increase in ocean alkalinity until Pacific mid-depth calcite burial increases to compensate.

  1. Stable isotope variations in the Quaternary epithermal calcite-fluorite deposit at Monte delle Fate near Cerveteri (Latium, central Italy)

    USGS Publications Warehouse

    Masi, U.; O'Neil, J.R.

    1980-01-01

    Carbon, oxygen and hydrogen isotope variations have been measured in samples from the epithermal fluorite vein deposit at Monte delle Fate, Latium. The ranges in ?? 13C and ??18O of calcite are -1.3 to 3.4 and 9.5 to 17.3, respectively. ??D values of water extracted from fluid inclusions are -49 to -39 for calcite and -41 to -34 for fluorite. Fluid inclusion filling temperatures (225??-240??C) and salinites (3.75) are nearly the same for both fluorite and sparry calcite. An elongated form of calcite, of minor abundance, precipitated at lower temperatures. The data indicate that (1) the CO2 involved in the mineralization was provided by the local marine limestones, (2) the waters were meteoric in origin and underwent an 18O shift of ??? 10 permil by exchange with marine country rocks, and (3) all geochemical features can be explained by the action of two hydrothermal fluids. Hot brines recently discovered in the Cesano geothermal area, 30 km to the east, have temperatures and some chemical characteristics similar to the hydrothermal fluids at Monte delle Fate. ?? 1980 Springer-Verlag.

  2. 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.

  3. Graphitic carbon formation through calcite reduction in blueschist metasediments from Alpine Corsica (France)

    NASA Astrophysics Data System (ADS)

    Galvez, M.; Beyssac, O.; Martinez, I.; Benzerara, K.; Malvoisin, B.

    2012-04-01

    The geochemistry of reduced carbon in subduction zones is strongly affected by mineral equilibria. We study here the geochemistry of carbon in siliceous-marbles at the direct contact with serpentinites in the Alpine eclogitic meta-ophiolithic units of northern Corsica (France). We have combined petrology, Raman spectroscopy and carbon isotopy to provide a description of both the organic and carbonate components of the rocks across a reaction front where the reaction CaCO3+SiO2+2H2=CaSiO3+C+2H2O is evidenced. The continuous reaction zone is composed by a centimeter thick pale nephrite layer at the contact with the serpentinites, followed by a thin wollastonite layer and a 5 to 20 cm thick dark zone composed of wollastonite, carbonaceous material (CM), quartz but no carbonates. There is a sharp transition to the overlying original metasediment composed of calcite+quartz which is significantly less rich in CM. Raman spectroscopy shows that CM is much more graphitic in the reaction zone than in the original sediment. Significant isotopic differences are observed apart the reaction front with δ13C (CM) and δ13C (calcite) around -15‰ and 1.3‰ respectively in the original rock far from the reaction zone, whereas δ13C (CM) is around -1‰ in the reaction zone. We interpret the graphitic CM in the reaction zone as formed from the destabilization and reduction of calcite due to the diffusion of reducing fluids from the underlying serpentinite unit. Mass balance calculations support this hypothesis and show that a complete reduction of carbonates might have occurred. The timing of this abiotic macromolecular and graphitic C formation is discussed. We show that the combined study of isotopic geochemistry and structure of inorganic and organic carbon in metamorphic rocks might be suited to reveal with great fidelity redox gradients in subduction zones.

  4. Neptunium(V) adsorption to calcite

    NASA Astrophysics Data System (ADS)

    Heberling, Frank; Brendebach, Boris; Bosbach, Dirk

    2008-12-01

    The migration behavior of the actinyl ions U(VI)O 22+, Np(V)O 2+ and Pu(V,VI)O 2(+,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 NpO 2+ adsorption onto calcite is studied in batch type experiments over a wide range of pH (6.0-9.4) and concentration (0.4 μM-40 μM) conditions. pH is adjusted by variation of CO 2 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 Å for the adsorbed and 1.82 ± 0.01 Å for the solution species. The equatorial environment of the neptunyl in solution shows about 5 oxygen neighbours at 2.45 ± 0.02 Å. For adsorbed neptunyl there are also about 5 oxygen neighbours at 2.46 ± 0.01 Å. 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 Å and 3 to 6 oxygen backscatterers (O-eq2) at 3.31 ± 0.02 Å. 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.

  5. 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

  6. Emission polarization study on quartz and calcite.

    PubMed

    Vincent, R K

    1972-09-01

    Spectral emission polarization of quartz and calcite polished plates for observation angles of 20 degrees and 70 degrees is calculated by the substitution of complex index of refraction values for each mineral into Fresnel's equations. The emission polarization is shown to be quite wavelength-dependent, demonstrating that selected narrow or medium-width (Deltalambda approximately 1.5 microm) spectral bands exhibit a significantly higher percentage of polarization than a broad spectral band (Deltalambda approximately 6microm) for these two minerals. Field measurements with a broadband infrared radiometer yield polarizations on the order of 2% for a coarse-grained granite rock and beach sand (both quartz-rich). This implies that a more sensitive detector with a selected mediumwidth filter may be capable of measuring emission polarization accurately enough to make this parameter useful as a remote sensing tool for discrimination among rocks on the basis of texture.

  7. 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

  8. 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.

  9. 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

  10. 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

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

    PubMed Central

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

    2015-01-01

    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

  12. 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.

  13. 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

  14. Decadal changes in the aragonite and calcite saturation state of the Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Feely, Richard A.; Sabine, Christopher L.; Byrne, Robert H.; Millero, Frank J.; Dickson, Andrew G.; Wanninkhof, Rik; Murata, Akihiko; Miller, Lisa A.; Greeley, Dana

    2012-09-01

    Based on measurements from the WOCE/JGOFS global CO2 survey, the CLIVAR/CO2 Repeat Hydrography Program and the Canadian Line P survey, we have observed an average decrease of 0.34% yr-1 in the saturation state of surface seawater in the Pacific Ocean with respect to aragonite and calcite. The upward migrations of the aragonite and calcite saturation horizons, averaging about 1 to 2 m yr-1, are the direct result of the uptake of anthropogenic CO2 by the oceans and regional changes in circulation and biogeochemical processes. The shoaling of the saturation horizon is regionally variable, with more rapid shoaling in the South Pacific where there is a larger uptake of anthropogenic CO2. In some locations, particularly in the North Pacific Subtropical Gyre and in the California Current, the decadal changes in circulation can be the dominant factor in controlling the migration of the saturation horizon. If CO2 emissions continue as projected over the rest of this century, the resulting changes in the marine carbonate system would mean that many coral reef systems in the Pacific would no longer be able to sustain a sufficiently high rate of calcification to maintain the viability of these ecosystems as a whole, and these changes perhaps could seriously impact the thousands of marine species that depend on them for survival.

  15. 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.

  16. 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

  17. 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.

  18. 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.

  19. 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

  20. 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

  1. 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.

  2. 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.

  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. Mg isotope fractionation during calcite precipitation: An experimental study

    NASA Astrophysics Data System (ADS)

    Saulnier, Ségolène; Rollion-Bard, Claire; Vigier, Nathalie; Chaussidon, Marc

    2012-08-01

    Experimental precipitations of calcite and other carbonate minerals were performed under various conditions of pH, temperature and solution Mg/Ca to determine the Mg partition coefficient and Mg isotope fractionation. Fifteen experiments were performed at pH ranging from 7.41 ± 0.07 to 8.51 ± 0.39, temperature ranging from 16.2 ± 0.7 to 26.5 ± 0.3 °C and Mg/Casolution ranging from 0.11 to 0.52 mol/mol. The apparent Mg partition coefficient between calcite and solution (DMg) spans a large range of values from 0.018 ± 0.014 to 0.15 ± 0.11 and carbonate Mg isotope fractionation (Δ26Mg) ranges from -2.53 ± 0.25‰ to -1.33 ± 0.14‰ and does not correlate with either pH or temperature. The range in DMg and Δ26Mg suggests non-equilibrium partitioning controlled by the processes of calcite growth, i.e. mixing between calcite grown at equilibrium and fluid inclusions, and entrapment of a surface Mg-rich calcite layer in isotopic equilibrium with the solution. The equilibrium Mg isotope fractionation between inorganic calcite and solution is estimated to be -2.13 ± 0.24‰. Additional Mg elemental and isotopic fractionations are observed to occur during biogenic formation of calcite due to variable removal of Mg by the organisms (high-Mg calcite corals, foraminifera) of seawater Mg from their calcification medium.

  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. 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.

  7. 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.

    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.

  8. 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

  9. Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands)

    NASA Astrophysics Data System (ADS)

    Lazzerini, Nicolas; Lécuyer, Christophe; Amiot, Romain; Angst, Delphine; Buffetaut, Eric; Fourel, François; Daux, Valérie; Betancort, Juan Francisco; Flandrois, Jean-Pierre; Marco, Antonio Sánchez; Lomoschitz, Alejandro

    2016-10-01

    Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ18Ocalc and δ13Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ18Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in 18O relative to 16O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ18Ocalc value of eggshell calcite to the δ18Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ13Ccalc and δ18Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ13Ccalc and high δ18Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions.

  10. Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands).

    PubMed

    Lazzerini, Nicolas; Lécuyer, Christophe; Amiot, Romain; Angst, Delphine; Buffetaut, Eric; Fourel, François; Daux, Valérie; Betancort, Juan Francisco; Flandrois, Jean-Pierre; Marco, Antonio Sánchez; Lomoschitz, Alejandro

    2016-10-01

    Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ(18)Ocalc and δ(13)Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ(18)Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in (18)O relative to (16)O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ(18)Ocalc value of eggshell calcite to the δ(18)Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ(13)Ccalc and δ(18)Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ(13)Ccalc and high δ(18)Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions.

  11. Oxygen isotope fractionation between bird eggshell calcite and body water: application to fossil eggs from Lanzarote (Canary Islands).

    PubMed

    Lazzerini, Nicolas; Lécuyer, Christophe; Amiot, Romain; Angst, Delphine; Buffetaut, Eric; Fourel, François; Daux, Valérie; Betancort, Juan Francisco; Flandrois, Jean-Pierre; Marco, Antonio Sánchez; Lomoschitz, Alejandro

    2016-10-01

    Oxygen and carbon isotope compositions of fossil bird eggshell calcite (δ(18)Ocalc and δ(13)Ccalc) are regularly used to reconstruct paleoenvironmental conditions. However, the interpretation of δ(18)Ocalc values of fossil eggshells has been limited to qualitative variations in local climatic conditions as oxygen isotope fractionations between calcite, body fluids, and drinking water have not been determined yet. For this purpose, eggshell, albumen water, and drinking water of extant birds have been analyzed for their oxygen and carbon isotope compositions. Relative enrichments in (18)O relative to (16)O between body fluids and drinking water of +1.6 ± 0.9 ‰ for semi-aquatic birds and of +4.4 ± 1.9 ‰ for terrestrial birds are observed. Surprisingly, no significant dependence to body temperature on the oxygen isotope fractionation between eggshell calcite and body fluids is observed, suggesting that bird eggshells precipitate out of equilibrium. Two empirical equations relating the δ(18)Ocalc value of eggshell calcite to the δ(18)Ow value of ingested water have been established for terrestrial and semi-aquatic birds. These equations have been applied to fossil eggshells from Lanzarote in order to infer the ecologies of the Pleistocene marine bird Puffinus sp. and of the enigmatic giant birds from the Pliocene. Both δ(13)Ccalc and δ(18)Ocalc values of Puffinus eggshells point to a semi-aquatic marine bird ingesting mostly seawater, whereas low δ(13)Ccalc and high δ(18)Ocalc values of eggshells from the Pliocene giant bird suggest a terrestrial lifestyle. This set of equations can help to quantitatively estimate the origin of waters ingested by extinct birds as well as to infer either local environmental or climatic conditions. PMID:27639729

  12. 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.

  13. Defluoridation of drinking water by boiling with brushite and calcite.

    PubMed

    Larsen, M J; Pearce, E I F

    2002-01-01

    Existing methods for defluoridating drinking water involve expensive high technology or are slow, inefficient and/or unhygienic. A new method is now suggested, encompassing brushite and calcite suspension followed by boiling. Our aim was to examine the efficiency of the method and the chemical reactions involved. Brushite, 0.3-0.5 g, and an equal weight of calcite were suspended in 1 litre water containing 5-20 ppm fluoride. The suspensions were boiled in an electric kettle, left to cool and the calcium salts to sediment. Solution ion concentrations were determined and sediments were examined by X-ray diffraction. In distilled water initially containing 5, 10 and 20 ppm fluoride the concentration was reduced to 0.06, 0.4 and 5.9 ppm, respectively. Using Aarhus tap water which contained 2.6 mmol/l calcium the final concentrations were 1.2, 2.5 and 7.7 ppm, respectively, and runs without calcite gave results similar to those with calcite. Without boiling the fluoride concentration remained unaltered, as did the brushite and calcite salts, despite occasional agitation by hand. All solutions were supersaturated with respect to fluorapatite and hydroxyapatite and close to saturation with respect to brushite. Boiling produced well-crystallised apatite and traces of calcite, while boiling of brushite alone left a poorly crystallised apatite. We conclude that boiling a brushite/calcite suspension rapidly converts the two salts to apatite which incorporates fluoride if present in solution, and that this process may be exploited to defluoridate drinking water.

  14. 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.

  15. 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

  16. Calcite and Picocyanobacteria in Lakes: Factors Affecting Their Interaction

    NASA Astrophysics Data System (ADS)

    Dittrich, M.; Obst, M.; Mavrocordatos, D.

    2003-12-01

    Calcites build large deposits which have been observed in the rock record throughout geological time at various localities around the globe. Carbonate deposits have affected atmospheric carbon dioxide concentration. As it has been generally accepted, inorganic precipitation represents a source of carbon dioxide on short geological time scales and a sink of inorganic carbon at long time scales from millions to thousands of millions years. However, recent research indicates that calcite deposits may result from microbial calcification instead of inorganic precipitation. In this case the process may reduce atmospheric carbon dioxide on geologically short time scales. Thus the effect of carbonate sediment deposition on global carbon cycling depends on the origin of carbonate. Thus it is essential to understand the cause and the key parameters affecting calcite precipitation. The role of algae and bacteria in calcite formation in lakes has not been evaluated in detail. Some evidence, however, exists supporting precipitation of calcium carbonate by microbes as the origin of whiting. Several field studies on lakes have also produced puzzling results: The peaks of algal blooms were often not found at the same time as precipitation events of calcite. We suspect that parts of the discrepancies in the interpretation of field observations are due to the activity of autotrophic picoplankton. The unicellular autotrophic picoplankton (APP) is a ubiquitous component of pelagic ecosystems. But it has often been overlooked due to its small cell size of 0.2 - 2 μ m in diameter. Coccoid picocyanobacteria of the Synechococcus-type dominate the picoplankton community in most oligotrophic systems. Recently, laboratory experiments and field observations suggested that APP may play an important role in calcite precipitation. The aim of this study was to examine the influence of environmental factors such as saturation state, concentration of different dissolved ions and characteristics of

  17. Hydrochemical controls on aragonite versus calcite precipitation in cave dripwaters

    NASA Astrophysics Data System (ADS)

    Rossi, Carlos; Lozano, Rafael P.

    2016-11-01

    Despite the paleoclimatic relevance of primary calcite to aragonite transitions in stalagmites, the relative role of fluid Mg/Ca ratio, supersaturation and CO32- concentration in controlling such transitions is still incompletely understood. Accordingly, we have monitored the hydrochemistry of 50 drips and 8 pools that are currently precipitating calcite and/or aragonite in El Soplao and Torca Ancha Caves (N. Spain), investigating the mineralogy and geochemistry of the CaCO3 precipitates on the corresponding natural speleothem surfaces. The data reveal that, apart from possible substrate effects, dripwater Mg/Ca is the only obvious control on CaCO3 polymorphism in the studied stalagmites and pools, where calcite- and aragonite-precipitating dripwaters are separated by an initial (i.e. at stalactite tips) Mg/Ca threshold at ≈1.1 mol/mol. Within the analyzed ranges of pH (8.2-8.6), CO32- concentration (1-6 mg/L), supersaturation (SIaragonite: 0.08-1.08; SIcalcite: 0.23-1.24), drip rate (0.2-81 drops/min) and dissolved Zn (6-90 μg/L), we observe no unequivocal influence of these parameters on CaCO3 mineralogy. Despite the almost complete overlapping supersaturations of calcite- and aragonite-precipitating waters, the latter are on average less supersaturated because the waters having Mg/Ca above ∼1.1 have mostly achieved such high ratios by previously precipitating calcite. Both calcite and aragonite precipitated at or near oxygen isotopic equilibrium, and Mg incorporation into calcite was consistent with literature-based predictions, indicating that in the studied cases CaCO3 precipitation was not significantly influenced by strong kinetic effects. In the studied cases, the calcites that precipitate at ∼11 °C from dripwaters with initial Mg/Ca approaching ∼1.1 incorporate ∼5 mol% MgCO3, close to the published value above which calcite solubility exceeds aragonite solubility, suggesting that aragonite precipitation in high-relative-humidity caves is

  18. 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.

  19. 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

  20. 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).

  1. 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.

  2. Continuous 500,000-year climate record from vein calcite in Devils Hole, Nevada

    USGS Publications Warehouse

    Winograd, I.J.; Coplen, T.B.; Landwehr, J.M.; Riggs, A.C.; Ludwig, K. R.; Szabo, B. J.; Kolesar, Peter T.; Revesz, K.M.

    1992-01-01

    Oxygen-18 (??18O) variations in a 36-centimeter-long core (DH-11) of vein calcite from Devils Hole, Nevada, yield an uninterrupted 500,000-year paleotemperature record that closely mimics all major features in the Vostok (Antarctica) paleotemperature and marine ??18O ice-volume records. The chronology for this continental record is based on 21 replicated mass-spectrometric uranium-series dates. Between the middle and latest Pleistocene, the duration of the last four glacial cycles recorded in the calcite increased from 80,000 to 130,000 years; this variation suggests that major climate changes were aperiodic. The timing of specific climatic events indicates that orbitally controlled variations in solar insolation were not a major factor in triggering deglaciations. Interglacial climates lasted about 20,000 years. Collectively, these observations are inconsistent with the Milankovitch hypothesis for the origin of the Pleistocene glacial cycles but they are consistent with the thesis that these cycles originated from internal nonlinear feedbacks within the atmosphere-ice sheet-ocean system.

  3. 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]).

  4. Time and metamorphic petrology: calcite to aragonite experiments.

    PubMed

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

    1992-10-01

    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 degrees C. Kinetic hindrance is likely to extend to higher temperatures in more complex transformations.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. 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

  13. Glycinebetaine and abiotic stress tolerance in plants

    PubMed Central

    Giri, Jitender

    2011-01-01

    The accumulation of osmolytes like glycinebetaine (GB) in cell is known to protect organisms against abiotic stresses via osmoregulation or osmoprotection. Transgenic plants engineered to produce GB accumulate very low concentration of GB, which might not be sufficient for osmoregulation. Therefore, other roles of GB like cellular macromolecule protection and ROS detoxification have been suggested as mechanisms responsible for abiotic stress tolerance in transgenic plants. In addition, GB influences expression of several endogenous genes in transgenic plants. The new insights gained about the mechanism of stress tolerance in GB accumulating transgenic plants are discussed. PMID:22057338

  14. 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.

  15. 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

  16. 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.

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

    PubMed

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

    2016-09-13

    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.

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

    PubMed Central

    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 Eu3+ 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

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

    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 Eu3+ 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.

  1. 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

  2. Inhibition by glycosaminoglycans of CaCO3 (calcite) crystallization.

    PubMed Central

    Grant, D; Long, W F; Williamson, F B

    1989-01-01

    Of a range of glycosaminoglycans, heparin and heparan sulphate were the most effective inhibitors in vitro of CaCO3 (calcite) crystallization as assayed by conductimetric measurements. The possible role of such glycosaminoglycans in modulating calcium-salt crystallizations in vivo is discussed. PMID:2719649

  3. 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

  4. 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

  5. Molecular ordering of ethanol at the calcite surface.

    PubMed

    Pasarín, I S; Yang, M; Bovet, N; Glyvradal, M; Nielsen, M M; Bohr, J; Feidenhans'l, R; Stipp, S L S

    2012-02-01

    To produce biominerals, such as shells, bones, and teeth, living beings create organic compounds that control the growth of the solid phase. Investigating the atomic scale behavior of individual functional groups at the mineral-fluid interface provides fundamental information that is useful for constructing accurate predictive models for natural systems. Previous investigations of the activity of coccolith-associated polysaccharides (CAP) on calcite, using atomic force microscopy (AFM) [Henriksen, K., Young, J. R., Bown, P. R., and Stipp, S. L. S. Palentology 2004, 43 (Part 3), 725-743] and molecular dynamics (MD) modeling [Yang, M., Stipp, S. L. S., and Harding, J. H. Cryst. Growth Des. 2008, 8 (11), 4066-4074], have suggested that OH functional groups control polysaccharide attachment. The purpose of this work was to characterize, using X-ray reflectivity (XR) combined with molecular dynamics (MD) simulations, the structuring on calcite of a layer of the simplest carbon chain molecule that contains an OH group, ethanol (CH(3)-CH(2)-OH). We found evidence that EtOH forms a highly ordered structure at the calcite surface, where the first layer molecules bond with calcite. The ethanol molecules stand up perpendicularly at the interface or nearly so. As a consequence, the fatty, CH(3) ends form a new surface, about 6 Å from the termination of the bulk calcite, and beyond that, there is a thin gap where ethanol density is low. Following is a more disordered layer that is two to three ethanol molecules thick, about 14 Å, where density more resembles that of bulk liquid ethanol. The good agreement between theory and experiment gives confidence that a theoretical approach can offer information about behavior in more complex systems.

  6. 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.

  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.

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

    PubMed

    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.

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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

  14. Does calcite encrustation in Chara provide a phosphorus nutrient sink?

    PubMed

    Siong, Kian; Asaeda, Takashi

    2006-01-01

    We studied the effect of calcite encrustation in stoneworts (Chara spp.) on P cycling in an aquatic ecosystem. Sequential fractionation was performed to quantify P fractions of the internodes of calcified (Ca-CF) and uncalcified (UCa-CF) Chara fibrosa Agardh ex Bruzelius. Our results showed that Ca-CF was able to store more P and about 14 to 23% of total P in Ca-CF was co-precipitated with encrusted calcite, while only 2 to 3% was found in UCa-CF. Furthermore, in Ca-CF, an increased amount of total P did not result in a higher release of bioavailable water-soluble and sodium hydroxide-extractable P. Extracellular calcification in Chara enhanced nutrient sink for P, provided a further bottom-up control of phytoplankton, and should be regarded as a positive feedback in stabilizing Chara dominance in lakes.

  15. 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.

  16. 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

  17. 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

  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. 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.

  20. 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.

  1. 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.

  2. Classifying benthic biotopes on sub-tropical continental shelf reefs: How useful are abiotic surrogates?

    NASA Astrophysics Data System (ADS)

    Richmond, Sarah; Stevens, Tim

    2014-02-01

    Biodiversity of marine areas beyond the reach of conventional diving technology (>30 m) is poorly known, yet subjected to increasing stresses from expanding recreational and commercial fishing, minerals exploration and other anthropogenic influences. In part, resource managers address this by using abiotic surrogates for patterns of biodiversity in planning marine protected areas or other management measures. However, the efficacy of these surrogates varies from place to place, and is often not quantified at the scale used by MPA designers and managers. This study surveyed and classified benthic assemblages of continental shelf rocky reefs across three depth categories from 30 to 70 m, using a suspended HD camera array, which is both non-destructive and cost-effective compared to any other methods of sampling at these depths. Five distinct benthic biotopes were defined, characterised primarily by variations in abundances of sea whips, sponges, kelp, and urchins. Derived patterns of benthic assemblage structure were compared to abiotic surrogates available at the scale (local) used in MPA planning. The individual factors with most influence on the classification were recreational fishing pressure, water temperature at the bottom, and distance from nearest estuary. The best combination of abiotic surrogates had a relatively strong relationship with the benthic assemblage, explaining 42% of the variation in assemblage structure (BIOENV ρ = 0.65), however the performance of a classification based on commonly used physical surrogates was relatively poor, explaining only 22% of variation. The results underline the limitations of using abiotic variables for habitat mapping at the local scale, and the need for robust surveys to quantify patterns of biodiversity.

  3. Visualization of acoustic cavitation effects on suspended calcite crystals.

    PubMed

    Wagterveld, R M; Boels, L; Mayer, M J; Witkamp, G J

    2011-01-01

    The acoustic cavitation (42,080 Hz, 7.1 W cm(-2) or 17 W) effects on suspended calcite crystals, sized between 5 and 50 μm, have been visualized for the first time using high speed photography. High speed recordings with a duration of 1 s containing up to 300,000 frames per second, revealed the effect of cluster and streamer cavitation on several calcite crystals. Cavitation clusters, evolved from cavitation inception and collapse, caused attrition, disruption of aggregates and deagglomeration, whereas streamer cavitation was observed to cause deagglomeration only. Cavitation on the surface gave the crystals momentum. However, it is shown that breakage of accelerated crystals by interparticle collisions is unrealistic because of their small sizes and low velocities. Crystals that were accelerated by bubble expansion, subsequently experienced a deceleration much stronger than expected from drag forces, upon bubble collapse. Experiments with pre-dried crystals seemed to support the current theory on bubble nucleation through the presence of pre-existing gas pockets. However, experiments with fully wetted crystals also showed the nucleation of bubbles on the crystal surface. Although microjet impingement on the crystal surface could not be directly visualized with high speed photography, scanning electron microscopy (SEM) analysis of irradiated calcite seeds showed deep circular indentations. It was suggested that these indentations might be caused by shockwave induced jet impingement. Furthermore, the appearance of voluminous fragments with large planes of fracture indicated that acoustic cavitation can also cause the breakage of single crystal structures.

  4. Heterogeneous conversion of calcite aerosol by nitric acid.

    PubMed

    Preszler Prince, A; Grassian, V H; Kleiber, P; Young, M A

    2007-02-01

    The reaction of nitric acid with calcite aerosol at varying relative humidities has been studied under suspended particle conditions in an atmospheric reaction chamber using infrared absorption spectroscopy. The reactant concentration in the chamber, as well as the appearance of gas phase products and surface adsorbed species, was spectroscopically monitored before and after mixing with CaCO(3) (calcite) particles. The interaction with HNO(3) was found to lead to gas phase CO(2) evolution and increased water uptake due to heterogeneous conversion of the carbonate to particulate nitrate. The reaction was enhanced as the relative humidity of the system was increased, especially at relative humidities above the reported deliquescence point of particulate Ca(NO(3))(2). The measured reaction extent demonstrates that the total calcite particulate mass is available for reaction with HNO(3) and the conversion process is not limited to the particle surface. The spectroscopy of the surface formed nitrate suggests a highly concentrated solution environment with a significant degree of ion pairing. The implications of the HNO(3) loss and the formation of the particulate nitrate product for atmospheric chemistry are discussed. PMID:17242744

  5. 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

  6. How tightly does calcite e-twin constrain stress?

    NASA Astrophysics Data System (ADS)

    Yamaji, Atsushi

    2015-03-01

    Mechanical twinning along calcite e-planes has been used for paleostress analyses. Since the twinning has a critical resolved shear stress at ˜10 MPa, not only principal stress axes but also differential stress can be determined from the twins. In this article, five-dimensional stress space used in plasticity theory was introduced to describe the yield loci of calcite e-twinning. The constraints to paleostress from twin and untwin data and from calcite grains twinned on 0, 1, 2 and 3 e-planes were quantified by using their information contents, which were defined in the stress space. The orientations of twinned and untwinned e-planes are known to constrain not only stress axes but also differential stress, D, but they loose the resolution of D if the twin lamellae were formed at D greater than 50-100 MPa. On the other hand, it is difficult to observe twin lamellae subparallel to a thin section. The stochastic modeling of this effect showed that 20-25% of twin lamellae can be overlooked. The degradation of the constraints by this sampling bias can be serious especially for the determination of D.

  7. Nucleation, growth and evolution of calcium phosphate films on calcite.

    PubMed

    Naidu, Sonia; Scherer, George W

    2014-12-01

    Marble, a stone composed of the mineral calcite, is subject to chemically induced weathering in nature due to its relatively high dissolution rate in acid rain. To protect monuments and sculpture from corrosion, we are investigating the application of thin layers of hydroxyapatite (HAP) onto marble. The motivation for using HAP is its low dissolution rate and crystal and lattice compatibility with calcite. A mild, wet chemical synthesis route, in which diammonium hydrogen phosphate salt was reacted with marble, alone and with cationic and anionic precursors under different reaction conditions, was used to produce inorganic HAP layers on marble. Nucleation and growth on the calcite substrate was studied, as well as metastable phase evolution, using scanning electron microscopy, grazing incidence X-ray diffraction, and atomic force microscopy. Film nucleation was enhanced by surface roughness. The rate of nucleation and the growth rate of the film increased with cationic (calcium) and anionic (carbonate) precursor additions. Calcium additions also influenced phase formation, introducing a metastable phase (octacalcium phosphate) and a different phase evolution sequence.

  8. 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.

  9. Nucleation, growth and evolution of calcium phosphate films on calcite.

    PubMed

    Naidu, Sonia; Scherer, George W

    2014-12-01

    Marble, a stone composed of the mineral calcite, is subject to chemically induced weathering in nature due to its relatively high dissolution rate in acid rain. To protect monuments and sculpture from corrosion, we are investigating the application of thin layers of hydroxyapatite (HAP) onto marble. The motivation for using HAP is its low dissolution rate and crystal and lattice compatibility with calcite. A mild, wet chemical synthesis route, in which diammonium hydrogen phosphate salt was reacted with marble, alone and with cationic and anionic precursors under different reaction conditions, was used to produce inorganic HAP layers on marble. Nucleation and growth on the calcite substrate was studied, as well as metastable phase evolution, using scanning electron microscopy, grazing incidence X-ray diffraction, and atomic force microscopy. Film nucleation was enhanced by surface roughness. The rate of nucleation and the growth rate of the film increased with cationic (calcium) and anionic (carbonate) precursor additions. Calcium additions also influenced phase formation, introducing a metastable phase (octacalcium phosphate) and a different phase evolution sequence. PMID:25233226

  10. 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.

  11. 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.

  12. 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

  13. 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

  14. 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.

  15. 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

  16. Alteration histories of fossil biogenic calcite as indicated by 87Sr/86Sr ratios

    NASA Astrophysics Data System (ADS)

    Ullmann, C. V.; Campbell, H. J.; Korte, C.

    2012-04-01

    The 87Sr/86Sr, δ18O and δ13C composition of biogenic calcite from stratigraphically well-defined marine fossils can be utilized to reconstruct paleoenvironments and the isotopic evolution of past seawater. A conceptual prerequisite for reliable results is a minimum of post-depositional alteration of the samples. In order to establish a measure of the degree of alteration it is common practise to check all biogenic calcite samples using cathodoluminescence, SEM, and trace element concentration analysis. However, none of these screening techniques is fool-proof. A combination of these approaches is necessary to select the best preserved samples. In this study we show that strontium isotope signatures can serve as an independent alteration indicator. Because the seawater 87Sr/86Sr ratio in fully marine environments is virtually constant during the lifespan (< 50 years) of the shelly organisms involved, and biofractionation of the 87Sr/86Sr ratio is corrected for by the recalculation to a constant 88Sr/86Sr of 0.1194, only altered samples exhibit variability of the 87Sr/86Sr ratio beyond analytical reproducibility and/or significant deviation from the strontium isotope curve for seawater. We measured 87Sr/86Sr, δ18O, δ13C and element ratios from a Late Kimmeridgian belemnite from New Zealand, and a Late Triassic (Rhaetian) brachiopod from New Caledonia. The 87Sr/86Sr ratios for the belemnite vary from 0.706724 to 0.706928 (n = 5) with three values being compatible with coeval seawater and two values being less radiogenic than the lowest seawater value of the Phanerozoic seawater curve. The low 87Sr/86Sr ratios coincide with elevated Mn and low Sr concentrations, and light δ18O values indicate diagenesis that involved fluids leaching less radiogenic Sr from the surrounding rocks, and re-crystallisation of the belemnite guard at elevated temperatures. The 87Sr/86Sr ratios of the brachiopod vary from 0.707813 to 0.707934 (n = 8) and are strongly correlated with Mg

  17. Oxylipins and plant abiotic stress resistance.

    PubMed

    Savchenko, T V; Zastrijnaja, O M; Klimov, V V

    2014-04-01

    Oxylipins are signaling molecules formed enzymatically or spontaneously from unsaturated fatty acids in all aerobic organisms. Oxylipins regulate growth, development, and responses to environmental stimuli of organisms. The oxylipin biosynthesis pathway in plants includes a few parallel branches named after first enzyme of the corresponding branch as allene oxide synthase, hydroperoxide lyase, divinyl ether synthase, peroxygenase, epoxy alcohol synthase, and others in which various biologically active metabolites are produced. Oxylipins can be formed non-enzymatically as a result of oxygenation of fatty acids by free radicals and reactive oxygen species. Spontaneously formed oxylipins are called phytoprostanes. The role of oxylipins in biotic stress responses has been described in many published works. The role of oxylipins in plant adaptation to abiotic stress conditions is less studied; there is also obvious lack of available data compilation and analysis in this area of research. In this work we analyze data on oxylipins functions in plant adaptation to abiotic stress conditions, such as wounding, suboptimal light and temperature, dehydration and osmotic stress, and effects of ozone and heavy metals. Modern research articles elucidating the molecular mechanisms of oxylipins action by the methods of biochemistry, molecular biology, and genetics are reviewed here. Data on the role of oxylipins in stress signal transduction, stress-inducible gene expression regulation, and interaction of these metabolites with other signal transduction pathways in cells are described. In this review the general oxylipin-mediated mechanisms that help plants to adjust to a broad spectrum of stress factors are considered, followed by analysis of more specific responses regulated by oxylipins only under certain stress conditions. New approaches to improvement of plant resistance to abiotic stresses based on the induction of oxylipin-mediated processes are discussed.

  18. 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

  19. 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.".

  20. Simulations of calcite crystallization on self-assembled monolayers.

    PubMed

    Freeman, Colin L; Harding, John H; Duffy, Dorothy M

    2008-09-01

    This paper presents simulations of calcium carbonate ordering in contact with self-assembled monolayers. The calculations use potential-based molecular dynamics to model the crystallization of calcium carbonate to calcite expressing both the (00.1) and (01.2) surfaces. The effect of monolayer properties: ionization; epitaxial matching; charge density; and headgroup orientation on the crystallization process are examined in detail. The results demonstrate that highly charged surfaces are vital to stimulate ordering and crystallization. Template directed crystallization requires charge epitaxy between both the crystal surface and the monolayer. The orientation of the headgroup appears to make no contribution to the selection of the crystal surface.

  1. 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.

  2. 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

  3. Local Adaptation in Marine Invertebrates

    NASA Astrophysics Data System (ADS)

    Sanford, Eric; Kelly, Morgan W.

    2011-01-01

    Local adaptation in the sea was regarded historically as a rare phenomenon that was limited to a handful of species with exceptionally low dispersal potential. However, a growing body of experimental studies indicates that adaptive differentiation occurs in numerous marine invertebrates in response to selection imposed by strong gradients (and more complex mosaics) of abiotic and biotic conditions. Moreover, a surprisingly high proportion of the marine invertebrates known or suspected of exhibiting local adaptation are species with planktonic dispersal. Adaptive divergence among populations can occur over a range of spatial scales, including those that are fine-grained (i.e., meters to kilometers), reflecting a balance between scales of gene flow and selection. Addressing the causes and consequences of adaptive genetic differentiation among invertebrate populations promises to advance community ecology, climate change research, and the effective management of marine ecosystems.

  4. Breeding for abiotic stresses for sustainable agriculture.

    PubMed

    Witcombe, J R; Hollington, P A; Howarth, C J; Reader, S; Steele, K A

    2008-02-27

    Using cereal crops as examples, we review the breeding for tolerance to the abiotic stresses of low nitrogen, drought, salinity and aluminium toxicity. All are already important abiotic stress factors that cause large and widespread yield reductions. Drought will increase in importance with climate change, the area of irrigated land that is salinized continues to increase, and the cost of inorganic N is set to rise. There is good potential for directly breeding for adaptation to low N while retaining an ability to respond to high N conditions. Breeding for drought and salinity tolerance have proven to be difficult, and the complex mechanisms of tolerance are reviewed. Marker-assisted selection for component traits of drought in rice and pearl millet and salinity tolerance in wheat has produced some positive results and the pyramiding of stable quantitative trait locuses controlling component traits may provide a solution. New genomic technologies promise to make progress for breeding tolerance to these two stresses through a more fundamental understanding of underlying processes and identification of the genes responsible. In wheat, there is a great potential of breeding genetic resistance for salinity and aluminium tolerance through the contributions of wild relatives.

  5. Multiple abiotic stress responsive rice cyclophilin

    PubMed Central

    Trivedi, Dipesh Kumar; Ansari, Mohammad Wahid; Tuteja, Narendra

    2013-01-01

    Cyclophilins (CYP), a member of immunophillin group of proteins, are more often conserved in all genera including plants. Here, we report on the identification of a new cyclophilin gene OsCYP-25 (LOC_Os09 g39780) from rice which found to be upregulated in response to various abiotic stresses viz., salinity, cold, heat and drought. It has an ORF of 540 bp, encoding a protein of 179 amino acids, consisting of PPIase domain, which is highly conserved. The OsCYP-25 promoter analysis revealed that different cis-regulatory elements (e.g., MYBCORE, MYC, CBFHV, GT1GMSCAM4, DRECRTCOREAT, CCAATBOX1, WRKY71OS and WBOXATNPR1) are involved to mediate OsCYP-25 response under stress. We have also predicted interacting partners by STRING software. In interactome, protein partners includes WD domain containing protein, the 60S ribosome subunit biogenesis protein, the ribosomal protein L10, the DEAD-box helicase, the EIF-2α, YT521-B protein, the 60S ribosomal protein and the PPR repeat domain containing protein. The in silico analysis showed that OsCYP-25 interacts with different proteins involved in cell growth, differentiation, ribosome biogenesis, RNA metabolism, RNA editing, gene expression, signal transduction or stress response. These findings suggest that OsCYP-25 might perform an important function in mediating wide range of cellular response under multiple abiotic stresses. PMID:24265852

  6. The ubiquitous nature of accessory calcite in granitoid rocks: Implications for weathering, solute evolution, and petrogenesis

    USGS Publications Warehouse

    White, A.F.; Schulz, M.S.; Lowenstern, J. B.; Vivit, D.V.; Bullen, T.D.

    2005-01-01

    Calcite is frequently cited as a source of excess Ca, Sr and alkalinity in solutes discharging from silicate terrains yet, no previous effort has been made to assess systematically the overall abundance, composition and petrogenesis of accessory calcite in granitoid rocks. This study addresses this issue by analyzing a worldwide distribution of more than 100 granitoid rocks. Calcite is found to be universally present in a concentration range between 0.028 to 18.8 g kg-1 (mean = 2.52 g kg-1). Calcite occurrences include small to large isolated anhedral grains, fracture and cavity infillings, and sericitized cores of plagioclase. No correlation exists between the amount of calcite present and major rock oxide compositions, including CaO. Ion microprobe analyses of in situ calcite grains indicate relatively low Sr (120 to 660 ppm), negligible Rb and 87Sr/86Sr ratios equal to or higher than those of coexisting plagioclase. Solutes, including Ca and alkalinity produced by batch leaching of the granitoid rocks (5% CO2 in DI water for 75 d at 25??C), are dominated by the dissolution of calcite relative to silicate minerals. The correlation of these parameters with higher calcite concentrations decreases as leachates approach thermodynamic saturation. In longer term column experiments (1.5 yr), reactive calcite becomes exhausted, solute Ca and Sr become controlled by feldspar dissolution and 87Sr/ 86Sr by biotite oxidation. Some accessory calcite in granitoid rocks is related to intrusion into carbonate wall rock or produced by later hydrothermal alteration. However, the ubiquitous occurrence of calcite also suggests formation during late stage (subsolidus) magmatic processes. This conclusion is supported by petrographic observations and 87Sr/86Sr analyses. A review of thermodynamic data indicates that at moderate pressures and reasonable CO2 fugacities, calcite is a stable phase at temperatures of 400 to 700??C. Copyright ?? 2005 Elsevier Ltd.

  7. Structure and reactivity of the calcite-water interface.

    PubMed

    Heberling, Frank; Trainor, Thomas P; Lützenkirchen, Johannes; Eng, Peter; Denecke, Melissa A; Bosbach, Dirk

    2011-02-15

    The zetapotential of calcite in contact with aqueous solutions of varying composition is determined for pre-equilibrated suspensions by means of electrophoretic measurements and for non-equilibrium solutions by means of streaming potential measurements. Carbonate and calcium are identified as charge determining ions. Studies of the equilibrium solutions show a shift of isoelectric point with changing CO(2) partial pressure. Changes in pH have only a weak effect in non-equilibrium solutions. The surface structure of (104)-faces of single crystal calcite in contact to solutions corresponding to those of the zetapotential investigations is determined from surface diffraction measurements. The results reveal no direct indication of calcium or carbonate inner-sphere surface species. The surface ions are found to relax only slightly from their bulk positions; the most significant relaxation is a ∼4° tilt of the surface carbonate ions towards the surface. Two ordered layers of water molecules are identified, the first at 2.35±0.05Å above surface calcium ions and the second layer at 3.24±0.06Å above the surface associated with surface carbonate ions. A Basic-Stern surface complexation model is developed to model observed zetapotentials, while only considering outer-sphere complexes of ions other than protons and hydroxide. The Basic-Stern SCM successfully reproduces the zetapotential data and gives reasonable values for the inner Helmholtz capacitance, which are in line with the Stern layer thickness estimated from surface diffraction results. PMID:21087772

  8. [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

  9. Porosity and hydric behavior of typical calcite microfabrics in stalagmites

    NASA Astrophysics Data System (ADS)

    Muñoz-García, M. B.; López-Arce, P.; Fernández-Valle, M. E.; Martín-Chivelet, J.; Fort, R.

    2012-07-01

    Petrophysical techniques commonly used for material characterization are applied for the first time to speleothem samples to investigate the porosity and hydric behavior of calcite stalagmites used in paleoclimatology. These techniques allow the determination of the stalagmites' potential to undergo diagenetic transformations when substantial changes in drip waters occur in the cave environment. The petrophysical techniques include water absorption under vacuum and by capillarity, nuclear magnetic resonance, environmental scanning electron microscopy, and mercury intrusion porosimetry. The studied samples comprise five common calcite microfabrics, which have markedly different porosities and hydric behaviors and, as a consequence, different sensibilities to diagenetic processes related to the influx of water. The experiments show that stalagmites can behave as complex, small-scale hydrological systems and that the circulation of water through them by complex nets of interconnected pores might be common. As the circulation of water favors diagenetic transformations that involve geochemical and isotopic changes, the characterization of flow patterns is key for outlining areas that are susceptible to such modifications, which is critical to paleoclimatic studies that are based on speleothems because geochemical and stable isotopic data are used as paleoenvironmental proxies and absolute ages are obtained by using radioactive isotope ratios. These potential modifications also have obvious implications for studies based on fluid inclusions in speleothems. The integrated methodology, which uses primarily non-destructive techniques, shows a high potential for characterization of any type of speleothem and other continental carbonates such as tufas or sinters.

  10. Isotopic analysis for degradation diagnosis of calcite matrix in mortar.

    PubMed

    Dotsika, E; Psomiadis, D; Poutoukis, D; Raco, B; Gamaletsos, P

    2009-12-01

    Mortar that was used in building as well as in conservation and restoration works of wall paintings have been analysed isotopically (delta(13)C and delta(18)O) in order to evaluate the setting environments and secondary processes, to distinguish the structural components used and to determine the exact causes that incurred the degradation phenomena. The material undergoes weathering and decay on a large proportion of its surface and in depth, due to the infiltration of water through the structural blocks. Mineralogical analysis indicated signs of sulphation and dissolution/recrystallisation processes taking place on the material, whereas stable isotopes provided information relative to the origin of the CO(2) and water during calcite formation and degradation processes. Isotopic change of the initial delta(13)C and delta(18)O in carbonate matrix was caused by alteration of the primary source of CO(2) and H(2)O in mortar over time, particularly by recrystallisation of calcite with porewater, evaporated or re-condensed water, and CO(2) from various sources of atmospheric and biogenic origin. Human influence (surface treatment) and biological growth (e.g. fungus) are major exogenic processes which may alter delta(18)O and delta(13)C in lime mortar.

  11. Crystallographic orientation inhomogeneity and crystal splitting in biogenic calcite.

    PubMed

    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

    2013-09-01

    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.

  12. 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

  13. 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.

  14. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    Applying classical molecular dynamics simulations, we calculate the parallel self-diffusion coefficients of different fluids (methane, nitrogen, and carbon dioxide) confined between two { 10 1 ¯ 4 } 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.

  17. Investigation of organic matter entrapped during calcite growth by a multi-method approach

    NASA Astrophysics Data System (ADS)

    Chalmin, E.; Perrette, Y.; Fanget, B.; Drysdale, R.

    2012-04-01

    Organic matter (OM) entrapped in calcite is regularly used for environmental studies; however, incorporation mechanisms and types of interaction remain poorly understood. This study used a new methodology to investigate interactions between OM and the calcite matrix during crystallization processes using humic acid entrapment. A multi-method approach confirmed that OM is both adsorbed onto the calcite surface and incorporated into the calcite lattice during crystallization. Our results also confirm the log-linear correlation between fluorescence intensity and calcite matrix OM concentration. Fourier transform infrared spectroscopy (FTIR) showed that OM in colloidal conformation is adsorbed onto the calcite surface as a result of the structure of the OH stretching band. Based on synchrotron analysis (XRF and XANES), we also developed a new method in which sulfur is used as a tracer for entrapped humic acid and for locating the OM electrostatically adsorbed onto the calcite surface. Changes in the sulfur environment, determined using XANES, indicated partitioning during calcite crystallization due to the effect of the matrix on OM incorporation. Desorption experiments revealed the stability of the OM atomic structure and the layered nature of that structure. These results have allowed us to devise a general model of OM incorporation into calcite.

  18. 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.

  19. 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).

  20. 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

  1. 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

  2. The abiotic litter decomposition in the drylands

    NASA Astrophysics Data System (ADS)

    Lee, H.; Throop, H.; Rahn, T. A.

    2009-12-01

    The decomposition of litter is an important ecosystem function that controls carbon and nutrient cycling, which is well understood from the relationship between temperature and moisture. However, the decomposition in the arid and semiarid environments (hereafter drylands) is relatively poorly predicted due to several abiotic factors such as the effect of ultraviolet radiation and physical mixing of fallen litter with soil. The relative magnitude of these abiotic factors to ecosystem scale litter decomposition is still in debate. Here, we examine the effect of two major abiotic factors in the drylands litter decomposition by conducting a controlled laboratory study using plant litter and soil collected from Sonoran and Chihuahuan desert areas. The first part of the experiment focused on the effect of soil-litter mixing. We established a complete block design of three levels of soil and litter mixing (no mixing, light soil-litter mixing, and complete soil-litter mixing) in combination with three levels of soil moisture (1%, 2%, and 6% volumetric water content) using 2g of two most dominant species litter, grass and mesquite, and 50g of air-dried soils in 500ml mason jar and incubated them under 25C. We measured CO2 fluxes from these soil-litter incubations and harvested the soil and litter at 0, 1, 2, 4, 8, and 16 weeks and analyzed them of carbon and nitrogen content as well as the actual mass loss in the litter. The second part of the experiment focused on the effect of ultraviolet radiation. We established short-term litter incubation on a quartz chamber and used different temperature, moisture, and minerals to find the mechanism of photodegradation of litter. We measured CO2 fluxes from the litter incubation under ultraviolet radiation and also measured 13CO2 from these emissions. We were able to detect changes in the rate of carbon mineralization as a result of our treatments in the first week of soil-litter mixing experiment. The carbon mineralization rate was

  3. 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

  4. Marine Careers.

    ERIC Educational Resources Information Center

    Gordon, Bernard L.

    The five papers in this publication on marine careers were selected so that science teachers, guidance councilors, and students could benefit from the experience and knowledge of individuals active in marine science. The areas considered are indicated by the titles: Professional Careers in Marine Science with the Federal Government, Marine Science…

  5. 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

  6. 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

  7. 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

  8. ABIOTIC IN SITU TECHNOLOGIES FOR GROUNDWATER REMEDIATION CONFERENCE: PROCEEDINGS

    EPA Science Inventory

    The USEPA conference on Abiotic In Situ Technologies for Groundwater Remediation was held in Dallas, TX, 8/31-9/2/99. The goal of the meeting was to disseminate current information on abiotic in situ groundwater treatment echnologies. Although much information is being provided a...

  9. 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

  10. Abiotic stresses induce different localizations of anthocyanins in Arabidopsis

    PubMed Central

    Kovinich, Nik; Kayanja, Gilbert; Chanoca, Alexandra; Otegui, Marisa S; Grotewold, Erich

    2015-01-01

    Anthocyanins are induced in plants in response to abiotic stresses such as drought, high salinity, excess light, and cold, where they often correlate with enhanced stress tolerance. Numerous roles have been proposed for anthocyanins induced during abiotic stresses including functioning as ROS scavengers, photoprotectants, and stress signals. We have recently found different profiles of anthocyanins in Arabidopsis (Arabidopsis thaliana) plants exposed to different abiotic stresses, suggesting that not all anthocyanins have the same function. Here, we discuss these findings in the context of other studies and show that anthocyanins induced in Arabidopsis in response to various abiotic stresses have different localizations at the organ and tissue levels. These studies provide a basis to clarify the role of particular anthocyanin species during abiotic stress. PMID:26179363

  11. Identification and prediction of abiotic stress responsive transcription factors involved in abiotic stress signaling in soybean.

    PubMed

    Tran, Lam-Son Phan; Mochida, Keiichi

    2010-03-01

    Abiotic stresses such as extreme temperature, drought, high salinity, cold and waterlogging often result in significant losses to the yields of economically important crops such as soybean (Glycine max L.). Transcription factors (TFs) which bind to DNA through specific cis-regulatory sequences either activate or repress gene transcription have been reported to act as control switches in stress signaling. Recent completion of the soybean genomic sequence has open wide opportunities for large-scale identification and annotations of regulatory TFs in soybean for functional studies. Within the soybean genome, we identified 5,035 TF models which grouped into 61 families. Detailed annotations of soybean TF genes can be accessed at SoybeanTFDB (soybeantfdb.psc.riken.jp). Moreover, we have reported a new idea of high throughput prediction and selection of abiotic stress responsive TFs based on the existence of known stress responsive cis-element(s) located in the promoter regions of respective TFs and GO annotations. We, therefore, have provided a basic platform for the genome-wide analysis of regulatory mechanisms underlying abiotic stress responses and a reliable tool for prediction and selection of stress responsive TFs for further functional studies and genetic engineering.

  12. 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.

  13. 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.

  14. Calcite orientations and composition ranges within teeth across Echinoidea.

    PubMed

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

    2014-08-01

    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

  15. 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.

  16. 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

  17. 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

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

    NASA Astrophysics Data System (ADS)

    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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. The quantitative determination of calcite associated with the carbonate-bearing apatites

    USGS Publications Warehouse

    Silverman, Sol R.; Fuyat, Ruth K.; Weiser, Jeanne D.

    1951-01-01

    The CO2 combined as calcite in carbonate-bearing apatites as been distinguished from that combined as carbonate-apatite, or present in some form other than calcite, by use of X-ray powder patterns, differential thermal analyses, and differential solubility tests. These methods were applied to several pure apatite minerals, to one fossil bone, and to a group of phosphorites from the Phosphoria formation of Permian age from Trail Canyon and the Conda mine, Idaho, and the Laketown district, Utah. With the exceptions of pure fluorapatite, pure carbonate-flueorapatite, and one phosphorite from Trail Canyon, these substances contain varying amounts of calcite, but in all the samples an appreciable part of the carbonite content is not present as calcite. The results of solubility tests, in which the particle size of sample and the length of solution time were varied, imply that the carbonate content is not due to shielded calcite entrapped along an internal network of surfaces.

  4. 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.

  5. Unusual micrometric calcite-aragonite interface in the abalone shell Haliotis (Mollusca, Gastropoda).

    PubMed

    Dauphin, Yannicke; Cuif, Jean-Pierre; Castillo-Michel, Hiram; Chevallard, Corinne; Farre, Bastien; Meibom, Anders

    2014-02-01

    Species of Haliotis (abalone) show high variety in structure and mineralogy of the shell. One of the European species (Haliotis tuberculata) in particular has an unusual shell structure in which calcite and aragonite coexist at a microscale with small patches of aragonite embedded in larger calcitic zones. A detailed examination of the boundary between calcite and aragonite using analytical microscopies shows that the organic contents of calcite and aragonite differ. Moreover, changes in the chemical composition of the two minerals seem to be gradual and define a micrometric zone of transition between the two main layers. A similar transition zone has been observed between the layers in more classical and regularly structured mollusk shells. The imbrication of microscopic patches of aragonite within a calcitic zone suggests the occurrence of very fast physiological changes in these taxa.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. Polyamines and abiotic stress tolerance in plants.

    PubMed

    Gill, Sarvajeet Singh; Tuteja, Narendra

    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.

  14. 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

  15. Phenotyping for abiotic stress tolerance in maize.

    PubMed

    Masuka, Benhilda; Araus, Jose Luis; Das, Biswanath; Sonder, Kai; Cairns, Jill E

    2012-04-01

    The ability to quickly develop germplasm having tolerance to several complex polygenic inherited abiotic and biotic stresses combined is critical to the resilience of cropping systems in the face of climate change. Molecular breeding offers the tools to accelerate cereal breeding; however, suitable phenotyping protocols are essential to ensure that the much-anticipated benefits of molecular breeding can be realized. To facilitate the full potential of molecular tools, greater emphasis needs to be given to reducing the within-experimental site variability, application of stress and characterization of the environment and appropriate phenotyping tools. Yield is a function of many processes throughout the plant cycle, and thus integrative traits that encompass crop performance over time or organization level (i.e. canopy level) will provide a better alternative to instantaneous measurements which provide only a snapshot of a given plant process. Many new phenotyping tools based on remote sensing are now available including non-destructive measurements of growth-related parameters based on spectral reflectance and infrared thermometry to estimate plant water status. Here we describe key field phenotyping protocols for maize with emphasis on tolerance to drought and low nitrogen.

  16. 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.

  17. 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.

  18. 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

  19. 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.

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

    PubMed

    Offeddu, Francesco Giancarlo; Cama, Jordi; Soler, Josep Maria; Putnis, Christine V

    2014-01-01

    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

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. Effect of Second-phase Particles on Static Adjustment of Calcite Grain Boundaries in Carbonate Mylonites

    NASA Astrophysics Data System (ADS)

    Ree, J.; Lee, S.; Jung, H.

    2010-12-01

    Static adjustment of grain boundaries during the waning stage of deformation with sustained heat (e.g. at the end of an orogeny) has not been studied much, although it is important for the interpretation of microstructural status during the main stage of deformation. We report here that static adjustment of calcite grain boundaries is dependent on second-phase particles in carbonate mylonites from the Geounri Shear Zone in the Taebaeksan Basin of South Korea. The carbonate mylonites consist of relic (porphyroclastic) calcites (120-400 μm) and dynamically recrystallized calcites (30-35 μm) with second-phase particles (15-20 μm) of quartz and phyllosilicates. Both calcite grains contain mechanical twins and the twins are wider (10-20 μm thick) in the relic calcites than in the dynamically recrystallized ones (1-3 μm thick). In the layers of carbonate mylonite with less than 3% of second phases, grain boundaries of calcites are straight with triple junctions. In contrast, calcite grain boundaries are lobate to wavy in the layers with more than 3% of second phases, suggesting dynamic grain boundary migration. Calcite grains in both layers show a strong lattice preferred orientation indicating dominant slip system of basal with minor one of rhomb . We interpret that the foam texture of calcite in the mylonite layers with less than 3% of second phases was produced during the waning stage of the main deformation with a sustained heat since both syntectonic and posttectonic chloritoid porphyroblasts occur in adjacent phyllonite layers in the shear zone. 3% volume fraction of second-phase particles might be a critical value above which deformation microstructures of the main phase were ‘frozen’ without static adjustment in our carbonate mylonites.

  6. 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.

  7. Circadian regulation of abiotic stress tolerance in plants.

    PubMed

    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.

  8. 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.

  9. 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

  10. 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.

  11. Microbiologically Induced Calcite Precipitation Mediated by Sporosarcina pasteurii.

    PubMed

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

    2016-04-16

    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.

  12. Calcite-forming bacteria for compressive strength improvement in mortar.

    PubMed

    Park, Sung-Jin; Park, Yu-Mi; Chun, Woo-Young; Kim, Wha-Jung; Ghim, Sa-Youl

    2010-04-01

    Microbiological calcium carbonate precipitation (MCP) has been investigated for its ability to improve the compressive strength of concrete mortar. However, very few studies have been conducted on the use of calcite-forming bacteria (CFB) to improve compressive strength. In this study, we discovered new bacterial genera that are capable of improving the compressive strength of concrete mortar. We isolated 4 CFB from 7 environmental concrete structures. Using sequence analysis of the 16S rRNA genes, the CFB could be partially identified as Sporosarcina soli KNUC401, Bacillus massiliensis KNUC402, Arthrobacter crystallopoietes KNUC403, and Lysinibacillus fusiformis KNUC404. Crystal aggregates were apparent in the bacterial colonies grown on an agar medium. Stereomicroscopy, scanning electron microscopy, and x-ray diffraction analyses illustrated both the crystal growth and the crystalline structure of the CaCO3 crystals. We used the isolates to improve the compressive strength of concrete mortar cubes and found that KNUC403 offered the best improvement in compressive strength.

  13. 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

  14. Calcium bilirubinate intercalated calcite single crystal: evidence for microstructure of pigment gallstones

    NASA Astrophysics Data System (ADS)

    Liu, H. Z.; Xu, D. J.; Soloway, Roger D.; Zhang, Y. Z.; Xu, Duan-Fu; Wu, JinGuang

    1994-01-01

    During the preparation of calcium bilirubinate (CaBR) single crystals, brown crystals were grown in a gel solution of CaCl2/Sodium bilirubinate. X-ray diffraction analysis proved that the crystal was calcite. FTIR investigations support this result. However, the subtracted spectra revealed that the CaBR dispersed in the crystals and interacted with calcite on the molecular level, since the maximum band shift of the CaBR in calcite from the correspond bands of CaBR was ca. 20 cm-1. It was confirmed that microstructure also by x- ray diffraction and photoacoustic Fourier transform infrared spectroscopy.

  15. 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.

  16. 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

  17. 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

  18. 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

  19. Calcium Isotopes in Marine Sediments and Soils: Paleoceanography, Diagenesis, and Soil Processes

    NASA Astrophysics Data System (ADS)

    Depaolo, D. J.; Fantle, M. S.; Turchyn, A.; Ewing, S.; Yang, W.

    2007-12-01

    Calcium has 6 stable isotopes covering a wide mass range from 40 to 48. Because it is a critical component of the carbon cycle and a major constituent of common minerals like calcite, apatite, and gypsum, there is growing interest in understanding its stable isotope fractionation patterns in nature. The first work on Ca isotopes emphasized fractionation in food chains and in the formation of biogenic mineral matter in vertebrates. More recent studies have emphasized the fractionations observed in marine carbonate deposits, plants, and hydrological systems. Laboratory experiments show that Ca isotopes are fractionated during precipitation of calcite and aragonite from aqueous solution. Comparison with natural carbonate indicates that the fractionations are probably kinetic in origin although the exact mechanisms are not understood. There is little difference between the fractionation observed in inorganic and organic systems; precipitation rate (or solution oversaturation) seems to be the controlling factor, rather than temperature. One promising aspect of Ca isotopes is in their application to marine carbonate diagenesis. Especially when combined with studies of Sr, C, S, U, and O isotopes in deep sea sediments, Ca isotopes can give unique information on calcite dissolution and recrystallization rates. In a pure carbonate section from DSDP site 807A, Ca isotopes in pore fluids are found to differ greatly from seawater values and require that the equilibrium fractionation factor for 44Ca/40Ca between calcite and dissolved carbonate is almost exactly 1.0000. This fractionation corresponds to very slow calcite deposition rates at near-equilibrium conditions, implying that this fractionation factor may be generally applicable to diagenetic calcite precipitation, distinguishing it from biogenic precipitation, for which the factor is about 0.9985. This property can also be used to establish the dissolution rates of young carbonate sediments in the uppermost few meters of

  20. Flexible minerals: self-assembled calcite spicules with extreme bending strength.

    PubMed

    Natalio, Filipe; Corrales, Tomas P; Panthöfer, Martin; Schollmeyer, Dieter; Lieberwirth, Ingo; Müller, Werner E G; Kappl, Michael; Butt, Hans-Jürgen; Tremel, Wolfgang

    2013-03-15

    Silicatein-α is responsible for the biomineralization of silicates in sponges. We used silicatein-α to guide the self-assembly of calcite "spicules" similar to the spicules of the calcareous sponge Sycon sp. The self-assembled spicules, 10 to 300 micrometers (μm) in length and 5 to 10 μm in diameter, are composed of aligned calcite nanocrystals. The spicules are initially amorphous but transform into calcite within months, exhibiting unusual growth along [100]. They scatter x-rays like twinned calcite crystals. Whereas natural spicules evidence brittle failure, the synthetic spicules show an elastic response, which greatly enhances bending strength. This remarkable feature is linked to a high protein content. With nano-thermogravimetric analysis, we measured the organic content of a single spicule to be 10 to 16%. In addition, the spicules exhibit waveguiding properties even when they are bent.

  1. 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.

  2. 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.

  3. 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

  4. Phase transformation of Mg-calcite to aragonite in active-forming hot spring travertines

    NASA Astrophysics Data System (ADS)

    Greer, Heather F.; Zhou, Wuzong; Guo, Li

    2015-08-01

    A travertine specimen collected from the western part of Yunnan Province of China was subjected to microstructural analysis by powder X-ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. A new formation mechanism was proposed whereby polycrystalline rhombohedral particles of magnesium-containing calcite underwent a phase transformation into sheaf-like clusters of aragonite microrods. It is proposed that a high concentration of magnesium ions and embedded biological matter poisoned the growth of calcite and therefore instigated the phase transformation of the core of the rhombohedral calcite particles to an aragonite phase with a higher crystallinity. The single crystalline aragonite microrods with a higher density than the Mg-calcite nanocrystallites grew at the expense of the latter to generate sheaf-like clusters. This newly discovered formation mechanism is expected to enhance previous knowledge on this geologically important phase transformation from a morphology point of view.

  5. 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)

  6. In Situ Carbon and Oxygen Isotope Analyses of Calcite in CM1 Chondrites

    NASA Astrophysics Data System (ADS)

    Telus, M.; Alexander, C. M. O.'D.; Wang, J.; Hauri, E. H.

    2016-08-01

    We present results from in situ C and O isotope analyses of calcite from CM1 chondrites. There are large isotope variations on small spatial scales. This provides some insight into the evolution of fluids in chondrite parent bodies.

  7. 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.

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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

  16. Fabrication of microporous calcite block from calcium hydroxide compact under carbon dioxide atmosphere at high temperature.

    PubMed

    Otsu, Akihiro; Tsuru, Kanji; Maruta, Michito; Munar, Melvin L; Matsuya, Shigeki; Ishikawa, Kunio

    2012-01-01

    Effects of carbonation temperature and compacting pressure on basic properties of calcite block were studied using Ca(OH)2 compact made with 0.2-2.0 MPa and their carbonation at 200-800ºC for 1 h. Microporous calcite was obtained only when carbonated at 600ºC using Ca(OH)2 compact made with 0.2 MPa even though thermogravimetry analysis showed that calcite powder was stable up to 920ºC under CO2 atmosphere. CaO formed by carbonation at 700ºC and 800ºC is thought to be caused by the limited CO2 diffusion interior to the Ca(OH)2 compact. Also, unreacted Ca(OH)2 was found for Ca(OH)2 compact prepared with 0.5 MPa or higher pressure even when carbonated at 600ºC. As a result of high temperature carbonation, crystallite size of the calcite, 58.0 nm, was significantly larger when compared to that of calcite prepared at room temperature, 35.5 nm. Porosity and diametral tensile strength of the microporous calcite were 39.5% and 6.4 MPa. PMID:22864212

  17. 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.

  18. Sea urchin tooth mineralization: calcite present early in the aboral plumula.

    PubMed

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

    2012-11-01

    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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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

  5. Multiple origins for zoned cathodoluminescent and noncathodoluminescent calcite cements in Pennsylvanian limestones

    SciTech Connect

    Goldstein, R.H.; Anderson, J.E.; Phares, R.A. )

    1991-03-01

    Noncathodoluminescent calcite containing brightly to moderately luminescent zones is a common early cement in limestones. Three such cements in Upper Pennsylvanian limestones from different areas were studied. All three units are overlain up-section by Permian evaporites and consist of carbonate-siliciclastic 'cyclothems' in which individual cycles were subject to subaerial exposure. With such similar settings, one might predict that petrographically similar calcite cements would have similar origins. In the Holder Formation (New Mexico), the zoned calcite predates compaction, and cross-cutting relationships with cycle-capping paleosols show that zoned cements precipitated during 15 events of subaerial exposure. Therefore, cements precipitated from freshwater during early and repeated subaerial exposure. For the Lansing-Kansas City groups in northwestern Kansas, the zoned calcite cements commonly are among the first precipitated but may postdate some compaction. All-liquid fluid inclusions indicated precipitation below about 50C, from brines of approximately 23 weight %. NaCl equivalent. The brines may have refluxed downward during deposition of Permian evaporites. A limestone of the Lansing-Kansas City groups of west-central Kansas contains early zoned calcite cement that predates compaction. The cement contains all-liquid fluid inclusions indicating precipitation below about 50C. The presence of nonluminescent calcite containing bright subzones is not indicative of a single diagenetic environment. Petrographically similar cements from similar settings may originate in markedly different diagenetic environments.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Plant cell organelle proteomics in response to abiotic stress.

    PubMed

    Hossain, Zahed; Nouri, Mohammad-Zaman; Komatsu, Setsuko

    2012-01-01

    Proteomics is one of the finest molecular techniques extensively being used for the study of protein profiling of a given plant species experiencing stressed conditions. Plants respond to a stress by alteration in the pattern of protein expression, either by up-regulating of the existing protein pool or by the synthesizing novel proteins primarily associated with plants antioxidative defense mechanism. Improved protein extraction protocols and advance techniques for identification of novel proteins have been standardized in different plant species at both cellular and whole plant level for better understanding of abiotic stress sensing and intracellular stress signal transduction mechanisms. In contrast, an in-depth proteome study of subcellular organelles could generate much detail information about the intrinsic mechanism of stress response as it correlates the possible relationship between the protein abundance and plant stress tolerance. Although a wealth of reviews devoted to plant proteomics are available, review articles dedicated to plant cell organelle proteins response under abiotic stress are very scanty. In the present review, an attempt has been made to summarize all significant contributions related to abiotic stresses and their impacts on organelle proteomes for better understanding of plants abiotic stress tolerance mechanism at protein level. This review will not only provide new insights into the plants stress response mechanisms, which are necessary for future development of genetically engineered stress tolerant crop plants for the benefit of humankind, but will also highlight the importance of studying changes in protein abundance within the cell organelles in response to abiotic stress.

  12. 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

  13. 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

  14. 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

  15. The role of disseminated calcite in the chemical weathering of granitoid rocks

    USGS Publications Warehouse

    White, A.F.; Bullen, T.D.; Vivit, D.V.; Schulz, M.S.; Clow, D.W.

    1999-01-01

    Accessory calcite, present at concentrations between 300 and 3000 mg kg-1, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO2, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57-98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering. The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport

  16. 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…

  17. 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)

  18. 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.

  19. 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

  20. 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

  1. 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

  2. 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

  3. Integrated metabolomics for abiotic stress responses in plants.

    PubMed

    Nakabayashi, Ryo; Saito, Kazuki

    2015-04-01

    Plants are considered to biosynthesize specialized (traditionally called secondary) metabolites to adapt to environmental stresses such as biotic and abiotic stresses. The majority of specialized metabolites induced by abiotic stress characteristically exhibit antioxidative activity in vitro, but their function in vivo is largely yet to be experimentally confirmed. In this review, we highlight recent advances in the identification of the role of abiotic stress-responsive specialized metabolites with an emphasis on flavonoids. Integrated 'omics' analysis, centered on metabolomics with a series of plant resources differing in their flavonoid accumulation, showed experimentally that flavonoids play a major role in antioxidation in vivo. In addition, the results also suggest the role of flavonoids in the vacuole. To obtain more in-depth insights, chemical and biological challenges need to be addressed for the identification of unknown specialized metabolites and their in vivo functions.

  4. 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.

  5. 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).

  6. Effect of inorganic anions on the morphology and structure of magnesium calcite.

    PubMed

    Kralj, Damir; Kontrec, Jasminka; Brecević, Ljerka; Falini, Giuseppe; Nöthig-Laslo, Vesna

    2004-04-01

    Calcium carbonate was precipitated from calcium hydroxide and carbonic acid solutions at 25 degrees C, with and without addition of different magnesium (MgSO(4), Mg(NO(3))(2) and MgCl(2)) and sodium salts (Na(2)SO(4), NaNO(3) and NaCl) of identical anions, in order to study the mode of incorporation of magnesium and inorganic anions and their effect on the morphology of calcite crystals over a range of initial reactant concentrations and limited c(i)(Mg(2+))/c(i)(Ca(2+)) molar ratios. The morphology, crystal size distribution, composition, structure, and specific surface area of the precipitated crystals, as well as the mode of cation and anion incorporation into the calcite crystal lattice, were studied by a combination of optical and scanning electron microscopy (SEM), electronic counting, a multiple BET method, thermogravimetry, FT-IR spectroscopy, X-ray diffraction (XRD), and electron paramagnetic resonance (EPR) spectroscopy. In the systems of high initial relative supersaturation, precipitation of an amorphous precursor phase preceded the formation of calcite, whereas in those of lower supersaturation calcite was the first and only polymorphic modification of calcium carbonate that appeared in the system. The magnesium content in calcite increased with the magnesium concentration in solution and was correlated with the type of magnesium salt used. Mg incorporation caused the formation of crystals elongated along the calcite c axis and, in some cases, the appearance of new [011] faces. Polycrystalline aggregates were formed when the c(i)(Mg(2+))/c(i)(Ca(2+)) molar ratios in solution were increased. Addition of sulfate ions, alone, caused formation of spherical calcite polycrystalline aggregates.

  7. 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.

  8. NAC transcription factors in plant abiotic stress responses.

    PubMed

    Nakashima, Kazuo; Takasaki, Hironori; Mizoi, Junya; Shinozaki, Kazuo; Yamaguchi-Shinozaki, Kazuko

    2012-02-01

    Abiotic stresses such as drought and high salinity adversely affect the growth and productivity of plants, including crops. The development of stress-tolerant crops will be greatly advantageous for modern agriculture in areas that are prone to such stresses. In recent years, several advances have been made towards identifying potential stress related genes which are capable of increasing the tolerance of plants to abiotic stress. NAC proteins are plant-specific transcription factors and more than 100 NAC genes have been identified in Arabidopsis and rice to date. Phylogenetic analyses indicate that the six major groups were already established at least in an ancient moss lineage. NAC transcription factors have a variety of important functions not only in plant development but also in abiotic stress responses. Stress-inducible NAC genes have been shown to be involved in abiotic stress tolerance. Transgenic Arabidopsis and rice plants overexpressing stress-responsive NAC (SNAC) genes have exhibited improved drought tolerance. These studies indicate that SNAC factors have important roles for the control of abiotic stress tolerance and that their overexpression can improve stress tolerance via biotechnological approaches. Although these transcription factors can bind to the same core NAC recognition sequence, recent studies have demonstrated that the effects of NAC factors for growth are different. Moreover, the NAC proteins are capable of functioning as homo- or hetero-dimer forms. Thus, SNAC factors can be useful for improving stress tolerance in transgenic plants, although the mechanism for mediating the stress tolerance of these homologous factors is complex in plants. Recent studies also suggest that crosstalk may exist between stress responses and plant growth. This article is part of a Special Issue entitled: Plant gene regulation in response to abiotic stress.

  9. 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.

  10. The puzzling presence of calcite in skeletons of modern solitary corals from the Mediterranean Sea

    NASA Astrophysics Data System (ADS)

    Goffredo, Stefano; Caroselli, Erik; Mezzo, Francesco; Laiolo, Leonardo; Vergni, Patrizia; Pasquini, Luca; Levy, Oren; Zaccanti, Francesco; Tribollet, Aline; Dubinsky, Zvy; Falini, Giuseppe

    2012-05-01

    The skeleton of scleractinian corals is commonly believed to be composed entirely of aragonite due to the current Mg/Ca molar ratio of seawater, which thermodynamically favours the deposition of this polymorph of calcium carbonate (CaCO3). However, some studies have shown that other forms of CaCO3 such as calcite can be present in significant amount (1-20%) inside tropical coral skeletons, significantly impacting paleo-reconstructions of SST or other environmental parameters based on geochemical proxies. This study aims at investigating for the first time, (1) the skeletal composition of two Mediterranean solitary corals, the azooxanthellate Leptopsammia pruvoti and the zooxanthellate Balanophyllia europaea, across their life cycle, (2) the distribution of the different CaCO3 forms inside skeletons, and (3) their implications in paleoclimatology. The origin of the different forms of CaCO3 observed inside studied coral skeletons and their relationships with the species' habitat and ecological strategies are also discussed. CaCO3 composition of L. pruvoti and B. europaea was investigated at six sites located along the Italian coasts. Skeleton composition was studied by means of X-ray powder diffraction and Fourier transform infrared spectroscopy. A significant amount of calcite (1-23%) was found in more than 90% of the studied coral skeletons, in addition to aragonite. This calcite was preferentially located in the basal and intermediate areas than at the oral pole of coral skeletons. Calcite was also mainly located in the epitheca that covered the exposed parts of the coral in its aboral region. Interestingly in B. europaea, the calcite content was negatively correlated with skeleton size (age). The presence of calcite in scleractinian corals may result from different mechanisms: (1) corals may biologically precipitate calcite crystals at their early stages in order to insure their settlement on the substrate of fixation, especially in surgy environments; (2

  11. Monitoring bacterially induced calcite precipitation in porous media using magnetic resonance imaging and flow measurements.

    PubMed

    Sham, E; Mantle, M D; Mitchell, J; Tobler, D J; Phoenix, V R; Johns, M L

    2013-09-01

    A range of nuclear magnetic resonance (NMR) techniques are employed to provide novel, non-invasive measurements of both the structure and transport properties of porous media following a biologically mediated calcite precipitation reaction. Both a model glass bead pack and a sandstone rock core were considered. Structure was probed using magnetic resonance imaging (MRI) via a combination of quantitative one-dimensional profiles and three-dimensional images, applied before and after the formation of calcite in order to characterise the spatial distribution of the precipitate. It was shown through modification and variations of the calcite precipitation treatment that differences in the calcite fill would occur but all methods were successful in partially blocking the different porous media. Precipitation was seen to occur predominantly at the inlet of the bead pack, whereas precipitation occurred almost uniformly along the sandstone core. Transport properties are quantified using pulse field gradient (PFG) NMR measurements which provide probability distributions of molecular displacement over a set observation time (propagators), supplementing conventional permeability measurements. Propagators quantify the local effect of calcite formation on system hydrodynamics and the extent of stagnant region formation. Collectively, the combination of NMR measurements utilised here provides a toolkit for determining the efficacy of a biological-precipitation reaction for partially blocking porous materials. PMID:23872026

  12. 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.

  13. 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.

  14. Trace concentration - Huge impact: Nitrate in the calcite/Eu(III) system

    NASA Astrophysics Data System (ADS)

    Hofmann, Sascha; Voïtchovsky, Kislon; Schmidt, Moritz; Stumpf, Thorsten

    2014-01-01

    The interactions of trivalent lanthanides and actinides with secondary mineral phases such as calcite is of high importance for the safety assessment of deep geological repositories for high level nuclear waste (HLW). Due to similar ionic radii, calcium-bearing mineral phases are suitable host minerals for Ln(III) and An(III) ions. Especially calcite has been proven to retain these metal ions effectively by both surface complexation and bulk incorporation. Since anionic ligands (e.g., nitrate) are omnipresent in the geological environment and due to their coordinating properties, their influence on retentive processes should not be underestimated. Nitrate is a common contaminant in most HLW forms as a result of using nitric acid in fuel reprocessing. It is also formed by microbial activity under aerobic conditions. In this study, atomic force microscopy investigations revealed a major influence of nitrate upon the surface of calcite crystals. NaNO3 causes serious modifications even in trace amounts (<10-7 M) and forms a soft surface layer of low crystallinity on top of the calcite crystal. Time-resolved laser fluorescence spectroscopy of Eu(III) showed that, within this layer, Eu(III) ions are incorporated, while losing most of their hydration shell. The results show that solid solution modelling for actinides in calcite must take into account the presence of nitrate in pore and ground waters.

  15. 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.

  16. Arsenic removal from high-arsenic water by enhanced coagulation with ferric ions and coarse calcite.

    PubMed

    Song, S; Lopez-Valdivieso, A; Hernandez-Campos, D J; Peng, C; Monroy-Fernandez, M G; Razo-Soto, I

    2006-01-01

    Arsenic removal from high-arsenic water in a mine drainage system has been studied through an enhanced coagulation process with ferric ions and coarse calcite (38-74 microm) in this work. The experimental results have shown that arsenic-borne coagulates produced by coagulation with ferric ions alone were very fine, so micro-filtration (membrane as filter medium) was needed to remove the coagulates from water. In the presence of coarse calcite, small arsenic-borne coagulates coated on coarse calcite surfaces, leading the settling rate of the coagulates to considerably increase. The enhanced coagulation followed by conventional filtration (filter paper as filter medium) achieved a very high arsenic removal (over 99%) from high-arsenic water (5mg/l arsenic concentration), producing a cleaned water with the residual arsenic concentration of 13 microg/l. It has been found that the mechanism by which coarse calcite enhanced the coagulation of high-arsenic water might be due to attractive electrical double layer interaction between small arsenic-borne coagulates and calcite particles, which leads to non-existence of a potential energy barrier between the heterogeneous particles.

  17. 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.

  18. 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.

  19. 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

  20. Pressure-induced phase transition of calcite and aragonite: A first principles study

    NASA Astrophysics Data System (ADS)

    Ukita, Masaya; Toyoura, Kazuaki; Nakamura, Atsutomo; Matsunaga, Katsuyuki

    2016-10-01

    The thermodynamic phase stabilities of calcite and aragonite have been investigated from lattice vibrational analyses based on first-principles calculations. Different pressure dependences in phonon feature were found between the two polymorphs, suggesting different physical origins of the pressure-induced phase transitions. In the most stable phase in calcite (calcite I), an imaginary phonon mode consisting of rotation of CO3 ions with slight displacement of Ca ions appears at the F point in the Brillouin zone above 0.8 GPa. Such a soft mode means that external pressure induces the lattice-dynamical instability of calcite I leading to the phase transition to calcite II. On the other hand, the origin of the phase transition in aragonite is not due to such a lattice-dynamical instability. The estimated thermodynamical properties indicate that a first-order phase transition occurs between aragonite and post-aragonite at 34.7 GPa, coinciding with the reported experimental value at room temperature (35 GPa).

  1. 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.

  2. Abiotic formation of valine peptides under conditions of high temperature and high pressure.

    PubMed

    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.

  3. Functional diversity in European estuaries: Relating the composition of fish assemblages to the abiotic environment

    NASA Astrophysics Data System (ADS)

    Nicolas, D.; Lobry, J.; Le Pape, O.; Boët, P.

    2010-07-01

    Based on a large standardised data set, the present study proposed a meta-analysis to describe general patterns in the functional diversity of estuarine fish assemblage in terms of both number of species and density along the European Atlantic coast. Fish species collected from 31 European estuaries from Portugal to Scotland were allocated to functional groups according to their ecological utilization of estuaries. A clustering analysis was performed to compare the overall functional structure of estuaries based on fish composition. Generalised linear models were computed to identify relationships between large-scale abiotic and intra-estuarine descriptors and functional attributes of estuarine fish assemblages. The total number of species, and more especially of marine species, was higher in larger estuaries with a wide entrance and, locally, in polyhaline waters. The total density was mainly related to the proportion of intertidal mudflats and, locally, was greater in mesohaline waters. In terms of relative density, northern systems were dominated by marine and catadromous species, while estuarine species were prevalent in the southern ones.

  4. 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.

  5. Mesozoic (Lower Jurassic) red stromatactis limestones from the Southern Alps (Arzo, Switzerland): calcite mineral authigenesis and syneresis-type deformation

    NASA Astrophysics Data System (ADS)

    Neuweiler, Fritz; Bernoulli, Daniel

    2005-02-01

    The Broccatello lithological unit (Lower Jurassic, Hettangian to lower parts of Upper Sinemurian) near the village of Arzo (southern Alps, southern Switzerland) is a mound-shaped carbonate deposit that contains patches of red stromatactis limestone. Within the largely bioclastic Broccatello unit, the stromatactis limestone is distinguished by its early-diagenetic cavity system, a relatively fine-grained texture, and an in-situ assemblage of calcified siliceous sponges (various demosponges and hexactinellids). A complex shallow subsurface diagenetic pathway can be reconstructed from sediment petrography in combination with comparative geochemical analysis (carbon and oxygen isotopes; trace and rare earth elements, REE + Y). This pathway includes organic matter transformation, aragonite and skeletal opal dissolution, patchy calcification and lithification, sediment shrinkage, sagging and collapse, partial REE remobilization, and multiple sediment infiltration. These processes occurred under normal-marine, essentially oxic conditions and were independent from local, recurring syn-sedimentary faulting. It is concluded that the stromatactis results from a combination of calcite mineral authigenesis and syneresis-type deformation. The natural stromatactis phenomenon may thus be best explained by maturation processes of particulate polymer gels expected to form in fine-grained carbonate sediments in the shallow subsurface. Conditions favorable for the evolution of stromatactis appear to be particularly frequent during drowning of tropical or subtropical carbonate platforms.

  6. 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

  7. 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.

  8. 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...

  9. 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

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. Origin of platy calcite crystals in hot-spring deposits in the Kenya Rift Valley

    SciTech Connect

    Jones, B.; Renault, R.W.

    1998-09-01

    Platy calcite crystals, which have their c axis parallel to their shortest length axis, are common components of travertine deposits found around some hot springs in the Kenya Rift Valley. They are composite crystals formed of numerous paper-thin subcrystals. Individual plates allowed to grow without obstruction develop a hexagonal motif. The Kenyan crystals typically form in hot (>75 C) waters that have a low Ca content (<10 mg/l), a high CO{sub 2} content, and a high rate of CO{sub 2} degassing. At Chemurkeu, aggregates of numerous small platy crystals collectively form lattice crystals that superficially resemble ray crystals. The walls of the lattice crystals are formed of large platy crystals that have their long and intermediate length axes aligned parallel to the plane of the long axis of the lattice crystal. Internally, the lattice crystals are formed of small platy calcite crystals arranged in a boxlike pattern that creates the appearance of a lattice when viewed in thin section. Lattice crystals are highly porous, with each pore being enclosed by platy crystals. At Lorusio, travertines are mainly formed of pseudodentrites that are constructed by numerous small platy crystals attached to a main stem which is a large platy crystal that commonly curves along its long axis. The pseudodentrites are the main construction blocks in ledges and lilypads that form in the vent pool and spring outflow channels, where the water is too hot for microbes other than hyperthermophiles. The platy calcite crystals in the Kenyan travertines are morphologically similar to platy calcite crystals that form as scale in pipes in the geothermal fields of New Zealand and hydrothermal angel wing calcite from the La Fe mine in Mexico. Comparison of the Kenyan and New Zealand crystals indicates that platy calcite crystals form from waters with a low Ca{sup 2+} content and a high CO{sub 3}/Ca ratio due to rapid rates of CO{sub 2} degassing.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. Reactive oxygen species signaling in plants under abiotic stress.

    PubMed

    Choudhury, Shuvasish; Panda, Piyalee; Sahoo, Lingaraj; Panda, Sanjib Kumar

    2013-04-01

    Abiotic stresses like heavy metals, drought, salt, low temperature, etc. are the major factors that limit crop productivity and yield. These stresses are associated with production of certain deleterious chemical entities called reactive oxygen species (ROS), which include hydrogen peroxide (H₂O₂), superoxide radical (O₂(-)), hydroxyl radical (OH(-)), etc. ROS are capable of inducing cellular damage by degradation of proteins, inactivation of enzymes, alterations in the gene and interfere in various pathways of metabolic importance. Our understanding on ROS in response to abiotic stress is revolutionized with the advancements in plant molecular biology, where the basic understanding on chemical behavior of ROS is better understood. Understanding the molecular mechanisms involved in ROS generation and its potential role during abiotic stress is important to identify means by which plant growth and metabolism can be regulated under acute stress conditions. ROS mediated oxidative stress, which is the key to understand stress related toxicity have been widely studied in many plants and the results in those studies clearly revealed that oxidative stress is the main symptom of toxicity. Plants have their own antioxidant defense mechanisms to encounter ROS that is of enzymic and non-enzymic nature . Coordinated activities of these antioxidants regulate ROS detoxification and reduces oxidative load in plants. Though ROS are always regarded to impart negative impact on plants, some reports consider them to be important in regulating key cellular functions; however, such reports in plant are limited. Molecular approaches to understand ROS metabolism and signaling have opened new avenues to comprehend its critical role in abiotic stress. ROS also acts as secondary messenger that signals key cellular functions like cell proliferation, apoptosis and necrosis. In higher eukaryotes, ROS signaling is not fully understood. In this review we summarize our understanding on ROS

  2. Common crystal nucleation mechanism in shell formation of two morphologically distinct calcite brachiopods.

    PubMed

    Pérez-Huerta, Alberto; Cusack, Maggie

    2008-01-01

    Closely related mineral-producing organisms share common biomineralisation processes. We demonstrate that, in cases of disparate mineral structures where crystal growth mechanisms are necessarily diverse, nucleation processes are the common underlying mechanism during shell formation. Detailed crystallography in the context of shell microstructure in two morphologically distinct calcite brachiopods indicates that, despite differences in shell growth and fabric, at the centre of growth, calcite crystals nucleate with the c-axis 0001 parallel to the shell surface. Such detailed contextual crystallography of biomineralisation using electron backscatter diffraction (EBSD) will have significant applications for future research in biological and medical sciences.

  3. Field Experiment to Stimulate Microbial Urease Activity in Groundwater for in situ Calcite Precipitation

    NASA Astrophysics Data System (ADS)

    Fujita, Y.; Taylor, J. L.; Tyler, T. L.; Banta, A. B.; Reysenbach, A. L.; Delwiche, M. E.; McLing, T. L.; Colwell, F. S.; Smith, R. W.

    2003-12-01

    Groundwater contamination by radionuclides and metals from past weapons processing activities is a significant problem for the United States Department of Energy. Removal of these pollutants from the subsurface can be prohibitively expensive and result in worker exposure, and therefore in situ containment and stabilization is an attractive remediation alternative. One potential approach for the immobilization of certain radionuclides and metals (e.g., 90Sr, 60Co, Pb, Cd) is to induce geochemical conditions that promote co-precipitation in calcite. Many aquifers in the arid western US are calcite-saturated, and calcite precipitated under an engineered remediation scheme in such aquifers should remain stable even after return to ambient conditions. We have proposed that an effective way to promote calcite precipitation is to utilize native microorganisms that hydrolyze urea. Urea hydrolysis results in carbonate and ammonium production, and an increase in pH. The increased carbonate alkalinity favors calcite precipitation, and the ammonium serves the additional role of promoting desorption of sorbed metal ions from the aquifer matrix by ion exchange. The desorbed metals are then accessible to co-precipitation in calcite, which can be a longer-term immobilization mechanism than sorption. The ability to hydrolyze urea is common among environmental microorganisms, and we have shown in the laboratory that microbial urea hydrolysis can be linked to calcite precipitation and co-precipitation of the trace metal strontium. As a next step in the development of our remediation approach, we aimed to demonstrate that we can stimulate the native microbial community to express urease in the field. In 2002 we conducted a preliminary field trial of our approach, using a well in the Eastern Snake River Plain Aquifer in Idaho Falls, Idaho, USA. A dilute molasses solution (0.00075%) was injected to promote overall biological growth, and then urea (50 mM) was added to the aquifer

  4. Speleothem Paleoclimatology and Modern Proxies: Calcite Farming In a Continuously Monitored Cave

    NASA Astrophysics Data System (ADS)

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

    2009-12-01

    Continuous high-resolution (sub-hourly) time-series of local meteorology (solar irradiance, relative humidity, rainfall, wind speed and direction, barometric pressure, and temperature), cave air chemistry (t, rh, bp, radon-222, pCO2, air-flow velocity and direction), and cave-ceiling drips in Hollow Ridge Cave in North Florida reveal variations that must color interpretations of annually resolved speleothem records. The style and vigor of ventilation and mixing strongly influence diurnal and seasonal cave-air 222Rn, pCO2 and δ13CO2. Cave-air pCO2 controls CO2 degassing from drip waters, leading to oversaturation of calcite and dripstones. Periodic high-resolution spatial snapshots of 222Rn and δ13C gradients taken inside the cave reveal interior ventilation and mixing pathways that help us understand connections between 222Rn-modeled CO2 exchange and drip rates, drip chemistry, speleothem growth, and soilgas and dripwater contributions to dripstone δ13C. Drip waters and aquifer water are collected every two weeks. Isotopes (δ18O, D/H), major anions (Cl- and SO42-), cations (Na+, K+, Ca2+, Mg2+, Sr2+) and tracers (Ba, U, Si, Mn) in the drips are related to rainfall, evapotranspiration and soil weathering reactions in the epikarst. Drip composition is then compared to the chemistry of contemporaneous calcite. Sulfate and Mn2+ can be interpreted as qualitative proxies for soil redox (saturated epikarst). Chloride correlates negatively with drip rate, while sulfate correlates positively with drip rate. We are growing artificial speleothems (“calcite farming”) on quartz slides under drips atop active speleothems. Early winter calcite precipitation ranged from 0.034~0.161 mg/day. Late winter precipitation ranged from 0.031~0.306 mg/day. Summer yielded no calcite growth. Calcite does not precipitate during months when slow ventilation results in high cave-air pCO2. A larger number of slides are currently deployed to accumulate an analytical quantity of calcite

  5. 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

  6. 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.

  7. Sturgeon and paddlefish (Acipenseridae) saggital otoliths are composed of the calcium carbonate polymorphs vaterite and calcite: acipenseridae otoliths are vaterite and calcite

    DOE PAGES

    Pracheil, Brenda M.; Chakoumakos, Bryan C.; Feygenson, Mikhail; Whitledge, Gregory W.; Koenigs, Ryan P.; Bruch, Ronald M.

    2016-07-27

    The otoliths of modern fishes are most commonly comprised of the metastable aragonite polymorph of calcium carbonate (CaCO3); however, sturgeons have otoliths reportedly comprised of the least stable of the three most-common polymorphs, vaterite. In this study, we used neutron diffraction to characterize CaCO3 polymorph composition of lake sturgeon and paddlefish otoliths. Based on previous summaries of CaCO3 composition over fish evolutionary history, we hypothesized that sturgeon and paddlefish otoliths would have similar polymorph composition. We found that despite previous reports of sturgeon otoliths being comprised entirely of vaterite, that all otoliths we examined in this study also had amore » calcite fraction that ranged from 17.9+ 6.0 wt. % to 35.9 + 2.9 wt. %. We also conducted a grinding experiment that demonstrated that calcite fractions were due to biological variation and not an artifact of polymorph transformation during preparation. Our study provides the initial characterization of the polymorph composition of the otoliths of lake sturgeon, and paddlefish and also provides the first-ever report of otoliths of Acipenserids as having a calcite fraction.« less

  8. Not all calcite ballast is created equal: differing effects of foraminiferan and coccolith calcite on the formation and sinking of aggregates

    NASA Astrophysics Data System (ADS)

    Schmidt, K.; De La Rocha, C. L.; Gallinari, M.; Cortese, G.

    2013-09-01

    Correlation between particulate organic carbon (POC) and calcium carbonate sinking through the deep ocean has led to the idea that ballast provided by calcium carbonate is important for the export of POC from the surface ocean. While this idea is certainly to some extent true, it is worth considering in more nuance, for example, examining the different effects on the aggregation and sinking of POC of small, non-sinking calcite particles like coccoliths and large, rapidly sinking calcite like planktonic foraminiferan tests. We have done that here in a simple experiment carried out in roller tanks that allow particles to sink continuously without being impeded by container walls. Coccoliths were efficiently incorporated into aggregates that formed during the experiment, increasing their sinking speed compared to similarly sized aggregates lacking added calcite ballast. The foraminiferan tests, which sank as fast as 700 m d-1, became associated with only very minor amounts of POC. In addition, when they collided with other, larger, foraminferan-less aggregates, they fragmented them into two smaller, more slowly sinking aggregates. While these effects were certainly exaggerated within the confines of the roller tanks, they clearly demonstrate that calcium carbonate ballast is not just calcium carbonate ballast- different forms of calcium carbonate ballast have notably different effects on POC aggregation, sinking, and export.

  9. Not all calcite ballast is created equal: differing effects of foraminiferan and coccolith calcite on the formation and sinking of aggregates

    NASA Astrophysics Data System (ADS)

    Schmidt, K.; De La Rocha, C. L.; Gallinari, M.; Cortese, G.

    2014-01-01

    Correlation between particulate organic carbon (POC) and calcium carbonate sinking through the deep ocean has led to the idea that ballast provided by calcium carbonate is important for the export of POC from the surface ocean. While this idea is certainly to some extent true, it is worth considering in more nuance, for example, examining the different effects on the aggregation and sinking of POC of small, non-sinking calcite particles like coccoliths and large, rapidly sinking calcite like planktonic foraminiferan tests. We have done that here in a simple experiment carried out in roller tanks that allow particles to sink continuously without being impeded by container walls. Coccoliths were efficiently incorporated into aggregates that formed during the experiment, increasing their sinking speed compared to similarly sized aggregates lacking added calcite ballast. The foraminiferan tests, which sank as fast as 700 m d-1, became associated with only very minor amounts of POC. In addition, when they collided with other, larger, foram-less aggregates, they fragmented them into two smaller, more slowly sinking aggregates. While these effects were certainly exaggerated within the confines of the rolling tanks, they clearly demonstrate that calcium carbonate ballast is not just calcium carbonate ballast - different forms of calcium carbonate ballast have notably different effects on POC aggregation, sinking, and export.

  10. 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

  11. 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

  12. 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

  13. 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.

  14. Marine energy.

    PubMed

    Kerr, David

    2007-04-15

    Marine energy is renewable and carbon free and has the potential to make a significant contribution to energy supplies in the future. In the UK, tidal power barrages and wave energy could make the largest contribution, and tidal stream energy could make a smaller but still a useful contribution. This paper provides an overview of the current status and prospects for electrical generation from marine energy. It concludes that a realistic potential contribution to UK electricity supplies is approximately 80 TWh per year but that many years of development and investment will be required if this potential is to be realized. PMID:17272244

  15. 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.

  16. 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

  17. Rosette-shaped calcite structures at surfaces: mechanistic implications for CaCO3 crystallization.

    PubMed

    Yang, Sung Ho; Choi, Insung S

    2010-07-01

    Biomineralization is believed to be achieved by the intimate cooperation of soluble macromolecules and an insoluble matrix at the specific inorganic-organic interface. It has been reported that positively charged matrices play an important role in controlling the structure of CaCO(3) at surfaces, although detailed mechanisms remain unclear. In this work, we studied the transformation from amorphous CaCO(3) to calcite crystals on surfaces by using thin films of poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and its quaternized form. The positively charged PDMAEMA film was found to possess unique properties for CaCO(3) crystallization: individually separated, single calcite crystals were formed on the PDMAEMA film in the absence of poly(acrylic acid) (PAA), while circularly fused calcite crystals were formed in the presence of PAA. The circularly fused (rosette-shaped) calcite crystals could be changed from a completely packed rosette to a ring-shaped, hollow structure by tuning the crystallization conditions. A number of factors, such as reaction time, amount of (NH(4))(2)CO(3), concentration of PAA, and charge of matrix-films, were varied systematically, and we now propose a mechanism based on these observations.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Molecular dynamics simulation of the phase transition between calcite and CaCO3-II

    NASA Astrophysics Data System (ADS)

    Kawano, Jun; Miyake, Akira; Shimobayashi, Norimasa; Kitamura, Masao

    2009-07-01

    Molecular dynamics (MD) simulation of calcium carbonate at high pressure was performed to understand the phase transition between calcite (R\\bar {3}c) and CaCO3-II (P 21/c). In the 300-800 K temperature range, the transition of calcite to CaCO3-II was reproduced at a pressure of around 8 GPa. This transition is of first order and reversible in the MD calculations except for runs at 300 K where a small hysteresis exists. The slope of the dP/dT curve at the phase boundary between calcite and CaCO3-II is negative at 300 K and turns positive at around 600 K, which was confirmed by analyzing the enthalpy change. Just below the transition pressure, the P 21/c structure appears and its orientation switches among three positions with time, resulting in the maintenance of the R\\bar {3}c structure as a whole. The P 21/c structure resembles the structure of CaCO3-II on an increase of temperature. It can be suggested that the existence of the P 21/c structure and the switching of its orientation just below the transition pressure are responsible for the change of the slope of the dP/dT curve at the boundary from negative to positive on an increase of temperature, because the switching increases entropy and results in an expansion of the stability field of calcite.

  9. 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

  10. Morphological and mechanical characterization of composite calcite/SWCNT-COOH single crystals.

    PubMed

    Calvaresi, Matteo; Falini, Giuseppe; Pasquini, Luca; Reggi, Michela; Fermani, Simona; Gazzadi, Gian Carlo; Frabboni, Stefano; Zerbetto, Francesco

    2013-08-01

    A growing number of classes of organic (macro)molecular materials have been trapped into inorganic crystalline hosts, such as calcite single crystals, without significantly disrupting their crystalline lattices. Inclusion of an organic phase plays a key role in enhancing the mechanical properties of the crystals, which are believed to share structural features with biogenic minerals. Here we report the synthesis and mechanical characterization of composite calcite/SWCNT-COOH single crystals. Once entrapped into the crystals SWCNT-COOH appeared both as aggregates of entangled bundles and nanoropes. Their observation was possible only after crystal etching, fracture or FIB (focused ion beam) cross-sectioning. SWCNT-COOHs occupied a small volume fraction and were randomly distributed into the host crystal. They did not strongly affect the crystal morphology. However, although the Young's modulus of composite calcite/SWCNT-COOH single crystals was similar to that of pure calcite their hardness increased by about 20%. Thus, SWCNT-COOHs provide an obstacle against the dislocation-mediated propagation of plastic deformation in the crystalline slip systems, in analogy with the well-known hardness increase in fiber-reinforced composites.

  11. 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

  12. 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

  13. 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

  14. 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.

  15. 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.

  16. Solid solution partitioning of Sr2+, Ba2+, and Cd2+ to calcite

    USGS Publications Warehouse

    Tesoriero, A.J.; Pankow, J.F.

    1996-01-01

    Although solid solutions play important roles in controlling the concentrations of minor metal ions in natural waters, uncertainties regarding their compositions, thermodynamics, and kinetics usually prevent them from being considered. A range of precipitation rates was used here to study the nonequilibrium and equilibrium partitioning behaviors of Sr2+, Ba2+, and Cd2+ to calcite (CaCO3(s)). The distribution coefficient of a divalent metal ion Me2+ for partitioning from an aqueous solution into calcite is given by DMe = (XMeCO3(s)/[Me2+])/(XCaCO3(s)/[Ca 2+]). The X values are solid-phase mole fractions; the bracketed values are the aqueous molal concentrations. In agreement with prior work, at intermediate to high precipitation rates R (nmol/mg-min), DSr, DBa, and DCd were found to depend strongly on R. At low R, the values of DSr, DBa, and DCd became constant with R. At 25??C, the equilibrium values for DSr, DBa, and DCd for dilute solid solutions were estimated to be 0.021 ?? 0.003, 0.012 ?? 0.005, and 1240 ?? 300, respectively. Calculations using these values were made to illustrate the likely importance of partitioning of these ions to calcite in groundwater systems. Due to its large equilibrium DMe value, movement of Cd2+ will be strongly retarded in aquifers containing calcite; Sr2+ and Ba2+ will not be retarded nearly as much.

  17. 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.

  18. Stimulation of microbial urea hydrolysis in groundwater to enhance calcite precipitation.

    PubMed

    Fujita, Yoshiko; Taylor, Joanna L; Gresham, Tina L T; Delwiche, Mark E; Colwell, Frederick S; Mcling, Travis L; Petzke, Lynn M; Smith, Robert W

    2008-04-15

    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. 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 1-2 orders of magnitude. Estimated ureolysis rates in recovered groundwater samples increased from < 0.1 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 d(-1). Although collateral impacts such as reduced permeability were observed, overall results indicated the viability of manipulating biogeochemical processes to promote contaminant sequestration.

  19. Pedogenesis and early diagenesis of a marine carbonate platform preceding development of a Chesterian transgressive systems tract

    SciTech Connect

    Srinivasan, K.; Driese, S.G.; Mora, C.I. . Dept. of Geological Sciences); Stapor, F.W. . Dept. of Geology)

    1992-01-01

    A regionally correlative, early Chesterian paleoweathering surface occurs in outcrops of the Monteagle Limestone (ML) and the overlying Hartselle Sandstone (HS) in the Cumberland Plateau region of TN, AL and GA. This surface constitutes a major sequence boundary that developed during a sea-level lowstand when the ML carbonate platform was subaerially exposed and subjected to pedogenesis and meteoric diagenesis. Evidence for pedogenesis of the ML includes reddening and micritization of skeletal allochems, presence of sesquioxidic glaebules and root traces, development of micro-karst pinnacles and fissures, and introduction of abundant vadose silt. The HS rests sharply on the ML with a distinctive scoured to fluted contact, lacking direct evidence for pedogenesis but showing features characteristic of early meteoric diagenesis. Petrographic evidence for subaerial exposure and meteoric diagenesis consists of extensive dissolution and calcitization. Partially dissolved grains are filled with micrite, iron oxides, and clear blocky calcite spar. Intergranular pores are filled with micrite, iron oxides, and clear blocky calcite spar. Intergranular pores are filled with micrite, iron oxides, clay, quartz silt, syntaxial overgrowths (dolomitized) and clear blocky (ferroan) calcite spar. Intergranular micrite, iron oxides, clay and quartz silt are attributed to vadose processes. Clear blocky (ferroan) spar is interpreted as freshwater phreatic. Other features include inclusions of dolomite rhombs in clear blocky calcite spar and zoned dolomite rhombs in the matrix. Under CL, echinoderm grains appear bright orange. Intergranular micrite and clear blocky calcite spar display dull orange luminescence. The dolomitized overgrowths are non-luminescent. Zoning in dolomite rhombs consists of a non-luminescent core with a bright rim. Stable C and O isotope compositions of calcitized grains and intergranular blocky calcite spar are depleted compared to Mississippian marine values.

  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. 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

  2. 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

  3. New insights into the carbon isotope composition of speleothem calcite from vegetation, soil, and subsurface processes

    NASA Astrophysics Data System (ADS)

    Meyer, K.; FENG, W.; Breecker, D. O.; Banner, J. L.; Guilfoyle, A.

    2012-12-01

    The purpose of this study was to provide new insights into the interpretation of speleothem (cave calcite deposit) δ13C values. We studied two caves in central Texas, which have been actively monitored for over 12 years. We compared δ13C values of soil CO2 (δ13Cs), cave drip water (δ13CDIC), and modern cave calcite (δ13Ccc). Measured average δ13C values of soil CO2 were -13.9 ± 1.4‰ under mixed, shallowly-rooted C3-C4 grasses and were -18.3 ± 0.7‰ under deeply-rooted ashe juniper trees (C3). The δ13CDIC value of minimally-degassed drip water in Natural Bridge Caverns was -10.7 ± 0.3‰. The carbon isotope composition of CO2 in equilibrium with this measured drip water is -18.1 ± 0.3‰. The agreement between juniper soil CO2 and drip water (within ~0.2‰) suggests that the δ13C value of drip water (δ13CDIC) that initially enters the cave is controlled by deeply-rooted plants and may be minimally influenced by host-rock dissolution and/or prior calcite precipitation (PCP). At Inner Space Caverns, δ13CDIC values varied with vegetation above the drip site, distance from the cave entrance, and distance along in-cave flow paths. Whereas CO2 derived from deeply-rooted plants defines the baseline for drip water δ13CDIC entering the caves, kinetic effects associated with the degassing of CO2 and simultaneous precipitation of calcite account for seasonal variability in δ13CDIC and δ13Ccc. We documented increases in δ13CDIC at a rate of up to 0.47‰/hour during the season of peak degassing (winter), suggesting that δ13CDIC variations may be controlled by total elapsed time of CO2 degassing from drip water (exposure time, Texp). We also observed seasonal shifts in the δ13C values of modern calcite grown on glass substrates that are correlated with shifts in drip water δ13CDIC values and drip-rate. We evaluated a 10-year record of modern calcite samples and contrasted the magnitude of variability between calcite precipitated under varying pCO2

  4. Permeability of calcite-cemented fractures in mudrocks: Flow highway or hindrance?

    NASA Astrophysics Data System (ADS)

    Landry, C. J.; Eichhubl, P.; Prodanovic, M.; Tokan-Lawal, A.

    2014-12-01

    Among natural fractures observed in core of Eagle Ford Shale, Texas, tall sub-vertical calcite-cemented fractures are the most spatially extensive. Similar sub-vertical opening-mode fractures are found in many mudrocks, and far more often than not they are completely cemented. Currently there is very little evidence that these calcite cements are anything but impermeable, and thus would hinder flow across the fractures while having an insignificant effect on flow parallel to the fractures. This suggests that natural fractures in mudrocks are barriers to flow, which goes against the general consensus that natural fractures in mudrocks enhance flow. We used scanning-electron microscopy (SEM) on broad-beam argon-ion milled samples of a calcite-cemented fracture with a kinematic aperture (width) of 200 μm to study the pore space of the calcite for any indication that completely cemented fractures are permeable. In the fracture calcite cement, we observed primary porosity between calcite grains that is generally well-connected with an average aperture between 25 and 100 nm. The permeability of these flow-paths was determined by lattice Boltzmann methods to be between 50 to 200 μD. These flow-paths have a spacing between 50 and 300 μm, therefore a square centimeter (length*height) of fracture cement will contain on average more than 100 flow-paths. Thus for flow across the fracture cement (orthogonal to the fracture) the overall cross-fracture permeability of the cement can be approximated using simple effective medium upscaling. The fracture cement studied here is found to have a cross-fracture permeability in the range of 25 to 100 nD. Although this is a very low permeability, it is within the range of the permeability of the host rock, and thus these calcite cements would have almost no effect on flow orthogonal to the plane of the fracture. These flow-paths are also connected within the cement creating the equivalent of a single tortuous flow-path along the plane

  5. Hormone balance and abiotic stress tolerance in crop plants.

    PubMed

    Peleg, Zvi; Blumwald, Eduardo

    2011-06-01

    Plant hormones play central roles in the ability of plants to adapt to changing environments, by mediating growth, development, nutrient allocation, and source/sink transitions. Although ABA is the most studied stress-responsive hormone, the role of cytokinins, brassinosteroids, and auxins during environmental stress is emerging. Recent evidence indicated that plant hormones are involved in multiple processes. Cross-talk between the different plant hormones results in synergetic or antagonic interactions that play crucial roles in response of plants to abiotic stress. The characterization of the molecular mechanisms regulating hormone synthesis, signaling, and action are facilitating the modification of hormone biosynthetic pathways for the generation of transgenic crop plants with enhanced abiotic stress tolerance.

  6. 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

  7. Molecular approaches to improve rice abiotic stress tolerance.

    PubMed

    Mizoi, Junya; Yamaguchi-Shinozaki, Kazuko

    2013-01-01

    Abiotic stress is a major factor limiting productivity of rice crops in large areas of the world. Because plants cannot avoid abiotic stress by moving, they have acquired various mechanisms for stress tolerance in the course of their evolution. Enhancing or introducing such mechanisms in rice is one effective way to develop stress-tolerant cultivars. Based on physiological studies on stress responses, recent progress in plant molecular biology has enabled discovery of many genes involved in stress tolerance. These genes include regulatory genes, which regulate stress response (e.g., transcription factors and protein kinases), and functional genes, which protect the cell (e.g., enzymes for generating protective metabolites and proteins). Both kinds of genes are used to increase stress tolerance in rice. In addition, several quantitative trait loci (QTLs) associated with higher stress tolerance have been cloned, contributing to the discovery of significantly important genes for stress tolerance.

  8. 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.

  9. Genomics Approaches for Crop Improvement against Abiotic Stress

    PubMed Central

    Akpınar, Bala Anı; Lucas, Stuart J.; Budak, Hikmet

    2013-01-01

    As sessile organisms, plants are inevitably exposed to one or a combination of stress factors every now and then throughout their growth and development. Stress responses vary considerably even in the same plant species; stress-susceptible genotypes are at one extreme, and stress-tolerant ones are at the other. Elucidation of the stress responses of crop plants is of extreme relevance, considering the central role of crops in food and biofuel production. Crop improvement has been a traditional issue to increase yields and enhance stress tolerance; however, crop improvement against abiotic stresses has been particularly compelling, given the complex nature of these stresses. As traditional strategies for crop improvement approach their limits, the era of genomics research has arisen with new and promising perspectives in breeding improved varieties against abiotic stresses. PMID:23844392

  10. An abiotic analogue of the nuclear pore complex hydrogel.

    PubMed

    Bird, Sean P; Baker, Lane A

    2011-09-12

    We describe an abiotic hydrogel that mimics selectivity of the nuclear pore complex. Copolymerization of peptide tetramers (phenylalanine-serine-phenylalanine-glycine, FSFG) with acrylamide results in hydrophobic interactions significant enough to allow the formation of freestanding hydrogel structures. Incorporation of FSFG motifs also renders the hydrogels selective. Selective binding of importins and nuclear transport receptor-cargo complexes is qualitatively demonstrated and compared with polyacrylamide, hydrogels prepared from a control peptide, and hydrogels prepared from the nuclear pore complex protein Nsp1. These abiotic hydrogels will enable further studies of the unique transport mechanisms of the nuclear pore complex and provide an interesting paradigm for the future development of synthetic platforms for separations and selective interfaces.

  11. Progress and challenges for abiotic stress proteomics of crop plants.

    PubMed

    Barkla, Bronwyn J; Vera-Estrella, Rosario; Pantoja, Omar

    2013-06-01

    Plants are continually challenged to recognize and respond to adverse changes in their environment to avoid detrimental effects on growth and development. Understanding the mechanisms that crop plants employ to resist and tolerate abiotic stress is of considerable interest for designing agriculture breeding strategies to ensure sustainable productivity. The application of proteomics technologies to advance our knowledge in crop plant abiotic stress tolerance has increased dramatically in the past few years as evidenced by the large amount of publications in this area. This is attributed to advances in various technology platforms associated with MS-based techniques as well as the accessibility of proteomics units to a wider plant research community. This review summarizes the work which has been reported for major crop plants and evaluates the findings in context of the approaches that are widely employed with the aim to encourage broadening the strategies used to increase coverage of the proteome. PMID:23512887

  12. 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.

  13. Progress and challenges for abiotic stress proteomics of crop plants.

    PubMed

    Barkla, Bronwyn J; Vera-Estrella, Rosario; Pantoja, Omar

    2013-06-01

    Plants are continually challenged to recognize and respond to adverse changes in their environment to avoid detrimental effects on growth and development. Understanding the mechanisms that crop plants employ to resist and tolerate abiotic stress is of considerable interest for designing agriculture breeding strategies to ensure sustainable productivity. The application of proteomics technologies to advance our knowledge in crop plant abiotic stress tolerance has increased dramatically in the past few years as evidenced by the large amount of publications in this area. This is attributed to advances in various technology platforms associated with MS-based techniques as well as the accessibility of proteomics units to a wider plant research community. This review summarizes the work which has been reported for major crop plants and evaluates the findings in context of the approaches that are widely employed with the aim to encourage broadening the strategies used to increase coverage of the proteome.

  14. 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.

  15. 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.

  16. 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.

  17. Energy harvesting by implantable abiotically catalyzed glucose fuel cells

    NASA Astrophysics Data System (ADS)

    Kerzenmacher, S.; Ducrée, J.; Zengerle, R.; von Stetten, F.

    Implantable glucose fuel cells are a promising approach to realize an autonomous energy supply for medical implants that solely relies on the electrochemical reaction of oxygen and glucose. Key advantage over conventional batteries is the abundant availability of both reactants in body fluids, rendering the need for regular replacement or external recharging mechanisms obsolete. Implantable glucose fuel cells, based on abiotic catalysts such as noble metals and activated carbon, have already been developed as power supply for cardiac pacemakers in the late-1960s. Whereas, in vitro and preliminary in vivo studies demonstrated their long-term stability, the performance of these fuel cells is limited to the μW-range. Consequently, no further developments have been reported since high-capacity lithium iodine batteries for cardiac pacemakers became available in the mid-1970s. In recent years research has been focused on enzymatically catalyzed glucose fuel cells. They offer higher power densities than their abiotically catalyzed counterparts, but the limited enzyme stability impedes long-term application. In this context, the trend towards increasingly energy-efficient low power MEMS (micro-electro-mechanical systems) implants has revived the interest in abiotic catalysts as a long-term stable alternative. This review covers the state-of-the-art in implantable abiotically catalyzed glucose fuel cells and their development since the 1960s. Different embodiment concepts are presented and the historical achievements of academic and industrial research groups are critically reviewed. Special regard is given to the applicability of the concept as sustainable micro-power generator for implantable devices.

  18. Changes in biotic and abiotic processes following mangrove clearing

    NASA Astrophysics Data System (ADS)

    Granek, Elise; Ruttenberg, Benjamin I.

    2008-12-01

    Mangrove forests, important tropical coastal habitats, are in decline worldwide primarily due to removal by humans. Changes to mangrove systems can alter ecosystem properties through direct effects on abiotic factors such as temperature, light and nutrient supply or through changes in biotic factors such as primary productivity or species composition. Despite the importance of mangroves as transitional habitats between land and sea, little research has examined changes that occur when they are cleared. We examined changes in a number of biotic and abiotic factors following the anthropogenic removal of red mangroves ( Rhizophora mangle) in the Panamanian Caribbean, including algal biomass, algal diversity, algal grazing rates, light penetration, temperature, sedimentation rates and sediment organic content. In this first study examining multiple ecosystem-level effects of mangrove disturbance, we found that areas cleared of mangroves had higher algal biomass and richness than intact mangrove areas. This increase in algal biomass and richness was likely due to changes in abiotic factors (e.g. light intensity, temperature), but not biotic factors (fish herbivory). Additionally the algal and cyanobacterial genera dominating mangrove-cleared areas were rare in intact mangroves and included a number of genera that compete with coral for space on reefs. Interestingly, sedimentation rates did not differ between intact and cleared areas, but the sediments that accumulated in intact mangroves had higher organic content. These findings are the first to demonstrate that anthropogenic clearing of mangroves changes multiple biotic and abiotic processes in mangrove forests and that some of these changes may influence adjacent habitats such as coral reefs and seagrass beds. Additional research is needed to further explore the community and ecosystem-level effects of mangrove clearing and their influence on adjacent habitats, but it is clear that mangrove conservation is an

  19. Polyamines in response to abiotic stress tolerance through transgenic approaches

    PubMed Central

    Pathak, Malabika Roy; Teixeira da Silva, Jaime A; Wani, Shabir H

    2014-01-01

    The distribution, growth, development and productivity of crop plants are greatly affected by various abiotic stresses. Worldwide, sustainable crop productivity is facing major challenges caused by abiotic stresses by reducing the potential yield in crop plants by as much as 70%. Plants can generally adapt to one or more environmental stresses to some extent. Physiological and molecular studies at transcriptional, translational, and transgenic plant levels have shown the pronounced involvement of naturally occurring plant polyamines (PAs), in controlling, conferring, and modulating abiotic stress tolerance in plants. PAs are small, low molecular weight, non-protein polycations at physiological pH, that are present in all living organisms, and that have strong binding capacity to negatively charged DNA, RNA, and different protein molecules. They play an important role in plant growth and development by controlling the cell cycle, acting as cell signaling molecules in modulating plant tolerance to a variety of abiotic stresses. The commonly known PAs, putrescine, spermidine, and spermine tend to accumulate together accompanied by an increase in the activities of their biosynthetic enzymes under a range of environmental stresses. PAs help plants to combat stresses either directly or by mediating a signal transduction pathway, as shown by molecular cloning and expression studies of PA biosynthesis-related genes, knowledge of the functions of PAs, as demonstrated by developmental studies, and through the analysis of transgenic plants carrying PA genes. This review highlights how PAs in higher plants act during environmental stress and how transgenic strategies have improved our understanding of the molecular mechanisms at play. PMID:24710064

  20. 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

  1. 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

  2. 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.

  3. The role of background electrolytes on the kinetics and mechanism of calcite dissolution

    NASA Astrophysics Data System (ADS)

    Ruiz-Agudo, E.; Kowacz, M.; Putnis, C. V.; Putnis, A.

    2010-02-01

    The influence of background electrolytes on the mechanism and kinetics of calcite dissolution was investigated using in situ Atomic Force Microscopy (AFM). Experiments were carried out far from equilibrium by passing alkali halide salt (NaCl, NaF, NaI, KCl and LiCl) solutions over calcite cleavage surfaces. This AFM study shows that all the electrolytes tested enhance the calcite dissolution rate. The effect and its magnitude is determined by the nature and concentration of the electrolyte solution. Changes in morphology of dissolution etch pits and dissolution rates are interpreted in terms of modification in water structure dynamics (i.e. in the activation energy barrier of breaking water-water interactions), as well as solute and surface hydration induced by the presence of different ions in solution. At low ionic strength, stabilization of water hydration shells of calcium ions by non-paired electrolytes leads to a reduction in the calcite dissolution rate compared to pure water. At high ionic strength, salts with a common anion yield similar dissolution rates, increasing in the order Cl - < I - < F - for salts with a common cation due to an increasing mobility of water around the calcium ion. Changes in etch pit morphology observed in the presence of F - and Li + are explained by stabilization of etch pit edges bonded by like-charged ions and ion incorporation, respectively. As previously reported and confirmed here for the case of F -, highly hydrated ions increased the etch pit nucleation density on calcite surfaces compared to pure water. This may be related to a reduction in the energy barrier for etch pit nucleation due to disruption of the surface hydration layer.

  4. 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.

  5. From synthetic to biogenic Mg-containing calcites: a comparative study using FTIR microspectroscopy.

    PubMed

    Long, Xia; Nasse, Michael J; Ma, Yurong; Qi, Limin

    2012-02-21

    The formation mechanism of the thermodynamically unstable calcite phase, very high Mg calcite, in biological organisms such as sea urchin or corallina algae has been an enigma for a very long time. In contrast to conventional methods such as KBr pellet Fourier Transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD), FTIR microspectroscopy (FTIRM) provides additional information about a local disorder such as an amorphous phase or the occlusion of Mg ions in the calcite lattice. In this work, we characterise for the first time systematically synthetic and biogenic Mg-containing calcium carbonate samples (especially sea urchin teeth--SUT) in detail by using two FTIRM instruments and compare these samples with KBr pellet FTIR measurements. Furthermore, we present spectra from geogenic calcite and dolomite minerals, recorded with both FTIRM systems, as well as KBr pellet FTIR spectra as references. We analyse the spectra by applying multi-peak curve fitting on the in-plane-bending (ν(4)) and out-of-plane (ν(2)) bands. Based on the obtained results we attribute the two singlet bands at ∼860-865 cm(-1) and ∼695-704 cm(-1) observed in the SUT FTIRM spectra to the existence of amorphous calcium carbonate (ACC), and report for the first time the existence of ACC at the mature end of SUT. In the other three studied biominerals, however, we did not find any ACC. Also, based on the FTIRM results, we observe that not only ν(4), but also ν(2) shifts to higher wavenumbers if more calcium ions are replaced by magnesium ions in the calcite lattices.

  6. 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

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. 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

  12. 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

  13. 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

  14. Titania may produce abiotic oxygen atmospheres on habitable exoplanets

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    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.

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

    PubMed

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

    2015-09-10

    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.

  16. 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.

  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. 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.

  19. 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

  20. Abiotic reductive immobilization of U(VI) by biogenic mackinawite.

    PubMed

    Veeramani, Harish; Scheinost, Andreas C; Monsegue, Niven; Qafoku, Nikolla P; Kukkadapu, Ravi; Newville, Matt; Lanzirotti, Antonio; 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 U(VI) reduction via direct electron transfer processes. In the present work, the propensity of biogenic mackinawite (Fe 1+x S, x = 0 to 0.11) to reduce U(VI) 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 U(VI) indicate the formation of nanoparticulate UO2. This study suggests the relevance of sulfide-bearing biogenic minerals in mediating abiotic U(VI) reduction, an alternative pathway in addition to direct enzymatic U(VI) reduction. PMID:23373896

  1. 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

  2. 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

  3. Abscisic Acid and Abiotic Stress Tolerance in Crop Plants.

    PubMed

    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

  4. Cell Wall Metabolism in Response to Abiotic Stress.

    PubMed

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

    2015-02-16

    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.

  5. 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.

  6. 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…

  7. Marine envenomations.

    PubMed

    Balhara, Kamna S; Stolbach, Andrew

    2014-02-01

    This article describes the epidemiology and presentation of human envenomation from marine organisms. Venom pathophysiology, envenomation presentation, and treatment options are discussed for sea snake, stingray, spiny fish, jellyfish, octopus, cone snail, sea urchin, and sponge envenomation. The authors describe the management of common exposures that cause morbidity as well as the keys to recognition and treatment of life-threatening exposures. PMID:24275176

  8. 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…

  9. 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

  10. 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

  11. [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.

  12. Quartz-calcite oxygen isotope thermometry: A calibration based on natural isotopic variations

    NASA Astrophysics Data System (ADS)

    Sharp, Z. D.; Kirschner, D. L.

    1994-10-01

    An empirical calibration for the quartz-calcite thermometer was derived from measured Δ18O( qz- cc) values from greenschist-facies marbles, veins composed of cogenetic quartz and calcite and various low-grade metamorphic rocks. The Δ18O( qz- cc) values vary systematically with independently determined formation temperature and can be fit to the expression 1000 ln α( qz- cc) = 0.87(±0.06) × 10 6/ T2. In contrast, published results from direct-exchange experiments between calcite and quartz are 1000 ln α( qz- cc) = 0.38(±0.06) × 10 6/ T2, far smaller than in the present study. Application of the experimental mineral-water and especially the direct-exchange calibrations to natural samples, yields unreasonably low geological temperatures. It is difficult to envision a mechanism whereby the measured fractionations in greenschist-grade marbles can be reconciled with the very low temperature estimates obtained with the direct-exchange experimental calibration. Oxygen diffusion rates in quartz are too slow to explain the discrepancy. Postmetamorphic exchange could have occurred with a hydrothermal fluid, but it is unlikely that the δ18O( calcite) values of all samples would be shifted by an amount that would result in a linear relationship between 1000 ln α( qz- cc) and T-2. More likely, the discrepancy is due to a kinetic effect in the experiments. The very small fractionations observed in the direct-exchange experiments may have been caused by diffusion-related effects during recrystallization of the quartz and calcite. The problem of recrystallization is eliminated in mineral-CO 2 exchange experiments. Combined CO 2-calcite and CO 2-quartz glass experiments yield the expression 1000 ln α (qz-cc) = 0.78 ( 0¯.08) , in good agreement with the empirical calibration. The new empirical calibration yields reasonable temperature estimates for a wide range of samples and can be used for thermometry in rock types and over temperature intervals where other quantitative

  13. 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

  14. 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.

  15. Marine Geology

    NASA Astrophysics Data System (ADS)

    van Andel, Tjeerd H.

    Marine geology was blessed early, about 30 years ago, with two great textbooks, one by P.H. Kuenen, the other by Francis P. Shepard, but in more recent years, no one has dared synthesize a field that has become so diverse and is growing so rapidly. There are many texts written for the beginning undergraduate student, mostly by marine geologists, but none can be handed conveniently to a serious advanced student or given to a colleague interested in what the field has wrought. The reason for this regrettable state is obvious; only an active, major scholar could hope to write such a book well, but the years would pass, his students dwindle, his grants vanish. He himself might be out of date before his book was. Kennett has earned a large measure of gratitude for his attempt to undertake this task. His personal price must have been high but so are our rewards.

  16. [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

  17. A preliminary study of the calcite beef found in the Cretaceous Jinju Formation, Gyeongsang Basin, South Korea

    NASA Astrophysics Data System (ADS)

    Ha, S.; Chae, Y. U.; Son, M.; Jeong, G. Y.; Paik, I. S.; Lim, H. S.

    2015-12-01

    The term "beef" refers to fibrous minerals in bedding-parallel veins, where the fibers are approximately perpendicular to the vein margins (Cobbold et al., 2013). It mostly appears within organic-rich black shale layers in sedimentary basin. Although the veins can consist of white gangue minerals, such as calcite, gypsum, or quartz, the commonest mineral in the fibers is calcite. According to the worldwide localities of calcite beef compiled by Cobbold et al (2012), they concentrated in some areas, especially around the Atlantic Ocean. However, they have been rarely reported in the western Pacific margin, except Australia and New Zealand. Recently, calcite beefs have been found in the Cretaceous Jinju Formation, Gyeongsang Basin, Korea. As far as we know, this is the first report of calcite beef in Korea. The lacustrine Jinju Formation is about 1,200 m thick, and made up mainly of lacustrine dark grey to black mudstones. In the study area, calcite beefs were commonly found in the organic-rich black shale layers. The vein thickness is anywhere between a few millimeters to maximum 3 centimeters, and their length ranges from a few centimeters to several tens of meters. The interval between successive veins is from a few centimeters to about 1 meter. Most of them occur parallel to the bedding planes, although some of them are developed along fault planes or within deformed layers. In case of relatively thick beefs, the center of veins often shows a dark grey to black central median line, defined by fine-grained calcite grains, fluid inclusion lines, or wall rock particles. Based on the orientation of fibrous calcite, they can be divided into two types: straight and sigmoidal types. The fibrous calcites are thought to have been symmetrically grown from the median lines to top and bottom of wall rock. The formation mechanism of horizontal fractures, and the formation temperature of beefs in the study area remain as a matter to be studied further.

  18. 3D Mapping of calcite and a demonstration of its relevance to permeability evolution in reactive fractures

    NASA Astrophysics Data System (ADS)

    Ellis, Brian R.; Peters, Catherine A.

    2016-09-01

    There is a need to better understand reaction-induced changes in fluid transport in fractured shales, caprocks and reservoirs, especially in the context of emerging energy technologies, including geologic carbon sequestration, unconventional natural gas, and enhanced geothermal systems. We developed a method for 3D calcite mapping in rock specimens. Such information is critical in reactive transport modeling, which relies on information about the locations and accessible surface area of reactive minerals. We focused on calcite because it is a mineral whose dissolution could lead to substantial pathway alteration because of its high solubility, fast reactivity, and abundance in sedimentary rocks. Our approach combines X-ray computed tomography (XCT) and scanning electron microscopy. The method was developed and demonstrated for a fractured limestone core containing about 50% calcite, which was 2.5 cm in diameter and 3.5 cm in length and had been scanned using XCT. The core was subsequently sectioned and energy dispersive X-ray spectroscopy was used to determine elemental signatures for mineral identification and mapping. Back-scattered electron microscopy was used to identify features for co-location. Finally, image analysis resulted in characteristic grayscale intensities of X-ray attenuation that identify calcite. This attenuation mapping ultimately produced a binary segmented 3D image of the spatial distribution of calcite in the entire core. To demonstrate the value of this information, permeability changes were investigated for hypothetical fractures created by eroding calcite from 2D rock surfaces. Fluid flow was simulated using a 2D steady state model. The resulting increases in permeability were profoundly influenced by the degree to which calcite is contiguous along the flow path. If there are bands of less reactive minerals perpendicular to the direction of flow, fracture permeability may be an order of magnitude smaller than when calcite is contiguous

  19. 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.

  20. 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)

  1. Stressed out symbiotes: hypotheses for the influence of abiotic stress on arbuscular mycorrhizal fungi.

    PubMed

    Millar, Niall S; Bennett, Alison E

    2016-11-01

    Abiotic stress is a widespread threat to both plant and soil communities. Arbuscular mycorrhizal (AM) fungi can alleviate effects of abiotic stress by improving host plant stress tolerance, but the direct effects of abiotic stress on AM fungi are less well understood. We propose two hypotheses predicting how AM fungi will respond to abiotic stress. The stress exclusion hypothesis predicts that AM fungal abundance and diversity will decrease with persistent abiotic stress. The mycorrhizal stress adaptation hypothesis predicts that AM fungi will evolve in response to abiotic stress to maintain their fitness. We conclude that abiotic stress can have effects on AM fungi independent of the effects on the host plant. AM fungal communities will change in composition in response to abiotic stress, which may mean the loss of important individual species. This could alter feedbacks to the plant community and beyond. AM fungi will adapt to abiotic stress independent of their host plant. The adaptation of AM fungi to abiotic stress should allow the maintenance of the plant-AM fungal mutualism in the face of changing climates.

  2. A thermodynamic adsorption/entrapment model for selenium(IV) coprecipitation with calcite

    NASA Astrophysics Data System (ADS)

    Heberling, Frank; Vinograd, Victor L.; Polly, Robert; Gale, Julian D.; Heck, Stephanie; Rothe, Jörg; Bosbach, Dirk; Geckeis, Horst; Winkler, Björn

    2014-06-01

    Selenium is an environmentally relevant trace element, while the radioisotope 79Se is of particular concern in the context of nuclear waste disposal safety. Oxidized selenium species are relatively soluble and show only weak adsorption at common mineral surfaces. However, a possible sorption mechanism for selenium in the geosphere is the structural incorporation of selenium(IV) (selenite, SeO32-) into calcite (CaCO3). In this study we investigate the interactions between selenite and calcite by a series of experimental and computational methods with the aim to quantify selenite incorporation into calcite at standard conditions. We further seek to describe the thermodynamics of selenite-doped calcite, and selenite coprecipitation with calcite. The structure of the incorporated species is investigated using Se K-edge EXAFS (isotropic and polarization dependent) and results are compared to density functional theory (DFT) calculations. These investigations confirm structural incorporation of selenite into calcite by the substitution of carbonate for selenite, leading to the formation of a Ca(SeO3)X(CO3)(1-X) solid solution. Coprecipitation experiments at low supersaturation indicate a linear increase of the selenite to carbonate ratio in the solid with the increase of the selenite to carbonate ratio in the contact solution. This relationship can be described under the assumption of an ideal mixing between calcite and a virtual CaSeO3 endmember, whose standard Gibbs free energy (G0(CaSeO3_exp) = -953 ± 6 kJ/mol, log10(KSP(CaSeO3_exp)) = -6.7 ± 1.0) is defined by linear extrapolation of the excess free energy from the dilute Henry’s law domain to X(CaSeO3) = 1. In contrast to this experimental result, DFT and force field calculations predict the virtual bulk CaSeO3 endmember to be significantly less stable and more soluble: G0(CaSeO3 bulk) = -912 ± 10 kJ/mol and log10(KSP(CaSeO3_bulk)) = 0.5 ± 1.7. To explain this discrepancy we introduce a thermodynamic adsorption

  3. Interpretation of speleothem calcite δ13C variations: Evidence from monitoring soil CO2, drip water, and modern speleothem calcite in central Texas

    NASA Astrophysics Data System (ADS)

    Meyer, Kyle W.; Feng, Weimin; Breecker, Daniel O.; Banner, Jay L.; Guilfoyle, Amber

    2014-10-01

    We studied the sources and transport of carbon in two active karst systems in central Texas, Inner Space Cavern (IS) and Natural Bridge North and South Caverns (NB), to provide new insights into the interpretation of speleothem (cave calcite deposit) carbon isotope compositions. We have determined the δ13C values of soil CO2 (δ13Cs) in grassland and savanna above these caves with δ13C values of cave drip water (δ13CHCO3-) and modern speleothem calcite grown on artificial substrates (δ13Ccc). We compare δ13CHCO3- values from direct drip sites, where water was sampled immediately upon discharging from the cave ceiling, to values from indirect sites, where water was sampled after flowing along a prolonged path within the cave that allowed for longer CO2 degassing and have found that direct drip sites yield consistently lower δ13CHCO3- values. The δ13CHCO3- values of direct drip water below savanna (-10.6 ± 0.5‰ and -12.6 ± 0.2‰, in NB and IS, respectively) are indistinguishable from (IS) or similar to (NB) calculated δ13CHCO3- values in equilibrium with measured soil CO2 beneath trees (-13.5‰ to -11.3‰ for juniper trees above NB, and -13.6‰ to -12.6‰ for mixed oak and elm trees above IS, respectively). At IS, the δ13CHCO3- values of direct drip water are higher below grassland (-9.7 ± 0.3‰) than below savanna (12.6 ± 0.2‰). These results suggest that the δ13CHCO3- values of drip waters that initially enter the caves are controlled by deep-rooted plants, where present, and are minimally influenced by host-rock dissolution and/or prior calcite precipitation (PCP). The δ13CHCO3- values of indirect drip water vary seasonally with relatively low values during the summer (-10.8 ± 0.8‰ and -9.2 ± 0.4‰ under juniper savanna at NB and under grassland at IS, respectively) that are similar to the direct drip δ13CHCO3- values (-10.6 ± 0.5‰ and -9.7 ± 0.3‰ under savanna at NB and under grassland at IS, respectively). The relatively high

  4. 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

  5. Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

    USGS Publications Warehouse

    Busenberg, Eurybiades; Plummer, L. Niel

    1989-01-01

    The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and

  6. The kinetics of the ordering of 13C-18O bonds in calcite and apatite

    NASA Astrophysics Data System (ADS)

    Stolper, D. A.; Halevy, I.; Eiler, J. M.

    2011-12-01

    Eiler and Schauble (2004) showed that the isotopes of C and O are not randomly distributed within single phases such as CO2 gas and carbonates, and in particular, that heavy isotopes of C and O tend to bond preferentially (clump) at lower temperatures. Consequently, the measurement of the deviation from a random distribution of C and O isotope distributions in a single phase can be used as a thermometer. As with other geothermometers based on homogeneous or heterogeneous equilibria, the clumped-isotope thermometer is susceptible to resetting (e.g., if the phase is reheated or experiences slow cooling). Thus, clumped-isotope "temperatures" of phases that have experienced complex thermal histories may, in fact, be closure temperatures, the interpretation of which requires quantification of the kinetics of redistribution of C and O isotopes as a function of temperature. These kinetics have received increasing attention (Dennis and Schrag, 2010; Passey 2010), and are likely to be critical for understanding clumped-isotope temperatures of samples that have been buried for long periods of time. To better constrain these kinetics we performed experiments on natural optical calcite from Mexico and carbonate-bearing apatite from the Siilinjarvi carbonatite (Finland). For each experiment, multiple single crystal grains (~2 mm in diameter) of calcite or apatite were loaded in open Pt capsules, pressurized with Ar gas, and held at 400-700 °C, 550 bars using a rapid quench TZM apparatus for 5 min to 520 hrs. After quenching, 13C-18O clumping was measured in the samples; the change from the initial Δ47 with time for each phase at each temperature was fit to simple mechanistic models of isotope exchange between sites in these phases. One conclusion of the experimental study is that resetting the internal ordering of carbonate groups proceeds more rapidly in calcites than in apatites. For example, heating apatite at 400 °C results in no change in clumping over a 24 hr period

  7. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; Kim, Yi-Yeoun; Schenk, Anna S.; Kulak, Alexander N.; Comyn, Timothy P.; Chammas, Oliver; Harder, Ross J.; Duffy, Dorothy M.; Robinson, Ian K.; Meldrum, Fiona C.

    2016-06-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates.

  8. Uranium immobilization by sulfate-reducing biofilms grown on hematite, dolomite, and calcite.

    SciTech Connect

    Marsili, E.; Beyenal, Haluk; Di Palma, L.; Merli, C.; Dohnalkova, Alice; Amonette, James E.; Lewandowski, Zbigniew

    2007-12-15

    Biofilms of sulfate-reducing bacteria Desulfovibrio desulfuricans G20 wereused to reduce dissolved U(VI)and subsequently immobilize U(IV) in the presence of uranium-complexing carbonates. The biofilms were grown in three identically operated fixed bed reactors, filled with three types of minerals: one noncarbonate-bearing mineral(hematite) and two carbonate-bearing minerals (calcite and dolomite). The source of carbonates in the reactors filled with calcite and dolomite were the minerals, while in the reactor filled with hematite it was a 10 mM carbonate buffer, pH 7.2, which we added to the growth medium. Our five-month study demonstrated that the sulfate-reducing biofilms grown in all reactors were able to immobilize/reduce uranium efficiently, despite the presence of uranium-complexing carbonates.

  9. X-ray driven reaction front dynamics at calcite-water interfaces

    DOE PAGES

    Laanait, Nouamane; Callagon, Erika Blanca R.; Zhang, Zhan; Sturchio, Neil C.; Lee, Sang Soo; Fenter, Paul

    2015-09-18

    The interface of minerals with aqueous solutions is central to geochemical reactivity, hosting processes that span multiple spatiotemporal scales. Understanding such processes requires spatially and temporally resolved observations, and experimental controls that precisely manipulate the interfacial thermodynamic state. Using the intense radiation fields of a focused synchrotron X-ray beam, we drove dissolution at the calcite-aqueous interface and simultaneously probed the dynamics of the propagating reaction fronts using surface X-ray microscopy. Evolving surface structures are controlled by the time-dependent solution composition as characterized by a kinetic reaction model. At extreme disequilibria, the onset of reaction front instabilities was observed with velocitiesmore » of >30 nanometers per second. As a result, these instabilities are identified as a signature of transport-limited dissolution of calcite under extreme disequilibrium.« less

  10. X-ray driven reaction front dynamics at calcite-water interfaces

    SciTech Connect

    Laanait, Nouamane; Callagon, Erika Blanca R.; Zhang, Zhan; Sturchio, Neil C.; Lee, Sang Soo; Fenter, Paul

    2015-09-18

    The interface of minerals with aqueous solutions is central to geochemical reactivity, hosting processes that span multiple spatiotemporal scales. Understanding such processes requires spatially and temporally resolved observations, and experimental controls that precisely manipulate the interfacial thermodynamic state. Using the intense radiation fields of a focused synchrotron X-ray beam, we drove dissolution at the calcite-aqueous interface and simultaneously probed the dynamics of the propagating reaction fronts using surface X-ray microscopy. Evolving surface structures are controlled by the time-dependent solution composition as characterized by a kinetic reaction model. At extreme disequilibria, the onset of reaction front instabilities was observed with velocities of >30 nanometers per second. As a result, these instabilities are identified as a signature of transport-limited dissolution of calcite under extreme disequilibrium.

  11. Preparation and formation mechanism of wood-block-like calcite particles

    SciTech Connect

    Guo Hua; Yu Jiaguo . E-mail: jiaguoyu@yahoo.com; Cheng Bei

    2006-08-15

    Pure calcite crystal with different morphologies such as wood-block and spherical aggregates were prepared by a precipitation reaction in the presence of citric acid. The as-prepared products were characterized with scanning electron microscope (SEM) and X-ray diffraction (XRD). The results showed that citric acid obviously influenced the formation of precipitates and the morphology of final products. The formation mechanism of wood-block-like particles was proposed according to theoretical deduction and the proposed growth mode. - Graphical abstract: Pure calcite crystal with different morphologies such as wood-block and spherical aggregates were prepared by a simple precipitation reaction in the presence of citric acid and the formation mechanism was proposed.

  12. Selective adsorption of L- and D-amino acids on calcite: Implications for biochemical homochirality

    NASA Technical Reports Server (NTRS)

    Hazen, R. M.; Filley, T. R.; Goodfriend, G. A.

    2001-01-01

    The emergence of biochemical homochirality was a key step in the origin of life, yet prebiotic mechanisms for chiral separation are not well constrained. Here we demonstrate a geochemically plausible scenario for chiral separation of amino acids by adsorption on mineral surfaces. Crystals of the common rock-forming mineral calcite (CaCO(3)), when immersed in a racemic aspartic acid solution, display significant adsorption and chiral selectivity of d- and l-enantiomers on pairs of mirror-related crystal-growth surfaces. This selective adsorption is greater on crystals with terraced surface textures, which indicates that d- and l-aspartic acid concentrate along step-like linear growth features. Thus, selective adsorption of linear arrays of d- and l-amino acids on calcite, with subsequent condensation polymerization, represents a plausible geochemical mechanism for the production of homochiral polypeptides on the prebiotic Earth.

  13. Mass-spectrometric 230Th-234U-238U dating of the Devils Hole calcite vein

    USGS Publications Warehouse

    Ludwig, K. R.; Simmons, K.R.; Szabo, B. J.; Winograd, I.J.; Landwehr, J.M.; Riggs, A.C.; Hoffman, R.J.

    1992-01-01

    The Devils Hole calcite vein contains a long-term climatic record, but requires accurate chronologic control for its interpretation. Mass-spectrometric U-series ages for samples from core DH-11 yielded 230Th ages with precisions ranging from less than 1,000 years (2??) for samples younger than ???140 ka (thousands of years ago) to less than 50,000 years for the oldest samples (???566 ka). The 2348U/238U ages could be determined to a precision of ???20,000 years for all ages. Calcite accumulated continuously from 566 ka until ???60 ka at an average rate of 0.7 millimeter per 103 years. The precise agreement between replicate analyses and the concordance of the 230Th/238U and 234U/238U ages for the oldest samples indicate that the DH-11 samples were closed systems and validate the dating technique in general.

  14. Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule.

    PubMed

    Politi, Yael; Metzler, Rebecca A; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P U P A; Gilbert, Pupa

    2008-11-11

    Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40-200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism.

  15. Transformation mechanism of amorphous calcium carbonate into calcite in the sea urchin larval spicule

    PubMed Central

    Politi, Yael; Metzler, Rebecca A.; Abrecht, Mike; Gilbert, Benjamin; Wilt, Fred H.; Sagi, Irit; Addadi, Lia; Weiner, Steve; Gilbert, P. U. P. A.

    2008-01-01

    Sea urchin larval spicules transform amorphous calcium carbonate (ACC) into calcite single crystals. The mechanism of transformation is enigmatic: the transforming spicule displays both amorphous and crystalline properties, with no defined crystallization front. Here, we use X-ray photoelectron emission spectromicroscopy with probing size of 40–200 nm. We resolve 3 distinct mineral phases: An initial short-lived, presumably hydrated ACC phase, followed by an intermediate transient form of ACC, and finally the biogenic crystalline calcite phase. The amorphous and crystalline phases are juxtaposed, often appearing in adjacent sites at a scale of tens of nanometers. We propose that the amorphous-crystal transformation propagates in a tortuous path through preexisting 40- to 100-nm amorphous units, via a secondary nucleation mechanism. PMID:18987314

  16. Comparison of the soluble matrices of the calcitic prismatic layer of Pinna nobilis (Mollusca, Bivalvia, Pteriomorpha).

    PubMed

    Dauphin, Y

    2002-07-01

    The calcitic prisms of the outer layer of the shell of Pinna nobilis, surrounded by thick organic walls, contain a soluble intracrystalline matrix. The structure and composition of the outer interprismatic walls are not well known. The current viewpoint is they are composed of an insoluble matrix. Another thick organic structure, the interlamellar sheet of the nacreous layer, is composed of insoluble and soluble matrices. The composition of two sets of soluble organic matrices from the calcitic layer of Pinna nobilis, extracted with and without the organic walls are compared. According to the various analyses (SEM and AFM, UV and FTIR spectrometry, HPLC, electrophoreses, XANES), the main characteristics of the two matrices are similar, but not identical. Thus, the organic walls contain soluble components. However, the three-layered structure of the interlamellar sheet of the nacreous layer has not been observed.

  17. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

    PubMed Central

    Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; Kim, Yi-Yeoun; Schenk, Anna S.; Kulak, Alexander N.; Comyn, Timothy P.; Chammas, Oliver; Harder, Ross J.; Duffy, Dorothy M.; Robinson, Ian K.; Meldrum, Fiona C.

    2016-01-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates. PMID:27302863

  18. Calcite and dolomite in intrusive carbonatites. II. Trace-element variations

    NASA Astrophysics Data System (ADS)

    Chakhmouradian, Anton R.; Reguir, Ekaterina P.; Couëslan, Christopher; Yang, Panseok

    2016-04-01

    The composition of calcite and dolomite from several carbonatite complexes (including a large set of petrographically diverse samples from the Aley complex in Canada) was studied by electron-microprobe analysis and laser-ablation inductively-coupled-plasma mass-spectrometry to identify the extent of substitution of rare-earth and other trace elements in these minerals and the effects of different igneous and postmagmatic processes on their composition. Analysis of the newly acquired and published data shows that the contents of rare-earth elements (REE) and certain REE ratios in magmatic calcite and dolomite are controlled by crystal fractionation of fluorapatite, monazite and, possibly, other minerals. Enrichment in REE observed in some samples (up to ~2000 ppm in calcite) cannot be accounted for by coupled substitutions involving Na, P or As. At Aley, the REE abundances and chondrite-normalized (La/Yb)cn ratios in carbonates decrease with progressive fractionation. Sequestration of heavy REE from carbonatitic magma by calcic garnet may be responsible for a steeply sloping "exponential" pattern and lowered Ce/Ce* ratios of calcite from Magnet Cove (USA) and other localities. Alternatively, the low levels of Ce and Mn in these samples could result from preferential removal of these elements by Ce4+- and Mn3+-bearing minerals (such as cerianite and spinels) at increasing f(O2) in the magma. The distribution of large-ion lithophile elements (LILE = Sr, Ba and Pb) in rock-forming carbonates also shows trends indicative of crystal fractionation effects (e.g., concomitant depletion in Ba + Pb at Aley, or Sr + Ba at Kerimasi), although the phases responsible for these variations cannot be identified unambiguously at present. Overall, element ratios sensitive to the redox state of the magma and its complexing characteristics (Eu/Eu*, Ce/Ce* and Y/Ho) are least variable and in both primary calcite and dolomite, approach the average chondritic values. In consanguineous

  19. Functionalizing single crystals: incorporation of nanoparticles inside gel-grown calcite crystals.

    PubMed

    Liu, Yujing; Yuan, Wentao; Shi, Ye; Chen, Xiaoqiang; Wang, Yong; Chen, Hongzheng; Li, Hanying

    2014-04-14

    Synthetic single crystals are usually homogeneous solids. Biogenic single crystals, however, can incorporate biomacromolecules and become inhomogeneous solids so that their properties are also extrinsically regulated by the incorporated materials. The discrepancy between the properties of synthetic and biogenic single crystals leads to the idea to modify the internal structure of synthetic crystals to achieve nonintrinsic properties by incorporation of foreign material. Intrinsically colorless and diamagnetic calcite single crystals are turned into colored and paramagnetic solids, through incorporation of Au and Fe3O4 nanoparticles without significantly disrupting the crystalline lattice of calcite. The crystals incorporate the nanoparticles and gel fibers when grown in agarose gel media containing the nanoparticles, whereas the solution-grown crystals do not. As such, our work extends the long-history gel method for crystallization into a platform to functionalize single-crystalline materials.

  20. Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers.

    PubMed

    Ihli, Johannes; Clark, Jesse N; Côté, Alexander S; Kim, Yi-Yeoun; Schenk, Anna S; Kulak, Alexander N; Comyn, Timothy P; Chammas, Oliver; Harder, Ross J; Duffy, Dorothy M; Robinson, Ian K; Meldrum, Fiona C

    2016-01-01

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates. PMID:27302863

  1. Infrared Signature of the Cation-π Interaction between Calcite and Aromatic Hydrocarbons.

    PubMed

    Wang, Haitao; Grant, Daniel J; Burns, Peter C; Na, Chongzheng

    2015-06-01

    The cation-π interaction is proposed as an important mechanism for the adsorption of aromatic hydrocarbons having non-zero quadrupole moments by mineral surfaces. Direct evidence supporting such a mechanism is, however, limited. Using the model mineral calcite, we probe the cation-π interaction with adsorbed benzene, toluene, and ethylbenzene (BTE) molecules using attenuated total reflectance Fourier transform infrared spectroscopy. We show that the presence of calcite increases the energy required to excite the synchronized bending of aromatic C-H bonds of BTE molecules. The unique conformation of this vibrational mode indicates that the planar aromatic rings of BTE molecules are constrained in a tilted face-down position by the cation-π interaction, as further confirmed by density functional theory calculations. Our results suggest that the shift of the excitation energy of the aromatic C-H bending may be used as an infrared signature for the cation-π interaction occurring on mineral surfaces.

  2. 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

  3. 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

  4. 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.

  5. 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

  6. Reconstruction of drip-water δ18O based on calcite oxygen and clumped isotopes of speleothems from Bunker Cave (Germany)

    NASA Astrophysics Data System (ADS)

    Kluge, T.; Affek, H. P.; Marx, T.; Aeschbach-Hertig, W.; Riechelmann, D. F. C.; Scholz, D.; Riechelmann, S.; Immenhauser, A.; Richter, D. K.; Fohlmeister, J.; Wackerbarth, A.; Mangini, A.; Spötl, C.

    2012-07-01

    The geochemical signature of many speleothems used for reconstruction of past continental climates is affected by kinetic isotope fractionation. This limits quantitative paleoclimate reconstruction and, in cases where the kinetic fractionation varies with time, also affects relative paleoclimate interpretations. In carbonate archive research, clumped isotope thermometry is typically used as proxy for absolute temperatures. In the case of speleothems, however, clumped isotopes provide a sensitive indicator for disequilibrium effects. The extent of kinetic fractionation co-varies in Δ47 and δ18O so that it can be used to account for disequilibrium in δ18O and to extract the past drip-water composition. Here we apply this approach to stalagmites from Bunker Cave (Germany) and calculate drip-water δ18Ow values for the Eemian, Marine Isotope Stage (MIS) 3, and the Holocene, relying on independent temperature estimates and accounting for disequilibrium. Applying the co-variation method to modern calcite precipitates yields drip-water δ18Ow values in agreement with modern cave drip-water δ18Ow of -7.9 ± 0.3‰, despite large and variable disequilibrium effects in both calcite δ18Oc and Δ47. Reconstructed paleo-drip-water δ18Ow values are lower during colder periods (e.g., MIS 3: -8.5 ± 0.4‰ and the early Holocene at 11 kyr: -9.3 ± 0.1‰) and show higher values during warmer climatic periods (e.g., the Eemian: -7.5 ± 0.2‰ and the Holocene Climatic Optimum: -7.2 ± 0.3‰). This new approach offers a unique possibility for quantitative climate reconstruction including the assessment of past hydrological conditions while accounting for disequilibrium effects.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. Physicochemical Processes and the Evolution of Strength in Calcite Fault Gouge at Room Temperature

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    The presence of calcite in and near faults, as the dominant material, cement, or vein fill, indicates that the mechanical behavior of carbonate-dominated material likely plays an important role in shallow- and mid-crustal faulting. Furthermore, a variety of physical and chemical processes control the evolution of strength and style of slip along seismogenic faults and thus play a critical role in the seismic cycle. Determining the role and contributions of these types of mechanisms is essential to furthering our understanding of the processes and timescales that lead to the strengthening of faults during interseismic periods and their behavior during the earthquake nucleation process. To further our understanding of these processes, we performed laboratory-shearing experiments on calcite gouge at normal stresses from 1 to 100 MPa, under conditions of saturation and at room temperature. We performed velocity stepping (0.1-1000μm/s) and slide-hold-slide (1-3000s) tests, to measure the velocity dependence of friction and the amount of frictional strengthening respectively, under saturated conditions with pore fluid that was in equilibrium with CaCO3. At 5 MPa normal stress, we also varied the environmental conditions by performing experiments under conditions of 5% RH and 50 % RH, and saturation with: silicone oil, demineralized water, and the equilibrated solution combined with 0.5M NaCl. Finally, we collected post experimental samples for microscopic analysis. Our combined analyses of rate-dependence, strengthening behavior, and microstructures show that calcite fault gouge transitions from brittle to semi-brittle behavior at high normal stress and low sliding velocities. Furthermore, our results also highlight how changes in pore water chemistry can have significant influence on the mechanical behavior of calcite gouge in both the laboratory and in natural faults. Our observations have important implications for earthquake nucleation and propagation on faults in

  12. 13C 12C exchange between calcite and graphite: A possible thermometer in Grenville marbles

    USGS Publications Warehouse

    Valley, J.W.; O'Neil, J.R.

    1981-01-01

    The fractionation of 13C between calcite and graphite, ??(Cc-Gr). is consistently small (2.6-4.8 permil) in 34 assemblages from upper amphibolite- and granulite-facies marbles of the Grenville Province. In 25 samples from the Adirondack Mountains, New York, it decreases regularly with increasing metamorphic temperature. The fractionations are independent of absolute ??13C values of calcite (-2.9 to +5.0). For T = 600-800??C, the Adirondack data are described by ??(Cc-Gr) = -0.00748T (??C) + 8.68. This good correlation between ?? and T suggests that carbon isotope equilibrium was attained in these high-grade marbles and that the theoretical calculations of this fractionation by Bottinga are approximately 2 permil too large in this temperature ran