Sample records for abiotic marine calcite

  1. 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

  2. Arsenic uptake in bacterial calcite

    NASA Astrophysics Data System (ADS)

    Catelani, Tiziano; Perito, Brunella; Bellucci, Francesco; Lee, Sang Soo; Fenter, Paul; Newville, Matthew; Rimondi, Valentina; Pratesi, Giovanni; Costagliola, Pilario

    2018-02-01

    Bio-mediated processes for arsenic (As) uptake in calcite were investigated by means of X-ray Diffraction (XRD) and X-ray Absorption Spectroscopy (XAS) coupled with X-ray Fluorescence measurements. The environmental bacterial strain Bacillus licheniformis BD5, sampled at the Bullicame Hot Springs (Viterbo, Central Italy), was used to synthesize calcite from As-enriched growth media. Both liquid and solid cultures were applied to simulate planktonic and biofilm community environments, respectively. Bacterial calcite samples cultured in liquid media had an As enrichment factor (Kd) 50 times higher than that from solid media. The XRD analysis revealed an elongation of the crystal lattice along the c axis (by 0.03 Å) for biogenic calcite, which likely resulted from the substitution of larger arsenate for carbonate in the crystal. The XAS data also showed a clear difference in the oxidation state of sorbed As between bacterial and abiotic calcite. Abiotic chemical processes yielded predominantly As(V) uptake whereas bacterial precipitation processes led to the uptake of both As(III) and As(V). The presence of As(III) in bacterial calcite is proposed to result from subsequent reduction of arsenate to arsenite by bacterial activities. To the best of our knowledge, this is the first experimental observation of the incorporation of As(III) in the calcite crystal lattice, revealing a critical role of biochemical processes for the As cycling in nature.

  3. Arsenic uptake in bacterial calcite

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Catelani, Tiziano; Perito, Brunella; Bellucci, Francesco

    Bio-mediated processes for arsenic (As) uptake in calcite were investigated by means of X-ray Diffraction (XRD) and Xray Absorption Spectroscopy (XAS) coupled with X-ray Fluorescence measurements. The environmental bacterial strain Bacillus licheniformis BD5, sampled at the Bullicame Hot Springs (Viterbo, Central Italy), was used to synthesize calcite from As-enriched growth media. Both liquid and solid cultures were applied to simulate planktonic and biofilm community environments, respectively. Bacterial calcite samples cultured in liquid media had an As enrichment factor (Kd) 50 times higher than that from solid media. The XRD analysis revealed an elongation of the crystal lattice along the cmore » axis (by 0.03Å) for biogenic calcite, which likely resulted from the substitution of larger arsenate for carbonate in the crystal. The XAS data also showed a clear difference in the oxidation state of sorbed As between bacterial and abiotic calcite. Abiotic chemical processes yielded predominantly As(V) uptake whereas bacterial precipitation processes led to the uptake of both As(III) and As(V). The presence of As(III) in bacterial calcite is proposed to result from subsequent reduction of arsenate to arsenite by bacterial activities. To the best of our knowledge, this is the first experimental observation of the incorporation of As(III) in the calcite crystal lattice, revealing a critical role of biochemical processes for the As cycling in nature.« less

  4. Fulvic acid like organic compounds control nucleation of marine calcite under suboxic conditions

    NASA Astrophysics Data System (ADS)

    Neuweiler, Fritz; D'Orazio, Valeria; Immenhauser, Adrian; Geipel, Gerhard; Heise, Karl-Heinz; Cocozza, Claudio; Miano, Teodoro M.

    2003-08-01

    Intracrystalline organic compounds, enclosed within in situ precipitated marine microcrystalline calcite (automicrite), might represent either an inclusion or the catalyst of such precipitation. We use evidence from a Lower Cretaceous deep-water carbonate mound to show (1) the original source, (2) the degree of condensation, (3) the redox conditions involved, and (4) the catalytic role of natural organic matter for the precipitation of automicrite. Fluorescence spectrometry of the intracrystalline organic fraction extracted from these carbonates identifies a marine fulvic acid like organic compound with a low degree of polycondensation. This finding points to a temporal correlation of the initial stage of geopolymer formation with the precipitation of automicrite. Furthermore, the rare earth element (REE) distribution patterns in the mineral show a consistent positive Ce anomaly, suggesting an episode of reductive dissolution of iron-manganese oxyhydroxides during automicrite formation. In general, a relative enrichment of middle-weight REEs is observed, resulting in a convex distribution pattern typical for, e.g., phosphate concretions or humic acid material. By merging the results of spectrometry and REE geochemistry we thus conclude that the marine calcite precipitation was catalyzed by marine fulvic acid like compounds during the early stages of humification under suboxic conditions. This indicates that humification, driven by the presence of a benthic biomass, is more important for calcite authigenesis than any site-specific microbial metabolism. The Neoproterozoic rise of carbonate mounds supports this hypothesis; there is molecular evidence for early metazoan divergence then, but not for a major evolutionary episode of microorganisms.

  5. 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

  6. {Carbon and oxygen isotope signals from marine ostracod calcite - results from present and past oceans}

    NASA Astrophysics Data System (ADS)

    Bornemann, A.; Speijer, R. P.

    2009-04-01

    Systematic stable isotope studies on ostracod calcite are generally rare, in particular for marine taxa only the work of DIDIÉ & BAUCH (2002) provides first clues towards an improved understanding of ostracod stable isotope data in paleoceanography. Here we present analyses from recent near surface sediments from the Gulf of Taranto, the Levantine Basin (15 ka, both Mediterranean Sea) and the Paleocene of Tunisia (southern Tethyan margin). Data are compared to those from selected benthic foraminiferal taxa from which the living habitat and the isotopic disequilibria from ambient sea-water are well known. In addition, size fractions of monospecific samples have been studied in order to test whether a size/mass dependent change exists with respect to the isotopic composition of the carapace calcite. Calcification of ostracod carapaces is a very rapid process, which often takes place within a few hours and the obtained signal provides only a snap-shot of the prevailing paleoceanographic conditions. Multiple mono-specific measurements show therefore a much higher variability than benthic foraminifera, but may give a more complete picture of the seasonal changes. Our study confirms the findings of DIDIÉ & BAUCH (2002) and others (for non-marine taxa) that ostracod calcite displays a positive species-specific deviation from the sea-water ^18O composition between 0.5 and 1.5 per mil with an intra-specific variability of less than 0.5 per mil. In contrast ^13C values cover a huge range with an off-set from sea-water of up to -5 per mil and show a high intra-specific variability of up to 2 per mil. Size-fraction data show no systematic change, although a statistically significant positive covariance between ^18O and ^13C has been observed. This covariance consists of a slope similar to a kinetic controlled fractionation as has been described from asymbiotic planktic foraminifera (Globigerina bulloides) and corals (MCCONNAUGHEY, 1989; SPERO & LEA, 1996). This suggests that

  7. 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

  8. An XRPD and EPR spectroscopy study of microcrystalline calcite bioprecipitated by Bacillus subtilis

    NASA Astrophysics Data System (ADS)

    Perito, B.; Romanelli, M.; Buccianti, A.; Passaponti, M.; Montegrossi, G.; Di Benedetto, F.

    2018-05-01

    We report in this study the first XRPD and EPR spectroscopy characterisation of a biogenic calcite, obtained from the activity of the bacterium Bacillus subtilis. Microcrystalline calcite powders obtained from bacterial culture in a suitable precipitation liquid medium were analysed without further manipulation. Both techniques reveal unusual parameters, closely related to the biological source of the mineral, i.e., to the bioprecipitation process and in particular to the organic matrix observed inside calcite. In detail, XRPD analysis revealed that bacterial calcite has slightly higher c/a lattice parameters ratio than abiotic calcite. This correlation was already noticed in microcrystalline calcite samples grown by bio-mineralisation processes, but it had never been previously verified for bacterial biocalcites. EPR spectroscopy evidenced an anomalously large value of W 6, a parameter that can be linked to occupation by different chemical species in the next nearest neighbouring sites. This parameter allows to clearly distinguish bacterial and abiotic calcite. This latter achievement was obtained after having reduced the parameters space into an unbiased Euclidean one, through an isometric log-ratio transformation. We conclude that this approach enables the coupled use of XRPD and EPR for identifying the traces of bacterial activity in fossil carbonate deposits.

  9. Evidence for abiotic sulfurization of marine dissolved organic matter in sulfidic environments

    NASA Astrophysics Data System (ADS)

    Pohlabeln, A. M.; Niggemann, J.; Dittmar, T.

    2016-02-01

    Sedimentary organic matter abiotically sulfurizes in sulfidic marine environments. Here we hypothesize that sulfurization also affects dissolved organic matter (DOM), and that sulfidic marine environments are sources of dissolved organic sulfur (DOS) to the ocean. To test these hypotheses we studied solid-phase extractable (SPE) DOS in the Black Sea at various water column depths (oxic and anoxic) and in sediment porewaters from the German Wadden Sea. The concentration and molecular composition of SPE-DOS from these sites and from the oxic water columns of the North Sea (Germany) and of the North Pacific were compared. In support of our hypotheses, SPE-DOS concentrations were elevated in sulfidic waters compared to oxic waters. For a detailed molecular characterization of SPE-DOS, selective wet-chemical alteration experiments targeting different sulfur-containing functional groups were applied prior to Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). These experiments included harsh hydrolysis, selective derivatization of thiols, oxidation, and deoxygenation to test for thioesters, sulfonic acid esters, alkylsulfates, thiols, non-aromatic thioethers, and sulfoxides. Additionally, collision-induced fragmentation experiments were applied to test for sulfonic acids. The tests revealed that the sulfonic acid group was the main structural feature in SPE-DOS, independent of the environmental conditions of the sampling site. Only in Wadden Sea anoxic porewater also non-aromatic thioethers were found which are presumably not stable in oxic waters. The findings from our field studies were confirmed in laboratory experiments, where we abiotically sulfurized marine and algal-derived DOM under conditions similar to that in anoxic marine sediments.

  10. Formation and mosaicity of coccolith segment calcite of the marine algae Emiliania huxleyi.

    PubMed

    Yin, Xiaofei; Ziegler, Andreas; Kelm, Klemens; Hoffmann, Ramona; Watermeyer, Philipp; Alexa, Patrick; Villinger, Clarissa; Rupp, Ulrich; Schlüter, Lothar; Reusch, Thorsten B H; Griesshaber, Erika; Walther, Paul; Schmahl, Wolfgang W

    2018-02-01

    Coccolithophores belong to the most abundant calcium carbonate mineralizing organisms. Coccolithophore biomineralization is a complex and highly regulated process, resulting in a product that strongly differs in its intricate morphology from the abiogenically produced mineral equivalent. Moreover, unlike extracellularly formed biological carbonate hard tissues, coccolith calcite is neither a hybrid composite, nor is it distinguished by a hierarchical microstructure. This is remarkable as the key to optimizing crystalline biomaterials for mechanical strength and toughness lies in the composite nature of the biological hard tissue and the utilization of specific microstructures. To obtain insight into the pathway of biomineralization of Emiliania huxleyi coccoliths, we examine intracrystalline nanostructural features of the coccolith calcite in combination with cell ultrastructural observations related to the formation of the calcite in the coccolith vesicle within the cell. With TEM diffraction and annular dark-field imaging, we prove the presence of planar imperfections in the calcite crystals such as planar mosaic block boundaries. As only minor misorientations occur, we attribute them to dislocation networks creating small-angle boundaries. Intracrystalline occluded biopolymers are not observed. Hence, in E. huxleyi calcite mosaicity is not caused by occluded biopolymers, as it is the case in extracellularly formed hard tissues of marine invertebrates, but by planar defects and dislocations which are typical for crystals formed by classical ion-by-ion growth mechanisms. Using cryo-preparation techniques for SEM and TEM, we found that the membrane of the coccolith vesicle and the outer membrane of the nuclear envelope are in tight proximity, with a well-controlled constant gap of ~4 nm between them. We describe this conspicuous connection as a not yet described interorganelle junction, the "nuclear envelope junction". The narrow gap of this junction likely

  11. 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

  12. 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

  13. 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

  14. An alternative pathway for marine nitrous oxide production at oxic-anoxic interfaces from coupled biotic-abiotic reactions

    NASA Astrophysics Data System (ADS)

    Glass, J. B.; Stanton, C. L.; Ochoa, H.; Haslun, J. A.; Gandhi, H.; Taillefert, M.; Dichristina, T. J.; Stewart, F. J.; Klotz, M. G.; Ostrom, N. E.

    2016-02-01

    Marine emissions of nitrous oxide (N2O), a potent greenhouse gas, comprise approximately a third of global sources. Recent evidence suggests that the dominant source of N2O in seawater is the activity of ammonia-oxidizing Thaumarchaeota that lack characterized N2O-generating enzymes. Nitrous oxide may arise from a novel enzyme and/or abiotic reactions between nitrification intermediates, hydroxylamine (NH2OH) and nitric oxide (NO), and redox-active metals in seawater. Isotopic site preference, or difference in δ15N between the two nitrogen atoms in N2O, has been used as tracer for microbial N2O production pathways (-10 to 0‰ for nitrifier-denitrification and denitrification vs. 30-37‰ for nitrification via NH2OH oxidation). Seawater N2O site preference falls in between these two characterized end members, suggesting simultaneous production via a combination of both microbial pathways or via a novel mechanism with intermediate site preference. Here we show significant N2O production in abiotic experiments after addition of iron to seawater containing NH2OH and NO. The N2O produced from chemical reduction of NO by Fe(II) had a site preference of 16‰ whereas N2O produced from abiotic NH2OH oxidation had a site preference of 31‰. We propose that coupled biotic-abiotic N2O production pathways could contribute significant sources of N2O at marine oxic-anoxic interfaces.

  15. A novel determination of calcite dissolution kinetics in seawater

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  16. Unusual calcite cementing of quartz grains on Chandeleur Island Beach, offshore Louisiana

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Mitchell-Tapping, H.J.

    1983-09-01

    A very unusual calcite cement was found in some beachchips from an unconsolidated beach surface of Chandeleur Island offshore approximately 35 nmi (65 km) south of Mississippi in the Gulf of Mexico. The beachchips are irregularly shaped and are well cemented by this unusual calcite. This calcite crystal structure has not been reported previously as existing in a marine environment. A similar cement has been found in freshwater lake beachrock and in some travertine samples. The calcite crystals are elongate parallel to the c-optic axis, and are composed of bunches of crystallite blades. The crystallite blades of each crystal bunchmore » are pointed and are more bladed than freshwater cement crystals. The intercrystallite pore space contains no fine calcite silt as was observed in the lake samples. Fresh water provided by rainfall may be held in the pore spaces and bounded to the quartz-grain surfaces by ionic attraction. Marine spray above and saline water concentrated underneath from a sandwich effect at the micropore level, allowing rapid growth and precipitation of these very unusual calcite crystals in a single-phase low-salinity fluid.« less

  17. 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

  18. Strontium Incorporation Into Calcite Generated by Bacterial Ureolysis

    NASA Astrophysics Data System (ADS)

    Fujita, Y.; Ingram, J. A.; Cortez, M. M.; Redden, G. D.; Smith, R. W.

    2002-12-01

    Strontium incorporation into calcite generated by bacterial ureolytic activity was investigated as part of a larger effort to evaluate the use of in situ urea hydrolysis for accelerating co-precipitation of trace metals and radionuclides in contaminated aquifers. 90Sr, a uranium fission product with a half-life of 29 years, is a significant subsurface contaminant at several Department of Energy facilities and could be immobilized using this remediation strategy. Experiments were conducted in a medium designed to simulate the groundwater of the Snake River Plain Aquifer in eastern Idaho, amended with strontium. Initially the solution was undersaturated with respect to calcite. As a model ureolytic organism, we used Bacillus pasteurii, a well-characterized bacterium known for high urease activity and previously shown to induce calcite precipitation in urea-amended medium. To gain information on the effect of the bacterial surfaces, we also looked at precipitation in the presence of a bacterial species that did not hydrolyze urea, as well as in the absence of bacteria. In the absence of bacterial ureolysis, carbonate precipitation was induced by addition of ammonium carbonate. All products were identified as calcite by X-ray diffraction. Strontium uptake was observed in all cases, but was greatest in the system including bacterial ureolysis. Sputter depth element profiling by time-of-flight secondary ion mass spectrometry (TOF-SIMS) confirmed this finding, showing highest Sr:Ca ratios in the bacterially generated calcite throughout the depth (~350 nm) investigated. Environmental Scanning Electron Microscopy (ESEM) of the solids revealed regular crystals containing the outlines of embedded or entombed bacterial cells, suggesting that calcite precipitated directly on the cell surfaces when present. Analysis by X-ray Absorption Near Edge Spectroscopy (XANES) indicated that in both the biotically and abiotically generated calcites the Sr was incorporated into the calcite

  19. Ikaite pseudomorphs in the Zaire deep-sea fan: An intermediate between calcite and porous calcite

    NASA Astrophysics Data System (ADS)

    Jansen, J. H. F.; Woensdregt, C. F.; Kooistra, M. J.; van der Gaast, S. J.

    1987-03-01

    Translucent brown aggregates of calcium-carbonate crystals have been found in cores from the Zaire deep-sea fan (west equatorial Africa). The aggregates are well preserved but very friable. Upon storage they become yellowish white and cloudy and release water. Chemical, mineralogical (XRD), petrographical, crystal-morphological, and stable-isotope data demonstrate that the crystals have passed through three phases: (1) an authigenic carbonate phase, probably calcium carbonate, which is represented by the external habit of the present crystals; (2) a translucent brown ikaite phase (CaCO3·6H2O), unstable at temperatures above 5 °C; and (3) a phase consisting of calcite microcrystals that are poorly cemented and form a porous mass within the crystal form of the morphologically unchanged first phase. The transformation from the first phase into ikaite was probably a kinetic replacement. The transformation from ikaite into the third phase occurred because of storage at room temperature. The presence of ikaite is indicative of a low-temperature, anaerobic, organic-carbon-rich marine environment. Ikaite is probably the precursor of a great number of porous calcite pseudomorphs, and possibly also of many marine authigenic microcrystalline carbonate nodules.

  20. Neoproterozoic marine carbonates and their paleoceanographic significance

    NASA Astrophysics Data System (ADS)

    Hood, Ashleigh van Smeerdijk; Wallace, Malcolm William

    2018-01-01

    The primary mineralogy of marine carbonate precipitates has been a crucial factor in constraining the major element composition of ancient oceans. Secular changes in Phanerozoic marine chemistry, including Mg/Ca, have been well-documented using the original carbonate mineralogy of ooids, marine cements and biominerals. However, the history of Precambrian seawater chemistry is not as well constrained, partially due to the prevalence of dolomitisation in the Precambrian geological record. The Neoproterozoic ( 1000 Ma to 541 Ma) record of primary carbonate mineralogy is documented here using a combination of literature data and new analysis of marine carbonate precipitates from the Otavi Fold Belt, Namibia, the Death Valley succession, USA and the Adelaide Fold Belt, Australia. These data suggest that the last 460 million years of the Proterozoic were dominated by aragonite and high-Mg calcite precipitation in shallow marine settings. In contrast, low-Mg calcite has only been recognised in a small number of formations. In addition to aragonite and calcite precipitation, marine dolomite precipitation was widespread in Neoproterozoic oceans, including mimetic (syn-sedimentary) dolomitisation and primary dolomite marine cementation. The combination of marine aragonite, high Mg-calcite and dolomite precipitation during the Neoproterozoic suggests extremely high seawater Mg/Ca conditions relative to Phanerozoic oceans. Marine dolomite precipitation may also be linked to widespread marine anoxia during this time.

  1. 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

  2. Review of aragonite and calcite crystal morphogenesis in thermal spring systems

    NASA Astrophysics Data System (ADS)

    Jones, Brian

    2017-06-01

    Aragonite and calcite crystals are the fundamental building blocks of calcareous thermal spring deposits. The diverse array of crystal morphologies found in these deposits, which includes monocrystals, mesocrystals, skeletal crystals, dendrites, and spherulites, are commonly precipitated under far-from-equilibrium conditions. Such crystals form through both abiotic and biotic processes. Many crystals develop through non-classical crystal growth models that involve the arrangement of nanocrystals in a precisely controlled crystallographic register. Calcite crystal morphogenesis has commonly been linked to a ;driving force;, which is a conceptual measure of the distance of the growth conditions from equilibrium conditions. Essentially, this scheme indicates that increasing levels of supersaturation and various other parameters that produce a progressive change from monocrystals and mesocrystals to skeletal crystals to crystallographic and non-crystallographic dendrites, to dumbbells, to spherulites. Despite the vast amount of information available from laboratory experiments and natural spring systems, the precise factors that control the driving force are open to debate. The fact that calcite crystal morphogenesis is still poorly understood is largely a reflection of the complexity of the factors that influence aragonite and calcite precipitation. Available information indicates that variations in calcite crystal morphogenesis can be attributed to physical and chemical parameters of the parent water, the presence of impurities, the addition of organic or inorganic additives to the water, the rate of crystal growth, and/or the presence of microbes and their associated biofilms. The problems in trying to relate crystal morphogenesis to specific environmental parameters arise because it is generally impossible to disentangle the controlling factor(s) from the vast array of potential parameters that may act alone or in unison with each other.

  3. 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.

  4. 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

  5. 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.

  6. 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

  7. Defects in Calcite.

    DTIC Science & Technology

    1991-05-13

    AD-A245 645 A TRIDENT SCHOLAR PROJECT REPORT NO. 181 "DEFECTS IN CALCITE " DTTC %N FEB 5-1912 UNITED STATES NAVAL ACADEMY ANNAPOLIS, MARYLAND 92-02841...report; no. 181 (1991) "DEFECTS IN CALCITE " A Trident Scholar Project Report by Midshipman Anthony J. Kotarski, Class of 1991 U. S. Naval Academy Annapolis...REPORT TYPE AND DATES COVERED 13 May 1991 Final 1990/91 . TITLE AND SUBTITLE s. FUNDING NUMBERS DEFECTS IN CALCITE 6. AUTHOR(S) Anthony J. Kotarski 7

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

    USGS Publications Warehouse

    Busenberg, E.; Plummer, Niel

    1985-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Reddy, Michael M.

    2012-08-01

    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.

  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. 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.

  12. The Effect of Different Oceanic Abiotic Factors on Prokaryotic Body Sizes

    NASA Astrophysics Data System (ADS)

    Pidathala, S.; Bellon, M.; Heim, N.; Payne, J.

    2016-12-01

    We are studying the impact of abiotic factors in the Pacific and Atlantic on prokaryotic body sizes and genome sizes because we are interested in the manner in which abiotic factors influence genome sizes independent of their influence on body sizes. Some research has been done in the past on marine bacterial evolution, including data collection on marine ecology in relation to bacterial body sizes (Straza 2009). We are using the abiotic factors: temperature, salinity, and pH to compare the biovolumes/genome sizes of different phyla by using R. We made 9 scatter plots to model these relationships. Regardless of the phyla or the ocean, we found that there is no relation between pH, temperature, and body size, with several exceptions: Deinococcus. thermus has an indirect relationship with size in respect to temperature; size only correlates to temperature for phyla that are thermophiles. We also found that bacteria like D. thermus and Thermotogae are taxa only found in higher temperatures. Additionally, almost all phyla have genome sizes restricted by certain pH levels:, Proteobacteria only reach genomes with acidity levels greater than 6. In terms of salinity levels, certain bacteria are only found within a small range, and others, like Proteobacteria, can only reach genomes at low salinity levels. Finally, Proteobacteria have large genome sizes between 30 and 40 °, and Crenarchaeota have constant genome sizes in higher temperatures. Conclusively, we discovered that these abiotic factors generally do not affect body size, with the exception of D. thermus' indirect relationship to temperature due to its small biovolume in high temperatures. However, we determined that these abiotic factors have a great impact on genome sizes. This is due to genome size independence from body size. Also, genome size could have served as an adaptive feature for bacteria in marine environments, explaining why different phyla may have diverged to accommodate their lifestyles.

  13. Morphology Controls on Calcite Recrystallization.

    PubMed

    Heberling, Frank; Paulig, Leonie; Nie, Zhe; Schild, Dieter; Finck, Nicolas

    2016-11-01

    Environmental scientists and geoscientists working in different fields regard the reactivity of calcite and corresponding changes in its trace elemental- or isotopic composition from diametrically opposed points of view. As one extreme, calcite based environmental remediation strategies rely on the fast recrystallization of calcite and the concurrent uptake and immobilization of pollutants. Paleo-ecological investigations denote the other extreme, and rely on the invariability of calcite composition over geological periods of time. We use long-term radiotracer experiments to quantify recrystallization rates of seven types of calcite powder with diverse morphology and particle size distribution. On the one hand our results demonstrate the long-term metastability of calcite with equilibrated crystal surfaces even at isotopic dis-equilibrium. On the other hand, we document the extremely high reactivity and interfacial free energy of freshly ground, rough calcite. Our results indicate that bulk calcite recrystallization is an interfacial free energy driven Ostwald-ripening process, in which particle roughness effects dominate over the effect of crystal habitus and particle size. We confirm that the dynamic equilibrium exchange of crystal constituents between kink sites involves an activation barrier of about 25 kJ/mol. At room temperature the equilibrium exchange is limited to a near surface region and proceeds at a rate of (3.6 ± 1.4)·10 -13 mol/(m 2 ·s).

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

    PubMed Central

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

    2002-01-01

    Shifts in the Mg/Ca ratio of seawater driven by changes in midocean ridge spreading rates have produced oscillations in the mineralogy of nonskeletal carbonate precipitates from seawater on time scales of 108 years. Since Cambrian time, skeletal mineralogies of anatomically simple organisms functioning as major reef builders or producers of shallow marine limestones have generally corresponded in mineral composition to nonskeletal precipitates. Here we report on experiments showing that the ambient Mg/Ca ratio actually governs the skeletal mineralogy of some simple organisms. In modern seas, coralline algae produce skeletons of high-Mg calcite (>4 mol % MgCO3). We grew three species of these algae in artificial seawaters having three different Mg/Ca ratios. All of the species incorporated amounts of Mg into their skeletons in proportion to the ambient Mg/Ca ratio, mimicking the pattern for nonskeletal precipitation. Thus, the algae calcified as if they were simply inducing precipitation from seawater through their consumption of CO2 for photosynthesis; presumably organic templates specify the calcite crystal structure of their skeletons. In artificial seawater with the low Mg/Ca ratio of Late Cretaceous seas, the algae in our experiments produced low-Mg calcite (<4 mol % MgCO3), the carbonate mineral formed by nonskeletal precipitation in those ancient seas. Our results suggest that many taxa that produce high-Mg calcite today produced low-Mg calcite in Late Cretaceous seas. PMID:12399549

  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. Formation of complex fibrous calcite veins in Upper Triassic strata of Wrangellia Terrain, British Columbia, Canada

    NASA Astrophysics Data System (ADS)

    Al-Aasm, I. S.; Coniglio, M.; Desrochers, A.

    1995-12-01

    Fibrous calcite veins are ubiquitous throughout the thinly bedded, organic-rich Upper Triassic marine mdrocks of the Queen Charlotte Islands and their lateral equivalents on Vancouver Island. These veins show variable and complex morphologies and can be grouped into several types: (a) simple; (b) anastomosing or composite; (c) boxwork; and (4) polygonal network oriented normal to bedding. Field, petrographic, and geochemical evidence suggest that vein opening, resulting from hydraulic fracturing due to elevated pore-fluid pressures, was an early phenomenon and occurred prior to significant compaction of the host sediments. Calcite fibers in the veins are up to 30 mm long and commonly oriented perpendicular to the wall but locally display conical structures. Fibrous calcites, with the exception of those in boxwork veins, are generally non-ferroan and dull to very weakly orange luminescent. The boxwork calcites are ferroan, zoned and show dull luminescence with some bright rims. δ18O values range from -8.2 to -21.6‰ (PDB) and δ13C values range from 2.0 to -4.4‰ (PDB). Although some variations are present among the different morphological types of calcite veins, oxygen and carbon isotopic values display important variations when compared geographically. The most depleted oxygen and carbon isotopic values are those of boxwork calcite and they are associated with areas where the effects of early Mesozoic plutonism were most severe. Precipitation of boxwork fibrous calcites is interpreted to have been related to hydrothermal discharge into unconsolidated host sediment, rather than to later burial. Although the hydrothermal influence on the formation of vein calcite is related to geological events specific to the Wrangellia Terrain, this study provides an alternative mechanism for the generation of fibrous calcite veins and demonstrates the local importance of hydrothermal input in the evolution of pore-water chemistry.

  17. Corrosion Protection by Calcite-Type Coatings

    DTIC Science & Technology

    1989-10-01

    CORROSION PROTECTION BY CALCITE -TYPE COATINGS OCTOBER, 1989 Prepared by: OCEAN CITY RESEARCH CORPORATION Tennessee Avenue & Beach Thorofare Ocean...REPORT DATE OCT 1989 2. REPORT TYPE N/A 3. DATES COVERED - 4. TITLE AND SUBTITLE Corrosion Protection by Calcite -Type Coatings 5a. CONTRACT... calcite -type coatings to segregated seawater ballast tanks. If perfected, a calcite coating approach could substantially reduce the cost of corrosion

  18. 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

  19. 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)

  20. A paired apatite and calcite clumped isotope thermometry approach to estimating Cambro-Ordovician seawater temperatures and isotopic composition

    NASA Astrophysics Data System (ADS)

    Bergmann, Kristin D.; Finnegan, Seth; Creel, Roger; Eiler, John M.; Hughes, Nigel C.; Popov, Leonid E.; Fischer, Woodward W.

    2018-03-01

    The secular increase in δ18O values of both calcitic and phosphatic marine fossils through early Phanerozoic time suggests either that (1) early Paleozoic surface temperatures were high, in excess of 40 °C (tropical MAT), (2) the δ18O value of seawater has increased by 7-8‰ VSMOW through Paleozoic time, or (3) diagenesis has altered secular trends in early Paleozoic samples. Carbonate clumped isotope analysis, in combination with petrographic and elemental analysis, can deconvolve fluid composition from temperature effects and therefore determine which of these hypotheses best explain the secular δ18O increase. Clumped isotope measurements of a suite of calcitic and phosphatic marine fossils from late Cambrian- to Middle-late Ordovician-aged strata-the first paired fossil study of its kind-document tropical sea surface temperatures near modern temperatures (26-38 °C) and seawater oxygen isotope ratios similar to today's ratios.

  1. Nickel adsorption on chalk and calcite

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  2. 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).

  3. U-Th dating of calcite corals from the Gulf of Aqaba

    NASA Astrophysics Data System (ADS)

    Yehudai, Maayan; Lazar, Boaz; Bar, Neta; Kiro, Yael; Agnon, Amotz; Shaked, Yonathan; Stein, Mordechai

    2017-02-01

    Most of the fossil corals in the elevated reef terraces along the Gulf of Aqaba (GOA) were extensively altered to calcite. This observation indicates extensive interaction with freshwater, possibly when the terraces passed through a coastal aquifer that existed along the shores of the GOA, implying a wetter climate during the time of recrystallization from aragonite to calcite. Thus, dating of the recrystallization events should yield the timing of past wetter conditions in the current hyper-arid area of the GOA. In the present study, 18 aragonite and calcite corals were collected from several elevated coral reef terraces off the coast, south of the city of Aqaba. While aragonite corals were dated with the conventional closed system age equation (assuming zero initial Th), the dating of the calcite corals required the development of adequate equations to allow the calculation of both the initial formation age of the aragonite corals and the time of recrystallization to calcite. The two age calculations were based on the assumptions that each reef terrace went through a single and rapid recrystallization event and that the pristine aragonite corals were characterized by a rather uniform initial U concentration, typical for pristine modern corals. Two recrystallization events were identified at 104 ± 6 ka and 124 ± 8 ka. The ages coincide with the timing of sapropel events S4 and S5, respectively, when the African monsoon induced enhanced wetness in the desert area. Considering the age uncertainties, the times of formation of the two major reef terraces are estimated to be ∼124 ka (reef terrace R2) and ∼130 ka (reef terrace R3), matching the peaks in the global sea level during the last interglacial MIS 5e stage. Apparently, sea level of the GOA did not fluctuate a lot during the period between ∼130 ka and ∼104 ka and remained close to the Marine Isotopic stage (MIS) 5e highstand. The availability of freshwater (during the sapropel periods) and limited sea

  4. Nickel adsorption on chalk and calcite.

    PubMed

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

    2014-12-01

    Nickel uptake from solution by two types of chalk and calcite was investigated in batch sorption studies. The goal was to understand the difference in sorption behavior between synthetic and biogenic calcite. Experiments at atmospheric partial pressure of CO2, in solutions equilibrated with calcite and chalk and pH ranging from 7.7 to 8.8, explored the influence of initial concentration and the amount and type of sorbent on Ni uptake. Adsorption increases with increased surface area and pH. A surface complexation model describes the data well. Stability constants for the Ni surface complex are log KNi=-1.12 on calcite and log KNi=-0.43 and -0.50 on the two chalk samples. The study confirms that synthetic calcite and chalk both take up nickel, but Ni binds more strongly on the biogenic calcite than on inorganically precipitated, synthetic powder, because of the presence of trace amounts of polysaccharides and clay nanoparticles on the chalk surface. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Coccolith calcite time capsules preserve a molecule-specific record of pCO2

    NASA Astrophysics Data System (ADS)

    McClelland, H. L. O.; Pearson, A.; Hermoso, M.; Wilkes, E.; Lee, R. B. Y.; Rickaby, R. E. M.

    2017-12-01

    Coccolithophores are single-celled phytoplankton that have contributed organic matter and calcite to marine sediments since the Late Triassic. The carbon isotopic compositions of both the calcite, and the organic matter, constitute valuable archives of information about the interaction between these organisms and the environments in which they lived. The isotopic composition of alkenone lipids, a recalcitrant component of coccolithophore organic carbon produced by a single family of coccolithophores, has been widely used to reconstruct pCO2 in the geological past. However, the robustness of this approach has remained controversial, due in part to the difficulties associated with reproducing pCO2 changes across periods of known pCO2 change, and uncertainties in relevant physiological variables such as growth rate and cell size. Meanwhile the calcite, produced in the form of plates called coccoliths, and which has had limited utility in paleoclimate reconstructions due to its large and variable departures from the isotopic composition of abiogenic calcite, has garnered increasing attention in recent years for the environmental and physiological information it contains. Here we show that polysaccharides preserved within the calcite crystal lattice of near monospecific fractions of fossil coccoliths constitute an ancient pristine source of organic carbon that unlike alkenones is unambiguously associated with the coccolith1. The isotopic composition of these polysaccharides, in tandem with that of the host coccolith calcite, and morphometrics from the same coccoliths2, can be used simultaneously constrain a recently published cellular carbon isotope flux model3, embedded in a more complex nutrient limitation model, in a powerful new approach to simultaneously predict cellular parameters and pCO2. We demonstrate the validity of this approach across a glacial / interglacial cycle. Lee, R. B. Y., et al,, Nat. Commun. 7, 13144 (2016). McClelland, H. L. O. et al. Sci. Rep. 6

  6. The Origin of Fibrous Calcite Veins: Aragonite?

    NASA Astrophysics Data System (ADS)

    Elburg, M. A.; Bons, P. D.

    2005-12-01

    Truly fibrous calcite veins occur mainly in carbonaceous shales and are characterised by high length:width ratios of their fibres (>10). Previous studies on their Sr isotopic geochemistry (Elburg et al., 2002: Geol. Soc. London Spec. Publ. 200, 103-118; Hilgers and Sindern, 2005: Geofluids, in press) have shown that some of the material could be derived from the local wall rock. These studies also showed that the veins were always enriched in Sr compared to the calcite in the host rocks. Aragonite can contain significantly more Sr than calcite, while it also tends to have a fibrous crystal habit. It is therefore possible that the fibrous habit of these veins, which now consist of calcite, are a reflection of their initial aragonitic mineralogy, rather than of any special tectonic regime during their formation. This idea was investigated by analysing the major and trace element geochemistry of selected fibrous and non-fibrous calcite veins from Arkaroola (northern Flinders Ranges, Australia). The fibrous vein analysed for major elements contains less than 1% MgCO3, whereas calcite in the host rock, with which it is in Sr isotopic equilibrium, contains 18% MgCO3. Calcite can contain significant Mg, whereas the aragonitic structure cannot accomodate this ion, so this result is consistent with the idea of an original aragonitic mineralogy of the veins. The fibrous veins show an enrichment in the middle rare earth elements (REE) compared to the calcite in the host rock and blocky veins. In a Post-Archean Average Shale normalised diagram, Eu is more strongly enriched compared to its neighbouring elements in the fibrous veins, but not in the host calcite, blocky veins, or in the silicate fraction of the host rock, suggesting more reducing conditions during fibrous vein formation. This data cannot be used as direct evidence for the fibrous veins' aragonitic mineralogy. It does, however, show that significant differences exist between calcite in host rocks, blocky and

  7. Repulsive hydration forces between calcite surfaces and their effect on the brittle strength of calcite-bearing rocks

    NASA Astrophysics Data System (ADS)

    Røyne, Anja; Dalby, Kim N.; Hassenkam, Tue

    2015-06-01

    The long-term mechanical strength of calcite-bearing rocks is highly dependent on the presence and nature of pore fluids, and it has been suggested that the observed effects are due to changes in nanometer-scale surface forces near fracture tips and grain contacts. In this letter, we present measurements of forces between two calcite surfaces in air and water-glycol mixtures using the atomic force microscope. We show a time- and load-dependent adhesion at low water concentrations and a strong repulsion in the presence of water, which is most likely due to hydration of the strongly hydrophilic calcite surfaces. We argue that this hydration repulsion can explain the commonly observed water-induced decrease in strength in calcitic rocks and single calcite crystals. Furthermore, this relatively simple experimental setup may serve as a useful tool for analyzing surface forces in other mineral-fluid combinations.

  8. Microbially Induced Calcite Precipitation Employing Environmental Isolates

    PubMed Central

    Kim, Gunjo; Youn, Heejung

    2016-01-01

    In this study, five microbes were employed to precipitate calcite in cohesionless soils. Four microbes were selected from calcite-precipitating microbes isolated from calcareous sand and limestone cave soils, with Sporosarcina pasteurii ATCC 11859 (standard strain) used as a control. Urease activities of the four microbes were higher than that of S. pasteurii. The microbes and urea–CaCl2 medium were injected at least four times into cohesionless soils of two different relative densities (60% and 80%), and the amount of calcite precipitation was measured. It was found that the relative density of cohesionless soils significantly affects the amount of calcite precipitation and that there is a weak correlation between urease activity and calcite precipitation. PMID:28773600

  9. Microbially Induced Calcite Precipitation Employing Environmental Isolates.

    PubMed

    Kim, Gunjo; Youn, Heejung

    2016-06-15

    In this study, five microbes were employed to precipitate calcite in cohesionless soils. Four microbes were selected from calcite-precipitating microbes isolated from calcareous sand and limestone cave soils, with Sporosarcina pasteurii ATCC 11859 (standard strain) used as a control. Urease activities of the four microbes were higher than that of S. pasteurii . The microbes and urea-CaCl₂ medium were injected at least four times into cohesionless soils of two different relative densities (60% and 80%), and the amount of calcite precipitation was measured. It was found that the relative density of cohesionless soils significantly affects the amount of calcite precipitation and that there is a weak correlation between urease activity and calcite precipitation.

  10. Peptides Enhance Mg Content of Calcite: Toward a Process-Based Understanding of Proxy Models

    NASA Astrophysics Data System (ADS)

    Dove, P.; Stephenson, A.; Wu, L.; Wu, K.; de Yoreo, J.; Hoyer, J.

    2008-12-01

    Investigations of modern organisms relating magnesium content of calcified skeletons to temperature often exhibit unexplained deviations from the signature expected for inorganically precipitated calcite. These 'vital effects' are believed to have kinetic and taxonomic origins but the mechanistic basis for measured offsets remains unclear. A complicating factor is that mineralization is isolated from the external environment within an organic-rich matrix whose roles in mineralization are implicated but not well understood. Here we show that a simple hydrophilic peptide, sharing the same acidic character as macromolecules isolated from sites of calcification, increases the magnesium content of calcite up to 3 mol%. Using in situ AFM, we demonstrate that (Asp3Gly)6Asp3 also enhances growth rate and step edge energy of calcite compared to inorganic controls. Kinetic and thermodynamic measurements indicate that biomolecules interact with calcite surfaces to lower the energy barrier to desolvating the more strongly hydrated magnesium ion, thereby increasing the probability of its incorporation relative to calcium. Comparisons to previous studies that correlate Mg content of carbonate minerals with temperature show this peptide-induced Mg- enhancement is equivalent to offsets of several degrees Centigrade. The findings suggest local macromolecule chemistry influences Mg signatures- a plausible origin of vital effects. Further, studies of nonskeletal carbonates have long-asked whether the natural marine humic and protein substances found in sedimentary environments may influence mineralization. These insights provide a physical basis for anecdotal evidence that organic chemistry modulates the mineralization of inorganic carbonates.

  11. Microstructures and rheology of a calcite-shale thrust fault

    NASA Astrophysics Data System (ADS)

    Wells, Rachel K.; Newman, Julie; Wojtal, Steven

    2014-08-01

    A thin (˜2 cm) layer of extensively sheared fault rock decorates the ˜15 km displacement Copper Creek thrust at an exposure near Knoxville, TN (USA). In these ultrafine-grained (<0.3 μm) fault rocks, interpenetrating calcite grains form an interconnected network around shale clasts. One cm below the fault rock layer, sedimentary laminations in non-penetratively deformed footwall shale are cut by calcite veins, small faults, and stylolites. A 350 μm thick calcite vein separates the fault rocks and footwall shale. The vein is composed of layers of (1) coarse calcite grains (>5 μm) that exhibit a lattice preferred orientation (LPO) with pores at twin-twin and twin-grain boundary intersections, and (2) ultrafine-grained (0.3 μm) calcite that exhibits interpenetrating grain boundaries, four-grain junctions and lacks a LPO. Coarse calcite layers crosscut ultrafine-grained layers indicating intermittent vein formation during shearing. Calcite in the fault rock layer is derived from vein calcite and grain-size reduction of calcite took place by plasticity-induced fracture. The ultrafine-grained calcite deformed primarily by diffusion-accommodated grain boundary sliding and formed an interconnected network around shale clasts within the shear zone. The interconnected network of ultrafine-grained calcite indicates that calcite, not shale, was the weak phase in this fault zone.

  12. 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

  13. 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.

  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. 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.

  16. 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.

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

    DOE PAGES

    Vandamme, Dries; Pohl, Philip I.; Beuckels, Annelies; ...

    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 potentialmore » 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.« less

  18. Marine botany. Second edition

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Dawes, C.J.

    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 identifymore » 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.« less

  19. Experimental diagenesis: insights into aragonite to calcite transformation of Arctica islandica shells by hydrothermal treatment

    NASA Astrophysics Data System (ADS)

    Casella, Laura A.; Griesshaber, Erika; Yin, Xiaofei; Ziegler, Andreas; Mavromatis, Vasileios; Müller, Dirk; Ritter, Ann-Christine; Hippler, Dorothee; Harper, Elizabeth M.; Dietzel, Martin; Immenhauser, Adrian; Schöne, Bernd R.; Angiolini, Lucia; Schmahl, Wolfgang W.

    2017-03-01

    Biomineralised hard parts form the most important physical fossil record of past environmental conditions. However, living organisms are not in thermodynamic equilibrium with their environment and create local chemical compartments within their bodies where physiologic processes such as biomineralisation take place. In generating their mineralised hard parts, most marine invertebrates produce metastable aragonite rather than the stable polymorph of CaCO3, calcite. After death of the organism the physiological conditions, which were present during biomineralisation, are not sustained any further and the system moves toward inorganic equilibrium with the surrounding inorganic geological system. Thus, during diagenesis the original biogenic structure of aragonitic tissue disappears and is replaced by inorganic structural features. In order to understand the diagenetic replacement of biogenic aragonite to non-biogenic calcite, we subjected Arctica islandica mollusc shells to hydrothermal alteration experiments. Experimental conditions were between 100 and 175 °C, with the main focus on 100 and 175 °C, reaction durations between 1 and 84 days, and alteration fluids simulating meteoric and burial waters, respectively. Detailed microstructural and geochemical data were collected for samples altered at 100 °C (and at 0.1 MPa pressure) for 28 days and for samples altered at 175 °C (and at 0.9 MPa pressure) for 7 and 84 days. During hydrothermal alteration at 100 °C for 28 days most but not the entire biopolymer matrix was destroyed, while shell aragonite and its characteristic microstructure was largely preserved. In all experiments up to 174 °C, there are no signs of a replacement reaction of shell aragonite to calcite in X-ray diffraction bulk analysis. At 175 °C the replacement reaction started after a dormant time of 4 days, and the original shell microstructure was almost completely overprinted by the aragonite to calcite replacement reaction after 10 days

  20. Effect of organic ligands on Mg partitioning and Mg isotope fractionation during low-temperature precipitation of calcite in the absence of growth rate effects

    NASA Astrophysics Data System (ADS)

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

    2017-06-01

    Calcite growth rate has been previously shown to be the dominating parameter controlling both Mg partitioning and Mg isotope fractionation during calcite growth. In natural calcite precipitation environments - characterized by abundant organic material - the presence of dissolved organic molecules may affect these two parameters. In order to assess the role of organic molecules, steady state calcite growth experiments have been performed at 25 °C, 1 bar pCO2 and constant, within analytical uncertainty growth rate (rp = 10-7.4 mol m-2 s-1) in the presence of aqueous Mg and six organic ligands in the concentration range from 0.01 to 10 mM. The organic ligands used in this study are: (i) acetic acid, (ii) citric acid, (iii) glutamic acid, (iv) salycilic acid, (v) glycine, and (vi) ethylenediaminetetraacetic acid (EDTA). These contain one or more carboxyl- and amino-groups that are commonly present in natural organic substances found in lacustrine, fluvial, soil, cave, as well as in marine and earliest diagenetic porewater environments. Results shown here indicate that the presence of these carboxyl- and amino-groups promotes an increase in the partition coefficient of Mg in calcite (DMg = (Mg/Ca)calcite/(Mg/Ca)fluid) that can be attributed to their adsorption onto the calcite surfaces and the subsequent reduction of the active sites of growth. This increase of DMg values as a function of the supersaturation degree of calcite in the fluid phase can be described by the linear equation:

  1. 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.

  2. The crystal structure of calcite III

    NASA Astrophysics Data System (ADS)

    Smyth, Joseph R.; Ahrens, Thomas J.

    The crystal structure of calcite III has been deduced from existing high pressure powder X-ray diffraction patterns, based on the assumption that it is a displacive modification of the calcite I structure. The structure is monoclinic with space group C2 and a Z of 6. There are two Ca and two C positions, and five O positions, and atom coordinates have been refined by distance-least-squares methods to give reasonable octahedral coordination for Ca and parallel, planar CO3 groups. Unit cell parameters refined from a published powder diffraction pattern at 4.1 GPa are: a = 8.746(8)Å b = 4.685(5)Å c = 8.275(8)Å and β= 94.4°. The structure has a calculated density of 2.949 Mg/m³ at 4.1 GPa which is less than that of aragonite at this pressure and consistent with early piston cylinder studies. This implies that calcite III is indeed a metastable intermediary between calcite I and aragonite.

  3. 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.

  4. 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.

  5. Quantifying the impact of early calcite cementation on the reservoir quality of carbonate rocks: A 3D process-based model

    NASA Astrophysics Data System (ADS)

    Hosa, Aleksandra; Wood, Rachel

    2017-06-01

    The reservoir properties of carbonate rocks are controlled by both deposition and diagenesis. The latter includes the early precipitation of calcite cements, which can exert a strong control on the evolution of subsequent diagenetic pathways. We quantify the impact of early marine cement growth in grainstones on evolving pore space by examining trends in the relationship between cementation and permeability using a 3D process-based model (Calcite3D). The model assumes varying proportions of polycrystalline and monocrystalline grain types, upon which we grow isopachous and syntaxial calcite cement types, respectively. We model two syntaxial cement shapes, compact and elongated, that approximate the geometries of typical rhombohedral calcite forms. Results demonstrate the effect of cement competition: an increasing proportion of monocrystalline grains creates stronger competition and a reduction in the impact of individual grains on final calcite cement volume and porosity. Isopachous cement is effective in closing pore throats and limiting permeability. We also show that the impact of syntaxial cement on porosity occlusion and therefore flow is highly dependent on monocrystalline grain location and the orientation of crystal axes. This demonstrates the importance of diagenetic overprint in controlling the evolution of rock properties, but also that this process can be essentially random. We also show that diagenesis alone can create notable heterogeneity in the permeability of carbonates. While Calcite3D is successful in modelling realistic changes in cement volumes and pore space morphology, modelled permeabilities (0.01 -30D) are above the range reported in reservoir grainstones due to the very high permeability of the initial synthetic sediment deposit (58.9D). Poroperm data generated by Calcite3D, however, exhibits a linear relationship between the logarithms of porosity and permeability with a high coefficient of determination, as observed in natural media.

  6. Effect of coccolith polysaccharides isolated from the coccolithophorid, Emiliania huxleyi, on calcite crystal formation in in vitro CaCO3 crystallization.

    PubMed

    Kayano, Keisuke; Saruwatari, Kazuko; Kogure, Toshihiro; Shiraiwa, Yoshihiro

    2011-02-01

    Marine coccolithophorids (Haptophyceae) produce calcified scales "coccoliths" which are composed of CaCO(3) and coccolith polysaccharides (CP) in the coccolith vesicles. CP was previously reported to be composed of uronic acids and sulfated residues, etc. attached to the polymannose main chain. Although anionic polymers are generally known to play key roles in biomineralization process, there is no experimental data how CP contributes to calcite crystal formation in the coccolithophorids. CP used was isolated from the most abundant coccolithophorid, Emiliania huxleyi. CaCO(3) crystallization experiment was performed on agar template layered onto a plastic plate that was dipped in the CaCO(3) crystallization solution. The typical rhombohedral calcite crystals were formed in the absence of CP. CaCO(3) crystals formed on the naked plastic plate were obviously changed to stick-like shapes when CP was present in the solution. EBSD analysis proved that the crystal is calcite of which c-axis was elongated. CP in the solution stimulated the formation of tabular crystals with flat edge in the agarose gel. SEM and FIB-TEM observations showed that the calcite crystals were formed in the gel. The formation of crystals without flat edge was stimulated when CP was preliminarily added in the gel. These observations suggest that CP has two functions: namely, one is to elongate the calcite crystal along c-axis and another is to induce tabular calcite crystal formation in the agarose gel. Thus, CP may function for the formation of highly elaborate species-specific structures of coccoliths in coccolithophorids.

  7. Modelling the evolution of complex conductivity during calcite precipitation on glass beads

    NASA Astrophysics Data System (ADS)

    Leroy, Philippe; Li, Shuai; Jougnot, Damien; Revil, André; Wu, Yuxin

    2017-04-01

    When pH and alkalinity increase, calcite frequently precipitates and hence modifies the petrophysical properties of porous media. The complex conductivity method can be used to directly monitor calcite precipitation in porous media because it is sensitive to the evolution of the mineralogy, pore structure and its connectivity. We have developed a mechanistic grain polarization model considering the electrochemical polarization of the Stern and diffuse layers surrounding calcite particles. Our complex conductivity model depends on the surface charge density of the Stern layer and on the electrical potential at the onset of the diffuse layer, which are computed using a basic Stern model of the calcite/water interface. The complex conductivity measurements of Wu et al. on a column packed with glass beads where calcite precipitation occurs are reproduced by our surface complexation and complex conductivity models. The evolution of the size and shape of calcite particles during the calcite precipitation experiment is estimated by our complex conductivity model. At the early stage of the calcite precipitation experiment, modelled particles sizes increase and calcite particles flatten with time because calcite crystals nucleate at the surface of glass beads and grow into larger calcite grains. At the later stage of the calcite precipitation experiment, modelled sizes and cementation exponents of calcite particles decrease with time because large calcite grains aggregate over multiple glass beads and only small calcite crystals polarize.

  8. Palaeoclimate determination from cave calcite deposits

    NASA Astrophysics Data System (ADS)

    Gascoyne, M.

    Calcite deposits formed in limestone caves have been found to be an excellent repository of palaeoclimatic data for terrestrial environments. The very presence of a relict deposit indicates non-glacial conditions at the time of formation, and both 14C and uranium-series methods can be used to date the deposit and, hence, the age of these climatic conditions. Variations in 13C and 18O content of the calcite, in 2H and 18O content of fluid inclusions, in trace element concentrations and, more recently, in pollen assemblages trapped in the calcite, are all potentially available as synchronous palaeoclimatic indicators. Previous work has tended to concentrate mainly on abundance of deposits as a palaeoclimatic indicator for the last 300,000 years. This literature is briefly reviewed here, together with the theory and methods of analysis of the U-series and stable isotopic techniques. The combined use of U-series ages and 13C and 18O variations in cave calcites illustrates the potential for palaeoclimate determination. Previously unpublished results of stable isotopic variations in dated calcites from caves in northern England indicate the level of detail of stable isotopic variations and time resolution that can be obtained, and the complexity of interpretation that may arise. Tentative palaeoclimatic signals for the periods 90-125 ka and 170-300 ka are presented. More comprehensive studies are needed in future work, especially in view of the difficulty in obtaining suitable deposits and the ethics of cave deposits conservation.

  9. 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.

  10. 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. © 2013.

  11. 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.

  12. Study of reverse flotation of calcite from scheelite in acidic media

    NASA Astrophysics Data System (ADS)

    Deng, Rongdong; Huang, Yuqing; Hu, Yuan; Ku, Jiangang; Zuo, Weiran; Yin, Wanzhong

    2018-05-01

    A new coated-reactive reverse flotation method based on the generation of CO2 bubbles at a calcite surface in acidic solution was used to separate calcite from scheelite. The dissolution kinetics of coated and uncoated calcite were studied in sulfuric acid. The CO2 bubbles generated on the uncoated calcite particle surface are enough to float the particle. However, most of these bubbles left the surface quickly, preventing calcite from floating. Here, a mixture of polyvinyl alcohol polymer and sodium dodecyl sulfonate was used to coat the mineral particles and form a stable membrane, resulting in the formation of a stable foam layer on the calcite surface. After the calcite is coated, the generated bubbles could be successfully captured on the calcite surface, and calcite particles could float to the air-water interface and remain there for more than one hour. Flotation tests indicated that a high-quality tungsten concentrate with a grade of more than 75% and a recovery of more than 99% could be achieved when the particle size was between 0.3 and 1.5 mm. The present results provide theoretical support for the development of a highly efficient flotation separation for carbonate minerals.

  13. 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.

  14. 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.

  15. Calcite precipitates in Slovenian bottled waters.

    PubMed

    Stanič, Tamara Ferjan; Miler, Miloš; Brenčič, Mihael; Gosar, Mateja

    2017-06-01

    Storage of bottled waters in varying ambient conditions affects its characteristics. Different storage conditions cause changes in the initial chemical composition of bottled water which lead to the occurrence of precipitates with various morphologies. In order to assess the relationship between water composition, storage conditions and precipitate morphology, a study of four brands of Slovenian bottled water stored in PET bottles was carried out. Chemical analyses of the main ions and measurements of the physical properties of water samples were performed before and after storage of water samples at different ambient conditions. SEM/EDS analysis of precipitates was performed after elapsed storage time. The results show that the presence of Mg 2+ , SO 4 2- , SiO 2 , Al, Mn and other impurities such as K + , Na + , Ba and Sr in the water controlled precipitate morphology by inhibiting crystal growth and leading to elongated rhombohedral calcite crystal forms which exhibit furrowed surfaces and calcite rosettes. Different storage conditions, however, affected the number of crystallization nuclei and size of calcite crystals. Hollow calcite spheres composed of cleavage rhombohedrons formed in the water with variable storage conditions by a combination of evaporation and precipitation of water droplets during high temperatures or by the bubble templating method.

  16. Nonmonotonic variation of seawater [sup 87]Sr/[sup 86]Sr across the Ivorian/Chadian boundary (Mississippian, Osagean): Evidence from marine cements within the Irish Waulsortian Limestone

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Douthit, T.L.; Meyers, W.J.; Hanson, G.N.

    1993-05-01

    Detailed analysis of compositionally unaltered marine fibrous cements (MFC) from a single core through the Mississippian irish Waulsortian Limestone indicates that the variation of seawater [sup 87]Sr/[sup 86]Sr is nonmonotonic across the Ivorian-Chadian boundary. This nonmonotonic variation has not been recognized by previous studies. Furthermore, marine cement yielded [sup 87]Sr/[sup 86]Sr ratios lower than previously reported values for the Ivorian-Chadian (sagean). Marine fibrous cements are interpreted to be compositionally unaltered on the basis of nonluminescent character and stable isotope (C, O) composition comparable to previous estimates of Mississippian marine calcite. The isotope chemistry (C, O, Sr) and cathodoluminescent character ofmore » the marine fibrous cements therefore remained intact during their conversion from high-Mg calcite to low-Mg calcite + microdolomite, a conversion that probably took place in marine water during precipitation of Zone 1 calcite cement, the oldest non-MFC cement. High stratigraphic resolution was obtained by restricting the sample set to a single core, 429 m long, thereby eliminating chronostratigraphic correlation errors. The core is estimated to represent about 9.8 million years of Waulsortian Limestone deposition. The maximum rate of change in seawater [sup 87]Sr/[sup 86]Sr is [minus]0.00012/Ma, comparable in magnitude to Tertiary values. The authors data document the presence of fine-scale seawater [sup 87]Sr/[sup 86]Sr modulations for the Ivorian/Chadian, in contrast to the previously published monotonic seawater [sup 87]Sr/[sup 86]Sr curve for this interval, and emphasize the importance of well characterized intraformational isotopic baselines.« less

  17. 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

  18. Surface Forces Apparatus Measurements of Interactions between Rough and Reactive Calcite Surfaces.

    PubMed

    Dziadkowiec, Joanna; Javadi, Shaghayegh; Bratvold, Jon E; Nilsen, Ola; Røyne, Anja

    2018-06-26

    nm-Range forces acting between calcite surfaces in water affect macroscopic properties of carbonate rocks and calcite-based granular materials and are significantly influenced by calcite surface recrystallization. We suggest that the repulsive mechanical effects related to nm-scale surface recrystallization of calcite in water could be partially responsible for the observed decrease of cohesion in calcitic rocks saturated with water. Using the surface forces apparatus, we simultaneously followed the calcite reactivity and measured the forces in water in two surface configurations: between two rough calcite surfaces (CC) and between rough calcite and a smooth mica surface (CM). We used nm-scale rough, polycrystalline calcite films prepared by atomic layer deposition. We measured only repulsive forces in CC in CaCO 3 -saturated water, which was related to roughness and possibly to repulsive hydration effects. Adhesive or repulsive forces were measured in CM in CaCO 3 -saturated water depending on calcite roughness, and the adhesion was likely enhanced by electrostatic effects. The pull-off adhesive force in CM became stronger with time, and this increase was correlated with a decrease of roughness at contacts, the parameter which could be estimated from the measured force-distance curves. That suggested a progressive increase of real contact areas between the surfaces, caused by gradual pressure-driven deformation of calcite surface asperities during repeated loading-unloading cycles. Reactivity of calcite was affected by mass transport across nm- to μm-thick gaps between the surfaces. Major roughening was observed only for the smoothest calcite films, where gaps between two opposing surfaces were nm-thick over μm-sized areas and led to force of crystallization that could overcome confining pressures of the order of MPa. Any substantial roughening of calcite caused a significant increase of the repulsive mechanical force contribution.

  19. A Raman spectroscopic comparison of calcite and dolomite.

    PubMed

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

    2014-01-03

    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. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

    Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

  1. REE Incorporation into Calcite Individual Crystals as One Time Spike Addition

    DOE PAGES

    Gabitov, Rinat; Sadekov, Aleksey; Migdisov, Artas

    2017-10-26

    Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH 4Cl + CaCl 2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca) calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca) calcite toward the crystal edge suggests the fast depletion of (REE/Ca) fluid due to strong REEmore » consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid.« less

  2. Replacement of Calcite (CaCO 3) by Cerussite (PbCO 3)

    DOE PAGES

    Yuan, Ke; Lee, Sang Soo; De Andrade, Vincent; ...

    2016-10-21

    The mobility of toxic elements, such as lead (Pb) can be attenuated by adsorption, incorporation, and precipitation on carbonate minerals in subsurface environments. Here in this paper, we report a study of the bulk transformation of single-crystal calcite (CaCO 3) into polycrystalline cerussite (PbCO 3) through reaction with acidic Pb-bearing solutions. This reaction began with the growth of a cerussite shell on top of calcite surfaces followed by the replacement of the remaining calcite core. The external shape of the original calcite was preserved by a balance between calcite dissolution and cerussite growth controlled by adjusting the Pb 2+ concentration and pH. The relation between the rounded calcite core and the surrounding lath-shaped cerussite aggregates was imaged by transmission X-ray microscopy, which revealed preferentially elongated cerussite crystals parallel to the surface and edge directions of calcite. The replacement reaction involved concurrent development ~100 nm wide pores parallel to calcite c-glide or (1more » $$\\overline{20}$$) planes, which may have provided permeability for chemical exchange during the reaction. X-ray reflectivity measurements showed no clear epitaxial relation of cerussite to the calcite (104) surface. These results demonstrate Pb sequestration through mineral replacement reactions and the critical role of nanoporosity (3% by volume) on the solid phase transformation through a dissolution-recrystallization mechanism.« less

  3. Acidization of shales with calcite cemented fractures

    NASA Astrophysics Data System (ADS)

    Kwiatkowski, Kamil; Szymczak, Piotr; Jarosiński, Marek

    2017-04-01

    Investigation of cores drilled from shale formations reveals a relatively large number of calcite-cemented fractures. Usually such fractures are reactivated during fracking and can contribute considerably to the permeability of the resulting fracture network. However, calcite coating on their surfaces effectively excludes them from production. Dissolution of the calcite cement by acidic fluids is investigated numerically with focus on the evolution of fracture morphology. Available surface area, breakthrough time, and reactant penetration length are calculated. Natural fractures in cores from Pomeranian shale formation (northern Poland) were analyzed and classified. Representative fractures are relatively thin (0.1 mm), flat and completely sealed with calcite. Next, the morphology evolution of reactivated natural fractures treated with low-pH fluids has been simulated numerically under various operating conditions. Depth-averaged equations for fracture flow and reactant transport has been solved by finite-difference method coupled with sparse-matrix solver. Transport-limited dissolution has been considered, which corresponds to the treatment with strong acids, such as HCl. Calcite coating in reactivated natural fractures dissolves in a highly non-homogeneous manner - a positive feedback between fluid transport and calcite dissolution leads to the spontaneous formation of wormhole-like patterns, in which most of the flow is focused. The wormholes carry reactive fluids deeper inside the system, which dramatically increases the range of the treatment. Non-uniformity of the dissolution patterns provides a way of retaining the fracture permeability even in the absence of the proppant, since the less dissolved regions will act as supports to keep more dissolved regions open. Evolution of fracture morphology is shown to depend strongly on the thickness of calcite layer - the thicker the coating the more pronounced wormholes are observed. However the interaction between

  4. 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.

  5. 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.

  6. Trophic Magnification of Parabens and Their Metabolites in a Subtropical Marine Food Web.

    PubMed

    Xue, Xiaohong; Xue, Jingchuan; Liu, Wenbin; Adams, Douglas H; Kannan, Kurunthachalam

    2017-01-17

    Despite the widespread use of parabens in a range of consumer products, little is known about bioaccumulation of these chemicals in aquatic environments. In this study, six parabens and four of their common metabolites were measured in abiotic (water, sediment) and biotic (fish including sharks, invertebrates, plants) samples collected from a subtropical marine food web in coastal Florida. Methyl paraben (MeP) was found in all abiotic (100%) and a majority of biotic (87%) samples. 4-Hydroxy benzoic acid (4-HB) was the most abundant metabolite, found in 97% of biotic and all abiotic samples analyzed. The food chain accumulation of MeP and 4-HB was investigated for this food web. The trophic magnification factor (TMF) of MeP was estimated to be 1.83, which suggests considerable bioaccumulation and biomagnification of this compound in the marine food web. In contrast, a low TMF value was found for 4-HB (0.30), indicating that this compound is metabolized and excreted along the food web. This is the first study to document the widespread occurrence of parabens and their metabolites in fish, invertebrates, seagrasses, marine macroalgae, mangroves, seawater, and ocean sediments and to elucidate biomagnification potential of MeP in a marine food web.

  7. Abiotic synthesis of organic compounds from carbon disulfide under hydrothermal conditions.

    PubMed

    Rushdi, Ahmed I; Simoneit, Bernd R T

    2005-12-01

    Abiotic formation of organic compounds under hydrothermal conditions is of interest to bio, geo-, and cosmochemists. Oceanic sulfur-rich hydrothermal systems have been proposed as settings for the abiotic synthesis of organic compounds. Carbon disulfide is a common component of magmatic and hot spring gases, and is present in marine and terrestrial hydrothermal systems. Thus, its reactivity should be considered as another carbon source in addition to carbon dioxide in reductive aqueous thermosynthesis. We have examined the formation of organic compounds in aqueous solutions of carbon disulfide and oxalic acid at 175 degrees C for 5 and 72 h. The synthesis products from carbon disulfide in acidic aqueous solutions yielded a series of organic sulfur compounds. The major compounds after 5 h of reaction included dimethyl polysulfides (54.5%), methyl perthioacetate (27.6%), dimethyl trithiocarbonate (6.8%), trithianes (2.7%), hexathiepane (1.4%), trithiolanes (0.8%), and trithiacycloheptanes (0.3%). The main compounds after 72 h of reaction consisted of trithiacycloheptanes (39.4%), pentathiepane (11.6%), tetrathiocyclooctanes (11.5%), trithiolanes (10.6%), tetrathianes (4.4%), trithianes (1.2%), dimethyl trisulfide (1.1%), and numerous minor compounds. It is concluded that the abiotic formation of aliphatic straight-chain and cyclic polysulfides is possible under hydrothermal conditions and warrants further studies.

  8. 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.

  9. Production Engineering for Growth of Synthetic Calcite Polarizer Material

    DTIC Science & Technology

    1974-08-01

    AD-A008 043 PRODUCTION ENGINEERING FOR GROWTH OF SYNTHETIC CALCITE POLARIZER MATERIAL Roger F. Belt, et al Litton Systems...Production Bngin««ring for Growth of Synthetic Calcit « Polarizer Material I. RCCIPItNT’tCATALOO NUMMN i. T.vpc or ncpoMT • rtmoo covtnto Final Report...VOKOt (CanlliMit en »xift •id« II ntffrt Kid Idtnlllr br block iwmbmr) Crystal Growth Hydrothermal Growth Calcite Polarizers 30. AtSTHACT

  10. Cretaceous joints in southeastern Canada: dating calcite-filled fractures

    NASA Astrophysics Data System (ADS)

    Schneider, David; Spalding, Jennifer; Gautheron, Cécile; Sarda, Philippe; Davis, Donald; Petts, Duane

    2017-04-01

    To resolve the timing of brittle tectonism is a challenge since the classical chronometers required for analyses are not often in equilibrium with the surrounding material or simply absent. In this study, we propose to couple LA-ICP-MS U-Pb and (U-Th)/He dating with geochemical proxies in vein calcite to tackle this dilemma. We examined intracratonic Middle Ordovician limestone bedrock that overlies Mesoproterozoic crystalline basement, which are cut by NE-trending fault zones that have historic M4-5 earthquakes along their trace. E-W to NE-SW vertical joint sets, the relatively youngest stress recorded in the bedrock, possess 1-7 mm thick calcite veins that seal fractures or coat fracture surfaces. The veins possess intragranular calcite that are lined with fine-grained calcite along the vein margin and can exhibit µm- to mm-scale offset (e.g. displaced fossil fragments in host rock). Calcite d18O and d13C values are analogous to the bulk composition of Middle to Late Ordovician limestones, and suggest vein formation from a source dominated by connate fluids. The calcite contain trails of fluid inclusions commonly along fractures, and 3He/4He analyses indicate a primitive, deep fluid signature (R/Ra: 0.5-2.7). Trace element geochemistry of the calcite is highly variable, generally following the elevated HREE and lower LREE of continental crust trends but individual crystals from a single vein may vary by three orders of magnitude. LA-ICP-MS geochemical traverse across veins show elevated concentrations along (sub)grain boundaries and the vein-host rock contact. Despite abundant helium concentrations, (U-Th)/He dating was unsuccessful yielding highly dispersed dates likely from excess helium derived from the fluid inclusions. However, LA-ICP-MS U-Pb dating on calcite separated from the veins yielded model ages of 110.7 ± 6.8 Ma (MSWD: 0.53; n: 16) to 81.4 ± 8.3 Ma (MSWD: 2.6; n: 17). Since all veins are from the same ENE-trend, we regressed all the calcite dates

  11. Stratigraphic implications of trace element and strontium-isotope analyses of Kimmeridgian shell calcite from the Lower Saxony Basin, Germany

    NASA Astrophysics Data System (ADS)

    Zuo, Fanfan; Heimhofer, Ulrich; Huck, Stefan; Erbacher, Jochen; Bodin, Stephane

    2017-04-01

    Stratigraphic uncertainties due to the lack of open marine marker fossils (e.g. ammonites) hamper the precise age assignment and stratigraphic correlation of Kimmeridgian strata found in the Lower Saxony Basin of Northern Germany. Correlation of these deposits with the Jurassic standard ammonite zonation is still difficult, since the existing ostracod biostratigraphy is facies-controlled and of only limited stratigraphic precision. In this study, a chemostratigraphic approach has been chosen and biogenic shell material produced by brachiopods, oysters and lithiotids is evaluated for its reliability to act as proxy of the original Jurassic seawater strontium isotope composition. Low-Mg calcite shells have been collected from three stratigraphic sections accessible in open-cast quarries located in the Lower Saxony Basin of Northern Germany. In order to identify diagenetically altered shell calcite, trace element and stable isotope analysis of 227 calcite samples (oysters=101; brachiopods=60; Trichites=52) has been carried out. The geochemical results reveal that (1) concentration of different trace elements varies between the different groups of shell-forming organisms, which may be related to vital effects and (2) high strontium contents, low Mn and Fe contents and the lack of correlation between these elements indicate near-pristine calcite shells, and therefore shells are supposed to record the ambient sea water composition during the Late Jurassic. Strontium-isotope (87Sr/86Sr) analysis of diagenetically screened samples indicates an Early Kimmeridgian age of the studied deposits, which is in accordance with ostracod biostratigraphic data. An increasing trend in 87Sr/86Sr with stratigraphic height fits well with the global strontium-isotope curve. Besides, similar 87Sr/86Sr ratios derived from different organisms from a single stratigraphic level highlight the suitability of the shells for strontium-isotope stratigraphy. Despite the shallow-marine character of

  12. Sand-calcite crystals from Garfield County, Utah

    USGS Publications Warehouse

    Sargent, Kenneth A.; Zeller, H.D.

    1984-01-01

    Sand-calcite crystals are found in the Morrison Formation of Jurassic age in south-central Garfield County, Utah. The outcrop area is less than 1 acre, yet the locality contains many fine specimens of single, double, and complex crystals in good hexagonal form. This is the first known occurrence of sand-calcite crystals in rocks of Jurassic age and is the first reported occurrence in Utah.

  13. Ostracod calcite records the 18O/16O ratio of the bicarbonate and carbonate ions in water

    NASA Astrophysics Data System (ADS)

    Devriendt, Laurent S.; McGregor, Helen V.; Chivas, Allan R.

    2017-10-01

    The δ18O of ostracod valves is widely used to infer water δ18O and temperature. However, ostracod δ18O appears sensitive to other environmental variables. In addition, there is species-dependent ostracod calcite 18O enrichment, relative to slowly precipitated inorganic calcite under the same conditions. Together these uncertainties complicate ostracod paleoclimate reconstructions. This study presents a new understanding of the causes of ostracod δ18O variations based on a global database of published ostracod δ18O values in lake, marine and coastal environments, and from culture experiments. The database includes associated field/experiment host water parameters including temperature (-1 to 32 °C), water δ18O (-13.2‰ to 4.3‰ VSMOW), pH (6.9-10.4), salinity (0-72 g/kg), calcite saturation states (0.6-26), and dissolved inorganic carbon concentration [DIC] (0.9-54.3 mmol/kg). The data show that: (1) the δ18O of marine and non-marine ostracods reflects the 18O/16O of the sum of host water CO32- and HCO3- ions. For example, at a given temperature, the δ18O of non-marine ostracods decreases by 4‰ to 6‰ as [CO32-]/[DIC] reaches 70%, depending on the ostracod species. In low [CO32-]/[DIC] settings (i.e. high HCO3-/CO32-), ostracod 18O/16O is close to the 18O/16O of HCO3- ions, which explains why on average ostracod δ18O is higher than the δ18O of inorganic calcite precipitated slowly under the same conditions. (2) Taxonomic offsets in ostracod δ18O vary with the host water [CO32-]/[DIC]. In environments where HCO3- ≫ CO32- (i.e. most freshwater lakes), the 18O/16O of Candonids is indistinguishable from the 18O/16O of HCO3- ions (difference of 0.10 ± 0.16‰) while the 18O/16O of Cyprids is lower than the 18O/16O of HCO3- ions by -0.77‰ to -0.32‰, Cytherids by -0.88 ± 0.29‰, and Limnocytherids by -1.12 ± 0.05‰. (3) The sensitivity of ostracod δ18O to [CO32-]/[DIC] also varies with taxonomy. For each percent increase in [CO32-]/[DIC

  14. 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

  15. Modeling Remineralization of Desalinated Water by Micronized Calcite Dissolution.

    PubMed

    Hasson, David; Fine, Larissa; Sagiv, Abraham; Semiat, Raphael; Shemer, Hilla

    2017-11-07

    A widely used process for remineralization of desalinated water consists of dissolution of calcite particles by flow of acidified desalinated water through a bed packed with millimeter-size calcite particles. An alternative process consists of calcite dissolution by slurry flow of micron-size calcite particles with acidified desalinated water. The objective of this investigation is to provide theoretical models enabling design of remineralization by calcite slurry dissolution with carbonic and sulfuric acids. Extensive experimental results are presented displaying the effects of acid concentration, slurry feed concentration, and dissolution contact time. The experimental data are shown to be in agreement within less than 10% with theoretical predictions based on the simplifying assumption that the slurry consists of uniform particles represented by the surface mean diameter of the powder. Agreement between theory and experiment is improved by 1-8% by taking into account the powder size distribution. Apart from the practical value of this work in providing a hitherto lacking design tool for a novel technology. The paper has the merit of being among the very few publications providing experimental confirmation to the theory describing reaction kinetics in a segregated flow system.

  16. 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, Niel; 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).

  17. 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]).

  18. 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. Copyright © 2016 Elsevier Inc. All rights reserved.

  19. The Tonian Beck Spring Dolomite: Marine dolomitization in a shallow, anoxic sea

    NASA Astrophysics Data System (ADS)

    Shuster, Alice Mary; Wallace, Malcolm William; van Smeerdijk Hood, Ashleigh; Jiang, Ganqing

    2018-06-01

    The reason for the abundance of dolomite lithologies in Earth's early geological record compared to modern environments remains contentious. This study provides new insight into this Precambrian "dolomite problem" by revisiting one of the most controversial dolomite localities, the Beck Spring Dolomite, of Death Valley, USA. Consistent with some previous studies, petrographic evidence indicates that although the Beck Spring Dolomite now consists almost entirely of dolomite, it was originally precipitated largely as aragonite and high-Mg calcite. Depositional constituents (microbialites and ooids) were likely originally aragonitic, and early marine length-fast cements (now dolomite) are suggested to have precipitated as high-Mg calcite then replaced syntaxially by dolomite. Based on petrographic and geochemical evidence, we suggest that marine dolomitization was the dominant synsedimentary diagenetic process in the unit, and for the most part, involved syntaxial and mimetic replacement. Further, a length-slow fibrous dolomite generation was precipitated during the later stages of marine diagenesis as a primary marine dolomite cement. This is indicated by the length-slow crystallographic structure of the cement and from its preserved geochemical and cathodoluminescence growth zonation. This new evidence for Tonian marine dolomite precipitation reinforces the idea of Precambrian marine environmental conditions, including the chemical composition of seawater, promoting dolomite formation at this time. The trace metal geochemical composition of well-preserved marine components, especially dolomite marine cements, reveals information about redox conditions in this Tonian shallow seawater. In terms of rare earth element geochemistry, the Beck Spring Dolomite has no significant Ce anomaly, and a ubiquitous positive Eu anomaly, consistent with widespread oceanic anoxia during deposition. Furthermore, the relatively low levels of iron and chalcophile elements Co, Cu, Pb and

  20. Catalysis and chemical mechanisms of calcite dissolution in seawater.

    PubMed

    Subhas, Adam V; Adkins, Jess F; Rollins, Nick E; Naviaux, John; Erez, Jonathan; Berelson, William M

    2017-07-18

    Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric [Formula: see text] on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13 C-labeled calcites in natural seawater. We show that the time-evolving enrichment of [Formula: see text] in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13 C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution-precipitation shifts significantly toward a dissolution-dominated mechanism below about [Formula: see text] Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of [Formula: see text] is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid-solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at [Formula: see text], which we interpret as the onset of homogeneous etch pit nucleation.

  1. Environmental variables and definitive host distribution: a habitat suitability modelling for endohelminth parasites in the marine realm

    PubMed Central

    Kuhn, Thomas; Cunze, Sarah; Kochmann, Judith; Klimpel, Sven

    2016-01-01

    Marine nematodes of the genus Anisakis are common parasites of a wide range of aquatic organisms. Public interest is primarily based on their importance as zoonotic agents of the human Anisakiasis, a severe infection of the gastro-intestinal tract as result of consuming live larvae in insufficiently cooked fish dishes. The diverse nature of external impacts unequally influencing larval and adult stages of marine endohelminth parasites requires the consideration of both abiotic and biotic factors. Whereas abiotic factors are generally more relevant for early life stages and might also be linked to intermediate hosts, definitive hosts are indispensable for a parasite’s reproduction. In order to better understand the uneven occurrence of parasites in fish species, we here use the maximum entropy approach (Maxent) to model the habitat suitability for nine Anisakis species accounting for abiotic parameters as well as biotic data (definitive hosts). The modelled habitat suitability reflects the observed distribution quite well for all Anisakis species, however, in some cases, habitat suitability exceeded the known geographical distribution, suggesting a wider distribution than presently recorded. We suggest that integrative modelling combining abiotic and biotic parameters is a valid approach for habitat suitability assessments of Anisakis, and potentially other marine parasite species. PMID:27507328

  2. Environmental variables and definitive host distribution: a habitat suitability modelling for endohelminth parasites in the marine realm

    NASA Astrophysics Data System (ADS)

    Kuhn, Thomas; Cunze, Sarah; Kochmann, Judith; Klimpel, Sven

    2016-08-01

    Marine nematodes of the genus Anisakis are common parasites of a wide range of aquatic organisms. Public interest is primarily based on their importance as zoonotic agents of the human Anisakiasis, a severe infection of the gastro-intestinal tract as result of consuming live larvae in insufficiently cooked fish dishes. The diverse nature of external impacts unequally influencing larval and adult stages of marine endohelminth parasites requires the consideration of both abiotic and biotic factors. Whereas abiotic factors are generally more relevant for early life stages and might also be linked to intermediate hosts, definitive hosts are indispensable for a parasite’s reproduction. In order to better understand the uneven occurrence of parasites in fish species, we here use the maximum entropy approach (Maxent) to model the habitat suitability for nine Anisakis species accounting for abiotic parameters as well as biotic data (definitive hosts). The modelled habitat suitability reflects the observed distribution quite well for all Anisakis species, however, in some cases, habitat suitability exceeded the known geographical distribution, suggesting a wider distribution than presently recorded. We suggest that integrative modelling combining abiotic and biotic parameters is a valid approach for habitat suitability assessments of Anisakis, and potentially other marine parasite species.

  3. Catalysis and chemical mechanisms of calcite dissolution in seawater

    PubMed Central

    Adkins, Jess F.; Rollins, Nick E.; Naviaux, John; Erez, Jonathan; Berelson, William M.

    2017-01-01

    Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric CO2 on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13C-labeled calcites in natural seawater. We show that the time-evolving enrichment of 𝜹13C in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution–precipitation shifts significantly toward a dissolution-dominated mechanism below about Ω= 0.7. Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of CO2 is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid–solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at Ω= 0.7, which we interpret as the onset of homogeneous etch pit nucleation. PMID:28720698

  4. Effect of molding pressure on fabrication of low-crystalline calcite block.

    PubMed

    Lin, Xin; Matsuya, Shigeki; Nakagawa, Masaharu; Terada, Yoshihiro; Ishikawa, Kunio

    2008-02-01

    We have reported that low-crystalline porous calcite block, which is useful as a bone substitute or a source material to prepare apatite-type bone fillers could be fabricated by exposing calcium hydroxide compact to carbon dioxide gas saturated with water vapor. In the present study, we investigated the effect of molding pressure on the transformation of calcium hydroxide into calcite and the mechanical strength of the carbonated compact. Transformation into calcite was almost completed within 72 h, however, a small amount of Ca(OH)(2) still remained unreacted at higher molding pressure because of incomplete penetration of CO(2) gas into the interparticle space due to dense packing of Ca(OH)(2) particles. On the other hand, high molding pressure resulted in an increase in diametral tensile strength (DTS) of the calcite compact formed. Critical porosity of the calcite block was calculated as approximately 68%.

  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. Influence of solution chemistry on the boron content in inorganic calcite grown in artificial seawater

    NASA Astrophysics Data System (ADS)

    Uchikawa, Joji; Harper, Dustin T.; Penman, Donald E.; Zachos, James C.; Zeebe, Richard E.

    2017-12-01

    The ratio of boron to calcium (B/Ca) in marine biogenic carbonates has been proposed as a proxy for properties of seawater carbonate chemistry. Applying this proxy to planktic foraminifera residing in the surface seawater largely in equilibrium with the atmosphere may provide a valuable handle on past atmospheric CO2 concentrations. However, precise controls on B/Ca in planktic foraminifera remain enigmatic because it has been shown to depend on multiple physicochemical seawater properties. To help establish a firm inorganic basis for interpreting the B/Ca records, we examined the effect of a suite of chemical parameters ([Ca2+], pH, [DIC], salinity and [PO43-]) on B/Ca in inorganic calcite precipitated in artificial seawater. These parameters were primarily varied individually while keeping all others constant, but we also tested the influence of pH and [DIC] at a constant calcite precipitation rate (R) by concurrent [Ca2+] adjustments. In the simple [Ca2+], pH and [DIC] experiments, both R and B/Ca increased with these parameters. In the pH-[Ca2+] and [DIC]-[Ca2+] experiments at constant R, on the other hand, B/Ca was invariant at different pH and decreased with [DIC], respectively. These patterns agree with the behavior of solution [BTotal/DIC] ratio such that, at a fixed [BTotal], it is independent of pH but decreases with [DIC]. Based on these results, R and [BTotal/DIC] ratio appear to be the primary controls on B/Ca in inorganic calcite, suggesting that both B(OH)4- and B(OH)3 are possibly involved in B incorporation. Moreover, B/Ca modestly increased with salinity and [PO43-]. Inorganic calcite precipitated at higher R and in the presence of oxyanions such as SO42- and PO43- in growth solutions often undergoes surface roughening due to formation of crystallographic defects, vacancies and, occasionally, amorphous/hydrous CaCO3. These non-lattice sites may provide additional space for B, particularly B(OH)3. Consequently, besides the macroscopic influence of

  7. Origin of cone-in-cone calcite veins during calcitization of dolomites and their subsequent diagenesis: A case study from the Gogolin Formation (Middle Triassic), SW Poland

    NASA Astrophysics Data System (ADS)

    Kowal-Linka, Monika

    2010-03-01

    Although bedding-parallel cone-in-cone structure calcite veins are present in the Middle Triassic Gogolin Formation in Opole Silesia, their occurrence is limited to the Emilówka Cellular Limestone Member. Marly limestones (dedolomites) consisting of calcite pseudospar are the host rocks. The veins, which are up to 3 mm high and 30 cm long, are built of densely packed cone columns, with individual cones up to 0.7 mm high and 0.6 mm wide at their bases, and with vertex angle values ranging from 30° to 50°. The cones are microfractured, and the adjacent cones are vertically shifted in oblique planes. The exceptionally small veins consist of calcite fibres up to 0.15 mm high. The veins are built of low-magnesium and non-ferroan calcite, characterized by low δ 18O values ranging from - 6.8‰ to - 7.4‰, and low δ 13C values ranging from - 2.9‰ to - 4.5‰ vs. PDB. These isotopic values are similar to those obtained from the host rocks (δ 18O from - 6.8‰ to - 7.4‰, and δ 13C from - 3.2‰ to - 3.6‰ vs. PDB) and they are strongly depleted in comparison with the isotopic values of other carbonate particles from the Gogolin Formation. The veins only formed in one lithostratigraphic member, suggesting that their origin is related to processes which acted only locally. There are two unique processes that the Emilówka Cellular Limestone Member alone in the Gogolin Formation underwent: early diagenetic evaporitic dolomitization of lime mud in the sabkha environment, and subsequent calcitization of dolomite. Dolomitization led to sediment cohesion loss, porosity increase and initial horizontal laminae separation as a result of the transformation of calcium carbonate to dolomite within anisotropic deposits. Similar values of geochemical parameters obtained from the vein calcite and the host rock calcite are evidence that vein-filling precipitation was contemporary with dedolomitization. Geochemical data combined with sedimentological research and burial history

  8. 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

  9. 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.

  10. Regulation of calcite crystal morphology by intracrystalline acidic proteins and glycoproteins.

    PubMed

    Albeck, S; Addadi, I; Weiner, S

    1996-01-01

    Many biologically formed calcite crystals contain intracrystalline macromolecules. The ways in which they interact with growing calcite crystals were evaluated by monitoring changes in the morphology of calcite crystals grown in vitro in their presence. Macromolecules were extracted from within isolated prisms from the prismatic layer of the shell of the mollusk Atrina rigida and from spines of the sea urchin Paracentrotus lividus. Two modes of interaction were identified; the interaction of highly acidic proteins with calcite planes perpendicular to the c crystallographic axis and the interaction of glycoproteins with planes roughly parallel to the c axis. By different preparative procedures we demonstrated that the polysaccharide moieties of the sea urchin spine glycoproteins are directly involved in the latter mode of interactions. We suggest that organisms utilize the abilities of these macromolecules to interact in different ways with calcite crystals, and in so doing fine-tune aspects of the control of crystal growth in vivo.

  11. 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

  12. Iodine Incorporation in Calcite: Insights from Computational and Experimental Study

    NASA Astrophysics Data System (ADS)

    Feng, X.; Redfern, S. A. T.

    2016-12-01

    The incorporation of iodine into calcite is important both in the context of radioactive waste disposal (carbonates seem to be the principal host for iodine at the Hnaford site) as well as in paleoproxy methods applied in paleo-oceanography, where iodine content has been proposed as a proxy for fO2. Here, we report on studies of iodine incorporation into calcite carried out by a combination of earlier X-Ray absorption spectroscopy, Raman spectroscopy, X-Ray diffraction and new ab initio DFT calculations (using VASP). Our results show that iodine is principally incorporated into the calcite lattice as IO3, replacing carbon in the carbonate group. The much larger size of iodine, and different outer shell electronic configuration, leads to a distortion of the calcite structure locally. Our DFT results show that the adjacent layers of CO3 groups are significantly distorted, over a length scale of around 0.5 nm, and that this distortion leads to a slight increase in enthalpy associated with the iodine point defect. The relationship to the distorted structure of calcite II is considered, and the role of iodine as an agent of "internal pressure" will be discussed.

  13. Abiotic degradation of hexahydro-l,3,5-trinitro-1,3,5-triazine in the presence of hydrogen sulfide and black carbon.

    PubMed

    Kemper, Jerome M; Ammar, Emaan; Mitch, William A

    2008-03-15

    We report that hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) was rapidly destroyed by sulfides in the presence of black carbon, forming nitrite and formaldehyde, rather than toxic nitrosated reduction products. Although traditionally viewed as inactive sorbents, black carbons have been noted to participate in the destruction of certain contaminants, such as azo dyes, via quinonoid groups. However, in our experiments sulfide modification of quinones did not seem to be involved. Although at least 1.2 mM sulfides were needed for the reaction to proceed, abiotic natural attenuation of RDX in marine sediments may occur, because these concentrations are found in certain marine sediments, together with black carbon. In the absence of natural black carbons, synthetic black carbons, such as activated carbon, may be added to sediments. As compared with other in situ techniques, such as bioremediation and zero-valent iron cutoff trenches, which often generate nitrosated byproducts, this in situ, abiotic technique may be an attractive alternative.

  14. 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

  15. Incorporation of Metals into Calcite in a Deep Anoxic Granite Aquifer.

    PubMed

    Drake, Henrik; Mathurin, Frédéric A; Zack, Thomas; Schäfer, Thorsten; Roberts, Nick Mw; Whitehouse, Martin; Karlsson, Andreas; Broman, Curt; Åström, Mats E

    2018-01-16

    Understanding metal scavenging by calcite in deep aquifers in granite is of importance for deciphering and modeling hydrochemical fluctuations and water-rock interaction in the upper crust and for retention mechanisms associated with underground repositories for toxic wastes. Metal scavenging into calcite has generally been established in the laboratory or in natural environments that cannot be unreservedly applied to conditions in deep crystalline rocks, an environment of broad interest for nuclear waste repositories. Here, we report a microanalytical study of calcite precipitated over a period of 17 years from anoxic, low-temperature (14 °C), neutral (pH: 7.4-7.7), and brackish (Cl: 1700-7100 mg/L) groundwater flowing in fractures at >400 m depth in granite rock. This enabled assessment of the trace metal uptake by calcite under these deep-seated conditions. Aquatic speciation modeling was carried out to assess influence of metal complexation on the partitioning into calcite. The resulting environment-specific partition coefficients were for several divalent ions in line with values obtained in controlled laboratory experiments, whereas for several other ions they differed substantially. High absolute uptake of rare earth elements and U(IV) suggests that coprecipitation into calcite can be an important sink for these metals and analogousactinides in the vicinity of geological repositories.

  16. Isotope compositions of C and O of magmatic calcites from the Udachnaya-East pipe kimberlite, Yakutia

    NASA Astrophysics Data System (ADS)

    Tomilenko, A. A.; Dublyansky, Yu. V.; Kuzmin, D. V.; Sobolev, N. V.

    2017-07-01

    It has been demonstrated for the first time that the isotopic compositions of carbon (δ13C) in magmatic calcites from the Udachnaya-East pipe kimberlite groundmass varies from-2.5 to-1.0‰ (V-PDB), while those of oxygen (δ18O) range from 15.0 to 18.2‰ (V-SMOW). The obtained results imply that during the terminal late magmatic and postmagmatic stages of the kimberlite pipe formation, the carbonates in the kimberlite groundmass became successively heavier isotopically, which indicates the hybrid nature of the carbonate component of the kimberlite: it was formed with contributions from mantle and sedimentary marine sources.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  18. 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

  19. Investigating calcite growth rates using a quartz crystal microbalance with dissipation (QCM-D)

    NASA Astrophysics Data System (ADS)

    Cao, Bo; Stack, Andrew G.; Steefel, Carl I.; DePaolo, Donald J.; Lammers, Laura N.; Hu, Yandi

    2018-02-01

    Calcite precipitation plays a significant role in processes such as geological carbon sequestration and toxic metal sequestration and, yet, the rates and mechanisms of calcite growth under close to equilibrium conditions are far from well understood. In this study, a quartz crystal microbalance with dissipation (QCM-D) was used for the first time to measure macroscopic calcite growth rates. Calcite seed crystals were first nucleated and grown on sensors, then growth rates of calcite seed crystals were measured in real-time under close to equilibrium conditions (saturation index, SI = log ({Ca2+}/{CO32-}/Ksp) = 0.01-0.7, where {i} represent ion activities and Ksp = 10-8.48 is the calcite thermodynamic solubility constant). At the end of the experiments, total masses of calcite crystals on sensors measured by QCM-D and inductively coupled plasma mass spectrometry (ICP-MS) were consistent, validating the QCM-D measurements. Calcite growth rates measured by QCM-D were compared with reported macroscopic growth rates measured with auto-titration, ICP-MS, and microbalance. Calcite growth rates measured by QCM-D were also compared with microscopic growth rates measured by atomic force microscopy (AFM) and with rates predicted by two process-based crystal growth models. The discrepancies in growth rates among AFM measurements and model predictions appear to mainly arise from differences in step densities, and the step velocities were consistent among the AFM measurements as well as with both model predictions. Using the predicted steady-state step velocity and the measured step densities, both models predict well the growth rates measured using QCM-D and AFM. This study provides valuable insights into the effects of reactive site densities on calcite growth rate, which may help design future growth models to predict transient-state step densities.

  20. Mechanism of calcite co-orientation in the sea urchin tooth.

    PubMed

    Killian, Christopher E; Metzler, Rebecca A; Gong, Y U T; Olson, Ian C; Aizenberg, Joanna; Politi, Yael; Wilt, Fred H; Scholl, Andreas; Young, Anthony; Doran, Andrew; Kunz, Martin; Tamura, Nobumichi; Coppersmith, Susan N; Gilbert, P U P A

    2009-12-30

    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(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 (muXRD). 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(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.

  1. 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

  2. Post-deformational relocation of mica grains in calcite-dolomite marbles identified by cathodoluminescence microscopy

    NASA Astrophysics Data System (ADS)

    Kuehn, Rebecca; Duschl, Florian; Leiss, Bernd

    2017-04-01

    Hot-cathodoluminescence-microscopy (CL) reveals micas which are rotated or shifted within a calcite fabric from a foliation parallel to a random orientation. This feature has been recognized in calcite-dolomite marble samples from the locations Hammerunterwiesenthal, Erzgebirge, Germany and the Alpi Apuane, Italy. As obtained from petrographic thin section analysis, the micas either moved totally within a single calcite grain or from a grain boundary position, and then the calcite grain growth was dragged with the movement of the mica grain. In the moved-through grain, features like fluid-inclusions, twins or cleavage faces are erased and a new, clear calcite phase developed. This indicates dissolution-precipitation as process which led to the new calcite phase. As former deformation features are erased it can be assumed that the mica relocation is a fluid-driven, post-deformational equilibration process. In CL the new calcite mineral phase shows a zonation indicating a polycyclic process. Calcite CL gradually changes from a very dark purple, exactly as the surrounding grains, to a bright orange CL and supports the idea of fluid-induced deformation relocation. We suppose a specific lattice relationship between mica and calcite as initial driving factor for mica relocation. This recrystallization mechanism is probably supported by fluids - either from an external source or developed during retrograde metamorphosis fluid inclusion studies shall identify formation temperatures and origin of involved fluids and thereby clarify the timing of the post-deformational mica rotation. EBSD analysis of involved calcite and mica grains shall reveal a possible systematic relationship between the orientation of the hosting grains, the orientation of the mica and the final position of the mica. It will be interesting to learn in the future, if this kind of calcite-mica microstructure is a general phenomenon and how it can contribute to the understanding of fabric development.

  3. 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.

  4. 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

  5. Benthic marine calcifiers coexist with CaCO3-undersaturated seawater worldwide

    NASA Astrophysics Data System (ADS)

    Lebrato, M.; Andersson, A. J.; Ries, J. B.; Aronson, R. B.; Lamare, M. D.; Koeve, W.; Oschlies, A.; Iglesias-Rodriguez, M. D.; Thatje, S.; Amsler, M.; Vos, S. C.; Jones, D. O. B.; Ruhl, H. A.; Gates, A. R.; McClintock, J. B.

    2016-07-01

    Ocean acidification and decreasing seawater saturation state with respect to calcium carbonate (CaCO3) minerals have raised concerns about the consequences to marine organisms that build CaCO3 structures. A large proportion of benthic marine calcifiers incorporate Mg2+ into their skeletons (Mg-calcite), which, in general, reduces mineral stability. The relative vulnerability of some marine calcifiers to ocean acidification appears linked to the relative solubility of their shell or skeletal mineralogy, although some organisms have sophisticated mechanisms for constructing and maintaining their CaCO3 structures causing deviation from this dependence. Nevertheless, few studies consider seawater saturation state with respect to the actual Mg-calcite mineralogy (ΩMg-x) of a species when evaluating the effect of ocean acidification on that species. Here, a global dataset of skeletal mole % MgCO3 of benthic calcifiers and in situ environmental conditions spanning a depth range of 0 m (subtidal/neritic) to 5600 m (abyssal) was assembled to calculate in situ ΩMg-x. This analysis shows that 24% of the studied benthic calcifiers currently experience seawater mineral undersaturation (ΩMg-x < 1). As a result of ongoing anthropogenic ocean acidification over the next 200 to 3000 years, the predicted decrease in seawater mineral saturation will expose approximately 57% of all studied benthic calcifying species to seawater undersaturation. These observations reveal a surprisingly high proportion of benthic marine calcifiers exposed to seawater that is undersaturated with respect to their skeletal mineralogy, underscoring the importance of using species-specific seawater mineral saturation states when investigating the impact of CO2-induced ocean acidification on benthic marine calcification.

  6. Abiotic Organic Chemistry in Hydrothermal Systems.

    NASA Astrophysics Data System (ADS)

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

    2004-12-01

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

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

    USGS Publications Warehouse

    Busenberg, Eurybiades; Plummer, 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

  8. 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

  9. In-situ growth of calcite at Devils Hole, Nevada: Comparison of field and laboratory rates to a 500,000 year record of near-equilibrium calcite growth

    USGS Publications Warehouse

    Plummer, Niel; Busenberg, E.; Riggs, A.C.

    2000-01-01

    Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7??C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34??C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of P(CO)(2), decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.

  10. In-situ growth of calcite at Devils Hole, Nevada--Comparison of field and laboratory rates to a 500,000 year record of near-equilibrium calcite growth

    USGS Publications Warehouse

    Plummer, Niel; Busenberg, Eurybiades; Riggs, Alan C.

    2000-01-01

    Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7 °C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34 °C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of PCO2, decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.

  11. Raman spectroscopic study of calcite III to aragonite transformation under high pressure and high temperature

    NASA Astrophysics Data System (ADS)

    Liu, Chuanjiang; Zheng, Haifei; Wang, Duojun

    2017-10-01

    In our study, a series of Raman experiments on the phase transition of calcite at high pressure and high temperature were investigated using a hydrothermal diamond anvil cell and Raman spectroscopy technique. It was found that calcite I transformed to calcite II and calcite III at pressures of 1.62 and 2.12 GPa and room temperature. With increasing temperature, the phase transition of calcite III to aragonite occurred. Aragonite was retained upon slowly cooling of the system, indicating that the transition of calcite III to aragonite was irreversible. Based on the available data, the phase boundary between calcite III and aragonite was determined by the following relation: P(GPa) = 0.013 × T(°C) + 1.22 (100°C ≤ T ≤ 170°C). It showed that the transition pressure linearly rose with increasing temperature. A better understanding of the stability of calcite III and aragonite is of great importance to further explore the thermodynamic behavior of carbonates and carbon cycling in the mantle.

  12. 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. Copyright © 2012 Elsevier Inc. All rights reserved.

  13. Post-extension shortening strains preserved in calcites of the Keweenawan rift

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Donnelly, K.; Craddock, J.; McGovern, M.

    1993-02-01

    The Keweenawan rift is part of failed triple junction system that underlies Lake Superior and the Michigan Basin. The rift experienced extensional stresses dating about 1.1 Ga, which were followed by compressional stresses from about 1,060 Ma to < 350 Ma. Associated with the rift are two thrust faults: the Douglas (dipping southeast) and the Keweenawan-Lake Owen (dipping northwest). To determine the direction of rifting, calcite twins were used to calculate strain ellipsoids (Groshong method) which are indicative of the intensity and direction of the stress applied to a rocks in a region at a given time. Rock samples whichmore » contain significant calcite within the zone of rifting were collected, slabbed, and made into thin sections. Calcite appears as amygdule, vein, and cement filings, as well as limestones. Analyses show that different calcite types show different stain orientations. Two principle directions of sub-horizontal shortening are present: one parallel to rift, and one normal to the rift, indicating that rifting motion varied out the time in which different calcite types were deposited. Shortening parallel to the rift is seen predominantly on the western margin while shortening normal to the rift is seen predominantly on the eastern margin.« less

  14. Site-specific incorporation of uranyl carbonate species at the calcite surface

    NASA Astrophysics Data System (ADS)

    Reeder, Richard J.; Elzinga, Evert J.; Tait, C. Drew; Rector, K. D.; Donohoe, Robert J.; Morris, David E.

    2004-12-01

    Spatially resolved luminescence spectra from U(VI) co-precipitated at the (101¯4) growth surface of synthetic calcite single crystals confirm heterogeneous incorporation corresponding to the distribution of structurally non-equivalent steps composing the vicinal surfaces of spiral growth hillocks. Spectral structure from U(VI) luminescence at the "-" vicinal regions and featureless, weak luminescence at the "+" vicinal regions are consistent with previously reported observations of enrichment at the former sites during calcite growth. Luminescence spectra differ between the non-equivalent regions of the crystal, with the spectral features from the "-" vicinal region corresponding to those observed in bulk calcite samples. Subtle spectral shifts are observed from U(VI) co-precipitated with microcrystalline calcite synthesized by a different method, and all of the U(VI)-calcite sample spectra differ significantly from that of U(VI) co-precipitated with aragonite. The step-selective incorporation of U(VI) can be explained by a proposed model in which the allowed orientation for adsorption of the dominant calcium uranyl triscarbonate species is controlled by the atomic arrangement at step edges. Differences in the tilt angles of carbonate groups between non-equivalent growth steps favor adsorption of the calcium uranyl triscarbonate species at "-" steps, as observed in experiments.

  15. 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

  16. Rheology and microstructure of synthetic halite/calcite porphyritic aggregates in torsion

    NASA Astrophysics Data System (ADS)

    Marques, F. O.; Burlini, L.; Burg, J.-P.

    2010-03-01

    Polymer jacketed porphyritic samples of 70% halite + 30% coarse calcite were subjected to torsion deformation to investigate the effects of a mixture of coarse calcite on the microstructure and mechanical properties of a two-phase aggregate. The experiments were run at 100 and 200 °C, a confining pressure of 250 MPa, and a constant shear strain rate of 3E-4 s -1. Ultimate strengths of single-phase halite synthetic aggregates at 100 and 200 °C were ca. 32 and 8 Nm, respectively, and of the two-phase aggregate 39 and 18 Nm, respectively; this shows that the two-phase aggregate was much stronger, especially at 200 °C. Stepping strain rate tests show that the two-phase aggregate behaved as power-law viscous, with stress exponents of ca. 19 and 13 at 100 °C at 200 °C, respectively. From these high exponents, we infer that the active deformation mechanisms were not efficient enough to rapidly relax the applied stress. Halite stress exponents at 100 and 200 °C are typically much lower, in the order of 4-6, which means that the calcite porphyroclasts were obstacles to halite plastic flow and hampered stress relaxation. The drop of the stress exponent with temperature indicates that the main deformation mechanism(s) was temperature sensitive. Matrix halite deformed plastically, while calcite rotated rigidly or deformed in a brittle fashion, with grain size reduction by fracturing (e.g. bookshelf and boudinage). We conclude that halite was softer than calcite in the investigated temperature range. Strain was homogeneous at the sample scale but not at the grain scale where the foliation delineated by plastically flattened halite contoured the rigid calcite clasts. The microstructures experimentally produced at 100 and 200 °C are very similar and find their counterparts in natural mylonites: rolling structures, σ and δ porphyroclast systems, bookshelf and boudinage in brittle calcite porphyroclasts, and ductile y and c' micro shear bands in the halite matrix.

  17. 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.

  18. 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.

  19. Manganese-calcium intermixing facilitates heteroepitaxial growth at the (1014) calcite-water interface

    DOE PAGES

    Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.; ...

    2017-09-05

    For this research, in situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10more » $$\\bar{1}$$4) surface of calcite (CaCO 3) single crystals following reaction with Mn2 +-bearing aqueous solutions. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces. In situ time-sequenced measurements demonstrated that the growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2 +-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO 3) and calcite display a 10% lattice mismatch, based on the area of their (10$$\\bar{1}$$4) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO 3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals in calcite-equilibrated aqueous solutions with up to 250 μM MnCl 2. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO 3 solid solution. The epitaxial solid solution had a spatially complex composition, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO 3 for the thickest coatings. The effective lattice mismatch was therefore much smaller than the nominal mismatch thus explaining the measured growth rates. Lastly, these findings highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

  20. Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations

    PubMed Central

    2018-01-01

    The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution. PMID:29614776

  1. Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations.

    PubMed

    Wetzel, Maria; Kempka, Thomas; Kühn, Michael

    2018-04-01

    The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution.

  2. 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.

  3. SIMS analyses of minor and trace element distributions in fracture calcite from Yucca Mountain, Nevada, USA

    NASA Astrophysics Data System (ADS)

    Denniston, Rhawn F.; Shearer, Charles K.; Layne, Graham D.; Vaniman, David T.

    1997-05-01

    Fracture-lining calcite samples from Yucca Mountain, Nevada, obtained as part of the extensive vertical sampling in studies of this site as a potential high-level waste repository, have been characterized according to microbeam-scale (25-30 μm) trace and minor element chemistry, and cathodoluminescent zonation patterns. As bulk chemical analyses are limited in spatial resolution and are subject to contamination by intergrown phases, a technique for analysis by secondary ion mass spectrometry (SIMS) of minor (Mn, Fe, Sr) and trace (REE) elements in calcite was developed and applied to eighteen calcite samples from four boreholes and one trench. SIMS analyses of REE in calcite and dolomite have been shown to be quantitative to abundances < 1 × chondrite. Although the low secondary ion yields associated with carbonates forced higher counting times than is necessary in most silicates, Mn, Fe, Sr, and REE analyses were obtained with sub-ppm detection limits and 2-15% analytical precision. Bulk chemical signatures noted by Vaniman (1994) allowed correlation of minor and trace element signatures in Yucca Mountain calcite with location of calcite precipitation (saturated vs. unsaturated zone). For example, upper unsaturated zone calcite exhibits pronounced negative Ce and Eu anomalies not observed in calcite collected below in the deep unsaturated zone. These chemical distinctions served as fingerprints which were applied to growth zones in order to examine temporal changes in calcite crystallization histories; analyses of such fine-scale zonal variations are unattainable using bulk analytical techniques. In addition, LREE (particularly Ce) scavenging of calcite-precipitating solutions by manganese oxide phases is discussed as the mechanism for Ce-depletion in unsaturated zone calcite.

  4. Fabrication of porous low crystalline calcite block by carbonation of calcium hydroxide compact.

    PubMed

    Matsuya, Shigeki; Lin, Xin; Udoh, Koh-ichi; Nakagawa, Masaharu; Shimogoryo, Ryoji; Terada, Yoshihiro; Ishikawa, Kunio

    2007-07-01

    Calcium carbonate (CaCO(3)) has been widely used as a bone substitute material because of its excellent tissue response and good resorbability. In this experimental study, we propose a new method obtaining porous CaCO(3) monolith for an artificial bone substitute. In the method, calcium hydroxide compacts were exposed to carbon dioxide saturated with water vapor at room temperature. Carbonation completed within 3 days and calcite was the only product. The mechanical strength of CaCO(3) monolith increased with carbonation period and molding pressure. Development of mechanical strength proceeded through two steps; the first rapid increase by bonding with calcite layer formed at the surface of calcium hydroxide particles and the latter increase by the full conversion of calcium hydroxide to calcite. The latter process was thought to be controlled by the diffusion of CO(2) through micropores in the surface calcite layer. Porosity of calcite blocks thus prepared had 36.8-48.1% depending on molding pressure between 1 MPa and 5 MPa. We concluded that the present method may be useful for the preparation of bone substitutes or the preparation of source material for bone substitutes since this method succeeded in fabricating a low-crystalline, and thus a highly reactive, porous calcite block.

  5. The K-PG boundary: how geological events lead to collapse of marine primary producers

    NASA Astrophysics Data System (ADS)

    Hir guillaume, Le; frederic, Fluteau; yves, Goddéris

    2017-04-01

    The cause(s) of Cretaceous/Paleogene (K-Pg) mass extinction event is a matter of debate since three decades. A first scenario connects the K-Pg crisis with the Chicxulub impact while the second scenario evokes the emplacement of the Deccan traps in India as the cause for the K-Pg biodiversity collapse. Pierazzo et al. (1998) estimated that the extraterrestrial bolide lead to an instantaneously CO2 degassing ranging from 880 Gt to 2,960 Gt into the atmosphere, together with a massive release of SO2 ranging from 150 to 460 Gt.. Self et al. (2006, 2008) and Chenet et al. (2009) suggested that the emplacement of the Deccan traps released 15,000 Gt to 35,000 Gt of CO2 and 6,800 Gt to 17,000 Gt of SO2 over a 250 kyr-long period (Schoene et al., 2015). To decipher and quantify the long term environmental consequences of both events, we tested different scenarios: a pulse-like magmatic degassing, a bolide impact, and a combination of both. To understand the environmental changes and quantify biodiversity responses, we improve GEOCLIM, a coupled climate-carbon numerical model, by implementing a biodiversity model in which marine species are described by specific death/born rates, sensitivity to abiotic factors (temperature, pH, dissolved O2, calcite saturation state) and feeding relationships, each of these characteristics is assigned randomly. Preliminary simulations accounting for the eruption of the Deccan traps show that successive cooling events (S-aerosols effect) combined with a progressive acidification of surface water (caused by CO2 and SO2 injections) cause a major collapse of the marine biomass. Additional simulations in which Chicxulub impact, different community structures of primary producers will be discussed.

  6. An Investigation of Possible Ways to Enhance the Deposition of Calcite-Type Coatings

    DTIC Science & Technology

    1984-01-01

    AN INVESTIGATION OF POSSIBLE WAYS TO ENHANCE THE DEPOSITION OF CALCITE -TYPE COATINGS JANUARY 1984 Prepared by: OCEAN CITY RESEARCH CORP. in...Enhance The Deposition of Calcite -Type Coatings 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e...City, New Jersey under the direction of Mr. The research study continued of applying calcite -type coatings George A. Gehring, Jr. an to investigation

  7. Uranium in foraminiferal calcite as a recorder of seawater uranium concentrations

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Russell, A.D.; Emerson, S.; Nelson, B.K.

    The authors present results of an investigation of uranium/calcium ratios in cleaned foraminiferal calcite as a recorder of seawater uranium concentrations. For accurate reconstruction of past seawater uranium content, shell calcite must incorporate uranium in proportion to seawater concentration and must preserve its original uranium composition over time. Laboratory culture experiments with live benthic (Amphistegina lobifera) and live planktonic (Globigerinell calida) foraminifera show that the U/Ca ratio of cleaned calcite tests is proportional to the concentration of uranium in solution. After correcting results for the presence of initial calcite, the apparent distribution coefficient D = (U/Ca[sub calcite])/(U/Ca)[sub solution] = 10.6more » [+-] 0.3 (x10[sup [minus]3]) for A. lobifera and D = 7.9 [+-] 0.1 (x10[sup [minus]3]) for G. calida. U/Ca ratios in planktonic foraminifera from core tops collected above 3900 m in the equatorial Atlantic and above 2100 m in the Pacific Ocean show no significant difference among the species analyzed. D estimated form core top samples ranges from 7.6 [+-] 0.4 (x10[sup [minus]3]) for O. universa to 8.4 [+-] 0.5 (x10[sup [minus]3]) for G. ruber. In benthic species C. wuellerstorfi, D = 7.0 [+-] 0.8 (x10[sup [minus]3]). U/Ca and Mg/Ca in G. tumida and G. sacculifer from core tops taken near and below the regional lysocline decrease with water depth. Smaller decreases in U/Ca and Mg/Ca with depth were observed in C. wuellerstorfi. In the planktonic species, the authors believe that U/CA and Mg/Ca are lower in the more dissolution-resistant fraction of calcite, leading to lower U/Ca in more highly dissolved samples.« less

  8. Calcification response of Pleurochrysis carterae to iron concentrations in batch incubations: implication for the marine biogeochemical cycle

    NASA Astrophysics Data System (ADS)

    Zou, Xiang; Sun, Shiyong; Lin, Sen; Shen, Kexuan; Dong, Faqin; Tan, Daoyong; Nie, Xiaoqin; Liu, Mingxue; Wei, Jie

    2017-12-01

    Calcified coccolithophores, a diverse and widely distributed group of marine microalgae, produce biogenic calcite in the form of coccoliths located on the cell surface. Using batch incubations of the coccolithophorid Pleurochrysis carterae, we investigated the responses of this calcification process to iron concentrations by changing the iron supply in the initial culture media from a normal concentration to 1 ppm (parts per million), 5 ppm, and 10 ppm. Time-dependent measurements of cell population, production of inorganic carbon (coccoliths), and organic carbon (organic cellular components) showed that elevated iron supply in the growth medium of P. carterae stimulates carbon sequestration by increasing growth along enhanced photosynthetic activity and calcification. In addition, the acquired time-dependent UV-Vis and FT-IR spectra revealed that iron fertilization-enhanced coccolith calcification is accompanied by a crystalline phase transition from calcite to aragonite or amorphous phase. Our results suggest that iron concentration has a significant influence on the marine carbon cycle of coccolithophores.

  9. The effectiveness of marine reserve systems constructed using different surrogates of biodiversity.

    PubMed

    Sutcliffe, P R; Klein, C J; Pitcher, C R; Possingham, H P

    2015-06-01

    Biological sampling in marine systems is often limited, and the cost of acquiring new data is high. We sought to assess whether systematic reserves designed using abiotic domains adequately conserve a comprehensive range of species in a tropical marine inter-reef system. We based our assessment on data from the Great Barrier Reef, Australia. We designed reserve systems aiming to conserve 30% of each species based on 4 abiotic surrogate types (abiotic domains; weighted abiotic domains; pre-defined bioregions; and random selection of areas). We evaluated each surrogate in scenarios with and without cost (cost to fishery) and clumping (size of conservation area) constraints. To measure the efficacy of each reserve system for conservation purposes, we evaluated how well 842 species collected at 1155 sites across the Great Barrier Reef seabed were represented in each reserve system. When reserve design included both cost and clumping constraints, the mean proportion of species reaching the conservation target was 20-27% higher for reserve systems that were biologically informed than reserves designed using unweighted environmental data. All domains performed substantially better than random, except when there were no spatial or economic constraints placed on the system design. Under the scenario with no constraints, the mean proportion of species reaching the conservation target ranged from 98.5% to 99.99% across all surrogate domains, whereas the range was 90-96% across all domains when both cost and clumping were considered. This proportion did not change considerably between scenarios where one constraint was imposed and scenarios where both cost and clumping constraints were considered. We conclude that representative reserve systems can be designed using abiotic domains; however, there are substantial benefits if some biological information is incorporated. © 2015 Society for Conservation Biology.

  10. 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.

  11. Direct ink writing of silica-bonded calcite scaffolds from preceramic polymers and fillers.

    PubMed

    Fiocco, L; Elsayed, H; Badocco, D; Pastore, P; Bellucci, D; Cannillo, V; Detsch, R; Boccaccini, A R; Bernardo, E

    2017-05-11

    Silica-bonded calcite scaffolds have been successfully 3D-printed by direct ink writing, starting from a paste comprising a silicone polymer and calcite powders, calibrated in order to match a SiO 2 /CaCO 3 weight balance of 35/65. The scaffolds, fabricated with two slightly different geometries, were first cross-linked at 350 °C, then fired at 600 °C, in air. The low temperature adopted for the conversion of the polymer into amorphous silica, by thermo-oxidative decomposition, prevented the decomposition of calcite. The obtained silica-bonded calcite scaffolds featured open porosity of about 56%-64% and compressive strength of about 2.9-5.5 MPa, depending on the geometry. Dissolution studies in SBF and preliminary cell culture tests, with bone marrow stromal cells, confirmed the in vitro bioactivity of the scaffolds and their biocompatibility. The seeded cells were found to be alive, well anchored and spread on the samples surface. The new silica-calcite composites are expected to be suitable candidates as tissue-engineering 3D scaffolds for regeneration of cancellous bone defects.

  12. 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.

  13. The coordination of sulfur in synthetic and biogenic Mg calcites: The red coral case

    NASA Astrophysics Data System (ADS)

    Perrin, J.; Rivard, C.; Vielzeuf, D.; Laporte, D.; Fonquernie, C.; Ricolleau, A.; Cotte, M.; Floquet, N.

    2017-01-01

    Sulfur has been recognized in biogenic calcites for a long time. However, its structural position is matter of debate. For some authors, sulfur is a marker of the organic matrix while it is part of the calcite structure itself for others. To better understand the place of sulfur in calcite, sulfated magnesian calcites (S-MgCalcite) have been synthetized at high pressure and temperature and studied by μ-XANES spectroscopy. S-MgCalcite XANES spectra show two different types of sulfur: sulfate (SO42-) as a predominant species and a small contribution of sulfite (SO32-), both substituting for carbonate ions in the calcite structure. To address the question of the position of sulfur in biogenic calcites, the oxidation states of sulfur in the skeleton and organic tissues of Corallium rubrum have been investigated by micro X-ray fluorescence (μ-XRF) and sulfur K-edge micro X-ray absorption near edge structure (μ-XANES) spectroscopy at the European Synchrotron Radiation Facility (ESRF, Grenoble, France) on beamline ID21. In the skeleton, sulfur is mainly present as oxidized sulfur SO42- (+VI), plus a weak sulfite contribution. XANES spectra indicate that sulfur is inorganically incorporated as sulfur structurally substituted to carbonate ions (SSS). Although an organic matrix is present in the red coral skeleton, reduced organic sulfur could not be detected by μ-XANES spectroscopy in the skeleton probably due to low organic/inorganic sulfur ratio. In the organic tissues surrounding the skeleton, several sulfur oxidation states have been detected including disulfide (S-S), thioether (R-S-CH3), sulfoxide (SO2), sulfonate (SO2O-) and sulfate (SO42-). The unexpected occurrence of inorganic sulfate within the organic tissues suggests the presence of pre-organized organic/inorganic complexes in the circulatory system of the red coral, precursors to biomineralization ahead of the growth front.

  14. Microbially induced separation of quartz from calcite using Saccharomyces cerevisiae.

    PubMed

    Padukone, S Usha; Natarajan, K A

    2011-11-01

    Cells of Saccharomyces cerevisiae and their metabolites were successfully utilized to achieve selective separation of quartz and calcite through microbially induced flotation and flocculation. S. cerevisiae was adapted to calcite and quartz minerals. Adsorption studies and electrokinetic investigations were carried out to understand the changes in the surface chemistry of yeast cells and the minerals after mutual interaction. Possible mechanisms in microbially induced flotation and flocculation are outlined. Copyright © 2011 Elsevier B.V. All rights reserved.

  15. Seasonal variations in modern speleothem calcite growth in Central Texas, U.S.A

    USGS Publications Warehouse

    Banner, J.L.; Guilfoyle, A.; James, E.W.; Stern, L.A.; Musgrove, M.

    2007-01-01

    Variations in growth rates of speleothem calcite have been hypothesized to reflect changes in a range of paleoenvironmental variables, including atmospheric temperature and precipitation, drip-water composition, and the rate of soil CO2 delivery to the subsurface. To test these hypotheses, we quantified growth rates of modern speleothem calcite on artificial substrates and monitored concurrent environmental conditions in three caves across the Edwards Plateau in central Texas. Within each of two caves, different drip sites exhibit similar annual cycles in calcite growth rates, even though there are large differences between the mean growth rates at the sites. The growth-rate cycles inversely correlate to seasonal changes in regional air temperature outside the caves, with near-zero growth rates during the warmest summer months, and peak growth rates in fall through spring. Drip sites from caves 130 km apart exhibit similar temporal patterns in calcite growth rate, indicating a controlling mechanism on at least this distance. The seasonal variations in calcite growth rate can be accounted for by a primary control by regional temperature effects on ventilation of cave-air CO2 concentrations and/or drip-water CO2 contents. In contrast, site-to-site differences in the magnitude of calcite growth rates within an individual cave appear to be controlled principally by differences in drip rate. A secondary control by drip rate on the growth rate temporal variations is suggested by interannual variations. No calcite growth was observed in the third cave, which has relatively high values of and small seasonal changes in cave-air CO2. These results indicate that growth-rate variations in ancient speleothems may serve as a paleoenvironmental proxy with seasonal resolution. By applying this approach of monitoring the modern system, speleothem growth rate and geochemical proxies for paleoenviromnental change may be evaluated and calibrated. Copyright ?? 2007, SEPM (Society for

  16. 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.

  17. Selective adsorption of benzhydroxamic acid on fluorite rendering selective separation of fluorite/calcite

    NASA Astrophysics Data System (ADS)

    Jiang, Wei; Gao, Zhiyong; Khoso, Sultan Ahmed; Gao, Jiande; Sun, Wei; Pu, Wei; Hu, Yuehua

    2018-03-01

    Fluorite, a chief source of fluorine in the nature, usually coexists with calcite mineral in ore deposits. Worldwide, flotation techniques with a selective collector and/or a selective depressant are commonly preferred for the separation of fluorite from calcite. In the present study, an attempt was made to use benzhydroxamic acid (BHA) as a collector for the selective separation of fluorite from calcite without using any depressant. Results obtained from the flotation experiments for single mineral and mixed binary minerals revealed that the BHA has a good selective collecting ability for the fluorite when 50 mg/L of BHA was used at pH of 9. The results from the zeta potential and X-ray photoelectron spectroscopy (XPS) indicated that the BHA easily chemisorbs onto the fluorite as compared to calcite. Crystal chemistry calculations showed the larger Ca density and the higher Ca activity on fluorite surface mainly account for the selective adsorption of BHA on fluorite, leading to the selective separation of fluorite from calcite. Moreover, a stronger hydrogen bonding with BHA and the weaker electrostatic repulsion with BHA- also contribute to the stronger interaction of BHA species with fluorite surface.

  18. 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

  19. 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; ...

    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

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pracheil, Brenda M.; Chakoumakos, Bryan C.; Feygenson, Mikhail

    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

  1. 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.

  2. Experimental postseismic recovery of fractured rocks assisted by calcite sealing

    NASA Astrophysics Data System (ADS)

    Aben, F. M.; Doan, M.-L.; Gratier, J.-P.; Renard, F.

    2017-07-01

    Postseismic recovery within fault damage zones involves slow healing of coseismic fractures leading to permeability reduction and strength increase with time. To better understand this process, experiments were performed by long-term fluid percolation with calcite precipitation through predamaged quartz-monzonite samples subjected to upper crustal conditions of stress and temperature. This resulted in a P wave velocity recovery of 50% of its initial drop after 64 days. In contrast, the permeability remained more or less constant for the duration of the experiment. Microstructures, fluid chemistry, and X-ray microtomography demonstrate that incipient calcite sealing and asperity dissolution are responsible for the P wave velocity recovery. The permeability is unaffected because calcite precipitates outside of the main flow channels. The highly nonparallel evolution of strength recovery and permeability suggests that fluid conduits within fault damage zones can remain open fluid conduits after an earthquake for much longer durations than suggested by the seismic monitoring of fault healing.

  3. The Real Difference between Biotic and Abiotic Methane

    NASA Astrophysics Data System (ADS)

    Cao, X.; Bao, H.; Peng, Y.

    2017-12-01

    Methane has both biotic and abiotic origins, and the identification of these two origins has important implications not only in understanding terrestrial processes but also in searching for extraterrestrial life. Carbon and hydrogen isotopes in methane have been used to identify certain biosignatures, but such efforts often suffer from ambiguity. Recent advancement in our capability in measuring multiply substituted isotopologues of methane (i.e. 13CDH3 and 12CD2H2) has found large 12CD2H2 depletion in abiotic methane. Quantum tunneling has been proposed to account for the apparent abiotic signature. However, quantum tunneling is neither unique to abiotic processes nor consistent with the observed not-so-depleted hydrogen isotope composition. Here we constructed a general kinetic model for methane formation from CO2, and validated it by fitting its parameters to observed 13CDH3, 12CD2H2, and 12CDH3. Our model revealed that the fundamental difference between biotic and abiotic methane isotopic signatures is in the source of hydrogens during methane formation. Hydrogens in biotic methane originate from the stronger carbon-hydrogen and sulfur-hydrogen bonds, while hydrogens in abiotic methane originate from the much weaker metal-hydrogen adsorption bond. This hydrogen source difference results in abiotic methane being more depleted in 12CD2H2 than the biotic one. Our model also shows that the primary kinetic hydrogen isotope effect is at approximately 0.6 for both abiotic and biotic pathways, a normal value further nullifying the role of quantum tunneling. The active and exclusive shuttling of reduced hydrogen via strong chemical bonds like carbon-hydrogen and sulfur-hydrogen in coenzymes is proposed here to be a unique signature of life. In an ironic sense, it is the equilibrated hydrogen isotope composition in the hydrogen donors that distinguishes the living from the non-living.

  4. Widespread abiotic methane in chromitites.

    PubMed

    Etiope, G; Ifandi, E; Nazzari, M; Procesi, M; Tsikouras, B; Ventura, G; Steele, A; Tardini, R; Szatmari, P

    2018-06-07

    Recurring discoveries of abiotic methane in gas seeps and springs in ophiolites and peridotite massifs worldwide raised the question of where, in which rocks, methane was generated. Answers will impact the theories on life origin related to serpentinization of ultramafic rocks, and the origin of methane on rocky planets. Here we document, through molecular and isotopic analyses of gas liberated by rock crushing, that among the several mafic and ultramafic rocks composing classic ophiolites in Greece, i.e., serpentinite, peridotite, chromitite, gabbro, rodingite and basalt, only chromitites, characterized by high concentrations of chromium and ruthenium, host considerable amounts of 13 C-enriched methane, hydrogen and heavier hydrocarbons with inverse isotopic trend, which is typical of abiotic gas origin. Raman analyses are consistent with methane being occluded in widespread microfractures and porous serpentine- or chlorite-filled veins. Chromium and ruthenium may be key metal catalysts for methane production via Sabatier reaction. Chromitites may represent source rocks of abiotic methane on Earth and, potentially, on Mars.

  5. A Laboratory Study Investigating the Feasibility of Applying Calcite-Type Coatings to Segregated Ballast Tanks

    DTIC Science & Technology

    1981-08-01

    A LABORATORY STUDY INVESTIGATIING THE FEASIBILITY OF APPLYING CALCITE -TYPE COATINGS TO SEGREGATED BALLAST TANKS AUGUST, 1981 Prepared by: Ocean City...Laboratory Study Investigating The Feasibility of Applying Calcite -Type Coatings to Segregated Ballast Tanks 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c...Executive Summary List of Figures I. Conclusions II. Introduction III. Background-The Development and Use of Calcite -Type Coatings IV. Experimental

  6. Diagnosing Abiotic Degradation

    EPA Science Inventory

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

  7. Quantitative single molecule measurements on the interaction forces of poly(L-glutamic acid) with calcite crystals.

    PubMed

    Sonnenberg, Lars; Luo, Yufei; Schlaad, Helmut; Seitz, Markus; Cölfen, Helmut; Gaub, Hermann E

    2007-12-12

    The interaction between poly(L-glutamic acid) (PLE) and calcite crystals was studied with AFM-based single molecule force spectroscopy. Block copolymers of poly(ethylene oxide) (PEO) and PLE were synthesized and covalently attached to the tip of an AFM cantilever. In desorption measurements the molecules were allowed to adsorb on the calcite crystal faces and afterward successively desorbed. The corresponding desorption forces were detected with high precision, showing for example a force transition between the two blocks. Because of its importance in the crystallization process in biominerals, the PLE-calcite interaction was investigated as a function of the pH as well as the calcium concentration of the aqueous solution. The sensitivity of the technique was underlined by resolving different interaction forces for calcite (104) and calcite (100).

  8. A reaction-transport model for calcite precipitation and evaluation of infiltration fluxes in unsaturated fractured rock.

    PubMed

    Xu, Tianfu; Sonnenthal, Eric; Bodvarsson, Gudmundur

    2003-06-01

    The percolation flux in the unsaturated zone (UZ) is an important parameter addressed in site characterization and flow and transport modeling of the potential nuclear-waste repository at Yucca Mountain, NV, USA. The US Geological Survey (USGS) has documented hydrogenic calcite abundances in fractures and lithophysal cavities at Yucca Mountain to provide constraints on percolation fluxes in the UZ. The purpose of this study was to investigate the relationship between percolation flux and measured calcite abundances using reactive transport modeling. Our model considers the following essential factors affecting calcite precipitation: (1) infiltration, (2) the ambient geothermal gradient, (3) gaseous CO(2) diffusive transport and partitioning in liquid and gas phases, (4) fracture-matrix interaction for water flow and chemical constituents, and (5) water-rock interaction. Over a bounding range of 2-20 mm/year infiltration rate, the simulated calcite distributions capture the trend in calcite abundances measured in a deep borehole (WT-24) by the USGS. The calcite is found predominantly in fractures in the welded tuffs, which is also captured by the model simulations. Simulations showed that from about 2 to 6 mm/year, the amount of calcite precipitated in the welded Topopah Spring tuff is sensitive to the infiltration rate. This dependence decreases at higher infiltration rates owing to a modification of the geothermal gradient from the increased percolation flux. The model also confirms the conceptual model for higher percolation fluxes in the fractures compared to the matrix in the welded units, and the significant contribution of Ca from water-rock interaction. This study indicates that reactive transport modeling of calcite deposition can yield important constraints on the unsaturated zone infiltration-percolation flux and provide useful insight into processes such as fracture-matrix interaction as well as conditions and parameters controlling calcite deposition.

  9. 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.

  10. 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.

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Hargis, Craig W.; Telesca, Antonio; Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu

    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 loweredmore » 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.« less

  12. Manganese-calcium intermixing facilitates heteroepitaxial growth at the 10 1 ¯ 4 calcite-water interface

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.

    2017-10-01

    In situ atomic force microscopy (AFM) measurements were performed to probe surface precipitates that formed on the (10-14) surface of calcite (CaCO3) single crystals following reaction with Mn2+-bearing aqueous solutions with a range of initial concentrations. Three-dimensional epitaxial islands were observed to precipitate and grow on the surfaces and in situ time-sequenced measurements demonstrated that their growth rates were commensurate with those obtained for epitaxial islands formed on calcite crystals reacted with Cd2+-bearing aqueous solutions of the same range in supersaturation with respect to the pure metal carbonate phase. This finding was unexpected as rhodochrosite (MnCO3) and calcite display amore » 10% lattice mismatch, based on the area of their (10-14) surface unit cells, whereas the lattice mismatch is only 4% for otavite (CdCO3) and calcite. Coatings of varying thicknesses were therefore synthesized by reacting calcite single crystals with calcite-equilibrated aqueous solutions with concentrations of up to 250 µM MnCl2 and analyzed to determine the composition of the surface precipitates. Ex situ X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), X-ray reflectivity (XRR), and AFM measurements of the reacted crystals demonstrated the formation of an epitaxial (Mn,Ca)CO3 solid solution with a spatially complex composition atop the calcite surface, whereby the first few nanometers were rich in Ca and the Mn content increased with distance from the original calcite surface, culminating in a topmost region of almost pure MnCO3 for the thickest coatings. These findings explain the measured growth rates (the effective lattice mismatch was much smaller than nominal mismatch) and highlight the strong influence played by the substrate on the composition of surface precipitates in aqueous conditions.« less

  13. Infrared spectroscopy and density functional theory investigation of calcite, chalk, and coccoliths--do we observe the mineral surface?

    PubMed

    Andersson, M P; Hem, C P; Schultz, L N; Nielsen, J W; Pedersen, C S; Sand, K K; Okhrimenko, D V; Johnsson, A; Stipp, S L S

    2014-11-13

    We have measured infrared spectra from several types of calcite: chalk, freshly cultured coccoliths produced by three species of algae, natural calcite (Iceland Spar), and two types of synthetic calcite. The most intense infrared band, the asymmetric carbonate stretch vibration, is clearly asymmetric for the coccoliths and the synthetic calcite prepared using the carbonation method. It can be very well fitted by two peaks: a narrow Lorenzian at lower frequency and a broader Gaussian at higher frequency. These two samples both have a high specific surface area. Density functional theory for bulk calcite and several calcite surface systems allows for assignment of the infrared bands. The two peaks that make up the asymmetric carbonate stretch band come from the bulk (narrow Lorenzian) and from a combination of two effects (broad Gaussian): the surface or near surface of calcite and line broadening from macroscopic dielectric effects. We detect water adsorbed on the high surface area synthetic calcite, which permits observation of the chemistry of thin liquid films on calcite using transmission infrared spectroscopy. The combination of infrared spectroscopy and density functional theory also allowed us to quantify the amount of polysaccharides associated with the coccoliths. The amount of polysaccharides left in chalk, demonstrated to be present in other work, is below the IR detection limit, which is 0.5% by mass.

  14. 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

  15. Effect of acidified water glass on the flotation separation of scheelite from calcite using mixed cationic/anionic collectors

    NASA Astrophysics Data System (ADS)

    Dong, Liuyang; Jiao, Fen; Qin, Wenqing; Zhu, Hailing; Jia, Wenhao

    2018-06-01

    In this paper, the effect of acidified water glass (AWG) on the flotation separation of scheelite from calcite using mixed collector of dodecylamine (DDA) and sodium oleate (NaOL) was investigated. The flotation results show that AWG could selectively depress the flotation of calcite at pH 7. A series of mechanism experiments confirm that the chemisorption of AWG on calcite surface is more intense than scheelite. Although the chemisorption of NaOL on calcite surface is almost unaffected by the presence of AWG, the chemisorption of AWG hinders the adsorption of DDA on calcite surface.

  16. 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…

  17. Influence of water on clumped-isotope bond reordering kinetics in calcite

    NASA Astrophysics Data System (ADS)

    Brenner, Dana C.; Passey, Benjamin H.; Stolper, Daniel A.

    2018-03-01

    Oxygen self-diffusion in calcite and many other minerals is considerably faster under wet conditions relative to dry conditions. Here we investigate whether this "water effect" also holds true for solid-state isotope exchange reactions that alter the abundance of carbonate groups with multiple rare isotopes ('clumped' isotope groups) via the process of solid-state bond reordering. We present clumped-isotope reordering rates for optical calcite heated under wet, high-pressure (100 MPa) conditions. We observe only modest increases in reordering rates under such conditions compared with rates for the same material reacted in dry CO2 under low-pressure conditions. Activation energies under wet, high-pressure conditions are indistinguishable from those for dry, low-pressure conditions, while rate constants are resolvably higher (up to ∼3 times) for wet, high-pressure relative to dry, low-pressure conditions in most of our interpretations of experimental results. This contrasts with the water effect for oxygen self-diffusion in calcite, which is associated with lower activation energies, and diffusion coefficients that are ≥103 times higher compared with dry (pure CO2) conditions in the temperature range of this study (385-450 °C). The water effect for clumped-isotopes leads to calculated apparent equilibrium temperatures ("blocking temperatures") for typical geological cooling rates that are only a few degrees higher than those for dry conditions, while O self-diffusion blocking temperatures in calcite grains are ∼150-200 °C lower in wet conditions compared with dry conditions. Since clumped-isotope reordering is a distributed process that occurs throughout the mineral volume, our clumped-isotope results support the suggestion of Labotka et al. (2011) that the water effect in calcite does not involve major changes in bulk (volume) diffusivity, but rather is primarily a surface phenomenon that facilitates oxygen exchange between the calcite surface and external

  18. Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Branson, Oscar; Bonnin, Elisa A.; Perea, Daniel E.

    Biomineralizing organisms exhibit exquisite control over skeletal morphology and composition. The promise of understanding and harnessing this feat of natural engineering has motivated an intense search for the mechanisms that direct in vivo mineral self-assembly. We used atom probe tomography, a sub-nanometer 3D chemical mapping technique, to examine the chemistry of a buried organic-mineral interface in biomineral calcite from a marine foraminifer. The chemical patterns at this interface capture the processes of early biomineralization, when the shape, mineralogy, and orientation of skeletal growth are initially established. Sodium is enriched by a factor of nine on the organic side of themore » interface. Based on this pattern, we suggest that sodium plays an integral role in early biomineralization, potentially altering interfacial energy to promote crystal nucleation, and that interactions between organic surfaces and electrolytes other than calcium or carbonate could be a crucial aspect of CaCO3 biomineralization.« less

  19. Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Branson, Oscar; Bonnin, Elisa A.; Perea, Daniel E.

    2016-10-28

    Biomineralizing organisms exhibit exquisite control over skeletal morphology and composition. The promise of understanding and harnessing this feat of natural engineering has motivated an intense search for the mechanisms that direct in vivo mineral self-assembly. We used atom probe tomography, a sub-nanometer 3D chemical mapping technique, to examine the chemistry of a buried organic-mineral interface in biomineral calcite from a marine foraminifer. The chemical patterns at this interface capture the processes of early biomineralization, when the shape, mineralogy, and orientation of skeletal growth are initially established. Sodium is enriched by a factor of nine on the organic side of themore » interface. Based on this pattern, we suggest that sodium plays an integral role in early biomineralization, potentially altering interfacial energy to promote crystal nucleation, and that interactions between organic surfaces and electrolytes other than calcium or carbonate could be a crucial aspect of CaCO3 biomineralization.« less

  20. Nanometer-Scale Chemistry of a Calcite Biomineralization Template: Implications for Skeletal Composition and Nucleation

    DOE PAGES

    Branson, Oscar; Bonnin, Elisa A.; Perea, Daniel E.; ...

    2016-10-28

    Biomineralizing organisms exhibit exquisite control over skeletal morphology and composition. The promise of understanding and harnessing this feat of natural engineering has motivated an intense search for the mechanisms that direct in vivo mineral self-assembly. We used atom probe tomography, a sub-nanometer 3D chemical mapping technique, to examine the chemistry of a buried organic-mineral interface in biomineral calcite from a marine foraminifer. Here, the chemical patterns at this interface capture the processes of early biomineralization, when the shape, mineralogy, and orientation of skeletal growth are initially established. Sodium is enriched by a factor of nine on the organic side ofmore » the interface. Based on this pattern, we suggest that sodium plays an integral role in early biomineralization, potentially altering interfacial energy to promote crystal nucleation, and that interactions between organic surfaces and electrolytes other than calcium or carbonate could be a crucial aspect of CaCO 3 biomineralization.« less

  1. 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.

  2. 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. Copyright © 2014 Elsevier Inc. All rights reserved.

  3. 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.

  4. Fish as major carbonate mud producers and missing components of the tropical carbonate factory

    USGS Publications Warehouse

    Perry, C.T.; Salter, M.A.; Harborne, A.R.; Crowley, S.F.; Jelks, H.L.; Wilson, R.W.

    2011-01-01

    Carbonate mud is a major constituent of recent marine carbonate sediments and of ancient limestones, which contain unique records of changes in ocean chemistry and climate shifts in the geological past. However, the origin of carbonate mud is controversial and often problematic to resolve. Here we show that tropical marine fish produce and excrete various forms of precipitated (nonskeletal) calcium carbonate from their guts ("low" and "high" Mg-calcite and aragonite), but that very fine-grained (mostly <2 ??m) high Mg-calcite crystallites (i.e., >4 mole % MgCO3) are their dominant excretory product. Crystallites from fish are morphologically diverse and species-specific, but all are unique relative to previously known biogenic and abiotic sources of carbonate within open marine systems. Using site specific fish biomass and carbonate excretion rate data we estimate that fish produce ???6.1 ?? 106 kg CaCO3/year across the Bahamian archipelago, all as mud-grade (the <63 ??m fraction) carbonate and thus as a potential sediment constituent. Estimated contributions from fish to total carbonate mud production average ???14% overall, and exceed 70% in specific habitats. Critically, we also document the widespread presence of these distinctive fish-derived carbonates in the finest sediment fractions from all habitat types in the Bahamas, demonstrating that these carbonates have direct relevance to contemporary carbonate sediment budgets. Fish thus represent a hitherto unrecognized but significant source of fine-grained carbonate sediment, the discovery of which has direct application to the conceptual ideas of how marine carbonate factories function both today and in the past.

  5. Abiotic Bromination of Soil Organic Matter

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Leri, Alessandra C.; Ravel, Bruce

    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 andmore » 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.« less

  6. 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.

  7. Spectroscopic characterization of natural calcite minerals.

    PubMed

    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 A, c=17.1188 A. 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.

  8. Direct observation of the transition from calcite to aragonite growth as induced by abalone shell proteins.

    PubMed Central

    Thompson, J B; Paloczi, G T; Kindt, J H; Michenfelder, M; Smith, B L; Stucky, G; Morse, D E; Hansma, P K

    2000-01-01

    The mixture of EDTA-soluble proteins found in abalone nacre are known to cause the nucleation and growth of aragonite on calcite seed crystals in supersaturated solutions of calcium carbonate. Past atomic force microscope studies of the interaction of these proteins with calcite crystals did not observe this transition because no information about the crystal polymorph on the surface was obtained. Here we have used the atomic force microscope to directly observe changes in the atomic lattice on a calcite seed crystal after the introduction of abalone shell proteins. The observed changes are consistent with a transition to (001) aragonite growth on a (1014) calcite surface. PMID:11106633

  9. Contribution of hydrolysis in the abiotic attenuation of RDX and HMX in coastal waters.

    PubMed

    Monteil-Rivera, Fanny; Paquet, Louise; Giroux, Romain; Hawari, Jalal

    2008-01-01

    Sinking of military ships, dumping of munitions during the two World Wars, and military training have resulted in the undersea deposition of numerous unexploded ordnances (UXOs). Leaching of energetic compounds such as hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) from these UXOs may cause adverse ecological effects so that the long-term fate of these chemicals in the sea should be known. The present study assesses the contribution of alkaline hydrolysis into the natural attenuation of RDX and HMX in coastal waters. Alkaline hydrolysis rates were shown to be unaffected by the presence of sodium chloride, the most common component in marine waters. Kinetic parameters (E(a), ln A, k(2)) quantified for the alkaline hydrolysis of RDX and HMX in deionized water (30-50 degrees C, pH 10-12) agreed relatively well with abiotic degradation rates determined in sterilized natural coastal waters (50 and 60 degrees C, variable salinity) even if the latter were generally slightly faster than the former. Furthermore, similar products (HCHO, NO(2)(-), O(2)NNHCH(2)NHCHO) were obtained on alkaline hydrolysis in deionized water and abiotic degradation in coastal waters. These two findings suggested that degradation of nitramines in sterilized natural coastal waters, away from light, was mainly governed by alkaline hydrolysis. Kinetic calculations using the present parameters showed that alkaline hydrolysis of RDX and HMX in marine waters at 10 degrees C would respectively take 112 +/- 10 and 2408 +/- 217 yr to be completed (99.0%). We concluded that under natural conditions hydrolysis should not contribute significantly to the natural attenuation of HMX in coastal waters whereas it could play an active role in the natural attenuation of RDX.

  10. Pelagic distribution of marine birds in the Eastern Bering Sea

    USGS Publications Warehouse

    Hunt, G.L.; D.M., Gould; Forsell, D.J.; Petersen, Jr., H.; Hood, Donald W.; Calder, J.A.

    1981-01-01

    Analyses of the most abundant marine bird species in the eastern Bering Sea indicate that their distribution and abundance are the result of complex interactions between biotic and abiotic elements of the environment. Of particular importance are the effects of ice systems, food availability, oceanographic frontal systems, and the location of suitable nesting sites. For most species, the southern ice edge acts as a barrier to northward movement in the spring. OCSEAP surveys indicate that previous estimates of seabird populations in the Bering Sea are probably extremely conservative and that more than 40 million seabirds may occupy these marine waters during the summer months.

  11. A model for microbially induced precipitation of vadose-zone calcites in fractures at LOS Alamos, New Mexico, USA

    NASA Astrophysics Data System (ADS)

    Newman, Brent D.; Campbell, Andrew R.; Norman, David I.; Ringelberg, David B.

    1997-05-01

    Fractures are unique environments that can concentrate the flow of water, nutrients, and contaminants. As such, fractures play an important role in controlling the flux of various substances into and through the vadose zone. Calcite fracture fillings are present in the near surface in the Bandelier Tuff Formation at Los Alamos, New Mexico, and provide a record of the geochemical and hydrologic processes that have occurred in fractures. The objective of this study was to examine calcite fracture fills in order to improve understanding of processes within fractures, and in particular those that lead to precipitation of calcite. Samples of calcite fillings were collected from vertical and horizontal fractures exposed in a shallow waste-burial pit. Scanning electron microscopy show morphologies which suggest that plants, fungi, and bacteria were important in the precipitation process. Quadrupole mass spectrometric analyses of fluid inclusion gases show predominantly methane (17-99%) and little to no oxygen (0-8%), suggesting the development of anaerobic conditions in the fractures. Ester-linked phospholipid biomarkers are evidence for a diverse microbial community in the fractures, and the presence of di-ether lipids indicate that the methane was generated by anaerobic bacteria. The calcite fillings apparently resulted from multiple biological and chemical processes in which plant roots in the fractures were converted to calcite. Roots grew into the fractures, eventually died, and were decomposed by bacteria and fungi. Anaerobic gases were generated from encapsulated organic material within the calcite via microbial decomposition, or were generated by microbes simultaneously with calcite precipitation. It is likely that the biological controls on calcite formation that occurred in the Los Alamos fractures also occurs in soils, and may explain the occurrence of other types of pedogenic calcites.

  12. Calcite saturation in the River Dee, NE Scotland.

    PubMed

    Wade, A J; Neal, C; Smart, R P; Edwards, A C

    2002-01-23

    The spatial and temporal variations in calcite (calcium carbonate) solubility within the Dee basin of NE Scotland were assessed using water chemistry data gathered from a network of 59 sites monitored for water quality from June 1996 to May 1997. Calcite solubility, expressed in terms of a saturation index (SIcalcite), was determined from measured streamwater pH, Gran alkalinity and calcium concentrations and water temperature. In general, the waters of the Dee system are undersaturated with respect to calcite, though the saturation index is higher during the summer months indicating a dependency on flow conditions and biological activity. Under low-flow conditions, the streamwaters are dominated by water derived from the lower soil horizons and deeper groundwater stores and therefore, ions such as Gran alkalinity and calcium are at their highest concentrations as they are derived mainly from bedrock weathering. The influence of biological activity on the carbonate system is also evident as the observed pH and estimated EpCO2 values indicate strong seasonal patterns, with the highest pH and lowest EpCO2 values occurring during the summer low-flow periods. Only at three sites in the lowland region of the catchment, during the summer low-flow period, are the waters oversaturated. As such, the Dee system represents an extreme 'end-member' case when compared to many UK rivers that span both under- and oversaturated conditions during the year. Regression analysis highlights a systematic change in the SIcalcite-pH relationship in a broad east-west direction across the Dee system. At sites draining the relatively impermeable upland areas, the regression of SIcalcite against pH gives a straight line with a gradient in the range 1.6-2.4. Correspondingly, under the most extreme alkaline conditions found at sites draining lowland agricultural areas, a straight-line relationship exists but with a gradient of unity. It is concluded that these changes in the SIcalcite

  13. Surface Complexation Modeling of Calcite Zeta Potential Measurement in Mixed Brines for Carbonate Wettability Characterization

    NASA Astrophysics Data System (ADS)

    Song, J.; Zeng, Y.; Biswal, S. L.; Hirasaki, G. J.

    2017-12-01

    We presents zeta potential measurements and surface complexation modeling (SCM) of synthetic calcite in various conditions. The systematic zeta potential measurement and the proposed SCM provide insight into the role of four potential determining cations (Mg2+, SO42- , Ca2+ and CO32-) and CO2 partial pressure in calcite surface charge formation and facilitate the revealing of calcite wettability alteration induced by brines with designed ionic composition ("smart water"). Brines with varying potential determining ions (PDI) concentration in two different CO2 partial pressure (PCO2) are investigated in experiments. Then, a double layer SCM is developed to model the zeta potential measurements. Moreover, we propose a definition for contribution of charged surface species and quantitatively analyze the variation of charged species contribution when changing brine composition. After showing our model can accurately predict calcite zeta potential in brines containing mixed PDIs, we apply it to predict zeta potential in ultra-low and pressurized CO2 environments for potential applications in carbonate enhanced oil recovery including miscible CO2 flooding and CO2 sequestration in carbonate reservoirs. Model prediction reveals that pure calcite surface will be positively charged in all investigated brines in pressurized CO2 environment (>1atm). Moreover, the sensitivity of calcite zeta potential to CO2 partial pressure in the various brine is found to be in the sequence of Na2CO3 > Na2SO4 > NaCl > MgCl2 > CaCl2 (Ionic strength=0.1M).

  14. 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.".

  15. Studies of biominerals relevant to the search for life on Mars.

    PubMed

    Blanco, Armando; D'Elia, Marcella; Licchelli, Domenico; Orofino, Vincenzo; Fonti, Sergio

    2006-12-01

    The evidence of the water erosion on Mars is particularly interesting since present climatic conditions are such that liquid water cannot exist at the surface. But, if water was present on the planet in the past, there may have been life, too. Since the discovery of carbonates on Mars also may have very important implications on the possibility that life developed there, we are studying minerals that can have biotic or abiotic origin: calcite (CaCO(3)) and aragonite, a metastable state of calcite.We have analysed biomineral aragonite, in the form of recent sea shells, as well as crystals of mineral aragonite. Infrared spectroscopy in the 2-25 mum wavelength range reveals that, after thermal processing, the biotic samples have a different spectral behaviour from the abiotic ones. As a result, it is possible to distinguish abiotic mineral aragonite from aragonite of recent biological origin.Obviously, if life existed in the past on the Red Planet, we could expect to find "ancient" biotic carbonates, which should therefore be investigated, in order to search for a way of discriminating them from abiotic minerals. For this reason, at the beginning we have considered samples of crushed fossil shells of aragonite composition. Afterwards, in order to take into account that fossilization processes almost always produce a transformation of metastable form (aragonite) into more stable form (calcite), we also studied samples of mineral calcite and different types of fossils completely transformed into calcite. All these biotic fossil samples show the same spectral behaviour as the fresh biotic material after thermal annealing at 485 degrees C. Instead, the calcite behaves like abiotic aragonite.Furthermore, it is known that seashells and other biominerals are formed through an intimate association of inorganic materials with organic macromolecules. The macromolecules control the nucleation, structure, morphology, crystal orientation and spatial confinement of the inorganic

  16. Role of sugars under abiotic stress.

    PubMed

    Sami, Fareen; Yusuf, Mohammad; Faizan, Mohammad; Faraz, Ahmad; Hayat, Shamsul

    2016-12-01

    Sugars are the most important regulators that facilitate many physiological processes, such as photosynthesis, seed germination, flowering, senescence, and many more under various abiotic stresses. Exogenous application of sugars in low concentration promote seed germination, up regulates photosynthesis, promotes flowering, delayed senescence under various unfavorable environmental conditions. However, high concentration of sugars reverses all these physiological process in a concentration dependent manner. Thus, this review focuses the correlation between sugars and their protective functions in several physiological processes against various abiotic stresses. Keeping in mind the multifaceted role of sugars, an attempt has been made to cover the role of sugar-regulated genes associated with photosynthesis, seed germination and senescence. The concentration of sugars determines the expression of these sugar-regulated genes. This review also enlightens the interaction of sugars with several phytohormones, such as abscisic acid, ethylene, cytokinins and gibberellins and its effect on their biosynthesis under abiotic stress conditions. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  17. Comparison of solidification/stabilization effects of calcite between Australian and South Korean cements

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Lee, Dongjin; Waite, T. David; Swarbrick, Gareth

    2005-11-15

    The differences in the effect of calcite on the strength and stability of Pb-rich wastes solidified and stabilized using Australian and South Korean ordinary Portland cements are examined in this study. Pb-rich waste stabilized using Australian OPC has been shown to possess both substantially higher unconfined compressive strength and lead immobilization ability than South Korean OPC as a result of its higher C{sub 3}S content and the associated enhanced degree of precipitation of lead on the surfaces of silicate phases present. Calcite addition is observed to have an accelerating effect on the OPC-induced solidification/stabilization of Pb-rich wastes as gauged bymore » the unconfined compressive strength and leachability of the solids formed. This effect is observed to be far more dramatic for South Korean OPC than for Australian OPC. Using scanning electron microscopy, waste stabilized with cement and calcite was observed to develop significantly greater proportions of hydrated crystals than wastes stabilized with cement alone. The results of X-ray diffraction studies have shown that the presence of calcite in South Korean OPC results in greater acceleration in the formation of portlandite than is the case for Australian OPC.« less

  18. Amorphous calcium carbonate transforms into calcite during sea urchin larval spicule growth

    PubMed Central

    Beniash, E.; Aizenberg, J.; Addadi, L.; Weiner, S.

    1997-01-01

    Sea urchin larvae form an endoskeleton composed of a pair of spicules. For more than a century it has been stated that each spicule comprises a single crystal of the CaCO3 mineral, calcite. We show that an additional mineral phase, amorphous calcium carbonate, is present in the sea urchin larval spicule, and that this inherently unstable mineral transforms into calcite with time. This observation significantly changes our concepts of mineral formation in this well-studied organism.

  19. 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

  20. 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.

  1. Strain rate dependent calcite microfabric evolution at natural conditions

    NASA Astrophysics Data System (ADS)

    Rogowitz, Anna; Grasemann, Bernhard; Huet, Benjamin; Habler, Gerlinde

    2014-05-01

    Crystal plastic deformational behaviour of calcite has been the focus of many experimental studies. Different strain rates, pressure and temperature conditions have been addressed to investigate a wide range of deformation regimes. However, a direct comparison with natural fault rocks remains difficult because of extreme differences between experimental and natural strain rates. A flanking structure developed in almost pure calcite marble on Syros (Cyclades, Greece). Due to rotation of a planar feature (crack) a heterogeneous strain field in the surrounding area occurred resulting in different strain domains and the formation of the flanking structure. Assuming that deformation was active continuously during the development of the flanking structure, the different strain domains correspond to different strain-rate domains. The outcrop thus represents the final state of a natural experiment and gives us a great opportunity to get natural constraints on strain rate dependent deformation behaviour of calcite. Comparing the microfabrics in the 1 to 2.5 cm thick shear zone and the surrounding host rocks, which formed under the same metamorphic conditions but with different strain rates, is the central focus of this study. Due to the extreme variation in strain and strain rate, different microstructures and textures can be observed corresponding to different deformation mechanisms. With increasing strain rate we observe a change in dominant deformation mechanism from dislocation glide to dislocation creep and finally diffusion creep. Additionally, a change from subgrain rotation to bulging recrystallization can be observed in the dislocation creep regime. Crystallographic preferred orientations (CPO) and the grade of intracrystalline deformation were measured on a FEI Quanta 3D FEG instrument equipped with an EDAX Digiview IV EBSD camera. At all strain rates clear CPOs developed leading to the assumption that calcite preferentially deforms within the dislocation creep

  2. Abiotic methane formation during experimental serpentinization of olivine

    PubMed Central

    2016-01-01

    Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH4). In many cases, the CH4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH4 synthesis have been observed. Here, the potential for abiotic formation of CH4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A 13C-labeled inorganic carbon source was used to unambiguously determine the origin of CH4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH4 was observed in one experiment performed under conditions that allowed an H2-rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH4. PMID:27821742

  3. Abiotic methane formation during experimental serpentinization of olivine.

    PubMed

    McCollom, Thomas M

    2016-12-06

    Fluids circulating through actively serpentinizing systems are often highly enriched in methane (CH 4 ). In many cases, the CH 4 in these fluids is thought to derive from abiotic reduction of inorganic carbon, but the conditions under which this process can occur in natural systems remain unclear. In recent years, several studies have reported abiotic formation of CH 4 during experimental serpentinization of olivine at temperatures at or below 200 °C. However, these results seem to contradict studies conducted at higher temperatures (300 °C to 400 °C), where substantial kinetic barriers to CH 4 synthesis have been observed. Here, the potential for abiotic formation of CH 4 from dissolved inorganic carbon during olivine serpentinization is reevaluated in a series of laboratory experiments conducted at 200 °C to 320 °C. A 13 C-labeled inorganic carbon source was used to unambiguously determine the origin of CH 4 generated in the experiments. Consistent with previous high-temperature studies, the results indicate that abiotic formation of CH 4 from reduction of dissolved inorganic carbon during the experiments is extremely limited, with nearly all of the observed CH 4 derived from background sources. The results indicate that the potential for abiotic synthesis of CH 4 in low-temperature serpentinizing environments may be much more limited than some recent studies have suggested. However, more extensive production of CH 4 was observed in one experiment performed under conditions that allowed an H 2 -rich vapor phase to form, suggesting that shallow serpentinization environments where a separate gas phase is present may be more favorable for abiotic synthesis of CH 4 .

  4. 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.

  5. 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

  6. 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

  7. 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

  8. Probing the energetics of organic–nanoparticle interactions of ethanol on calcite

    DOE PAGES

    Wu, Di; Navrotsky, Alexandra

    2015-04-13

    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. In this paper, 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. Furthermore, these thermochemical observations directly support a structuremore » 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. Finally, these differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces.« less

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

    NASA Astrophysics Data System (ADS)

    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.

  10. 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

  11. [Transgenic rice breeding for abiotic stress tolerance--present and future].

    PubMed

    Zhao, Feng-Yun; Zhang, Hui

    2007-01-01

    Environmental stresses and the continuing deterioration of arable land, along with an explosive increase in world population, pose serious threats to global agricultural production and food security. Improving the tolerance of the major crop plants to abiotic stresses has been a main goal in agriculture for a long time. As rice is considered one of the major crops, the development of new cultivars with enhanced abiotic stress-tolerance will undoubtedly have an important effect on global food production. The transgenic approach offers an attractive alternative to conventional techniques for the genetic improvement of rice cultivars. In recent years, an array of stress-related genes has already been transferred to rice to improve its resistance against abiotic stresses. Many transgenic rice plants with enhanced abiotic stress-tolerance have been obtained. This article focuses on the progress in the study of abiotic stress tolerance in transgenic rice breeding.

  12. Viruses Occur Incorporated in Biogenic High-Mg Calcite from Hypersaline Microbial Mats

    PubMed Central

    De Wit, Rutger; Gautret, Pascale; Bettarel, Yvan; Roques, Cécile; Marlière, Christian; Ramonda, Michel; Nguyen Thanh, Thuy; Tran Quang, Huy; Bouvier, Thierry

    2015-01-01

    Using three different microscopy techniques (epifluorescence, electronic and atomic force microscopy), we showed that high-Mg calcite grains in calcifying microbial mats from the hypersaline lake “La Salada de Chiprana”, Spain, contain viruses with a diameter of 50–80 nm. Energy-dispersive X-ray spectrometer analysis revealed that they contain nitrogen and phosphorus in a molar ratio of ~9, which is typical for viruses. Nucleic acid staining revealed that they contain DNA or RNA. As characteristic for hypersaline environments, the concentrations of free and attached viruses were high (>1010 viruses per g of mat). In addition, we showed that acid treatment (dissolution of calcite) resulted in release of viruses into suspension and estimated that there were ~15 × 109 viruses per g of calcite. We suggest that virus-mineral interactions are one of the possible ways for the formation of nano-sized structures often described as “nanobacteria” and that viruses may play a role in initiating calcification. PMID:26115121

  13. 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

  14. 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

  15. Novel Determination of the Orientation of Calcite on Mineral Substrates

    NASA Astrophysics Data System (ADS)

    Zhao, L.; Ji, X.; Teng, H.

    2016-12-01

    In the threat of global warming, the transformation from CO2 to stable carbonate minerals is significant to geological CO2 sequestration in the long term.Previous efforts have found that when carbonate minerals nucleate on some mineral substrates ,the time of carbon capture can be shorted .Many efforts have been focused on the dynamics when carbonate minerals nucleate on mineral substrates, but few have studied the orientation of carbonate minerals on mineral substrates. In our experiment, we mainly focused on the orientation of calcite on mineral substrates.We mixed NaHCO3 and CaCl2 to nucleate when mineral substrates were added and a multi-parameter analyzer was used to monitor in real time to determine the induction time for nucleation. On the basis of classical nucleation theory, we got a brand new formula to decide the orientation of calcite on mineral substrates. lntind=(2-cosθ+cos3θ)*16πγ3vm2(12*(kBT)3*(lnS)2)+ln(1/N0v)+ ΔEa/(kBT)where θ is the angle between the substrate and the nuclei, tind is the induction time for nucleation, γ is he average surface free energy, N0 is the total number of particles per unit volume of solution, ΔEa is the activation energy for molecular motion across the embryo-matrix interface, S is the supersaturation index ,kB is the Boltzmann constant. Using the new formula above , when biotite was used as substrate mineral ,we found that the angle between the biotite and the nuclei was 119°. Angle measured on SEM images also supported our conclusion above. Combined with SEM and Debye ring analysed by Rigaku 2D data processing software, we only found one point of (006) in Debye ring, unlike (104)(many points in one ring and it meant that the orientation of (104) is random ). That meant (001) of calcite was first formed on biotite (001). In that case we inferred that 119° was formed by (001) of botite and (012) of calcite for the intersection angle of (001) and (012) was 120°. Future research will focus on the orientation of

  16. 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. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Investigating controls on boron isotope ratios in shallow marine carbonates

    NASA Astrophysics Data System (ADS)

    Zhang, Shuang; Henehan, Michael J.; Hull, Pincelli M.; Reid, R. Pamela; Hardisty, Dalton S.; Hood, Ashleigh v. S.; Planavsky, Noah J.

    2017-01-01

    The boron isotope-pH proxy has been widely used to reconstruct past ocean pH values. In both planktic foraminifera and corals, species-specific calibrations are required in order to reconstruct absolute values of pH, due to the prevalence of so-called vital effects - physiological modification of the primary environmental signals by the calcifying organisms. Shallow marine abiotic carbonate (e.g. ooids and cements) could conceivably avoid any such calibration requirement, and therefore provide a potentially useful archive for reconstructions in deep (pre-Cenozoic) time. However, shallow marine abiotic carbonates could also be affected by local shifts in pH caused by microbial photosynthesis and respiration, something that has up to now not been fully tested. In this study, we present boron isotope measurements from shallow modern marine carbonates, from the Bahama Bank and Belize to investigate the potential of using shallow water carbonates as pH archives, and to explore the role of microbial processes in driving nominally 'abiogenic' carbonate deposition. For Bahama bank samples, our boron-based pH estimates derived from a range of carbonate types (i.e. ooids, peloids, hardground cements, carbonate mud, stromatolitic micrite and calcified filament micrite) are higher than the estimated modern mean-annual seawater pH values for this region. Furthermore, the majority (73%) of our marine carbonate-based pH estimates fall out of the range of the estimated pre-industrial seawater pH values for this region. In shallow sediment cores, we did not observe a correlation between measured pore water pH and boron-derived pH estimates, suggesting boron isotope variability is a depositional rather than early diagenetic signal. For Belize reef cements, conversely, the pH estimates are lower than likely in situ seawater pH at the time of cement formation. This study indicates the potential for complications when using shallow marine non-skeletal carbonates as marine pH archives

  18. 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.

  19. 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.

  20. Trace metal distribution and isotope variations in low-temperature calcite and groundwater in granitoid fractures down to 1 km depth

    NASA Astrophysics Data System (ADS)

    Drake, Henrik; Tullborg, Eva-Lena; Hogmalm, K. Johan; Åström, Mats E.

    2012-05-01

    Studies of low-temperature fracture calcite in Proterozoic or Archaean crystalline rocks are very limited, mainly because this calcite usually is, first, not very abundant and second, very fine-grained or forms rims on older (and much more abundant) hydrothermal calcite and is thus difficult to distinguish. Knowledge of chemical characteristics and the correlation with groundwater chemistry is thus scarce for low-temperature calcite in these settings, and consequently, knowledge of the recent palaeohydrogeological history is limited. Boreholes drilled with triple-tube technique in the upper 1 km of the Palaeoproterozoic crystalline crust at Laxemar, SE Sweden, have enabled preservation of fragile and potentially recently formed fracture minerals. Earlier investigations of these boreholes have resulted in an extensive set of groundwater chemistry data from various depths, and in detailed knowledge of the fracture mineral assemblages (ranging from 1.8 Ga to present). This has made it possible to identify and sample low-temperature, potentially recently formed, calcite from water-flowing fractures for which representative groundwater chemical data exists. This, in turn, provides an opportunity to detailed comparisons of fracture calcite (age span in the order of million years, with possibility of post-glacial contributes) and groundwater (age in the order of decades to more than a million year depending on depth) in terms of both isotopic and geochemical properties, giving input to the understanding of groundwater history, partition coefficients derived in laboratory experiment, and reliability of calcite geochemistry in terms of representing the actual source fluid composition. In this study, the focus is on trace elements (Fe, Mg, Mn and Sr), stable isotopes and Sr isotopes and, for the groundwater data set, also aquatic speciation with Visual MINTEQ. An optimised step-by-step sample specific analytical procedure was used for the collection of calcite coatings. The

  1. Abiotic and Biotic Mechanisms Controlling In Situ Remediation of NDMA

    DTIC Science & Technology

    2009-05-01

    FINAL REPORT Abiotic and Biotic Mechanisms Controlling In Situ Remediation of NDMA SERDP Project ER-1421 MAY 2009 James E. Szecsody...00-2009 4. TITLE AND SUBTITLE Abiotic and Biotic Mechanisms Controlling In Situ Remediation of NDMA 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c...investigate whether in situ coupled abiotic/biotic degradation of N-nitrosodimethylamine ( NDMA , an emerging contaminant) could be used as a permeable

  2. Fish as major carbonate mud producers and missing components of the tropical carbonate factory

    PubMed Central

    Perry, Chris T.; Salter, Michael A.; Harborne, Alastair R.; Crowley, Stephen F.; Jelks, Howard L.; Wilson, Rod W.

    2011-01-01

    Carbonate mud is a major constituent of recent marine carbonate sediments and of ancient limestones, which contain unique records of changes in ocean chemistry and climate shifts in the geological past. However, the origin of carbonate mud is controversial and often problematic to resolve. Here we show that tropical marine fish produce and excrete various forms of precipitated (nonskeletal) calcium carbonate from their guts (“low” and “high” Mg-calcite and aragonite), but that very fine-grained (mostly < 2 μm) high Mg-calcite crystallites (i.e., MgCO3) are their dominant excretory product. Crystallites from fish are morphologically diverse and species-specific, but all are unique relative to previously known biogenic and abiotic sources of carbonate within open marine systems. Using site specific fish biomass and carbonate excretion rate data we estimate that fish produce ∼6.1 × 106 kg CaCO3/year across the Bahamian archipelago, all as mud-grade (the < 63 μm fraction) carbonate and thus as a potential sediment constituent. Estimated contributions from fish to total carbonate mud production average ∼14% overall, and exceed 70% in specific habitats. Critically, we also document the widespread presence of these distinctive fish-derived carbonates in the finest sediment fractions from all habitat types in the Bahamas, demonstrating that these carbonates have direct relevance to contemporary carbonate sediment budgets. Fish thus represent a hitherto unrecognized but significant source of fine-grained carbonate sediment, the discovery of which has direct application to the conceptual ideas of how marine carbonate factories function both today and in the past. PMID:21368155

  3. 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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    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 vadosemore » 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

  4. Elasticity and yielding of a calcite paste: scaling laws in a dense colloidal suspension.

    PubMed

    Liberto, Teresa; Le Merrer, Marie; Barentin, Catherine; Bellotto, Maurizio; Colombani, Jean

    2017-03-08

    We address the mechanical characterization of a calcite paste as a model system to investigate the relation between the microstructure and macroscopic behavior of colloidal suspensions. The ultimate goal is to achieve control of the elastic and yielding properties of calcite which will prove valuable in several domains, from paper coating to paint manufacture and eventually in the comprehension and control of the mechanical properties of carbonate rocks. Rheological measurements have been performed on calcite suspensions over a wide range of particle concentrations. The calcite paste exhibits a typical colloidal gel behavior, with an elastic regime and a clear yield strain above which it enters a plastic regime. The yield strain shows a minimum when increasing the solid concentration, connected to a change in the power law scaling of the storage modulus. In the framework of the classical fractal elasticity model for colloidal suspensions proposed by Shih et al. [Phys. Rev. A, 1990, 42, 4772], we interpret this behavior as a switch with the concentration from the strong-link regime to the weak-link regime, which had never been observed so far in one well-defined system without external or chemical forcing.

  5. 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. © The Author 2014. Published by Oxford University Press on behalf of the Society for Experimental Biology. All rights reserved. For permissions, please email: journals.permissions@oup.com.

  6. Abiotic Supramolecular Systems

    DTIC Science & Technology

    2011-05-02

    REPORT Abiotic Supramolecular Systems 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: The goal of this research project was to develop new concepts for the...decision, unless so designated by other documentation. 12. DISTRIBUTION AVAILIBILITY STATEMENT Approved for Public Release; Distribution Unlimited UU...9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES) 6. AUTHORS 7. PERFORMING ORGANIZATION NAMES AND ADDRESSES U.S. Army Research Office P.O

  7. 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.

  8. Contamination of short-chain chlorinated paraffins to the biotic and abiotic environments in the Bohai Sea.

    PubMed

    Jiang, Wanyanhan; Huang, Tao; Chen, Han; Lian, Lulu; Liang, Xiaoxue; Jia, Chenhui; Gao, Hong; Mao, Xiaoxuan; Zhao, Yuan; Ma, Jianmin

    2018-02-01

    Short-chain chlorinated paraffins (SCCPs) have been produced and emitted intensively around the Bohai Sea, potentially causing risks to this unique ecosystem and one of primary fishery resources in China and busiest seaways in the world. Little is known about fate, cycling, and sources of SCCPs in the Bohai Sea biotic and abiotic environment. In this study, we combined a marine food web model with a comprehensive atmospheric transport-multiple phase exchange model to quantify SCCPs in the biotic and abiotic environment in the Bohai Sea. We performed multiple modeling scenario investigations to examine SCCP levels in water, sediment, and phytoplankton. We assessed numerically dry and wet depositions, biomagnification and bioaccumulation of SCCPs in the Bohai Sea marine food web. Results showed declining SCCP levels in water and sediment with increasing distance from the coastline, and so do dry and wet depositions. The net deposition overwhelmed the water-air exchange of SCCPs due to their current use in China, though the diffusive gas deposition fluctuated monthly subject to mean wind speed and temperature. A risk assessment manifests that SCCPs levels in the Bohai Sea fish species are at present not posing risks to the residents in the Bohai Sea Rim region. We identified that the SCCP emission sources in the south of the Bohai Sea made a primary contribution to its loadings to the seawater and fish contamination associated with the East Asian summer monsoon. In contrast, the SCCP emissions from the north and northwest regions of the Bohai Sea were major sources contributing to their loading and contamination to Bohai Sea food web during the wintertime, potentially driven by the East Asian winter monsoon. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Experimental Study of Sr Partitioning into Calcite at Various Linear Growth Rates and Temperatures: Preliminary Results.

    NASA Astrophysics Data System (ADS)

    Gabitov, R. I.; Watson, B. E.

    2004-05-01

    The surface of a crystal in equilibrium with surrounding fluid can have a composition that differs from the bulk crystal. If growth rate of the crystal exceeds a minimum value at which partitioning-equilibrium can be maintained, then the crystal surface composition may be "captured" by the newly-formed lattice. The degree of this entrapment increases with increasing crystal growth rate. Non-equlibrium partitioning of Sr into calcite probably occurs by this entrapment mechanism. Sr and calcite are geochemically significant in understanding the thermal history of the ocean because the substitution of Sr for Ca in calcite is temperature dependent. To improve our understanding of the partitioning of Sr into calcite, we conducted two different types of experiment: 1) calcite growth from Sr-bearing solution with analysis of the crystal cross-section by electron microprobe (bulk crystal-liquid runs); and 2) treatment of calcite cleavage surfaces with Sr-bearing solutions and examination of the top few nm surface layer by X-ray photoelectron spectroscopy (surface-liquid runs). In the series of bulk-liquid experiments crystals were grown by three different procedures: 1) precipitation on glass slide (pre-coated with calcite), where a steady flow of CaCl2 - SrCl2 and Na2CO3 solutions were mixed just before passage through a tube and allowed to drip onto a slide ("cave"-type experiments, ionic strength I=0.01); 2) growth from a CaCl2 - NH4Cl - SrCl2 solution by diffusion of CO2 from an ammonium carbonate source ("drift" experiments, I=0.52); 3) coarsening of small calcite crystals in the CaCO3-SrCO3-NaCl-H2O system at 800-950° C and 0.5-1 kb in a cold seal apparatus. The growth rate of individual crystals was determined by periodic monitoring of crystal size with time or roughly by comparison of final size with duration of the experiment. Surface-liquid experiments were performed by treatment of cleavage surfaces of natural calcite fragments in a Sr(ClO4)2 solution for 1

  10. A Synthetic Calcite Standard for Determination of Relative Mn/Cr Sensitivity Factor

    NASA Astrophysics Data System (ADS)

    Fujiya, W.; Ichimura, K.; Takahata, N.; Sugiura, N.; Sano, Y.

    2009-12-01

    Primitive chondrites which suffered from aqueous alteration often contain carbonates such as calcites, dolomites and breunnerites. 53Mn-53Cr decay system (half-life: 3.7 Myr) is applicable to dating their precipitation and many authors have measured their Mn-Cr ages using the SIMS. However, the relative Mn/Cr sensitivity factor: RSF (measured Mn+/Cr+ ratio divided by the true ratio) is not well established due to the absence of suitable standards, therefore the ages have systematic uncertainties. We prepared a synthetic Mn and Cr bearing calcite to evaluate the Mn/Cr RSF. Here we report the technical details of preparation for the standard and its Mn/Cr RSF. We also measured the Mn/Cr RSF of San Carlos olivine which is often assumed to be the same as that of a carbonate, and compared it with that of our synthetic calcite. The Cr-bearing calcite was produced in a N2 filled closed system by the reaction Ca2+ + CO32- = CaCO3 in an aqueous solution. The reaction proceeded by continuous addition of ammonium carbonate vapor to the solution. The crystal size of the calcite was ~300 μm. A small amount of hydrazine was added to the solution in order to keep chromous ion from oxidation. Mn and Cr concentrations in the calcite grains were determined by the SEM-EDS. A weak, defocused beam was used due to prevent electron beam damage. In a spherical grain, radial zoning of Mn and Cr concentrations occur and they decrease towards the periphery. At the center of the grains, Mn and Cr concentrations are ~0.5 atomic % and the values of the Mn/Cr ratios are relatively constant. The Mn/Cr RSF was determined with the CAMECA NanoSIMS 50 at Ocean Research Institute of Univ. of Tokyo. A primary O- beam of ~1 nA and 5 μm diameter was used. 43Ca+, 52Cr+, 53Cr+ and 55Mn+ ions were analyzed in a combined peak-jumping/multi-detection mode. The total measurement time was typically ~20 minutes. The measurements were started after presputtering of 15 minutes. The mass resolution power was

  11. 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...

  12. Microstructure of calcite deformed by high-pressure torsion: An X-ray line profile study

    NASA Astrophysics Data System (ADS)

    Schuster, Roman; Schafler, Erhard; Schell, Norbert; Kunz, Martin; Abart, Rainer

    2017-11-01

    Calcite aggregates were deformed to high strain using high-pressure torsion and applying confining pressures of 1-6 GPa and temperatures between room temperature and 450 °C. The run products were characterized by X-ray diffraction, and key microstructural parameters were extracted employing X-ray line profile analysis. The dominant slip system was determined as r { 10 1 bar 4 } ⟨ 2 bar 021 ⟩ with edge dislocation character. The resulting dislocation density and the size of the coherently scattering domains (CSD) exhibit a systematic dependence on the P-T conditions of deformation. While high pressure generally impedes recovery through reducing point defect mobility, the picture is complicated by pressure-induced phase transformations in the CaCO3 system. Transition from the calcite stability field to those of the high-pressure polymorphs CaCO3-II, CaCO3-III and CaCO3-IIIb leads to a change of the microstructural evolution with deformation. At 450 °C and pressures within the calcite stability field, dislocation densities and CSD sizes saturate at shear strains exceeding 10 in agreement with earlier studies at lower pressures. In the stability field of CaCO3-II, the dislocation density exhibits a more complex behavior. Furthermore, at a given strain and strain rate, the dislocation density increases and the CSD size decreases with increasing pressure within the stability fields of either calcite or of the high-pressure polymorphs. There is, however, a jump from high dislocation densities and small CSDs in the upper pressure region of the calcite stability field to lower dislocation densities and larger CSDs in the low-pressure region of the CaCO3-II stability field. This jump is more pronounced at higher temperatures and less so at room temperature. The pressure influence on the deformation-induced evolution of dislocation densities implies that pressure variations may change the rheology of carbonate rocks. In particular, a weakening is expected to occur at

  13. Calcite growth-rate inhibition by fulvic acids isolated from Big Soda Lake, Nevada, USA, The Suwannee River, Georgia, USA and by polycarboxylic acids

    USGS Publications Warehouse

    Reddy, Michael M.; Leenheer, Jerry

    2011-01-01

    Calcite crystallization rates are characterized using a constant solution composition at 25°C, pH=8.5, and calcite supersaturation (Ω) of 4.5 in the absence and presence of fulvic acids isolated from Big Soda Lake, Nevada (BSLFA), and a fulvic acid from the Suwannee River, Georgia (SRFA). Rates are also measured in the presence and absence of low-molar mass, aliphatic-alicyclic polycarboxylic acids (PCA). BSLFA inhibits calcite crystal-growth rates with increasing BSLFA concentration, suggesting that BSLFA adsorbs at growth sites on the calcite crystal surface. Calcite growth morphology in the presence of BSLFA differed from growth in its absence, supporting an adsorption mechanism of calcite-growth inhibition by BSLFA. Calcite growth-rate inhibition by BSLFA is consistent with a model indicating that polycarboxylic acid molecules present in BSLFA adsorb at growth sites on the calcite crystal surface. In contrast to published results for an unfractionated SRFA, there is dramatic calcite growth inhibition (at a concentration of 1 mg/L) by a SRFA fraction eluted by pH 5 solution from XAD-8 resin, indicating that calcite growth-rate inhibition is related to specific SRFA component fractions. A cyclic PCA, 1, 2, 3, 4, 5, 6-cyclohexane hexacarboxylic acid (CHXHCA) is a strong calcite growth-rate inhibitor at concentrations less than 0.1 mg/L. Two other cyclic PCAs, 1, 1 cyclopentanedicarboxylic acid (CPDCA) and 1, 1 cyclobutanedicarboxylic acid (CBDCA) with the carboxylic acid groups attached to the same ring carbon atom, have no effect on calcite growth rates up to concentrations of 10 mg/L. Organic matter ad-sorbed from the air onto the seed crystals has no effect on the measured calcite crystal-growth rates.

  14. Do biofilms and clays alter the chemistry and fabric of a hyper-alklaine, saline, non-marine carbonate precipitate?

    NASA Astrophysics Data System (ADS)

    Rogerson, Michael; Saunders, Paul; Mercedes-Martin, Ramon; Brasier, Alex; Pedley, Martyn

    2015-04-01

    Non-marine carbonates comprise a hugely diverse family of deposits, which reflect a constellation of forcing factors from local hydraulics to regional climatology. However, the two dominant controls on precipitation are solution chemistry and benthic microbial biogeochemistry. Here, we present a unifying concept for understanding how these controls influence deposit characteristics, and re-emphasise the importance of biofilms. It is generally accepted that biofilms play an important part in the precipitation of authigenic minerals in a wide variety of settings. In carbonate settings, biofilms are recognised to increase the amount of calcite precipitation and alter the geometry and coarse scale petrography of the precipitate. They determine at what water marginal water chemistries calcite starts to precipitate and microbialites give way to chemical limestones. Biofilms also interact with ambient water, controlling chemical accumulation transport. New evidence, drawn from unique experimental approaches, is demonstrating that biofilm influence extends to control of calcite trace element composition, and crystal scale fabric. Under tightly controlled temperature and chemical conditions, fully replicated experiments show that Mg incorporation into tufa carbonate defies the expected thermodynamic control. However, there is a pronounced influence on (Mg/Ca)calcite from precipitation rate, so that rapidly forming precipitates develop with very low magnesium content indicating kinetic control on fractionation. Calcite precipitation rate in these experiments is controlled by biofilm growth rate and reflects kinetic fractionation arises from the electrochemical activity of extracellular organic acids. These effects are therefore likely to occur wherever these molecules occur, including stromatolites, soil and lake carbonates and (via colloidal organic acids) speleothems. The presence of Extracellular polymeric substances (EPS), even without the presence of cells, also alters

  15. The Labrador Sea during the Last Glacial Maximum: Calcite dissolution or low biogenic carbonate fluxes?

    NASA Astrophysics Data System (ADS)

    Marshall, Nicole; de Vernal, Anne; Mucci, Alfonso; Filippova, Alexandra; Kienast, Markus

    2017-04-01

    Low concentrations of biogenic carbonate characterize the sediments deposited in the Labrador Sea during the last glaciation. This may reflect poor calcite preservation and/or low biogenic carbonate productivity and fluxes. Regional bottom water ventilation was reduced during the Last Glacial Maximum (LGM), so the calcite lysocline might have been shallower than at present in the deep Labrador Sea making dissolution of calcite shells in the deep Labrador Sea possible. To address the issue, a multi-proxy approach based on micropaleontological counts (coccoliths, foraminifers, palynomorphs) and biogeochemical analyses (alkenones) was applied in the investigation of core HU2008-029-004-PC recovered in the northwestern Labrador Sea. Calcite dissolution indices based on the relative abundance benthic foraminifera shells to their organic linings as well as on fragmentation of planktonic foraminifera shells were used to evaluate changes in calcite dissolution/ preservation since the LGM. In addition, the ratio of the concentrations of coccoliths, specifically of the alkenone-producer Emiliania huxleyi, and alkenones (Emiliania huxleyi: alkenones) was explored as a potential new proxy of calcite dissolution. A sharp increase in coccoliths, foraminifers and organic linings from nearly none to substantial concentrations at 12 ka, reflect a jump to significantly greater biogenic fluxes at the glacial-interglacial transition. Furthermore, conventional dissolution indices (shells/linings of benthic foraminifera and fragmentation of planktic foraminifers) reveal that dissolution is not likely responsible for the lower glacial abundances of coccoliths and foraminifers. Only the low Emiliania huxleyi: alkenones ratios in glacial sediments could be interpreted as evidence of increased dissolution during the LGM. Given the evidence of allochthonous alkenone input into the glacial Labrador Sea, the latter observations must be treated with caution. Overall, the records indicate that

  16. Morphology and formation mechanism in precipitation of calcite induced by Curvibacter lanceolatus strain HJ-1

    NASA Astrophysics Data System (ADS)

    Zhang, Chonghong; Li, Fuchun; Lv, Jiejie

    2017-11-01

    Precipitation of calcium carbobate induced by microbial activities is common occurrence in controlled solution, but the formation mechanism and morphology in precipitation of calcite in solution systems is unclear, and the role of microbes is disputed. Here, culture experiment was performed for 50 days using the Curvibacter lanceolatus strain HJ-1 in a M2 culture medium, and the phase composition and morphology of the precipitates were characterized by the X-ray diffraction (XRD), Fourier transform infrared (FT-IR), and scanning electron microscopy (SEM) techniques. We show that the precipitation processes in our experiment lead to unusual morphologies of crystals corresponding to different growth stages, and the morphologies of the precipitated crystal aggregates ranging from the main rod-, cross-, star-, cauliflower-like morphologies to spherulitic structure. The complex and unusual morphologies of the precipitated calcite by strain HJ-1 may provide a reference point for better understanding the biomineralization mechanism of calcite, moreover, morphological transition of minerals revealed that the multi-ply crystals-aggregation mechanism for calcite growth in crystallisation media.

  17. Nanobacteria-like calcite single crystals at the surface of the Tataouine meteorite

    PubMed Central

    Benzerara, Karim; Menguy, Nicolas; Guyot, François; Dominici, Christian; Gillet, Philippe

    2003-01-01

    Nanobacteria-like objects evidenced at the surface of the orthopyroxenes of the Tataouine meteorite in South Tunisia have been studied by scanning and transmission electron microscopies. A method of micromanipulation has been developed to ensure that exactly the same objects were studied by both methods. We have shown that the nanobacteria-like objects are spatially correlated with filaments of microorganisms that colonized the surface of the meteoritic pyroxene during its 70 years of residence in the aridic Tataouine soil. Depressions of a few micrometers in depth are observed in the pyroxene below the carbonates, indicating preferential dissolution of the pyroxene and calcite precipitation at these locations. The nanobacteria-like small rods that constitute calcium carbonate rosettes are well crystallized calcite single crystals surrounded by a thin amorphous layer of carbonate composition that smoothes the crystal edges and induces rounded shapes. Those morphologies are unusual for calcite single crystals observed in natural samples. A survey of recent literature suggests that the intervention of organic compounds derived from biological activity is likely in their formation. PMID:12792020

  18. Nanobacteria-like calcite single crystals at the surface of the Tataouine meteorite.

    PubMed

    Benzerara, Karim; Menguy, Nicolas; Guyot, Francois; Dominici, Christian; Gillet, Philippe

    2003-06-24

    Nanobacteria-like objects evidenced at the surface of the orthopyroxenes of the Tataouine meteorite in South Tunisia have been studied by scanning and transmission electron microscopies. A method of micromanipulation has been developed to ensure that exactly the same objects were studied by both methods. We have shown that the nanobacteria-like objects are spatially correlated with filaments of microorganisms that colonized the surface of the meteoritic pyroxene during its 70 years of residence in the aridic Tataouine soil. Depressions of a few micrometers in depth are observed in the pyroxene below the carbonates, indicating preferential dissolution of the pyroxene and calcite precipitation at these locations. The nanobacteria-like small rods that constitute calcium carbonate rosettes are well crystallized calcite single crystals surrounded by a thin amorphous layer of carbonate composition that smoothes the crystal edges and induces rounded shapes. Those morphologies are unusual for calcite single crystals observed in natural samples. A survey of recent literature suggests that the intervention of organic compounds derived from biological activity is likely in their formation.

  19. Molecular modeling studies of interactions between sodium polyacrylate polymer and calcite surface

    NASA Astrophysics Data System (ADS)

    Ylikantola, A.; Linnanto, J.; Knuutinen, J.; Oravilahti, A.; Toivakka, M.

    2013-07-01

    The interactions between calcite pigment and sodium polyacrylate dispersing agent, widely used in papermaking as paper coating components, were investigated using classical force field and quantum chemical approaches. The objective was to understand interactions between the calcite surface and sodium polyacrylate polymer at 300 K using molecular dynamics simulations. A quantum mechanical ab initio Hartree-Fock method was also used to obtain detailed information about the sodium polyacrylate polymer structure. The effect of water molecules (moisture) on the interactions was also examined. Calculations showed that molecular weight, branching and the orientation of sodium polyacrylate polymers influence the interactions between the calcite surface and the polymer. The force field applied, and also water molecules, were found to have an impact on all systems studied. Ab initio Hartree-Fock calculations indicated that there are two types of coordination between sodium atoms and carboxylate groups of the sodium polyacrylate polymer, inter- and intra-carboxylate group coordination. In addition, ab initio Hartree-Fock calculations of the structure of the sodium polyacrylate polymer produced important information regarding interactions between the polymers and carboxylated styrene-butadiene latex particles.

  20. 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)

  1. A membraneless single compartment abiotic glucose fuel cell

    NASA Astrophysics Data System (ADS)

    Slaughter, Gymama; Sunday, Joshua

    2014-09-01

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

  2. Abiotic gene transfer: rare or rampant?

    PubMed Central

    Kotnik, Tadej; Weaver, James C.

    2016-01-01

    Phylogenetic studies reveal that horizontal gene transfer (HGT) plays a prominent role in evolution and genetic variability of life. Five biotic mechanisms of HGT among prokaryotic organisms have been extensively characterized: conjugation, competence, transduction, gene-transfer-agent (GTA) particles, and transitory fusion with recombination, but it is not known whether they can account for all natural HGT. It is even less clear how HGT could have occurred before any of these mechanisms had developed. Here, we consider contemporary conditions and experiments on microorganisms to estimate possible roles of abiotic HGT – currently and throughout evolution. Candidate mechanisms include freeze-and-thaw, microbeads-agitation, and electroporation-based transformation, and we posit that these laboratory techniques have analogues in nature acting as mechanisms of abiotic HGT: freeze-and-thaw cycles in polar waters, sand-agitation at foreshores and riverbeds, and lightning-triggered electroporation in near-surface aqueous habitats. We derive conservative order-of-magnitude estimates for rates of microorganisms subjected to freeze-and-thaw cycles, sand-agitation, and lightning-triggered electroporation, at 1024, 1019, and 1017 per year, respectively. Considering the yield of viable transformants, which is by far the highest in electroporation, we argue this may still favor lightning-triggered transformation over the other two mechanisms. Electroporation-based gene transfer also appears to be the most general of these abiotic candidates, and perhaps even of all known HGT mechanisms. Future studies should provide improved estimates of gene transfer rates and cell viability, currently and in the past, but to assess the importance of abiotic HGT in nature, will likely require substantial progress – also in knowledge of biotic HGT. PMID:27067073

  3. Designing cooperatively folded abiotic uni- and multimolecular helix bundles

    NASA Astrophysics Data System (ADS)

    de, Soumen; Chi, Bo; Granier, Thierry; Qi, Ting; Maurizot, Victor; Huc, Ivan

    2018-01-01

    Abiotic foldamers, that is foldamers that have backbones chemically remote from peptidic and nucleotidic skeletons, may give access to shapes and functions different to those of peptides and nucleotides. However, design methodologies towards abiotic tertiary and quaternary structures are yet to be developed. Here we report rationally designed interactional patterns to guide the folding and assembly of abiotic helix bundles. Computational design facilitated the introduction of hydrogen-bonding functionalities at defined locations on the aromatic amide backbones that promote cooperative folding into helix-turn-helix motifs in organic solvents. The hydrogen-bond-directed aggregation of helices not linked by a turn unit produced several thermodynamically and kinetically stable homochiral dimeric and trimeric bundles with structures that are distinct from the designed helix-turn-helix. Relative helix orientation within the bundles may be changed from parallel to tilted on subtle solvent variations. Altogether, these results prefigure the richness and uniqueness of abiotic tertiary structure behaviour.

  4. Systems biology approach in plant abiotic stresses.

    PubMed

    Mohanta, Tapan Kumar; Bashir, Tufail; Hashem, Abeer; Abd Allah, Elsayed Fathi

    2017-12-01

    Plant abiotic stresses are the major constraint on plant growth and development, causing enormous crop losses across the world. Plants have unique features to defend themselves against these challenging adverse stress conditions. They modulate their phenotypes upon changes in physiological, biochemical, molecular and genetic information, thus making them tolerant against abiotic stresses. It is of paramount importance to determine the stress-tolerant traits of a diverse range of genotypes of plant species and integrate those traits for crop improvement. Stress-tolerant traits can be identified by conducting genome-wide analysis of stress-tolerant genotypes through the highly advanced structural and functional genomics approach. Specifically, whole-genome sequencing, development of molecular markers, genome-wide association studies and comparative analysis of interaction networks between tolerant and susceptible crop varieties grown under stress conditions can greatly facilitate discovery of novel agronomic traits that protect plants against abiotic stresses. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  5. Gallium isotope fractionation during Ga adsorption on calcite and goethite

    NASA Astrophysics Data System (ADS)

    Yuan, Wei; Saldi, Giuseppe D.; Chen, JiuBin; Vetuschi Zuccolini, Marino; Birck, Jean-Louis; Liu, Yujie; Schott, Jacques

    2018-02-01

    Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △71Gasolid-solution up to -1.27‰ and -0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for 'closed system' equilibrium and 'Rayleigh fractionation' models indicates that the experimental data are consistent with a 'closed system' equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga-O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH)4- to 6 and 1.94 Å in the >Ca-O-GaOH(OH2)4+ surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH)20 surface complexes (Ga-O distances of 1.96-1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH)4- is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga-O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  7. An efficient phosphorus scavenging from aqueous solution using magnesiothermally modified bio-calcite.

    PubMed

    Ahmad, Munir; Ahmad, Mahtab; Usman, Adel R A; Al-Faraj, Abdullah S; Ok, Yong Sik; Hussain, Qaiser; Abduljabbar, Adel S; Al-Wabel, Mohammad I

    2018-07-01

    Bio-calcite (BC) derived from waste hen eggshell was subjected to thermal treatments (calcined bio-calcite (CBC)). The BC and CBC were further modified via magnesiothermal treatments to produce modified bio-calcite (MBC) and modified calcined bio-calcite (MCBC), respectively, and evaluated as a novel green sorbent for P removal from aqueous solutions in the batch experiments. Modified BC exhibited improved structural and chemical properties, such as porosity, surface area, thermal stability, mineralogy and functional groups, than pristine material. Langmuir and Freundlich models well described the P sorption onto both thermally and magnesiothermally sorbents, respectively, suggesting mono- and multi-layer sorption. Langmuir predicted highest P sorption capacities were in the order of: MCBC (43.33 mg g -1 ) > MBC (35.63 mg g- 1 ) > CBC (34.38 mg g -1 ) > BC (30.68 mg g -1 ). The MBC and MCBC removed 100% P up to 50 mg P L -1 , which reduced to 35.43 and 39.96%, respectively, when P concentration was increased up to 1000 mg L -1 . Dynamics of P sorption was well explained by the pseudo-second-order rate equation, with the highest sorption rate of 4.32 mg g -1  min -1 for the MCBC. Hydroxylapatite [Ca 10 (PO 4 ) 6 (OH) 2 ] and brushite [CaH(PO 4 )·2H 2 O] were detected after P sorption onto the modified sorbents by X-ray diffraction analysis, suggesting chemisorption as the operating sorption mechanism.

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

    DOE PAGES

    Laanait, Nouamane; Callagon, Erika Blanca R.; Zhang, Zhan; ...

    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

  9. Microstructural Damage During High-Strain Torsion Experiments on Calcite-Anhydrite Aggregates

    NASA Astrophysics Data System (ADS)

    Cross, A. J.; Skemer, P. A.

    2016-12-01

    Ductile shear zones play a critical role in localising deformation in the Earth's crust and mantle. Severe grain size reduction - a ubiquitous feature of natural mylonites - is commonly thought to cause strain weakening via a transition to grain size sensitive deformation mechanisms. Although grain size reduction is modulated by grain growth in single-phase aggregates, grain boundary pinning in well-mixed poly-phase composites can inhibit grain growth, leading to microstructural `damage' which is likely a critical element of strain localization in the lithosphere. While dynamic recrystallization has been widely explored in rock mechanics and materials science, the mechanisms behind phase-mixing remain poorly understood. In this contribution we present results from high-strain, deformation experiments on calcite-anhydrite composites. Experiments were conducted in torsion at T = 500-700°C and P 1.5 GPa, using the new Large Volume Torsion (LVT) solid-medium apparatus, to shear strains of 0.5-30. As shear strain increases, progressive thinning and necking of initially large (≤ 1 mm) calcite domains is observed, resulting in an increase in the proportion of interphase boundaries. Grain-size is negatively correlated with the fraction of interphase boundaries, such that calcite grains in well-mixed regions are significantly smaller than those in single-phase domains. Crucially, progressive deformation leads to a reduction in grain-size beyond the lower limit established by the grain size piezometer for mono-phase calcite, implying microstructural damage. These data therefore demonstrate continued microstructural evolution in two-phase composites that is not possible in single-phase aggregates. These observations mark a new `geometric' mechanism for phase mixing, complementing previous models for phase mixing involving chemical reactions, material diffusion, and/or grain boundary sliding.

  10. Salicylic acid-induced abiotic stress tolerance and underlying mechanisms in plants

    PubMed Central

    Khan, M. Iqbal R.; Fatma, Mehar; Per, Tasir S.; Anjum, Naser A.; Khan, Nafees A.

    2015-01-01

    Abiotic stresses (such as metals/metalloids, salinity, ozone, UV-B radiation, extreme temperatures, and drought) are among the most challenging threats to agricultural system and economic yield of crop plants. These stresses (in isolation and/or combination) induce numerous adverse effects in plants, impair biochemical/physiological and molecular processes, and eventually cause severe reductions in plant growth, development and overall productivity. Phytohormones have been recognized as a strong tool for sustainably alleviating adverse effects of abiotic stresses in crop plants. In particular, the significance of salicylic acid (SA) has been increasingly recognized in improved plant abiotic stress-tolerance via SA-mediated control of major plant-metabolic processes. However, the basic biochemical/physiological and molecular mechanisms that potentially underpin SA-induced plant-tolerance to major abiotic stresses remain least discussed. Based on recent reports, this paper: (a) overviews historical background and biosynthesis of SA under both optimal and stressful environments in plants; (b) critically appraises the role of SA in plants exposed to major abiotic stresses; (c) cross-talks potential mechanisms potentially governing SA-induced plant abiotic stress-tolerance; and finally (d) briefly highlights major aspects so far unexplored in the current context. PMID:26175738

  11. Diversity dynamics of marine planktonic diatoms across the Cenozoic.

    PubMed

    Rabosky, Daniel L; Sorhannus, Ulf

    2009-01-08

    Diatoms are the dominant group of phytoplankton in the modern ocean. They account for approximately 40% of oceanic primary productivity and over 50% of organic carbon burial in marine sediments. Owing to their role as a biological carbon pump and effects on atmospheric CO(2) levels, there is great interest in elucidating factors that influenced the rapid rise in diatom diversity during the past 40 million years. Two biotic controls on diversification have been proposed to explain this diversity increase: (1) geochemical coupling between terrestrial grasslands and marine ecosystems through the global silicon cycle; and (2) competitive displacement of other phytoplankton lineages. However, these hypotheses have not been tested using sampling-standardized fossil data. Here we show that reconstructions of species diversity in marine phytoplankton reject these proposed controls and suggest a new pattern for oceanic diatom diversity across the Cenozoic. Peak species diversity in marine planktonic diatoms occurred at the Eocene-Oligocene boundary and was followed by a pronounced decline, from which diversity has not recovered. Although the roles of abiotic and biotic drivers of diversification remain unclear, major features of oceanic diatom evolution are decoupled from both grassland expansion and competition among phytoplankton groups.

  12. The analysis of thermoluminescent glow peaks of natural calcite after beta irradiation.

    PubMed

    Yildirim, R Güler; Kafadar, V Emir; Yazici, A Necmeddin; Gün, Esen

    2012-09-01

    In this study, the thermoluminescence properties of natural calcite samples were examined in detail. The glow curve of the sample irradiated with beta radiation shows two main peaks, P1 (at 115 °C) and P4 (at 254 °C). The additive dose, variable heating rate, computer glow curve deconvolution, peak shape and three point methods have been used to evaluate the trapping parameters, namely the order of kinetics (b), activation energy (E) and the frequency factor (s) associated with the dosimetric thermoluminescent glow peaks (P1 and P4) of natural calcite after different dose levels with beta irradiation.

  13. Integrated Approach for Understanding Impurity Adsorption on Calcite: Mechanisms for Micro-scale Surface Phenomena

    NASA Astrophysics Data System (ADS)

    Vinson, M. D.; Arvidson, R. S.; Luttge, A.

    2004-12-01

    A longstanding goal within the field of environmental geochemistry has been the development of a fundamental understanding of the kinetics that governs the interactions of solution-borne impurities with the calcite mineral surface. Recent dissolution experiments using Mg2+, Mn2+, and Sr2+ have shown distinct differences in the interaction of these three impurity ions with the calcite crystal surface. Because the dissolution of carbonate minerals in soils and sediments influences the uptake and migration of groundwater contaminants, a rigorous understanding of the basic processes that occur at the mineral-fluid interface is necessary. We have used vertical scanning interferometry (VSI) coupled with scanning probe microscopy (SPM) to examine calcite crystal dissolution in the presence of Mg2+, Mn2+, and Sr2+, all known dissolution inhibitors and possible groundwater contaminants. We have studied the kinetics of impurity-crystal interactions at a pH 8.8, and in the presence or absence of dissolved inorganic carbon. Our data show that, when individually introduced into undersaturated solutions, Mg2+ and Mn2+ are shown to activate the calcite crystal surface, resulting in enhanced etch pit nucleation rates and step density. Conversely, Sr2+ is shown to cause passivation of the calcite surface. The effect is intensified when solutions are saturated with respect to atmospheric CO2. Results indicate that aqueous CO32- (or HCO3-) may influence how aqueous metal ionic complexes interact with the crystal surface. Furthermore, the influence is differently exhibited, and passivation or activation ultimately depends on the properties of the diffusing metal ion or metal-hydroxide complex. These properties include for example, differences in hydration enthalpy, the effective ionic radius, and electron shell configuration.

  14. Interdependence of specialization and biodiversity in Phanerozoic marine invertebrates.

    PubMed

    Nürnberg, Sabine; Aberhan, Martin

    2015-03-17

    Studies of the dynamics of biodiversity often suggest that diversity has upper limits, but the complex interplay between ecological and evolutionary processes and the relative role of biotic and abiotic factors that set upper limits to diversity are poorly understood. Here we statistically assess the relationship between global biodiversity and the degree of habitat specialization of benthic marine invertebrates over the Phanerozoic eon. We show that variation in habitat specialization correlates positively with changes in global diversity, that is, times of high diversity coincide with more specialized faunas. We identify the diversity dynamics of specialists but not generalists, and origination rates but not extinction rates, as the main drivers of this ecological interdependence. Abiotic factors fail to show any significant relationship with specialization. Our findings suggest that the overall level of specialization and its fluctuations over evolutionary timescales are controlled by diversity-dependent processes--driven by interactions between organisms competing for finite resources.

  15. Interpreting the Marine Calcium Isotope Record: Influence of Reef Builders

    NASA Astrophysics Data System (ADS)

    Boehm, F.; Eisenhauer, A.; Farkas, J.; Kiessling, W.; Veizer, J.; Wallmann, K.

    2008-12-01

    The calcium isotopic composition of seawater as recorded in brachiopod shells varied substantially during the Paleozoic (Farkas et al. 2007, Geochim. Cosmochim. Acta, 71, 5117-5134). The most prominent feature of the record is an excursion to higher 44Ca/40Ca values that started during the Early Carboniferous and lasted until the Permian. The shift occurred shortly after the transition from a calcite-sea to an aragonite-sea (Sandberg 1983, Nature 305, 19-22; Stanley and Hardie 1998, Pal3, 144, 3-19). It therefore has been interpreted to reflect a change in the average calcium isotope fractionation of carbonates produced in the oceans. Aragonite is depleted by about 0.6 permil in 44Ca/40Ca compared to calcite (Gussone et al. 2005, Geochim. Cosmochim. Acta, 69, 4485-4494). Consequently a transient shift from calcite dominated to an aragonite dominated calcium carbonate sedimentation could have caused the observed 0.5 permil isotope shift. We compare the marine calcium isotope record with a new compilation of the Phanerozoic trends in the skeletal mineralogy of marine invertebrates (Kiessling et al. 2008, Nature Geoscience, 1, 527-530). The compilation is based on data collected in the PaleoReef database and the Paleobiology Database, which include information on Phanerozoic reef complexes and taxonomic collection data of Phanerozoic biota, respectively. We find a strong positive correlation between the calcium isotope ratios and the abundance of aragonitic reef builders from the Silurian until the Permian at a sample resolution of about 10 million years. The two records, however, diverge in the Triassic, when reefs were dominated by aragonite but the calcium isotope values remained at a relatively low level. We also find a good correlation between calcium isotopes and the proportion of aragonite in the general record of Phanerozoic biota. However, in this case the records start to diverge already in the latest Carboniferous. The observations suggest that the

  16. Three-dimensional hydration layer mapping on the (10.4) surface of calcite using amplitude modulation atomic force microscopy.

    PubMed

    Marutschke, Christoph; Walters, Deron; Walters, Deron; Hermes, Ilka; Bechstein, Ralf; Kühnle, Angelika

    2014-08-22

    Calcite, the most stable modification of calcium carbonate, is a major mineral in nature. It is, therefore, highly relevant in a broad range of fields such as biomineralization, sea water desalination and oil production. Knowledge of the surface structure and reactivity of the most stable cleavage plane, calcite (10.4), is pivotal for understanding the role of calcite in these diverse areas. Given the fact that most biological processes and technical applications take place in an aqueous environment, perhaps the most basic - yet decisive - question addresses the interaction of water molecules with the calcite (10.4) surface. In this work, amplitude modulation atomic force microscopy is used for three-dimensional (3D) mapping of the surface structure and the hydration layers above the surface. An easy-to-use scanning protocol is implemented for collecting reliable 3D data. We carefully discuss a comprehensible criterion for identifying the solid-liquid interface within our data. In our data three hydration layers form a characteristic pattern that is commensurate with the underlying calcite surface.

  17. Inhibiting Effect of Additives on Pressure Solution of Calcite

    NASA Astrophysics Data System (ADS)

    Traskine, V.; Skvortsova, Z.; Badun, G.; Chernysheva, M.; Simonov, Ya.; Gazizullin, I.

    2018-05-01

    The task of protection of cultural heritage requires a better understanding of combined effects of mechanical and chemical factors involved in environmental deterioration of monuments. The present paper deals with extending some known physicochemical methods proposed for inhibiting the decay of unstressed materials to their study during water-assisted deformation. The tests have been carried out on natural limestone samples and calcite powders in CaCO3 saturated aqueous solutions under static loads causing measurable pressure solution creep. In the solutions containing 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotriacetic acid, or ethylenediaminetetraacetic acid, the creep rate decreases considerably with increasing concentration of additives. The extent of creep deceleration has been found to be proportional to the independently estimated calcite surface area occupied by adsorbed species. This fact enables us to discriminate the adsorption-induced effect from other variables controlling the pressure solution rate and may be used in screening of compounds able to minimize the environmental impact on marble and limestone objects undergoing mechanical stresses.

  18. 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

  19. Abiotic regulation: a common way for proteins to modulate their functions.

    PubMed

    Zou, Zhi; Fu, Xinmiao

    2015-01-01

    Modulation of protein intrinsic activity in cells is generally carried out via a combination of four common ways, i.e., allosteric regulation, covalent modification, proteolytic cleavage and association of other regulatory proteins. Accumulated evidence indicate that changes of certain abiotic factors (e.g., temperature, pH, light and mechanical force) within or outside the cells directly influence protein structure and thus profoundly modulate the functions of a wide range of proteins, termed as abiotic regulatory proteins (e.g., heat shock factor, small heat shock protein, hemoglobin, zymogen, integrin, rhodopsin). Such abiotic regulation apparently differs from the four classic ways in perceiving and response to the signals. Importantly, it enables cells to directly and also immediately response to extracellular stimuli, thus facilitating the ability of organisms to resist against and adapt to the abiotic stress and thereby playing crucial roles in life evolution. Altogether, abiotic regulation may be considered as a common way for proteins to modulate their functions.

  20. Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

    NASA Astrophysics Data System (ADS)

    Podder, J.; Lin, J.; Sun, W.; Botis, S. M.; Tse, J.; Chen, N.; Hu, Y.; Li, D.; Seaman, J.; Pan, Y.

    2017-02-01

    Calcium carbonates such as calcite are the dominant hosts of inorganic iodine in nature and are potentially important for the retention and removal of radioactive iodine isotopes (129I and 131I) in contaminated water. However, little is known about the structural environment of iodine in carbonates. In this study, iodate (IO3-) doped calcite and vaterite have been synthesized using the gel-diffusion method at three NaIO3 concentrations (0.002; 0.004; 0.008 M) and a pH value of 9.0, under ambient temperature and pressure. Inductively coupled plasma mass spectrometry (ICP-MS) analyses show that iodine is preferentially incorporated into calcite over vaterite. Synchrotron iodine K-edge X-ray absorption near-edge structure (XANES) spectra confirm that IO3- is the dominant iodine species in synthetic calcite and vaterite. Analyses of iodine K-edge extended X-ray absorption fine structure (EXAFS) data, complemented by periodic first-principles calculations at the density functional theory (DFT) levels, demonstrate that the I5+ ion of the IO3- group in calcite and vaterite is bonded by three and two additional O atoms (i.e., coordination numbers = 6 and 5), respectively, and is incorporated via the charged coupled substitution I5+ + Na+ ↔ C4+ + Ca2+, with the Na+ cation at a nearest Ca2+ site being the most energetically favorable configuration.

  1. Relative Shock Effects in Mixed Powders of Calcite, Gypsum, and Quartz: A Calibration Scheme from Shock Experiments

    NASA Technical Reports Server (NTRS)

    Bell, Mary S.

    2009-01-01

    The shock behavior of calcite and gypsum is important in understanding the Cretaceous/Tertiary event and other terrestrial impacts that contain evaporite sediments in their targets. Most interest focuses on issues of devolatilization to quantify the production of CO2 or SO2 to better understand their role in generating a temporary atmosphere and its effects on climate and biota [e.g., papers in 1,2,3,4]. Devolatilization of carbonate is also important because the dispersion and fragmentation of ejecta is strongly controlled by the expansion of large volumes of gas during the impact process as well [5,6]. Shock recovery experiments for calcite yield seemingly conflicting results: early experimental devolatilization studies [7,8,9] suggested that calcite was substantially outgassed at 30 GPa (> 50%). However, the recent petrographic work of [10,11,12] presented evidence that essentially intact calcite is recovered from 60 GPa experiments. [13] reported results of shock experiments on anhydrite, gypsum, and mixtures of those phases with silica. Their observations indicate little or no devolatilization of anhydrite shocked to 42 GPa and that the fraction of sulfur, by mass, that degassed is approx.10(exp -2) of theoretical prediction. In another (preliminary) report of shock experiments on calcite, anhydrite, and gypsum, [14] observe calcite recrystallization when shock loaded at 61 GPa, only intensive plastic deformation in anhydrite shock loaded at 63 GPa, and gypsum converted to anhydrite when shock loaded at 56 GPa. [15] shock loaded anhydrite and quartz to a peak pressure of 60 GPa. All of the quartz grains were trans-formed to glass and the platy anhydrite grains were completely pseudomorphed by small crystallized anhydrite grains. However, no evidence of interaction between the two phases could be observed and they suggest that recrystallization of anhydrite grains is the result of a solid state transformation. [16] reanalyzed the calcite and anhydrite shock

  2. Abiotic controls on N2O emissions from soils and wetlands

    NASA Astrophysics Data System (ADS)

    Horwath, W. R.

    2016-12-01

    The increase in atmospheric nitrous oxide (N2O) is a critical climate change issue contributing to global warming. Most studies on N2O production attribute microbial processes and their associated enzymatic reactions to be the main driver affecting emissions. The role of redox capable iron, manganese and organic compounds that can react with intermediates in the nitrogen cycle has also been shown to produce N2O abiotically. The importance of the abiotic pathways, however, is highly debated. The abiotic production of N2O is related to biophysiochemical controls and unique isotopic signatures of nitrogen cycle intermediates (hydroxylamine, nitric oxide, and nitrite), redox-active metals (iron and manganese) and organic matter (humic and fulvic acids). In a range of soils, we find that the iron directly associated with organic compounds is the strongest variable relating to N2O emissions. In addition to these factors, management is also assumed to affect abiotic N2O production through its impact on nitrogen cycle intermediates, but the environmental and physiochemical conditions that are changed by management are rarely considered in the abiotic production of N2O. We find that the amount and quality of organic compounds in soils directly determines the fate of soil N2O production (i.e. be emitted or consumed). Water depth in rice paddies and wetlands also plays a significant role in partitioning production and consumption of N2O. What is evident from studies on N2O emission is that abiotic reactions are coupled to biotic processes and they cannot be easily separated. The biotic/abiotic interactions have important ecological outcomes that influence abiotic production mechanisms and should be recognized as important controllers of N2O production and consumption processes in soils and sediments.

  3. Depth and Medium-Scale Spatial Processes Influence Fish Assemblage Structure of Unconsolidated Habitats in a Subtropical Marine Park

    PubMed Central

    Schultz, Arthur L.; Malcolm, Hamish A.; Bucher, Daniel J.; Linklater, Michelle; Smith, Stephen D. A.

    2014-01-01

    Where biological datasets are spatially limited, abiotic surrogates have been advocated to inform objective planning for Marine Protected Areas. However, this approach assumes close correlation between abiotic and biotic patterns. The Solitary Islands Marine Park, northern NSW, Australia, currently uses a habitat classification system (HCS) to assist with planning, but this is based only on data for reefs. We used Baited Remote Underwater Videos (BRUVs) to survey fish assemblages of unconsolidated substrata at different depths, distances from shore, and across an along-shore spatial scale of 10 s of km (2 transects) to examine how well the HCS works for this dominant habitat. We used multivariate regression modelling to examine the importance of these, and other environmental factors (backscatter intensity, fine-scale bathymetric variation and rugosity), in structuring fish assemblages. There were significant differences in fish assemblages across depths, distance from shore, and over the medium spatial scale of the study: together, these factors generated the optimum model in multivariate regression. However, marginal tests suggested that backscatter intensity, which itself is a surrogate for sediment type and hardness, might also influence fish assemblages and needs further investigation. Species richness was significantly different across all factors: however, total MaxN only differed significantly between locations. This study demonstrates that the pre-existing abiotic HCS only partially represents the range of fish assemblages of unconsolidated habitats in the region. PMID:24824998

  4. 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

  5. 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.

  6. Crystalline order of a water/glycine film coadsorbed on the (104) calcite surface.

    PubMed

    Magdans, Uta; Torrelles, Xavier; Angermund, Klaus; Gies, Hermann; Rius, Jordi

    2007-04-24

    For biomineralization processes, the interaction of the surface of calcite crystals with organic molecules is of particular importance. Especially, biologically controlled biomineralization as in exoskeletons of mollusks and echinoderms, e.g., sea urchin with single-crystal-like spines and shells,1-3 requires molecular control of seed formation and growth process. So far, experiments showing the obvious influence of organic molecules on the morphology and habit of calcite crystals have demonstrated the molecular dimension of the interaction.4-7 Details of the kinetics of growth and dissolution of mineral surfaces influenced by additives are available,8,9 but other experimental data about the structure of the organic/inorganic interface on the atomic scale are rare. On the other hand, complicated organic macromolecules which are involved in biomineralization are numerous, with only a small fraction solved in structure and function so far.10-13 Therefore, model systems have to be designed to provide a basic understanding for the interaction process.14 Using grazing incidence X-ray diffraction combined with molecular modeling techniques, we show that glycine molecules order periodically on the calcite (104) face in competition with the solvent water when exposed to an aqueous solution of the most simple amino acid. In contrast to the general concept of the charge-matching fit of organic molecules on mineral surfaces,4,14 glycine is not attached to the calcite surface directly but substitutes for water molecules in the second hydration layer.

  7. Chemical Evidence for Episodic Growth of a Fibrous Antitaxial Calcite Vein From Externally Derived Fluid

    NASA Astrophysics Data System (ADS)

    Barker, S. L.; Cox, S. F.; Eggins, S. M.; Gagan, M. K.

    2005-12-01

    Fibrous, massive and crustiform textured quartz and calcite veins occur within a deformed limestone-shale sequence at Taemas, in the Lachlan Fold Belt, eastern New South Wales, Australia. Stable isotope analyses of veins and host rock indicate that these veins formed from upwardly migrating, externally derived fluids. High spatial resolution (100 μm) analyses reveal per mil scale variations of stable C and O isotope ratios, and radiogenic Sr isotope ratios in a 1.5 cm thick, fibrous, antitaxial-growth calcite vein. LA-ICP-MS analyses (30 μm resolution) demonstrate significant variations in Fe, Mn, Sr, REE and Eu/Eu* parallel to the long axes of fibres. Stable and radiogenic isotopic ratio variations, and trace and REE concentration changes correlate with different cathodoluminesence zones, and slight changes in fibre orientation and thickness. The covariance of calcite textures and chemistry indicate that this fibrous vein grew episodically. Moreover, calcite in this vein was precipitated from externally derived fluid, which underwent variable fluid-rock interaction, and had a fluctuating oxidation state. This fibrous, antitaxial growth vein likely formed from fluid that migrated along fracture-controlled flow pathways.

  8. Coralline alga reveals first marine record of subarctic North Pacific climate change

    USGS Publications Warehouse

    Halfar, J.; Steneck, R.; Schone, B.; Moore, G.W.K.; Joachimski, M.; Kronz, A.; Fietzke, J.; Estes, James A.

    2007-01-01

    While recent changes in subarctic North Pacific climate had dramatic effects on ecosystems and fishery yields, past climate dynamics and teleconnection patterns are poorly understood due to the absence of century-long high-resolution marine records. We present the first 117-year long annually resolved marine climate history from the western Bering Sea/Aleutian Island region using information contained in the calcitic skeleton of the long-lived crustose coralline red alga Clathromorphum nereostratum, a previously unused climate archive. The skeletal ??18O-time series indicates significant warming and/or freshening of surface waters after the middle of the 20th century. Furthermore, the time series is spatiotemporally correlated with Pacific Decadal Oscillation (PDO) and tropical El Nio??-Southern Oscillation (ENSO) indices. Even though the western Bering Sea/Aleutian Island region is believed to be outside the area of significant marine response to ENSO, we propose that an ENSO signal is transmitted via the Alaskan Stream from the Eastern North Pacific, a region of known ENSO teleconnections. Copyright 2007 by the American Geophysical Union.

  9. Influence of calcite and dissolved calcium on uranium(VI) sorption to a hanford subsurface sediment.

    PubMed

    Dong, Wenming; Ball, William P; Liu, Chongxuan; Wang, Zheming; Stone, Alan T; Bai, Jing; Zachara, John M

    2005-10-15

    The influence of calcite and dissolved calcium on U(VI) adsorption was investigated using a calcite-containing sandy silt/clay sediment from the U. S. Department of Energy Hanford site. U(VI) adsorption to sediment, treated sediment, and sediment size fractions was studied in solutions that both had and had not been preequilibrated with calcite, at initial [U(VI)] = 10(-7)-10(-5) mol/L and final pH = 6.0-10.0. Kinetic and reversibility studies (pH 8.4) showed rapid sorption (30 min), with reasonable reversibility in the 3-day reaction time. Sorption from solutions equilibrated with calcite showed maximum U(VI) adsorption at pH 8.4 +/- 0.1. In contrast, calcium-free systems showed the greatest adsorption at pH 6.0-7.2. At pH > 8.4, U(VI) adsorption was identical from calcium-free and calcium-containing solutions. For calcite-presaturated systems, both speciation calculations and laser-induced fluorescence spectroscopic analyses indicated that aqueous U(VI) was increasingly dominated by Ca2UO2(CO3)3(0)(aq) at pH < 8.4 and thatformation of Ca2UO2(CO3)3(0)(aq) is what suppresses U(VI) adsorption. Above pH 8.4, aqueous U(VI) speciation was dominated by UO2(CO3)3(4-) in all solutions. Finally, results also showed that U(VI) adsorption was additive in regard to size fraction but not in regard to mineral mass: Carbonate minerals may have blocked U(VI) access to surfaces of higher sorption affinity.

  10. The shifting influence of abiotic drivers during landslide succession in Puerto Rico

    Treesearch

    L. R. Walker; A. B. Shiels; P. J. Bellingham; A. D. Sparrow; N. Fetcher; F. H. Landau; D. J. Lodge

    2013-01-01

    Summary 1. Abiotic variables are critical drivers of succession in most primary seres, but how their influence on biota changes over time is rarely examined. Landslides provide good model systems for examining abiotic influences because they are spatially and temporally heterogeneous habitats with distinct abiotic and biotic gradients and post-landslide erosion. 2. In...

  11. Microstructural analysis of calcite-filled fractures inherited from basement structures, southern Ontario, Canada: long term instability of the craton?

    NASA Astrophysics Data System (ADS)

    Spalding, Jennifer; Schneider, David

    2016-04-01

    Intra-cratonic regions are generally characterized by tectonic stability and low seismicity. In southern Ontario, Canada, moderate levels of seismicity have been recorded over the last few decades reaching magnitudes of 5 MN, indicating that the geosphere is not as stable as predicted. The stratigraphy of the region consists of Ordovician limestone with a thickness of ~200 m that unconformably overlays the Mesoproterozoic crystalline Grenville Province. Subsequent tectonism including repeated Paleozoic orogenies and rifting along the east coast of North America has reactivated Proterozoic structures that have propagated into the overlying carbonate platform forming mesoscopic-scale brittle structures. Exposed along the shores of Lake Ontario are decameter-scale fracture zones, with a fracture spacing of 0.5 to 10 meters. The dominant fracture set trends E-W, and often forms conjugate sets with less prominent NNE-oriented fractures. More locally, an older NW-oriented fracture set is cross cut by the E-W and NNE oriented fractures. Regionally, there have been six directions of maximum horizontal stress in southern Ontario since the Precambrian, with the current orientation of maximum stress oriented ENE as a consequence of far field Atlantic ridge-push forces generated at distant plate boundaries. Calcite mineralization along fractured surfaces locally form sub-horizontal slickenside fabrics which are covered by a layer of euhedral calcite crystals, suggesting that fracture dilation (and fluid flow) occurred after fracture slip to allow the growth of calcite crystals. Due to the proximity of the carbonate units to the crystalline basement, we expect the calcitic veins to be enriched in rare earth elements and are presently conducting geochemical analyses. The calcite veins and surfaces vary from 2.5 cm to 1 mm thicknesses, often with larger calcite crystals in the center of the vein and smaller crystals at the vein boundaries, likely representing nucleation on small

  12. Multiple Stressors in a Changing World: The Need for an Improved Perspective on Physiological Responses to the Dynamic Marine Environment.

    PubMed

    Gunderson, Alex R; Armstrong, Eric J; Stillman, Jonathon H

    2016-01-01

    Abiotic conditions (e.g., temperature and pH) fluctuate through time in most marine environments, sometimes passing intensity thresholds that induce physiological stress. Depending on habitat and season, the peak intensity of different abiotic stressors can occur in or out of phase with one another. Thus, some organisms are exposed to multiple stressors simultaneously, whereas others experience them sequentially. Understanding these physicochemical dynamics is critical because how organisms respond to multiple stressors depends on the magnitude and relative timing of each stressor. Here, we first discuss broad patterns of covariation between stressors in marine systems at various temporal scales. We then describe how these dynamics will influence physiological responses to multi-stressor exposures. Finally, we summarize how multi-stressor effects are currently assessed. We find that multi-stressor experiments have rarely incorporated naturalistic physicochemical variation into their designs, and emphasize the importance of doing so to make ecologically relevant inferences about physiological responses to global change.

  13. Microbial Diversity and Mineralogical-Mechanical Properties of Calcitic Cave Speleothems in Natural and in Vitro Biomineralization Conditions

    PubMed Central

    Dhami, Navdeep K.; Mukherjee, Abhijit; Watkin, Elizabeth L. J.

    2018-01-01

    Natural mineral formations are a window into important processes leading to carbon storage and mineralized carbonate structures formed through abiotic and biotic processes. In the current study, we made an attempt to undertake a comprehensive approach to characterize the mineralogical, mechanical, and microbial properties of different kinds of speleothems from karstic caves; with an aim to understand the bio-geo-chemical processes in speleothem structures and their impact on nanomechanical properties. We also investigated the biomineralization abilities of speleothem surface associated microbial communities in vitro. Mineralogical profiling using techniques such as X-ray powder Diffraction (XRD) and Tescan Integrated Mineral Analyzer (TIMA) demonstrated that calcite was the dominant mineral in the majority of speleothems with Energy Dispersive X-ray Analysis (EDS) indicating a few variations in the elemental components. Differing proportions of polymorphs of calcium carbonate such as aragonite and vaterite were also recorded. Significant variations in trace metal content were recorded through Inductively Coupled Plasma Mass Spectrometer (ICP-MS). Scanning Electron Microscopy (SEM) analysis revealed differences in morphological features of the crystals which varied from triangular prismatic shapes to etched spiky forms. Microbial imprints and associations were seen in a few sections. Analysis of the associated microbial diversity showed significant differences between various speleothems at Phylum level; although Proteobacteria and Actinobacteria were found to be the predominant groups. Genus level microbial associations showed a relationship with the geochemistry, mineralogical composition, and metal content of the speleothems. The assessment of nanomechanical properties measured by Nanoindentation revealed that the speleothems with a dominance of calcite were stronger than the speleothems with mixed calcium carbonate polymorphs and silica content. The in vitro

  14. Fabrication of low-crystalline carbonate apatite foam bone replacement based on phase transformation of calcite foam.

    PubMed

    Maruta, Michito; Matsuya, Shigeki; Nakamura, Seiji; Ishikawa, Kunio

    2011-01-01

    Carbonate apatite (CO(3)Ap) foam may be an ideal bone substitute as it is sidelined to cancellous bone with respect to its chemical composition and structure. However, CO(3)Ap foam fabricated using α-tricalcium phosphate foam showed limited mechanical strength. In the present study, feasibility of the fabrication of calcite which could be a precursor of CO(3)Ap was studied. Calcite foam was successfully fabricated by the so-called "ceramic foam" method using calcium hydroxide coated polyurethane foam under CO(2)+O(2) atmosphere. Then the calcite foam was immersed in Na(2)HPO(4) aqueous solution for phase transformation based on dissolution-precipitation reaction. When CaO-free calcite foam was immersed in Na(2)HPO(4) solution, low-crystalline CO(3)Ap foam with 93-96% porosity and fully interconnected porous structure was fabricated. The compressive strength of the foam was 25.6 ± 6 kPa. In light of these results, we concluded that the properties of the precursor foam were key factors for the fabrication of CO(3)Ap foams.

  15. Resetting of Mg isotopes between calcite and dolomite during burial metamorphism: Outlook of Mg isotopes as geothermometer and seawater proxy

    NASA Astrophysics Data System (ADS)

    Hu, Zhongya; Hu, Wenxuan; Wang, Xiaomin; Lu, Yizhou; Wang, Lichao; Liao, Zhiwei; Li, Weiqiang

    2017-07-01

    Magnesium isotopes are an emerging tool to study the geological processes recorded in carbonates. Calcite, due to its ubiquitous occurrence and the large Mg isotope fractionation associated with the mineral, has attracted great interests in applications of Mg isotope geochemistry. However, the fidelity of Mg isotopes in geological records of carbonate minerals (e.g., calcite and dolomite) against burial metamorphism remains poorly constrained. Here we report our investigation on the Mg isotope systematics of a dolomitized Middle Triassic Geshan carbonate section in eastern China. Magnesium isotope analysis was complemented by analyses of Sr-C-O isotopic compositions, major and trace element concentrations, and petrographic and mineralogical features. Multiple lines of evidence consistently indicated that post-depositional diagenesis of carbonate minerals occurred to the carbonate rocks. Magnesium isotope compositions of the carbonate rocks closely follow a mixing trend between a high δ26Mg dolomite end member and a low δ26Mg calcite end member, irrespective of sample positions in the section and calcite/dolomite ratio in the samples. By fitting the measured Mg isotope data using a two-end member mixing model, an inter-mineral Δ26Mgdolomite-calcite fractionation of 0.72‰ was obtained. Based on the experimentally derived Mg isotope fractionation factors for dolomite and calcite, a temperature of 150-190 °C was calculated to correspond to the 0.72‰ Δ26Mgdolomite-calcite fractionation. Such temperature range matches with the burial-thermal history of the local strata, making a successful case of Mg isotope geothermometry. Our results indicate that both calcite and dolomite had been re-equilibrated during burial metamorphism, and based on isotope mass balance of Mg, the system was buffered by dolomite in the section. Therefore, burial metamorphism may reset Mg isotope signature of calcite, and Mg isotope compositions in calcite should be dealt with caution in

  16. Synthesis of sub-millimeter calcite from aqueous solution

    NASA Astrophysics Data System (ADS)

    Reimi, M. A.; Morrison, J. M.; Burns, P. C.

    2011-12-01

    A novel aqueous synthesis that leads to the formation of calcite (CaCO3) crystals, up to 500μm in diameter, will be used to facilitate the study of contaminant transport in aqueous environmental systems. Existing processes tend to be complicated and often yield nanometer-sized or amorphous CaCO3. The synthesis method presented here, which involves slow mixing of concentrated solutions of CaCl2 ¬and (NH4)2CO3, produces single crystals of rhombohedral calcite in 2 to 4 days. Variations on the experimental method, including changes in pH and solution concentration, were explored to optimize the synthesis. Scanning Electron Microscope images show the differences in size and purity observed when the crystals are grown at pH values ranging from 2 to 6. The crystals grown from solutions of pH 2 were large (up to 500 micrometers in diameter) with minimal polycrystalline calcium carbonate, while crystals grown from solutions with pH values beyond 4 were smaller (up to 100 micrometers in diameter) with significant polycrystalline calcium carbonate. The synthesis method, materials characterization, and use in future actinide contaminant studies will be discussed.

  17. Chemistry of the calcite/water interface: Influence of sulfate ions and consequences in terms of cohesion forces

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Pourchet, Sylvie, E-mail: sylvie.pourchet@u-bourgogne.fr; Pochard, Isabelle; Brunel, Fabrice

    2013-10-15

    Calcite suspensions are used to mimic the behavior of more complex cementitious systems. Therefore the characterization of calcite–water interface in strong alkaline conditions, through ionic adsorption, electrokinetic measurements, static rheology and atomic force microscopy is a prerequisite. Calcium, a potential determining ion for calcite, adsorbs specifically onto the weakly positively charged calcite surface in water. This leads to an increase of the repulsive electric double layer force and thus weakens the particle cohesion. Sulfate adsorption, made at constant calcium concentration and ionic strength, significantly increases the attractive interactions between the calcite particles despite its very low adsorption. This is attributedmore » to a lowering of the electrostatic repulsion in connection with the evolution of the zeta potential. The linear relationship found between the yield stress and ζ{sup 2} proves that the classical DLVO theory applies for these systems, contrary to what was previously observed with C–S–H particles under the same conditions.« less

  18. Physical and stable-isotope evidence for formation of secondary calcite and silica in the unsaturated zone, Yucca Mountain, Nevada

    USGS Publications Warehouse

    Whelan, J.F.; Paces, J.B.; Peterman, Z.E.

    2002-01-01

    Calcite and silica form coatings on fracture footwalls and cavity floors in the welded tuffs at Yucca Mountain, the potential site of a high-level radioactive waste repository. These secondary mineral deposits are heterogeneously distributed in the unsaturated zone (UZ) with fewer than 10% of possible depositional sites mineralized. The paragenetic sequence, compiled from deposits throughout the UZ, consists of an early-stage assemblage of calcite??fluorite??zeolites that is frequently capped by chalcedony??quartz. Intermediate- and late-stage deposits consist largely of calcite, commonly with opal on buried growth layers or outermost crystal faces of the calcite. Coatings on steep-dipping fractures usually are thin (??? 3 mm) with low-relief outer surfaces whereas shallow-dipping fractures and lithophysal cavities typically contain thicker, more coarsely crystalline deposits characterized by unusual thin, tabular calcite blades up to several cms in length. These blades may be capped with knobby or corniced overgrowths of late-stage calcite intergrown with opal. The observed textures in the fracture and cavity deposits are consistent with deposition from films of water fingering down fracture footwalls or drawn up faces of growing crystals by surface tension and evaporated at the crystal tips. Fluid inclusion studies have shown that most early-stage and some intermediate-stage calcite formed at temperatures of 35 to 85??C. Calcite deposition during the past several million years appears to have been at temperatures < 30??C. The elevated temperatures indicated by the fluid inclusions are consistent with temperatures estimated from calcite ??18O values. Although others have interpreted the elevated temperatures as evidence of hydrothermal activity and flooding of the tuffs of the potential repository, the authors conclude that the temperatures and fluid-inclusion assemblages are consistent with deposition in a UZ environment that experienced prolonged heat input from

  19. Multimodel inference to quantify the relative importance of abiotic factors in the population dynamics of marine zooplankton

    NASA Astrophysics Data System (ADS)

    Everaert, Gert; Deschutter, Yana; De Troch, Marleen; Janssen, Colin R.; De Schamphelaere, Karel

    2018-05-01

    The effect of multiple stressors on marine ecosystems remains poorly understood and most of the knowledge available is related to phytoplankton. To partly address this knowledge gap, we tested if combining multimodel inference with generalized additive modelling could quantify the relative contribution of environmental variables on the population dynamics of a zooplankton species in the Belgian part of the North Sea. Hence, we have quantified the relative contribution of oceanographic variables (e.g. water temperature, salinity, nutrient concentrations, and chlorophyll a concentrations) and anthropogenic chemicals (i.e. polychlorinated biphenyls) to the density of Acartia clausi. We found that models with water temperature and chlorophyll a concentration explained ca. 73% of the population density of the marine copepod. Multimodel inference in combination with regression-based models are a generic way to disentangle and quantify multiple stressor-induced changes in marine ecosystems. Future-oriented simulations of copepod densities suggested increased copepod densities under predicted environmental changes.

  20. Transient calcite fracture fillings in a welded tuff, Snowshoe Mountain, Colorado

    USGS Publications Warehouse

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

    2000-01-01

    The core from two boreholes (13.1 and 19.2 m depth) drilled 500 m apart in the fractured, welded tuff near the summit of the Snowshoe Mountain, Colorado (47??30'N, 106??55'W) had unique petrographic and hydrodynamic properties. Borehole SM-4 had highly variable annual water levels, in contrast to SM-1a, whose water level remained near the land surface. Core samples from both boreholes (n = 10 and 11) were examined petrographically in thin sections impregnated with epoxy containing rhodamine to mark the pore system features, and were analyzed for matrix porosity and permeability. Core from the borehole sampling the vadose zone was characterized by open fractures with enhanced porosity around phenocrysts due to chemical weathering. Fractures within the borehole sampling the phreatic zone were mineralized with calcite and had porosity characteristics similar to Unweathered and unfractured rock. At the top of the phreatic zone petrography indicates that calcite is dissolving, thereby changing the hydrogeochemical character of the rock (i.e. permeability, porosity, reactive surface area, and mineralogy). Radiocarbon ages and C and O stable isotopes indicate that calcite mineralization occurred about 30 to 40 ka ago and that there was more than one mineralization event. Results of this study also provide some relationships between primary porosity development from 3 types of fracture in a welded tuff. (C) 2000 Elsevier Science Ltd.

  1. Protein metabolism in marine animals: the underlying mechanism of growth.

    PubMed

    Fraser, Keiron P P; Rogers, Alex D

    2007-01-01

    Growth is a fundamental process within all marine organisms. In soft tissues, growth is primarily achieved by the synthesis and retention of proteins as protein growth. The protein pool (all the protein within the organism) is highly dynamic, with proteins constantly entering the pool via protein synthesis or being removed from the pool via protein degradation. Any net change in the size of the protein pool, positive or negative, is termed protein growth. The three inter-related processes of protein synthesis, degradation and growth are together termed protein metabolism. Measurement of protein metabolism is vital in helping us understand how biotic and abiotic factors affect growth and growth efficiency in marine animals. Recently, the developing fields of transcriptomics and proteomics have started to offer us a means of greatly increasing our knowledge of the underlying molecular control of protein metabolism. Transcriptomics may also allow us to detect subtle changes in gene expression associated with protein synthesis and degradation, which cannot be detected using classical methods. A large literature exists on protein metabolism in animals; however, this chapter concentrates on what we know of marine ectotherms; data from non-marine ectotherms and endotherms are only discussed when the data are of particular relevance. We first consider the techniques available to measure protein metabolism, their problems and what validation is required. Protein metabolism in marine organisms is highly sensitive to a wide variety of factors, including temperature, pollution, seasonality, nutrition, developmental stage, genetics, sexual maturation and moulting. We examine how these abiotic and biotic factors affect protein metabolism at the level of whole-animal (adult and larval), tissue and cellular protein metabolism. Available gene expression data, which help us understand the underlying control of protein metabolism, are also discussed. As protein metabolism appears to

  2. A review of selection-based tests of abiotic surrogates for species representation.

    PubMed

    Beier, Paul; Sutcliffe, Patricia; Hjort, Jan; Faith, Daniel P; Pressey, Robert L; Albuquerque, Fabio

    2015-06-01

    Because conservation planners typically lack data on where species occur, environmental surrogates--including geophysical settings and climate types--have been used to prioritize sites within a planning area. We reviewed 622 evaluations of the effectiveness of abiotic surrogates in representing species in 19 study areas. Sites selected using abiotic surrogates represented more species than an equal number of randomly selected sites in 43% of tests (55% for plants) and on average improved on random selection of sites by about 8% (21% for plants). Environmental diversity (ED) (42% median improvement on random selection) and biotically informed clusters showed promising results and merit additional testing. We suggest 4 ways to improve performance of abiotic surrogates. First, analysts should consider a broad spectrum of candidate variables to define surrogates, including rarely used variables related to geographic separation, distance from coast, hydrology, and within-site abiotic diversity. Second, abiotic surrogates should be defined at fine thematic resolution. Third, sites (the landscape units prioritized within a planning area) should be small enough to ensure that surrogates reflect species' environments and to produce prioritizations that match the spatial resolution of conservation decisions. Fourth, if species inventories are available for some planning units, planners should define surrogates based on the abiotic variables that most influence species turnover in the planning area. Although species inventories increase the cost of using abiotic surrogates, a modest number of inventories could provide the data needed to select variables and evaluate surrogates. Additional tests of nonclimate abiotic surrogates are needed to evaluate the utility of conserving nature's stage as a strategy for conservation planning in the face of climate change. © 2015 Society for Conservation Biology.

  3. The Effect of Additives on the Early Stages of Growth of Calcite Single Crystals

    PubMed Central

    Freeman, Colin L.; Gong, Xiuqing; Levenstein, Mark A.; Wang, Yunwei; Kulak, Alexander; Anduix‐Canto, Clara; Lee, Phillip A.; Li, Shunbo; Chen, Li; Christenson, Hugo K.

    2017-01-01

    Abstract As crystallization processes are often rapid, it can be difficult to monitor their growth mechanisms. In this study, we made use of the fact that crystallization proceeds more slowly in small volumes than in bulk solution to investigate the effects of the soluble additives Mg2+ and poly(styrene sulfonate) (PSS) on the early stages of growth of calcite crystals. Using a “Crystal Hotel” microfluidic device to provide well‐defined, nanoliter volumes, we observed that calcite crystals form via an amorphous precursor phase. Surprisingly, the first calcite crystals formed are perfect rhombohedra, and the soluble additives have no influence on the morphology until the crystals reach sizes of 0.1–0.5 μm for Mg2+ and 1–2 μm for PSS. The crystals then continue to grow to develop morphologies characteristic of these additives. These results can be rationalized by considering additive binding to kink sites, which is consistent with crystal growth by a classical mechanism. PMID:28767197

  4. Revisiting the Role of Plant Transcription Factors in the Battle against Abiotic Stress.

    PubMed

    Khan, Sardar-Ali; Li, Meng-Zhan; Wang, Suo-Min; Yin, Hong-Ju

    2018-05-31

    Owing to diverse abiotic stresses and global climate deterioration, the agricultural production worldwide is suffering serious losses. Breeding stress-resilient crops with higher quality and yield against multiple environmental stresses via application of transgenic technologies is currently the most promising approach. Deciphering molecular principles and mining stress-associate genes that govern plant responses against abiotic stresses is one of the prerequisites to develop stress-resistant crop varieties. As molecular switches in controlling stress-responsive genes expression, transcription factors (TFs) play crucial roles in regulating various abiotic stress responses. Hence, functional analysis of TFs and their interaction partners during abiotic stresses is crucial to perceive their role in diverse signaling cascades that many researchers have continued to undertake. Here, we review current developments in understanding TFs, with particular emphasis on their functions in orchestrating plant abiotic stress responses. Further, we discuss novel molecular mechanisms of their action under abiotic stress conditions. This will provide valuable information for understanding regulatory mechanisms to engineer stress-tolerant crops.

  5. Crab regulation of cross-ecosystem resource transfer by marine foraging fire ants.

    PubMed

    Garcia, Erica A; Bertness, Mark D; Alberti, Juan; Silliman, Brian R

    2011-08-01

    Permeability of boundaries in biological systems is regulated by biotic and/or abiotic factors. Despite this knowledge, the role of biotic factors in regulating resource transfer across ecosystem boundaries has received little study. Additionally, little is known about how cross-ecosystem resource transfer affects source populations. We used experiments, observations and stable isotopes, to evaluate: (1) the proportion of intertidal-foraging black fire ant (Solenopsis richteri) diet derived from marine sources, (2) how black fire ant cross-ecosystem resource transfer is altered by the dominant bioengineer in the intertidal, a burrowing crab (Neohelice granulata), (3) the top-down impact of these terrestrial ants on a marine resource, and (4) the effect of marine resources on recipient black fire ants. We found that more than 85% of the black fire ant diet is derived from marine sources, the number of intertidal foraging ants doubles in the absence of crab burrows, and that ants cause a 50% reduction in intertidal polychaetes. Also, ant mound density is three times greater adjacent to marine systems. This study reveals that cross-ecosystem foraging terrestrial ants can clearly have strong impacts on marine resources. Furthermore, ecosystem engineers that modify and occupy habitat in these ecosystem boundaries can strongly regulate the degree of cross-ecosystem resource transfer and resultant top down impacts.

  6. Controlling the size and morphology of precipitated calcite particles by the selection of solvent composition

    NASA Astrophysics Data System (ADS)

    Konopacka-Łyskawa, Donata; Kościelska, Barbara; Karczewski, Jakub

    2017-11-01

    Precipitated calcium carbonate is used as an additive in the manufacture of many products. Particles with specific characteristics can be obtained by the selection of precipitation conditions, including temperature and the composition of solvent. In this work, calcium carbonate particles were obtained in the reaction of calcium hydroxide with carbon dioxide at 65 °C. Initial Ca(OH)2 suspensions were prepared in pure water and aqueous solutions of ethylene glycol or glycerol of the concentration range up to 20% (vol.). The course of reaction was monitored by conductivity measurements. Precipitated solids were analyzed by FTIR, XRD, SEM and the particles size distribution was determined by a laser diffraction method. The adsorption of ethylene glycol or glycerol on the surface of scalenohedral and rhombohedral calcite was testes by a normal-phase high-performance liquid chromatography. The addition of organic solvents changed the viscosity of reaction mixtures, the rate of carbon dioxide absorption and the solubility of inorganic components and therefore influence calcium carbonate precipitation conditions. All synthesized calcium carbonate products were in a calcite form. Scalenohedral calcite crystals were produced when water was a liquid phase, whereas addition of organic solvents resulted in the formation of rhombo-scalenohedral particles. The increase in organic compounds concentration resulted in the decrease of mean particles size from 2.4 μm to 1.7 μm in ethylene glycol solutions and to 1.4 μm in glycerol solutions. On the basis of adsorption tests, it was confirm that calcite surface interact stronger with glycerol than ethylene glycol. The interaction between scalenohedral calcite and used organic additives was higher in comparison to the pure rhombohedral form applied as a stationary phase.

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

    NASA Astrophysics Data System (ADS)

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

    1999-02-01

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

  8. 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.

  9. Development of a functionalized coating for inhibition of marine corrosion and biofouling

    NASA Astrophysics Data System (ADS)

    Gittens, Jeanette Elizabeth

    The financial loss incurred by corrosion of metals in the marine environment has led to a need to develop effective, economic and environmentally friendly methods of protection. Traditional methods of counteracting the development of surface biofilms and biofouling within aqueous environments have involved implementing chemical biocides, often with a deleterious effect on non-target organisms. Sol gel coating technology offers a convenient route for immobilizing functional additives, such as inhibitors or, in the case of this study, biologically active microorganisms. Paenibacillus polymyxa biofilms inhibit the corrosion of metal substrates and this strain has the advantage of forming endospores can withstand the solvent and acid concentrations required in sol-gel formulation. Encapsulation of viable P. polymyxa endospores within the sol-gel matrix allowed germination on exposure to nutrients, when germinating endospores and vegetative cells were seen after fluorescence microscopy to be distributed throughout the coating. Laboratory electrochemical impedance tests were used to characterize the corrosion behaviour of the endospore-containing (biotic) sol-gel coating in comparison to an abiotic (no endospores) sol-gel only coating and one containing non-viable (killed) endospores. The technology enabled manipulation of the sol-gel formulation and the method of application to produce biotic sol-gel with enhanced corrosion inhibition properties on aluminium alloy. Field trials in a marine environment confirmed the corrosion protecting properties of the biotic coating and that the biotic coatings inhibited macroscopic biofouling for at least 29 weeks relative to the controls without encapsulated live endospores. Production of polymyxin by the encapsulated bacteria, which was proposed as a mechanism by which they inhibit MIC, was less than 1 mug per ml and below the threshold of detection by liquid chromatography mass spectrometry and antimicrobial bioassay. Microcosm

  10. 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.

  11. Combined effects of Corexit EC 9500A with secondary abiotic and biotic factors in the rotifer Brachionus plicatilis.

    PubMed

    Williams, Michael B; Powell, Mickie L; Watts, Stephen A

    2016-10-01

    We examined lethality and behavioral effects of Corexit EC 9500A (C-9500A) exposure on the model marine zooplankton Brachionus plicatilis singularly and in combination with abiotic and biotic factors. C-9500A exposure at standard husbandry conditions (17.5ppt, 24°C, 200 rotifer*mL(-1) density) identified the 24h median lethal concentration, by Probit analysis, to be 107ppm for cultured B. plicatilis. Rotifers surviving exposure to higher concentrations (100 and 150ppm) exhibited a decreased swimming velocity and a reduced net to gross movement ratio. Significant interaction between C-9500A exposure and temperature or salinity was observed. Upper thermal range was reduced and maximal salinity stress was seen as ca. 25ppt. Increased or decreased nutritional availability over the exposure period did not significantly alter mortality of B. plicatilis populations at the concentrations tested. Results from this study may be useful for predicting possible outcomes on marine zooplankton following dispersant application under diverse natural conditions. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. Biocalcification by halophilic bacteria for remediation of concrete structures in marine environment.

    PubMed

    Bansal, Roohi; Dhami, Navdeep Kaur; Mukherjee, Abhijit; Reddy, M Sudhakara

    2016-11-01

    Microbial carbonate precipitation has emerged as a promising technology for remediation and restoration of concrete structures. Deterioration of reinforced concrete structures in marine environments is a major concern due to chloride-induced corrosion. In the current study, halophilic bacteria Exiguobacterium mexicanum was isolated from sea water and tested for biomineralization potential under different salt stress conditions. The growth, urease and carbonic anhydrase production significantly increased under salt stress conditions. Maximum calcium carbonate precipitation was recorded at 5 % NaCl concentration. Application of E. mexicanum on concrete specimens significantly increased the compressive strength (23.5 %) and reduced water absorption about five times under 5 % salt stress conditions compared to control specimens. SEM and XRD analysis of bacterial-treated concrete specimens confirmed the precipitation of calcite. The present study results support the potential of this technology for improving the strength and durability properties of building structures in marine environments.

  13. Marine pisolites from Upper Proterozoic carbonates of East Greenland and Spitsbergen

    NASA Technical Reports Server (NTRS)

    Swett, K.; Knoll, A. H.

    1989-01-01

    Upper Proterozoic carbonate successions from central East Greenland (the Limestone-Dolomite 'Series' of the Eleonore Bay Group) and Svalbard (the Backlundtoppen Formation of the Akademikerbreen) Group, Spitsbergen, and the Upper Russo Formation of the Raoldtoppen Group, Nordaustlandet) contain thick sequences dominated by pisolites. These rocks were generated in shallow marine environments, and the pisoids are essentially oversized ooids. A marine environment is supported by the thickness and lateral extent of the carbonates; by a sedimentary association of pisolites with stromatolites, flake-conglomerates, calcarenites, calcilutites, microphytolites, and ooids similar to that found in numerous other Proterozoic carbonate successions; by sedimentary structures, including cross-beds and megaripples that characterize the pisolitic beds; and by microorganisms that inhabit modern marine ooids of the Bahama Banks. Petrographic features and strontium abundances suggest that the pisoids were originally aragonitic, but neomorphism, silicification, calcitization, and dolomitization have extensively modified original mineralogies and fabrics. The East Greenland and Svalbard pisolitic carbonates reflect similar depositional environments and diagenetic histories, reinforcing previous bio-, litho-, and chemostratigraphic interpretations that the two sequences accumulated contiguously in a coastal zone of pisoid genesis which extended for at least 600, and probably 1000 or more, kilometres.

  14. Marine pisolites from Upper Proterozoic carbonates of East Greenland and Spitsbergen.

    PubMed

    Swett, K; Knoll, A H

    1989-01-01

    Upper Proterozoic carbonate successions from central East Greenland (the Limestone-Dolomite 'Series' of the Eleonore Bay Group) and Svalbard (the Backlundtoppen Formation of the Akademikerbreen) Group, Spitsbergen, and the Upper Russo Formation of the Raoldtoppen Group, Nordaustlandet) contain thick sequences dominated by pisolites. These rocks were generated in shallow marine environments, and the pisoids are essentially oversized ooids. A marine environment is supported by the thickness and lateral extent of the carbonates; by a sedimentary association of pisolites with stromatolites, flake-conglomerates, calcarenites, calcilutites, microphytolites, and ooids similar to that found in numerous other Proterozoic carbonate successions; by sedimentary structures, including cross-beds and megaripples that characterize the pisolitic beds; and by microorganisms that inhabit modern marine ooids of the Bahama Banks. Petrographic features and strontium abundances suggest that the pisoids were originally aragonitic, but neomorphism, silicification, calcitization, and dolomitization have extensively modified original mineralogies and fabrics. The East Greenland and Svalbard pisolitic carbonates reflect similar depositional environments and diagenetic histories, reinforcing previous bio-, litho-, and chemostratigraphic interpretations that the two sequences accumulated contiguously in a coastal zone of pisoid genesis which extended for at least 600, and probably 1000 or more, kilometres.

  15. Ecological and evolutionary genomics of marine photosynthetic organisms.

    PubMed

    Coelho, Susana M; Simon, Nathalie; Ahmed, Sophia; Cock, J Mark; Partensky, Frédéric

    2013-02-01

    Environmental (ecological) genomics aims to understand the genetic basis of relationships between organisms and their abiotic and biotic environments. It is a rapidly progressing field of research largely due to recent advances in the speed and volume of genomic data being produced by next generation sequencing (NGS) technologies. Building on information generated by NGS-based approaches, functional genomic methodologies are being applied to identify and characterize genes and gene systems of both environmental and evolutionary relevance. Marine photosynthetic organisms (MPOs) were poorly represented amongst the early genomic models, but this situation is changing rapidly. Here we provide an overview of the recent advances in the application of ecological genomic approaches to both prokaryotic and eukaryotic MPOs. We describe how these approaches are being used to explore the biology and ecology of marine cyanobacteria and algae, particularly with regard to their functions in a broad range of marine ecosystems. Specifically, we review the ecological and evolutionary insights gained from whole genome and transcriptome sequencing projects applied to MPOs and illustrate how their genomes are yielding information on the specific features of these organisms. © 2012 Blackwell Publishing Ltd.

  16. Strain rate dependent calcite microfabric evolution - An experiment carried out by nature

    NASA Astrophysics Data System (ADS)

    Rogowitz, Anna; Grasemann, Bernhard; Huet, Benjamin; Habler, Gerlinde

    2014-12-01

    A flanking structure developed along a secondary shear zone in calcite marbles, on Syros (Cyclades, Greece), provides a natural laboratory for directly studying the effects of strain rate variations on calcite deformation at identical pressure and temperature conditions. The presence and rotation of a fracture during progressive deformation caused extreme variations in finite strain and strain rate, forming a localized ductile shear zone that shows different microstructures and textures. Textures and the degree of intracrystalline deformation were measured by electron backscattered diffraction. Marbles from the host rocks and the shear zone, which deformed at various strain rates, display crystal-preferred orientation, suggesting that the calcite preferentially deformed by intracrystalline-plastic deformation. Increasing strain rate results in a switch from subgrain rotation to bulging recrystallization in the dislocation-creep regime. With increasing strain rate, we observe in fine-grained (3 μm) ultramylonitic zones a change in deformation regime from grain-size insensitive to grain-size sensitive. Paleowattmeter and the paleopiezometer suggest strain rates for the localized shear zone around 10-10 s-1 and for the marble host rock around 10-12 s-1. We conclude that varying natural strain rates can have a first-order effect on the microstructures and textures that developed under the same metamorphic conditions.

  17. Geochemistry of speleothems affected by aragonite to calcite recrystallization - Potential inheritance from the precursor mineral

    NASA Astrophysics Data System (ADS)

    Domínguez-Villar, David; Krklec, Kristina; Pelicon, Primož; Fairchild, Ian J.; Cheng, Hai; Edwards, Lawrence R.

    2017-03-01

    Formerly aragonite speleothems recrystallized to calcite result from solutions subsaturated in aragonite and supersaturated in calcite that infiltrate into the speleothem through the interconnected porosity. In most cases, the crystal replacement takes place through a thin solution film. This diagenetic process can occur under open or semi-closed geochemical conditions. Thus, secondary calcite crystals record the composition of the fluid at the time of diagenesis affected by calcite partition coefficients and fractionation factors (open system) or partly inherit the composition of the primary aragonite (semi-closed system). So, whether or not recrystallized aragonite speleothems can record reliable geochemical signals from the time of speleothem primary deposition still is an open debate. We studied a stalagmite from Eagle Cave (Spain) predominantly composed of secondary calcite that replaced aragonite, although a core of primary aragonite extending 45 mm along the growth direction was preserved at the base of the sample. We obtained Mg and Sr compositional maps, paired U-Th dating and δ18O and δ13C profiles across the diagenetic front. Additionally, two parallel isotope records were obtained along the speleothem growth direction in the aragonite and calcite sectors. Our results support that recrystallization of this speleothem took place in open system conditions for δ18O, δ13C, Mg and Sr, but in semi-closed system conditions for U and Th. The recrystallization of this sample took place during one or several events, likely after the Younger Dryas as a result of climate change influencing drip water composition. Based on compositional zoned patterns, we suggest that the advance of diagenetic fronts in this speleothem had an average rate of 50 ± 45 μm/yr. Such recrystallization rate can transform any aragonite speleothem into calcite within a few centuries. We suggest that the volume of water interacting with the speleothem at the time of recrystallization is

  18. Research advances in major cereal crops for adaptation to abiotic stresses

    PubMed Central

    Maiti, RK; Satya, Pratik

    2014-01-01

    With devastating increase in population there is a great necessity to increase crop productivity of staple crops but the productivity is greatly affected by various abiotic stress factors such as drought, salinity. An attempt has been made a brief account on abiotic stress resistance of major cereal crops viz. In spite of good successes obtained on physiological and use molecular biology, the benefits of this high cost technology are beyond the reach of developing countries. This review discusses several morphological, anatomical, physiological, biochemical and molecular mechanisms of major cereal crops related to the adaptation of these crop to abiotic stress factors. It discusses the effect of abiotic stresses on physiological processes such as flowering, grain filling and maturation and plant metabolisms viz. photosynthesis, enzyme activity, mineral nutrition, and respiration. Though significant progress has been attained on the physiological, biochemical basis of resistance to abiotic stress factors, very little progress has been achieved to increase productivity under sustainable agriculture. Therefore, there is a great necessity of inter-disciplinary research to address this issue and to evolve efficient technology and its transfer to the farmers’ fields. PMID:25523172

  19. Research advances in major cereal crops for adaptation to abiotic stresses.

    PubMed

    Maiti, R K; Satya, Pratik

    2014-01-01

    With devastating increase in population there is a great necessity to increase crop productivity of staple crops but the productivity is greatly affected by various abiotic stress factors such as drought, salinity. An attempt has been made a brief account on abiotic stress resistance of major cereal crops viz. In spite of good successes obtained on physiological and use molecular biology, the benefits of this high cost technology are beyond the reach of developing countries. This review discusses several morphological, anatomical, physiological, biochemical and molecular mechanisms of major cereal crops related to the adaptation of these crop to abiotic stress factors. It discusses the effect of abiotic stresses on physiological processes such as flowering, grain filling and maturation and plant metabolisms viz. photosynthesis, enzyme activity, mineral nutrition, and respiration. Though significant progress has been attained on the physiological, biochemical basis of resistance to abiotic stress factors, very little progress has been achieved to increase productivity under sustainable agriculture. Therefore, there is a great necessity of inter-disciplinary research to address this issue and to evolve efficient technology and its transfer to the farmers' fields.

  20. Clumped isotope thermometry of calcite and dolomite in a contact metamorphic environment

    NASA Astrophysics Data System (ADS)

    Lloyd, Max K.; Eiler, John M.; Nabelek, Peter I.

    2017-01-01

    Clumped isotope compositions of slowly-cooled calcite and dolomite marbles record apparent equilibrium temperatures of roughly 150-200 °C and 300-350 °C, respectively. Because clumped isotope compositions are sensitive to the details of T-t path within these intervals, measurements of the Δ47 values of coexisting calcite and dolomite can place new constraints on thermal history of low-grade metamorphic rocks over a large portion of the upper crust (from ∼5 to ∼15 km depth). We studied the clumped isotope geochemistry of coexisting calcite and dolomite in marbles from the Notch Peak contact metamorphic aureole, Utah. Here, flat-lying limestones were intruded by a pluton, producing a regular, zoned metamorphic aureole. Calcite Δ47 temperatures are uniform, 156 ± 12 °C (2σ s.e.), across rocks varying from high-grade marbles that exceeded 500 °C to nominally unmetamorphosed limestones >5 km from the intrusion. This result appears to require that the temperature far from the pluton was close to this value; an ambient temperature just 20 °C lower would not have permitted substantial re-equilibration, and should have preserved depositional or early diagenetic Δ47 values several km from the pluton. Combining this result with depth constraints from overlying strata suggests the country rock here had an average regional geotherm of 22.3-27.4 °C/km from the late Jurassic Period until at least the middle Paleogene Period. Dolomite Δ47 in all samples above the talc + tremolite-in isograd record apparent equilibrium temperatures of 328-12+13 °C (1σ s.e.), consistent with the apparent equilibrium blocking temperature we expect for cooling from peak metamorphic conditions. At greater distances, dolomite Δ47 records temperatures of peak (anchi)metamorphism or pre-metamorphic diagenetic conditions. The interface between these domains is the location of the 330 °C isotherm associated with intrusion. Multiple-phase clumped isotope measurements are complemented by

  1. An assessment of calcite crystal growth mechanisms based on crystal size distributions

    USGS Publications Warehouse

    Kile, D.E.; Eberl, D.D.; Hoch, A.R.; Reddy, M.M.

    2000-01-01

    Calcite crystal growth experiments were undertaken to test a recently proposed model that relates crystal growth mechanisms to the shapes of crystal size distributions (CSDs). According to this approach, CSDs for minerals have three basic shapes: (1) asymptotic, which is related to a crystal growth mechanism having constant-rate nucleation accompanied by surface-controlled growth; (2) lognormal, which results from decaying-rate nucleation accompanied by surface-controlled growth; and (3) a theoretical, universal, steady-state curve attributed to Ostwald ripening. In addition, there is a fourth crystal growth mechanism that does not have a specific CSD shape, but which preserves the relative shapes of previously formed CSDs. This mechanism is attributed to supply-controlled growth. All three shapes were produced experimentally in the calcite growth experiments by modifying nucleation conditions and solution concentrations. The asymptotic CSD formed when additional reactants were added stepwise to the surface of solutions that were supersaturated with respect to calcite (initial Ω = 20, where Ω = 1 represents saturation), thereby leading to the continuous nucleation and growth of calcite crystals. Lognormal CSDs resulted when reactants were added continuously below the solution surface, via a submerged tube, to similarly supersaturated solutions (initial Ω = 22 to 41), thereby leading to a single nucleation event followed by surface-controlled growth. The Ostwald CSD resulted when concentrated reactants were rapidly mixed, leading initially to high levels of supersaturation (Ω >100), and to the formation and subsequent dissolution of very small nuclei, thereby yielding CSDs having small crystal size variances. The three CSD shapes likely were produced early in the crystallization process, in the nanometer crystal size range, and preserved during subsequent growth. Preservation of the relative shapes of the CSDs indicates that a supply-controlled growth mechanism

  2. Biochemical and bioaccumulation approaches for investigating marine pollution using Mediterranean rainbow wrasse, Coris julis (Linneaus 1798).

    PubMed

    Tomasello, Barbara; Copat, Chiara; Pulvirenti, Valentina; Ferrito, Venera; Ferrante, Margherita; Renis, Marcella; Sciacca, Salvatore; Tigano, Concetta

    2012-12-01

    A multibiomarkers approach was used in order to estimate and monitor marine pollution. Coris julis (Linneaus, 1758) was chosen as a sentinel organism, and the specimens were collected from three well-known sites along the Ionic coast of Sicily: the protected marine area (P.M.A) "Cyclop's Islands" of Acitrezza (CT), used as a control site, Riposto (CT), and the industrial site of Augusta (SR). Abiotic levels of contaminants were also detected. High levels of biotic and abiotic accumulation were found at the industrial site in which the presence of genotoxic and oxidative damage were also evidenced, measured by Micronuclei, Alkaline and Fpg-modified Comet assays. The protein expression analysis showed metallothioneins (MTs) as good tissue-specific markers of metal accumulation. Their levels were significantly higher in muscle than in liver tissue for all the sampling sites, with a positive correlation among tissue levels and the degree of pollution at the sites. Conversely, heat shock proteins 70 (HSP70) expression was higher in Augusta and Riposto than in the control site, but no significant difference was found between the examined tissues among all sites. Copyright © 2012 Elsevier Inc. All rights reserved.

  3. 3D calcite heterostructures for dynamic and deformable mineralized matrices

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Yi, Jaeseok; Wang, Yucai; Jiang, Yuanwen

    Scales are rooted in soft tissues, and are regenerated by specialized cells. The realization of dynamic synthetic analogues with inorganic materials has been a significant challenge, because the abiological regeneration sites that could yield deterministic growth behavior are hard to form. Here we overcome this fundamental hurdle by constructing a mutable and deformable array of three-dimensional calcite heterostructures that are partially locked in silicone. Individual calcite crystals exhibit asymmetrical dumbbell shapes and are prepared by a parallel tectonic approach under ambient conditions. Furthermore, the silicone matrix immobilizes the epitaxial nucleation sites through self-templated cavities, which enables symmetry breaking in reactionmore » dynamics and scalable manipulation of the mineral ensembles. With this platform, we devise several mineral-enabled dynamic surfaces and interfaces. For example, we show that the induced growth of minerals yields localized inorganic adhesion for biological tissue and reversible focal encapsulation for sensitive components in flexible electronics.« less

  4. 3D calcite heterostructures for dynamic and deformable mineralized matrices

    DOE PAGES

    Yi, Jaeseok; Wang, Yucai; Jiang, Yuanwen; ...

    2017-09-11

    Scales are rooted in soft tissues, and are regenerated by specialized cells. The realization of dynamic synthetic analogues with inorganic materials has been a significant challenge, because the abiological regeneration sites that could yield deterministic growth behavior are hard to form. Here we overcome this fundamental hurdle by constructing a mutable and deformable array of three-dimensional calcite heterostructures that are partially locked in silicone. Individual calcite crystals exhibit asymmetrical dumbbell shapes and are prepared by a parallel tectonic approach under ambient conditions. Furthermore, the silicone matrix immobilizes the epitaxial nucleation sites through self-templated cavities, which enables symmetry breaking in reactionmore » dynamics and scalable manipulation of the mineral ensembles. With this platform, we devise several mineral-enabled dynamic surfaces and interfaces. For example, we show that the induced growth of minerals yields localized inorganic adhesion for biological tissue and reversible focal encapsulation for sensitive components in flexible electronics.« less

  5. Amino Acid-Assisted Incorporation of Dye Molecules within Calcite Crystals.

    PubMed

    Marzec, Bartosz; Green, David C; Holden, Mark A; Coté, Alexander S; Ihli, Johannes; Khalid, Saba; Kulak, Alexander; Walker, Daniel; Tang, Chiu; Duffy, Dorothy M; Kim, Yi-Yeoun; Meldrum, Fiona C

    2018-05-23

    Biomineralisation processes invariably occur in the presence of multiple organic additives, which act in combination to give exceptional control over structures and properties. However, few synthetic studies have investigated the cooperative effects of soluble additives. This work addresses this challenge and focuses on the combined effects of amino acids and coloured dye molecules. The experiments demonstrate that strongly coloured calcite crystals only form in the presence of Brilliant Blue R (BBR) and four of the seventeen soluble amino acids, as compared with almost colourless crystals using the dye alone. The active amino acids are identified as those which themselves effectively occlude in calcite, suggesting a mechanism where they can act as chaperones for individual molecules or even aggregates of dyes molecules. These results provide new insight into crystal-additive interactions and suggest a novel strategy for generating materials with target properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. High-pressure deformation of calcite marble and its transformation to aragonite under non-hydrostatic conditions

    USGS Publications Warehouse

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

    1993-01-01

    We conducted deformation experiments on Carrara marble in the aragonite and calcite stability fields to observe the synkinematic transformation of calcite to aragonite, and to identify any relationships between transformation and deformation or sample strength. Deformation-induced microstructures in calcite crystals varied most significantly with temperature, ranging from limited slip and twinning at 400??C, limited recrystallization at 500??C, widespread recrystallization at 600 and 700??C, to grain growth at 800-900??C. Variations in confining pressure from 0.3 to 2.0 GPa have no apparent effect on calcite deformation microstructures. Aragonite grew in 10-6-10-7 s-1strain rate tests conducted for 18-524 h at confining pressures of 1.7-2.0 GPa and temperatures of 500-600??C. As in our previously reported hydrostatic experiments on this same transformation, the aragonite nucleated on calcite grain boundaries. The extent of transformation varied from a few percent conversion near pistons at 400??C, 2.0 GPa and 10-4 s-1 strain rate in a 0.8 h long experiment, to 98% transformation in a 21-day test at a strain rate of 10-7 s-7, a temperature of 600??C and a pressure of 2.0 GPa. At 500??C, porphyroblastic 100-200 ??m aragonite crystals grew at a rate faster than 8 ?? 10-1m s-1. At 600??C, the growth of aragonite neoblasts was slower, ???6 ?? 10-1 m s -1, and formed 'glove-and-finger' cellularprecipitation-like textures identical to those observed in hydrostatic experiments. The transformation to aragonite is not accompanied by a shear instability or anisotropic aragonite growth, consistent with its relatively small volume change and latent heat in comparison with compounds that do display those features. ?? 1993.

  7. Flotation selectivity of novel alkyl dicarboxylate reagents for apatite-calcite separation.

    PubMed

    Karlkvist, Tommy; Patra, Anuttam; Rao, Kota Hanumantha; Bordes, Romain; Holmberg, Krister

    2015-05-01

    The investigation aims to demonstrate the conceptual thoughts behind developing mineral specific reagents for use in flotation of calcium containing ores. For this purpose, a series of dicarboxylate-based surfactants with varying distance between the carboxylate groups (one, two or three methylene groups) was synthesized. A surfactant with the same alkyl chain length but with only one carboxylate group was also synthesized and evaluated. The adsorption behavior of these new reagents on pure apatite and pure calcite surfaces was studied using Hallimond tube flotation, FTIR and ζ potential measurements. The relation between the adsorption behavior of a given surfactant at a specific mineral surface and its molecular structure over a range of concentrations and pH values, as well as the region of maximum recovery, was established. It was found that one of the reagents, with a specific distance between the carboxylate groups, was much more selective for a particular mineral surface than the other homologues. For example, out of the four compounds synthesized, only the one where the carboxylate groups were separated by a single methylene group floated apatite but not calcite, whereas calcite was efficiently floated with the monocarboxylic reagent, but not with the other reagents synthesized. This selective adsorption of a given surfactant to a particular mineral surface relative to other mineral surfaces as evidenced in the flotation studies was substantiated by ζ potential and infra-red spectroscopy data. Copyright © 2014 Elsevier Inc. All rights reserved.

  8. Uranium isotope fractionation induced by aqueous speciation: Implications for U isotopes in marine CaCO3 as a paleoredox proxy

    NASA Astrophysics Data System (ADS)

    Chen, Xinming; Romaniello, Stephen J.; Anbar, Ariel D.

    2017-10-01

    Natural variations of 238U/235U in marine CaCO3 rocks are being explored as a novel paleoredox proxy to investigate oceanic anoxia events. Although it is generally assumed that U isotopes in CaCO3 directly record 238U/235U of seawater, recently published laboratory experiments demonstrate slight U isotope fractionation during U(VI) incorporation into abiotic calcium carbonates. This fractionation is hypothesized to depend on aqueous U(VI) speciation, which is controlled by pH, ionic strength, pCO2 and Mg2+ and Ca2+ concentrations. Secular variation in seawater chemistry could lead to changes in aqueous U(VI) speciation, and thus, may affect the extent of U isotope fractionation during U(VI) incorporation into CaCO3. In this study, we combine estimates of seawater composition over the Phanerozoic with a model of aqueous U speciation and isotope fractionation to explore variations in the expected offset between the U isotope composition of seawater and primary marine CaCO3 through time. We find that U isotope fractionation between U in primary marine CaCO3 and seawater could have varied between 0.11 and 0.23‰ over the Phanerozoic due to secular variations in seawater chemistry. Such variations would significantly impact estimates of the extent of marine anoxia derived from the U isotope record. For example, at the Permo-Triassic boundary, this effect might imply that the estimated extent of anoxia is ∼32% more extreme than previously inferred. One significant limitation of our model is that the existing experimental database covers only abiotic carbonate precipitation, and does not include a possible range of biological effects which might enhance or suppress the range of isotopic fractionation calculated here. As biotic carbonates dominate the marine carbonate record, more work is need to assess controls on U isotopic fractionation into biotic marine carbonates.

  9. Stable isotopic compositions of early calcite cements in the Middle Devonian Coralville Formation (Cedar Valley Group), eastern Iowa

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Ludvigson, G.A.; Gonzalez, L.S.; Witzke, B.J.

    1993-03-01

    The Middle-Upper Devonian Cedar Valley Gp in Iowa is subdivided into four formations each representing a broad transgressive-regressive (T-R) cycle of deposition. Cycles consist of basal open marine facies that shallow upward into capping peritidal facies. Results from ongoing diagenetic studies of the Coralville Fm (late Givetian), the second T-R cycle of the Cedar Valley Gp, have focused attention on the origins of early cements. Early calcite cements in the Coralville Fm of Johnson County, Iowa, include blocky equant spars filling fenestral voids in birdseye limestones of the Iowa City Mbr and isopachous bladed spars that occur throughout the Coralville.more » Bladed spars fill stromatactis and microkarstic voids in the Iowa City Mbr, and sheltered voids in underlying open-marine skeletal packstones of the Cou Falls Mbr (lower Coralville cycle). The bladed spars include nonluminescent inclusion-free domains that contain up to 4,000 ppm Mg, and luminescent inclusion-rich domains that contain less than 2,000 ppm Mg. Birdseye spars have a constructive oscillatory luminescent-nonluminescent zonation controlled by Mn contents and contain less than 1,000 ppm Mg. Nonluminescent domains in bladed spars have the heaviest oxygen isotopic compositions of all components in the Coralville, similar to the isotopically heaviest nonluminescent brachiopods but have [delta][sup 13]C values ranging from [minus]3 to [minus]5 [per thousand]. They are interpreted to have precipitated from marine fluids saturated by CO[sub 2] produced from bacterial oxidation of organic matter. Altered luminescent domains in the bladed spars have the same [delta][sup 13]C compositions, but have widely varying [delta][sup 18]O compositions, ranging to [minus]9 [per thousand].« less

  10. Abiotic stresses affect Trichoderma harzianum T39-induced resistance to downy mildew in grapevine.

    PubMed

    Roatti, Benedetta; Perazzolli, Michele; Gessler, Cesare; Pertot, Ilaria

    2013-12-01

    Enhancement of plant defense through the application of resistance inducers seems a promising alternative to chemical fungicides for controlling crop diseases but the efficacy can be affected by abiotic factors in the field. Plants respond to abiotic stresses with hormonal signals that may interfere with the mechanisms of induced systemic resistance (ISR) to pathogens. In this study, we exposed grapevines to heat, drought, or both to investigate the effects of abiotic stresses on grapevine resistance induced by Trichoderma harzianum T39 (T39) to downy mildew. Whereas the efficacy of T39-induced resistance was not affected by exposure to heat or drought, it was significantly reduced by combined abiotic stresses. Decrease of leaf water potential and upregulation of heat-stress markers confirmed that plants reacted to abiotic stresses. Basal expression of defense-related genes and their upregulation during T39-induced resistance were attenuated by abiotic stresses, in agreement with the reduced efficacy of T39. The evidence reported here suggests that exposure of crops to abiotic stress should be carefully considered to optimize the use of resistance inducers, especially in view of future global climate changes. Expression analysis of ISR marker genes could be helpful to identify when plants are responding to abiotic stresses, in order to optimize treatments with resistance inducers in field.

  11. The effect of CO2-fluid-rock interactions on the porosity and permeability of calcite-bearing sandstone

    NASA Astrophysics Data System (ADS)

    Lamy-Chappuis, B.; Yardley, B.; Grattoni, C.

    2013-12-01

    Brine acidification following CO2 dissolution will initiate fluid-rock interactions that could significantly modify porosity, permeability and therefore the capacity and injectivity of a reservoir. We have investigated experimentally the dissolution of calcite in sandstone cores injected with CO2-saturated brine, and the effect this has on permeability. A series of CT (Computerized Tomography) - monitored experiments were conducted on a Jurassic sandstone (porosity = 30%, permeability = 10mD, calcite content = 5% in the form of dispersed shell fragments). Brine saturated with CO2 at pressures up to 1 MPa was injected into 5cm long, 3.75cm diameter cores at a flow rate of 1 ml/min and room temperature. The data showed quasi-instantaneous dissolution of the calcite even at low CO2 concentrations (0.15 Molar) and high fluid interstitial velocities (1mm/s), with the migration of a calcite dissolution front through the core recorded by successive CT scans. The resulting permeability increase was 60 - 80% whereas the predicted permeability change for the observed increase in porosity is only 10 - 20% using the Kozeny-Carman relationship. This result is particularly significant because the effect of porosity increase on permeability is usually modelled with this relationship, irrespective of the mechanism of porosity increase. Micro-CT scans (pixel resolution: 2.5 microns) of unreacted cores were used to generate 3D porosity models with calcite either treated as solid (pre-reaction model) or converted to pores (post-reaction model). FLUENT simulations performed using these models predicted the observed large relative changes in permeability with calcite dissolution but overestimated absolute permeability by an order of magnitude. This was probably due to the scan resolution being too coarse to correctly model pore throats. The observed large change in permeability for a small change in porosity may have resulted from increase in connectivity, focused dissolution at the

  12. Relative Abundances of Calcite and Silica in Fracture Coatings as a Possible Indicator of Evaporation in a Thick Unsaturated Zone, Yucca Mountain, Nevada

    NASA Astrophysics Data System (ADS)

    Marshall, B. D.; Moscati, R. J.

    2005-12-01

    Yucca Mountain, a ridge of shallowly dipping, Miocene-age volcanic rocks in southwest Nevada, is the proposed site for a nuclear waste repository to be constructed in the 500- to 700-m-thick unsaturated zone (UZ). At the proposed repository, the 300-m-thick Topopah Spring Tuff welded unit (TSw) is overlain by approximately 30 m of nonwelded tuffs (PTn); the Tiva Canyon Tuff welded unit (TCw) overlies the PTn with a range in thickness from 0 to approximately 130 m at the site. The amount of water percolation through the UZ is low and difficult to measure directly, but local seepage into mined tunnels has been observed in the TCw. Past water seepage in the welded tuffs is recorded by widespread, thin (0.3 cm) coatings of calcite and silica on fracture surfaces and within cavities. Abundances of calcite and silica in the coatings were determined by X-ray microfluorescence mapping and subsequent multispectral image analysis of over 200 samples. The images were classified into constituent phases including opal-chalcedony-quartz (secondary silica) and calcite. In the TCw samples, the median calcite/silica ratio is 8; in the TSw samples within 35 m below the PTn, median calcite/silica falls to 2, perhaps reflecting an increase in soluble silica from the presence of glass in the nonwelded tuffs. In the deeper parts of the TSw, median calcite/silica reaches 100 and many samples contain no detectable secondary silica phase. Evaporation and changing pCO2 control precipitation of calcite from water percolating downward in the UZ, but precipitation of opal requires only evaporation. Calcite/silica ratios, therefore, can constrain the relative importance of evaporation in the UZ. Although calcite/silica values scatter widely within the TSw, reflecting the spatial variability of gas and water flow, average calcite/silica ratios increase with stratigraphic depth, indicating less evaporation at the deeper levels of the UZ. Coupled with the much smaller calcite/silica ratios

  13. Calcite Decarbonation and its Influence on the Mechanical Behaviour of Carbonate-bearing Faults

    NASA Astrophysics Data System (ADS)

    Carpenter, Brett; Collettini, Cristiano; Mollo, Silvio; Viti, Cecilia

    2014-05-01

    Calcite decarbonation has been identified as one of the important, thermally-activated physicochemical processes that are triggered by temperature rise during fast fault motion. This process has been observed in the laboratory during high-velocity friction experiments where the dynamic weakening that occurs for carbonate-rich gouges is strictly controlled by the thermal decomposition of calcite. Furthermore, this process has also been identified along ancient, exhumed faults and is an important indicator of seismic slip. The thermally-induced decarbonation (CaCO3 → CaO + CO2) and microcracking (due to thermal expansion) of calcite are likely to be primary mechanisms in controlling the mechanical and hydrologic properties of carbonate rocks. In addition, the process and products of decarbonation will likely exert significant influence on the behaviour of faults at both geologic and earthquake time scales by causing changes in (1) the effective normal stress on the fault and (2) the frictional behaviour of material within it. Due to the paucity of scientific information on the effects of decarbonation and thermal microcracking on the mechanical properties of carbonate fault rocks, we present results from experiments performed on portlandite (>90 wt.%), a hydrous mineral formed by the recombination of CaO and water, and stable product of the decarbonation reaction. We produced portlandite by thermally-treating powdered Carrara Marble (calcite >98 wt.%) in the laboratory at 1100 °C under air buffering conditions. We then sheared gouge layers of this water-reacted, decarbonation product under saturated conditions at room temperature. These tests were designed to evaluate the frictional strength, stability, and healing behaviour of portlandite-bearing rocks to better understand how its presence affects fault mechanics. Our data indicate that the conversion of calcite to portlandite, results in a distinct change in the mechanical behaviour of the fault gouge. The

  14. Mineral contents and their solubility on calcium carbonat calcite nanocrystals from cockle shell powder (Anadara granosa Linn)

    NASA Astrophysics Data System (ADS)

    Widyastuti, S.; Pramushinta, I. A.

    2018-03-01

    Prepared and characterized calcium carbonat calcite nanocrystals improves solubility. Calcium carbonat calcite nanocrystals were synthesized using precipitation method from the waste of blood clam cockle shells (Anadara granosa Linn). This study was conducted to analyze mineral composition of nanocrystals calcium carbonat calcite cockle (Anadara granosa) shell for calcium fortification of food applications and to evaluate the solubilities of Calsium and Phospor. The sample of nanocrystals from cockle shells was evaluated to determine the content of 11 macro-and micro-elements. These elements are Calcium (Ca), Magnesium (Mg), Sodium (Na), Phosphorus (P), Potassium (K), Ferrum (Fe), Copper (Cu), Nickel (Ni), Zink (Zn), Boron (B) and Silica (Si)). Cockleshell powders were found to contain toxic elements below detectable levels. The solubilities of Calcium and Phospor were p<0.05.

  15. A simple reactive-transport model of calcite precipitation in soils and other porous media

    NASA Astrophysics Data System (ADS)

    Kirk, G. J. D.; Versteegen, A.; Ritz, K.; Milodowski, A. E.

    2015-09-01

    Calcite formation in soils and other porous media generally occurs around a localised source of reactants, such as a plant root or soil macro-pore, and the rate depends on the transport of reactants to and from the precipitation zone as well as the kinetics of the precipitation reaction itself. However most studies are made in well mixed systems, in which such transport limitations are largely removed. We developed a mathematical model of calcite precipitation near a source of base in soil, allowing for transport limitations and precipitation kinetics. We tested the model against experimentally-determined rates of calcite precipitation and reactant concentration-distance profiles in columns of soil in contact with a layer of HCO3--saturated exchange resin. The model parameter values were determined independently. The agreement between observed and predicted results was satisfactory given experimental limitations, indicating that the model correctly describes the important processes. A sensitivity analysis showed that all model parameters are important, indicating a simpler treatment would be inadequate. The sensitivity analysis showed that the amount of calcite precipitated and the spread of the precipitation zone were sensitive to parameters controlling rates of reactant transport (soil moisture content, salt content, pH, pH buffer power and CO2 pressure), as well as to the precipitation rate constant. We illustrate practical applications of the model with two examples: pH changes and CaCO3 precipitation in the soil around a plant root, and around a soil macro-pore containing a source of base such as urea.

  16. Common Ion Effects In Zeoponic Substrates: Dissolution And Cation Exchange Variations Due to Additions of Calcite, Dolomite and Wollastonite

    NASA Technical Reports Server (NTRS)

    Beiersdorfer, R. E.; Ming, D. W.; Galindo, C., Jr.

    2003-01-01

    c1inoptilolite-rich tuff-hydroxyapatite mixture (zeoponic substrate) has the potential to serve as a synthetic soil-additive for plant growth. Essential plant macro-nutrients such as calcium, phosphorous, magnesium, ammonium and potassium are released into solution via dissolution of the hydroxyapatite and cation exchange on zeolite charged sites. Plant growth experiments resulting in low yield for wheat have been attributed to a Ca deficiency caused by a high degree of cation exchange by the zeolite. Batch-equilibration experiments were performed in order to determine if the Ca deficiency can be remedied by the addition of a second Ca-bearing, soluble, mineral such as calcite, dolomite or wollastonite. Variations in the amount of calcite, dolomite or wollastonite resulted in systematic changes in the concentrations of Ca and P. The addition of calcite, dolomite or wollastonite to the zeoponic substrate resulted in an exponential decrease in the phosphorous concentration in solution. The exponential rate of decay was greatest for calcite (5.60 wt. % -I), intermediate for wollastonite (2.85 wt.% -I) and least for dolomite (1.58 wt.% -I). Additions of the three minerals resulted in linear increases in the calcium concentration in solution. The rate of increase was greatest for calcite (3.64), intermediate for wollastonite (2.41) and least for dolomite (0.61). The observed changes in P and Ca concentration are consistent with the solubilities of calcite, dolomite and wollastonite and with changes expected from a common ion effect with Ca. Keywords: zeolite, zeoponics, common-ion effect, clinoptilolite, hydroxyapatite

  17. Molecular models of alginic acid: Interactions with calcium ions and calcite surfaces

    NASA Astrophysics Data System (ADS)

    Perry, Thomas D.; Cygan, Randall T.; Mitchell, Ralph

    2006-07-01

    Cation binding by polysaccharides is observed in many environments and is important for predictive environmental modeling, and numerous industrial and food technology applications. The complexities of these cation-organic interactions are well suited for predictive molecular modeling and the analysis of conformation and configuration of polysaccharides and their influence on cation binding. In this study, alginic acid was chosen as a model polymer system and representative disaccharide and polysaccharide subunits were developed. Molecular dynamics simulation of the torsion angles of the ether linkage between various monomeric subunits identified local and global energy minima for selected disaccharides. The simulations indicate stable disaccharide configurations and a common global energy minimum for all disaccharide models at Φ = 274 ± 7°, Ψ = 227 ± 5°, where Φ and Ψ are the torsion angles about the ether linkage. The ability of disaccharide subunits to bind calcium ions and to associate with the (101¯4) surface of calcite was also investigated. Molecular models of disaccharide interactions with calcite provide binding energy differences for conformations that are related to the proximity and residence densities of the electron-donating moieties with calcium ions on the calcite surface, which are controlled, in part, by the torsion of the ether linkage between monosaccharide units. Dynamically optimized configurations for polymer alginate models with calcium ions were also derived.

  18. Regulation of MIR Genes in Response to Abiotic Stress in Hevea brasiliensis

    PubMed Central

    Gébelin, Virginie; Leclercq, Julie; Hu, Songnian; Tang, Chaorong; Montoro, Pascal

    2013-01-01

    Increasing demand for natural rubber (NR) calls for an increase in latex yield and also an extension of rubber plantations in marginal zones. Both harvesting and abiotic stresses lead to tapping panel dryness through the production of reactive oxygen species. Many microRNAs regulated during abiotic stress modulate growth and development. The objective of this paper was to study the regulation of microRNAs in response to different types of abiotic stress and hormone treatments in Hevea. Regulation of MIR genes differs depending on the tissue and abiotic stress applied. A negative co-regulation between HbMIR398b with its chloroplastic HbCuZnSOD target messenger is observed in response to salinity. The involvement of MIR gene regulation during latex harvesting and tapping panel dryness (TPD) occurrence is further discussed. PMID:24084713

  19. Simple, simultaneous gravimetric determination of calcite and dolomite in calcareous soils

    USDA-ARS?s Scientific Manuscript database

    Literature pertaining to determination of calcite and dolomite is not modern and describes slow methods that require expensive specialized apparatus. The objective of this paper was to describe a new method that requires no specialized equipment. Linear regressions and correlation coefficients for...

  20. Advances in crop proteomics: PTMs of proteins under abiotic stress.

    PubMed

    Wu, Xiaolin; Gong, Fangping; Cao, Di; Hu, Xiuli; Wang, Wei

    2016-03-01

    Under natural conditions, crop plants are frequently subjected to various abiotic environmental stresses such as drought and heat wave, which may become more prevalent in the coming decades. Plant acclimation and tolerance to an abiotic stress are always associated with significant changes in PTMs of specific proteins. PTMs are important for regulating protein function, subcellular localization and protein activity and stability. Studies of plant responses to abiotic stress at the PTMs level are essential to the process of plant phenotyping for crop improvement. The ability to identify and quantify PTMs on a large-scale will contribute to a detailed protein functional characterization that will improve our understanding of the processes of crop plant stress acclimation and stress tolerance acquisition. Hundreds of PTMs have been reported, but it is impossible to review all of the possible protein modifications. In this review, we briefly summarize several main types of PTMs regarding their characteristics and detection methods, review the advances in PTMs research of crop proteomics, and highlight the importance of specific PTMs in crop response to abiotic stress. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Adsorption of a novel reagent scheme on scheelite and calcite causing an effective flotation separation.

    PubMed

    Gao, Yuesheng; Gao, Zhiyong; Sun, Wei; Yin, Zhigang; Wang, Jianjun; Hu, Yuehua

    2018-02-15

    The efficient separation of scheelite from calcium-bearing minerals, especially calcite, remains a challenge in practice. In this work, a novel reagent scheme incorporating a depressant of sodium hexametaphosphate (SHMP) and a collector mixture of octyl hydroxamic acid (HXMA-8) and sodium oleate (NaOl) was employed in both single and mixed binary mineral flotation, and it proved to be highly effective for the separation. Furthermore, the role of the pH value in the separation was evaluated. Additionally, the mechanism of the selective separation was investigated systemically via zeta potential measurements, fourier transform infrared (FTIR) spectroscopy analysis, X-ray photoelectron (XPS) spectroscopy analysis and crystal chemistry calculations. It turns out that the selective chemisorption of SHMP on calcite (in the form of complexation between H 2 PO 4 - /HPO 4 2- and Ca 2+ ) over scheelite is ascribed to the stronger reactivity and higher density of Ca ions on the commonly exposed surfaces of calcite minerals. The intense adsorption of HXMA-8 on scheelite over calcite due to the match of the OO distances in WO 4 2- of scheelite and CONHOH of HXMA-8 holds the key to the successful separation. We were also interested in warranting the previous claim that NaOl is readily adsorbed on both minerals via chemisorption. Our results provided valuable insights into the application of mixed collectors and an effective depressant for flotation separation. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Effects of limestone petrography and calcite microstructure on OPC clinker raw meals burnability

    NASA Astrophysics Data System (ADS)

    Galimberti, Matteo; Marinoni, Nicoletta; Della Porta, Giovanna; Marchi, Maurizio; Dapiaggi, Monica

    2017-10-01

    Limestone represents the main raw material for ordinary Portland cement clinker production. In this study eight natural limestones from different geological environments were chosen to prepare raw meals for clinker manufacturing, aiming to define a parameter controlling the burnability. First, limestones were characterized by X-Ray Fluorescence, X-Ray Powder Diffraction and Optical Microscopy to assess their suitability for clinker production and their petrographic features. The average domains size and the microstrain of calcite were also determined by X-Ray Powder Diffraction line profile analysis. Then, each limestone was admixed with clay minerals to achieve the adequate chemical composition for clinker production. Raw meals were thermally threated at seven different temperatures, from 1000 to 1450 °C, to evaluate their behaviour on heating by ex situ X-Ray Powder Diffraction and to observe the final clinker morphology by Scanning Electron Microscopy. Results indicate the calcite microstrain is a reliable parameter to predict the burnability of the raw meals, in terms of calcium silicates growth and lime consumption. In particular, mixtures prepared starting from high-strained calcite exhibit a better burnability. Later, when the melt appears this correlation vanishes; however differences in the early burnability still reflect on the final clinker composition and texture.

  3. 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

  4. Mineralogical, crystallographic, and isotopic constraints on the precipitation of aragonite and calcite at Shiqiang and other hot springs in Yunnan Province, China

    NASA Astrophysics Data System (ADS)

    Jones, Brian; Peng, Xiaotong

    2016-11-01

    Two active spring vent pools at Shiqiang (Yunnan Province, China) are characterized by a complex array of precipitates that coat the wall around the pool and the narrow ledges that surround the vent pool. These precipitates include arrays of aragonite crystals, calcite cone-dendrites, red spar calcite, unattached dodecahedral and rhombohedral calcite crystals, and late stage calcite that commonly coats and disguises the earlier formed precipitates. Some of the microbial mats that grow on the ledges around the pools have been partly mineralized by microspheres that are formed of Si and minor amounts of Fe. The calcite and aragonite that are interspersed with each other at all scales are both primary precipitates. Some laminae, for example, change laterally from aragonite to calcite over distances of only a few millimetres. The precipitates at Shiqiang are similar to precipitates found in and around the vent pools of other springs found in Yunnan Province, including those at Gongxiaoshe, Zhuyuan, Eryuan, and Jifei. In all cases, the δDwater and δ18Owater indicate that the spring water is of meteoric origin. These are thermogene springs with the carrier CO2 being derived largely from the mantle and reaction of the waters with bedrock. Variations in the δ13Ctravertine values indicate that the waters in these springs were mixed, to varying degrees, with cold groundwater and its soil-derived CO2. Calcite and aragonite precipitation took place once the spring waters had become supersaturated with respect to CaCO3, probably as a result of rapid CO2 degassing. These precipitates, which were not in isotopic equilibrium with the spring water, are characterized by their unusual crystal morphologies. The precipitation of calcite and aragonite, seemingly together, can probably be attributed to microscale variations in the saturation levels that are, in turn, attributable to microscale variations in the rate of CO2 degassing.

  5. Can plant-natural enemy communication withstand disruption by biotic and abiotic factors?

    PubMed

    Clavijo McCormick, Andrea

    2016-12-01

    The attraction of natural enemies towards herbivore-induced plant volatiles is a well-documented phenomenon. However, the majority of published studies are carried under optimal water and nutrient regimes and with just one herbivore. But what happens when additional levels of ecological complexity are added? Does the presence of a second herbivore, microorganisms, and abiotic stress interfere with plant-natural enemy communication? or is communication stable enough to withstand disruption by additional biotic and abiotic factors?Investigating the effects of these additional levels of ecological complexity is key to understanding the stability of tritrophic interactions in natural ecosystems and may aid to forecast the impact of environmental disturbances on these, especially in climate change scenarios, which are often associated with modifications in plant and arthropod species distribution and increased levels of abiotic stress.This review explores the literature on natural enemy attraction to herbivore-induced volatiles when, besides herbivory, plants are challenged by additional biotic and abiotic factors.The aim of this review was to establish the impact of different biotic and abiotic factors on plant-natural enemy communication and to highlight critical aspects to guide future research efforts.

  6. Nano-structured calcite produced by micro-organisms in ancient and modern loess in Chinese Loess Plateau

    NASA Astrophysics Data System (ADS)

    Xu, H.; Chen, T.; Lu, H.; Wang, X.

    2005-12-01

    The results from transmission electron microscopy (TEM) and field emission gun scanning microscopy (FEG-SEM) investigation show that there are calcite nano-fibers (CNFs) formed during pedogenic process. The CNFs are widely distributed in the loess and red clay samples of Caoxian, Luochuan, Lingtai, Lantian, and Xifeng profiles as well as the samples of modern surface loess soils in Chinese Loess Plateau. Diameters of all the NFCs are about 40 nm, the length of the CNFs ranges from tens nanometer to several micrometers. Elongation direction of NFCs is unusual near parallel (105)* or (115)*. Crystals of NFCs arrange as bird net like and lattice-like frameworks. X-ray EDS spectra show the weak peaks of magnesium, phosphorous, and sulfur. Our investigation indicates that CNFs are in pore space of loess and paleosol and made up most of carbonate except for caliche nodular layers. Concentration of NFCs in the loess layers are significantly higher than those of paleosol layers because of leaching of carbonate in the paleosol forming environment (warn and wet paleoclimate). The "nanobacteria-like CNFs are well crystalline calcite single crystals with smoothes surfaces. The morphologies of CNFs are very unusual and different from the calcite single crystals observed in most geological environments. The CNFs are directly related to microbial activities in both ancient and modern loess. It is proposed that the intervention of organic compounds derived from microbial activities control the formation of the calcite nano-fibers. Both morphology and bulk composition of CNFs indicate that the formation of the CNFs involves bio-organics derived from microorganisms in loess deposit environment. Formation conditions of the calcite nano-fibers may information about paleoclimate, paleo-environment and paleoecology. So, the discovery of CNFs in loess-paloesol sequences can provide a new route for reconstruct paleoclimate by oxygen and carbon isotope from the CNFs.

  7. Mercury in Arctic Marine Ecosystems: Sources, Pathways, and Exposure

    PubMed Central

    Kirk, Jane L.; Lehnherr, Igor; Andersson, Maria; Braune, Birgit M.; Chan, Laurie; Dastoor, Ashu P.; Durnford, Dorothy; Gleason, Amber L.; Loseto, Lisa L.; Steffen, Alexandra; St. Louis, Vincent L.

    2014-01-01

    Mercury in the Arctic is an important environmental and human health issue. The reliance of Northern Peoples on traditional foods, such as marine mammals, for subsistence means that they are particularly at risk from mercury exposure. The cycling of mercury in Arctic marine systems is reviewed here, with emphasis placed on the key sources, pathways and processes which regulate mercury levels in marine food webs and ultimately the exposure of human populations to this contaminant. While many knowledge gaps exist limiting our ability to make strong conclusions, it appears that the long range transport of mercury from Asian emissions is an important source of atmospheric Hg to the Arctic and that mercury methylation resulting in monomethylmercury production (an organic form of mercury which is both toxic and bioaccumulated) in Arctic marine waters is the principal source of mercury incorporated into food webs. Mercury concentrations in biological organisms have increased since the onset of the industrial age and are controlled by a combination of abiotic factors (e.g., monomethylmercury supply), food web dynamics and structure, and animal behavior (e.g., habitat selection and feeding behavior). Finally, although some Northern Peoples have high mercury concentrations of mercury in their blood and hair, harvesting and consuming traditional foods has many nutritional, social, cultural and physical health benefits which must be considered in risk management and communication. PMID:23102902

  8. Heteroepitaxial growth of cadmium carbonate at dolomite and calcite surfaces: Mechanisms and rates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Callagon, Erika Blanca R.; Lee, Sang Soo; Eng, Peter J.

    Here, the systematic variation of rates and the mechanism of cadmium uptake on the (104) surface of dolomite (CaMg(CO 3) 2) were investigated using in situ and ex situ atomic force microscopy (AFM), ex situ specular X-ray reflectivity (XR), and ex situ X-ray fluorescence (XRF). Selected experiments were performed on the calcite (CaCO 3) (104) surface for comparison. Aqueous solutions of CdCl 2, CaCl 2, and NaHCO 3, undersaturated with respect to calcite and supersaturated with respect to otavite (CdCO 3) and the (Cd xCa 1-x)CO 3 solid solution, were reacted with dolomite surfaces for minutes to days. Calcite substratesmore » were reacted with solutions containing 1-50 μM CdCl 2, and with no added Ca or CO 3. Thin carbonate films following the Stranski-Krastanov growth mode were observed on both substrates. Specular XR and XRF revealed the formation of nm-thick Cd-rich carbonate films that were structurally ordered with respect to the dolomite (104) plane. Epitaxial films adopted the calcite crystal structure with a d 104- spacing (3.00 Å) larger than those of pure dolomite (2.88 Å) and otavite (2.95 Å) indicating either a solid solution with x approximate to 0.5, or a strained Cd-rich carbonate with a composition near that of otavite. The growth rate r of this phase increases with the initial supersaturation of the solution with respect to the solid solution, beta max, and follows the empirical relationship, as determined from XRF measurements, given by: r = 10 -4.88 ± 0.42 (β 2.29 ± 0.24 max - 1), (in units of atoms of Cd/Å 2/h).The morphology of the overgrowth also varied with β max, as exemplified by AFM observations. Growth at step edges occurred over the entire β max range considered, and additional growth features including 3 Å high monolayer islands and ~ 25 Å high tall islands were observed when log β max > 1. On calcite, in situ XR indicated that this phase is similar to the Cd-rich overgrowth formed on dolomite and images obtained from X

  9. Heteroepitaxial growth of cadmium carbonate at dolomite and calcite surfaces: Mechanisms and rates

    DOE PAGES

    Callagon, Erika Blanca R.; Lee, Sang Soo; Eng, Peter J.; ...

    2016-12-10

    Here, the systematic variation of rates and the mechanism of cadmium uptake on the (104) surface of dolomite (CaMg(CO 3) 2) were investigated using in situ and ex situ atomic force microscopy (AFM), ex situ specular X-ray reflectivity (XR), and ex situ X-ray fluorescence (XRF). Selected experiments were performed on the calcite (CaCO 3) (104) surface for comparison. Aqueous solutions of CdCl 2, CaCl 2, and NaHCO 3, undersaturated with respect to calcite and supersaturated with respect to otavite (CdCO 3) and the (Cd xCa 1-x)CO 3 solid solution, were reacted with dolomite surfaces for minutes to days. Calcite substratesmore » were reacted with solutions containing 1-50 μM CdCl 2, and with no added Ca or CO 3. Thin carbonate films following the Stranski-Krastanov growth mode were observed on both substrates. Specular XR and XRF revealed the formation of nm-thick Cd-rich carbonate films that were structurally ordered with respect to the dolomite (104) plane. Epitaxial films adopted the calcite crystal structure with a d 104- spacing (3.00 Å) larger than those of pure dolomite (2.88 Å) and otavite (2.95 Å) indicating either a solid solution with x approximate to 0.5, or a strained Cd-rich carbonate with a composition near that of otavite. The growth rate r of this phase increases with the initial supersaturation of the solution with respect to the solid solution, beta max, and follows the empirical relationship, as determined from XRF measurements, given by: r = 10 -4.88 ± 0.42 (β 2.29 ± 0.24 max - 1), (in units of atoms of Cd/Å 2/h).The morphology of the overgrowth also varied with β max, as exemplified by AFM observations. Growth at step edges occurred over the entire β max range considered, and additional growth features including 3 Å high monolayer islands and ~ 25 Å high tall islands were observed when log β max > 1. On calcite, in situ XR indicated that this phase is similar to the Cd-rich overgrowth formed on dolomite and images obtained from X

  10. Biotic and abiotic degradation of CL-20 and RDX in soils.

    PubMed

    Crocker, Fiona H; Thompson, Karen T; Szecsody, James E; Fredrickson, Herbert L

    2005-01-01

    The caged cyclic nitramine 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a new explosive that has the potential to replace existing military explosives, but little is known about its environmental toxicity, transport, and fate. We quantified and compared the aerobic environmental fate of CL-20 to the widely used cyclic nitramine explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in surface and subsurface soil microcosms. Soil-free controls and biologically attenuated soil controls were used to separate abiotic processes from biologically mediated processes. Both abiotic and biological processes significantly degraded CL-20 in all soils examined. Apparent abiotic, first-order degradation rates (k) for CL-20 were not significantly different between soil-free controls (0.018 < k < 0.030 d(-1)) and biologically attenuated soil controls (0.003 < k < 0.277 d(-1)). The addition of glucose to biologically active soil microcosms significantly increased CL-20 degradation rates (0.068 < k < 1.22 d(-1)). Extents of mineralization of (14)C-CL-20 to (14)CO(2) in biologically active soil microcosms were 41.1 to 55.7%, indicating that the CL-20 cage was broken, since all carbons are part of the heterocyclic cage. Under aerobic conditions, abiotic degradation rates of RDX were generally slower (0 < k < 0.032 d(-1)) than abiotic CL-20 degradation rates. In biologically active soil microcosms amended with glucose aerobic RDX degradation rates varied between 0.010 and 0.474 d(-1). Biodegradation was a key factor in determining the environmental fate of RDX, while a combination of biotic and abiotic processes was important with CL-20. Our data suggest that CL-20 should be less recalcitrant than RDX in aerobic soils.

  11. The chemistry of gamete attraction: chemical structures, biosynthesis, and (a)biotic degradation of algal pheromones.

    PubMed Central

    Boland, W

    1995-01-01

    Female gametes of marine brown algae release and/or attract their conspecific males by chemical signals. The majority of these compounds are unsaturated, nonfunctionalized acyclic, and/or alicyclic C11 hydrocarbons. Threshold concentrations for release and attraction are generally observed in the range of 1-1000 pmol. The blends may contain various configurational isomers of the genuine pheromones as well as mixtures of enantiomers. Higher plants produce the C11 hydrocarbons from dodeca-3,6,9-trienoic acid; brown algae exploit the family of icosanoids for biosynthesis of the same compounds. The biosynthetic routes comprise several spontaneously occurring pericyclic reactions such as [3.3]-sigmatropic rearrangements, [1.7]-hydrogen shifts, and electrocyclic ring closures. All pheromones are (a)biotically degraded by ubiquitous oxidative pathways involving singlet oxygen or hydroxyl radicals, which may be produced through the agency of heavy metals, huminic acids, or light. PMID:7816845

  12. Abiotic Stress Signaling in Wheat – An Inclusive Overview of Hormonal Interactions During Abiotic Stress Responses in Wheat

    PubMed Central

    Abhinandan, Kumar; Skori, Logan; Stanic, Matija; Hickerson, Neil M. N.; Jamshed, Muhammad; Samuel, Marcus A.

    2018-01-01

    Rapid global warming directly impacts agricultural productivity and poses a major challenge to the present-day agriculture. Recent climate change models predict severe losses in crop production worldwide due to the changing environment, and in wheat, this can be as large as 42 Mt/°C rise in temperature. Although wheat occupies the largest total harvested area (38.8%) among the cereals including rice and maize, its total productivity remains the lowest. The major production losses in wheat are caused more by abiotic stresses such as drought, salinity, and high temperature than by biotic insults. Thus, understanding the effects of these stresses becomes indispensable for wheat improvement programs which have depended mainly on the genetic variations present in the wheat genome through conventional breeding. Notably, recent biotechnological breakthroughs in the understanding of gene functions and access to whole genome sequences have opened new avenues for crop improvement. Despite the availability of such resources in wheat, progress is still limited to the understanding of the stress signaling mechanisms using model plants such as Arabidopsis, rice and Brachypodium and not directly using wheat as the model organism. This review presents an inclusive overview of the phenotypic and physiological changes in wheat due to various abiotic stresses followed by the current state of knowledge on the identified mechanisms of perception and signal transduction in wheat. Specifically, this review provides an in-depth analysis of different hormonal interactions and signaling observed during abiotic stress signaling in wheat. PMID:29942321

  13. 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.

  14. Effect of otoconial proteins fetuin A, osteopontin, and otoconin 90 on the nucleation and growth of calcite

    DOE PAGES

    Hong, Mina; Moreland, K. Trent; Chen, Jiajun; ...

    2014-10-30

    Here, we investigated the roles of three proteins associated with the formation of otoconia including fetuin A, osteopontin (OPN), and otoconin 90 (OC90). In situ atomic force microscopy (AFM) studies of the effects of these proteins on the growth of atomic steps on calcite surfaces were performed to obtain insight into their effects on the growth kinetics. We also used scanning electron microscopy to examine the effects of these proteins on crystal morphology. All three proteins were found to be potent inhibitors of calcite growth, although fetuin A promoted growth at concentrations below about 40 nM and only became anmore » inhibitor at higher concentrations. We then used in situ optical microscopy to observe calcite nucleation on films of these proteins adsorbed onto mica surfaces. By measuring the calcite nucleation rate as a function of supersaturation, the value of the interfacial energy that controls the free energy barrier to heterogeneous nucleation was determined for each protein. OPN and OC90 films led to significantly reduced interfacial energies as compared to the value for homogeneous calcite nucleation in bulk solution. The value for fetuin A was equal to that for bulk solution within experimental error. Zeta potential measurements showed all of the proteins possessed negative surface charge and varied in magnitude according to sequence fetuin A > OC90 > OPN. In addition, the interfacial energies exhibited an inverse scaling with the zeta potential. In analogy to previous measurements on polysaccharide films, this scaling indicates the differences between the proteins arise from the effect of protein surface charge on the solution–substrate interfacial energy.« less

  15. Direct Experimental Evidence for Differing Reactivity Alterations of Minerals following Irradiation: The Case of Calcite and Quartz

    NASA Astrophysics Data System (ADS)

    Pignatelli, Isabella; Kumar, Aditya; Field, Kevin G.; Wang, Bu; Yu, Yingtian; Le Pape, Yann; Bauchy, Mathieu; Sant, Gaurav

    2016-01-01

    Concrete, used in the construction of nuclear power plants (NPPs), may be exposed to radiation emanating from the reactor core. Until recently, concrete has been assumed immune to radiation exposure. Direct evidence acquired on Ar+-ion irradiated calcite and quartz indicates, on the contrary, that, such minerals, which constitute aggregates in concrete, may be significantly altered by irradiation. More specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, calcite only experiences random rotations, and distortions of its carbonate groups. As a result, irradiated quartz shows a reduction in density of around 15%, and an increase in chemical reactivity, described by its dissolution rate, similar to a glassy silica. Calcite however, shows little change in dissolution rate - although its density noted to reduce by ≈9%. These differences are correlated with the nature of bonds in these minerals, i.e., being dominantly ionic or covalent, and the rigidity of the mineral’s atomic network that is characterized by the number of topological constraints (nc) that are imposed on the atoms in the network. The outcomes have major implications on the durability of concrete structural elements formed with calcite or quartz bearing aggregates in nuclear power plants.

  16. Direct Experimental Evidence for Differing Reactivity Alterations of Minerals following Irradiation: The Case of Calcite and Quartz

    PubMed Central

    Pignatelli, Isabella; Kumar, Aditya; Field, Kevin G.; Wang, Bu; Yu, Yingtian; Le Pape, Yann; Bauchy, Mathieu; Sant, Gaurav

    2016-01-01

    Concrete, used in the construction of nuclear power plants (NPPs), may be exposed to radiation emanating from the reactor core. Until recently, concrete has been assumed immune to radiation exposure. Direct evidence acquired on Ar+-ion irradiated calcite and quartz indicates, on the contrary, that, such minerals, which constitute aggregates in concrete, may be significantly altered by irradiation. More specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, calcite only experiences random rotations, and distortions of its carbonate groups. As a result, irradiated quartz shows a reduction in density of around 15%, and an increase in chemical reactivity, described by its dissolution rate, similar to a glassy silica. Calcite however, shows little change in dissolution rate - although its density noted to reduce by ≈9%. These differences are correlated with the nature of bonds in these minerals, i.e., being dominantly ionic or covalent, and the rigidity of the mineral’s atomic network that is characterized by the number of topological constraints (nc) that are imposed on the atoms in the network. The outcomes have major implications on the durability of concrete structural elements formed with calcite or quartz bearing aggregates in nuclear power plants. PMID:26822012

  17. Iodine-129 and iodine-127 speciation in groundwater at the Hanford site, US: iodate incorporation into calcite.

    PubMed

    Zhang, Saijin; Xu, Chen; Creeley, Danielle; Ho, Yi-Fang; Li, Hsiu-Ping; Grandbois, Russell; Schwehr, Kathleen A; Kaplan, Daniel I; Yeager, Chris M; Wellman, Dawn; Santschi, Peter H

    2013-09-03

    The geochemical transport and fate of radioiodine depends largely on its chemical speciation that is greatly affected by environmental factors. This study reports, for the first time, the speciation of stable and radioactive iodine in the groundwater from the Hanford Site. Iodate was the dominant species and accounted for up to 84% of the total iodine present. The alkaline pH (pH ∼ 8) and predominantly oxidizing environment may have prevented reduction of the iodate. In addition, groundwater samples were found to have large amounts of calcite precipitate which were likely formed as a result of CO2 degassing during removal from the deep subsurface (>70m depth). Further analyses indicated that between 7 and 40% of the dissolved (127)I and (129)I that was originally in the groundwater had coprecipitated in the calcite. Iodate was the main species incorporated into calcite and this incorporation process could be impeded by elevating the pH and decreasing ionic strength in groundwater. This study provides critical information for predicting the long-term fate and transport of (129)I. Furthermore, the common sampling artifact resulting in the precipitation of calcite by degassing CO2, had the unintended consequence of providing insight into a potential solution for the in situ remediation of groundwater (129)I.

  18. Direct experimental evidence for differing reactivity alterations of minerals following irradiation. The case of calcite and quartz

    DOE PAGES

    Pignatelli, Isabella; Kumar, Aditya; Field, Kevin G.; ...

    2016-01-29

    Concrete, used in the construction of nuclear power plants (NPPs), may be exposed to radiation emanating from the reactor core. Until recently, concrete has been assumed immune to radiation exposure. Direct evidence acquired on Ar+ -ion irradiated calcite and quartz indicates, on the contrary, that, such minerals, which constitute aggregates in concrete, may be significantly altered by irradiation. More specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, calcite only experiences random rotations, and distortions of its carbonate groups. As a result, irradiated quartz shows a reduction in density of around 15%,more » and an increase in chemical reactivity, described by its dissolution rate, similar to a glassy silica. However, calcite shows little change in dissolution rate - although its density noted to reduce by 9%. These differences are correlated with the nature of bonds in these minerals, i.e., being dominantly ionic or covalent, and the rigidity of the mineral's atomic network that is characterized by the number of topological constraints (nc) that are imposed on the atoms in the network. Our outcomes have major implications on the durability of concrete structural elements formed with calcitic or quartzitic aggregates in nuclear power plants.« less

  19. Interdisciplinary knowledge exchange across scales in a globally changing marine environment.

    PubMed

    McDonald, Karlie S; Hobday, Alistair J; Fulton, Elizabeth A; Thompson, Peter A

    2018-07-01

    The effects of anthropogenic global environmental change on biotic and abiotic processes have been reported in aquatic systems across the world. Complex synergies between concurrent environmental stressors and the resilience of the system to regime shifts, which vary in space and time, determine the capacity for marine systems to maintain structure and function with global environmental change. Consequently, an interdisciplinary approach that facilitates the development of new methods for the exchange of knowledge between scientists across multiple scales is required to effectively understand, quantify and predict climate impacts on marine ecosystem services. We use a literature review to assess the limitations and assumptions of current pathways to exchange interdisciplinary knowledge and the transferability of research findings across spatial and temporal scales and levels of biological organization to advance scientific understanding of global environmental change in marine systems. We found that species-specific regional scale climate change research is most commonly published, and "supporting" is the ecosystem service most commonly referred to in publications. In addition, our paper outlines a trajectory for the future development of integrated climate change science for sustaining marine ecosystem services such as investment in interdisciplinary education and connectivity between disciplines. © 2018 John Wiley & Sons Ltd.

  20. 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

  1. MicroRNAs As Potential Targets for Abiotic Stress Tolerance in Plants

    PubMed Central

    Shriram, Varsha; Kumar, Vinay; Devarumath, Rachayya M.; Khare, Tushar S.; Wani, Shabir H.

    2016-01-01

    The microRNAs (miRNAs) are small (20–24 nt) sized, non-coding, single stranded riboregulator RNAs abundant in higher organisms. Recent findings have established that plants assign miRNAs as critical post-transcriptional regulators of gene expression in sequence-specific manner to respond to numerous abiotic stresses they face during their growth cycle. These small RNAs regulate gene expression via translational inhibition. Usually, stress induced miRNAs downregulate their target mRNAs, whereas, their downregulation leads to accumulation and function of positive regulators. In the past decade, investigations were mainly aimed to identify plant miRNAs, responsive to individual or multiple environmental factors, profiling their expression patterns and recognizing their roles in stress responses and tolerance. Altered expressions of miRNAs implicated in plant growth and development have been reported in several plant species subjected to abiotic stress conditions such as drought, salinity, extreme temperatures, nutrient deprivation, and heavy metals. These findings indicate that miRNAs may hold the key as potential targets for genetic manipulations to engineer abiotic stress tolerance in crop plants. This review is aimed to provide recent updates on plant miRNAs, their biogenesis and functions, target prediction and identification, computational tools and databases available for plant miRNAs, and their roles in abiotic stress-responses and adaptive mechanisms in major crop plants. Besides, the recent case studies for overexpressing the selected miRNAs for miRNA-mediated enhanced abiotic stress tolerance of transgenic plants have been discussed. PMID:27379117

  2. Trace Elements in Calcifying Marine Invertebrates Indicate Diverse Sensitivities to the Seawater Carbonate System

    NASA Astrophysics Data System (ADS)

    Doss, W. C.

    2015-12-01

    Surface ocean absorption of anthropogenic CO2 emissions resulting in ocean acidification may interfere with the ability of calcifying marine organisms to biomineralize, since the drop in pH is accompanied by reductions in CaCO3 saturation state. However, recent experiments show that net calcification rates of cultured benthic invertebrate taxa exhibit diverse responses to pCO2-induced changes in saturation state (Ries et al., 2009). Advancement of geochemical tools as biomineralization indicators will enable us to better understand these results and therefore help predict the impacts of ongoing and future decrease in seawater pH on marine organisms. Here we build upon previous work on these specimens by measuring the elemental composition of biogenic calcite and aragonite precipitated in four pCO2 treatments (400; 600; 900; and 2850 ppm). Element ratios (including Sr/Ca, Mg/Ca, Li/Ca, B/Ca, U/Ca, Ba/Ca, Cd/Ca, and Zn/Ca) were analyzed in 18 macro-invertebrate species representing seven phyla (crustacea, cnidaria, echinoidea, rhodophyta, chlorophyta, gastropoda, bivalvia, annelida), then compared to growth rate data and experimental seawater carbonate system parameters: [CO32-], [HCO3-], pH, saturation state, and DIC. Correlations between calcite or aragonite composition and seawater carbonate chemistry are highly taxa-specific, but do not resemble trends observed in growth rate for all species. Apparent carbonate system sensitivities vary widely by element, ranging from strongly correlated to no significant response. Interpretation of these results is guided by mounting evidence for the capacity of individual species to modulate pH and/or saturation state at the site of calcification in response to ambient seawater chemistry. Such biomineralization pathways and strategies in turn likely influence elemental fractionation during CaCO3 precipitation. Ries, J.B., A.L. Cohen, A.L., and D.C. McCorkle (2009), Marine calcifiers exhibit mixed responses to CO2-induced ocean

  3. The mineralogical responses of marine calcifiers to CO2-induced ocean acidification

    NASA Astrophysics Data System (ADS)

    Ries, J. B.; Cohen, A. L.; McCorkle, D. C.

    2008-12-01

    We have conducted 6-month laboratory experiments to investigate the effect of pCO2-induced reductions in seawater CaCO3 saturation state on biocalcification by 18 aragonitic and calcitic (low-high Mg) taxa representing eight of the major marine calcifying groups: Chlorophyta; Rhodophyta; Crustacea; Bivalvia; Gastropoda; Annelida; Cnidaria; and Echinodermata. The CaCO3 saturation states of the experimental seawaters, constrained by intercalibrated determinations of pH, alkalinity, and DIC, were attained with bubbled air-CO2 mixtures of 400 (ambient), 600, 900, and 2850 ppm pCO2, yielding Ωarag of 2.5 (ambient), 2.0, 1.5, 0.7, respectively. We previously showed that while rates of net calcification obtained from buoyant weighing declined with increasing pCO2 for nearly half of the species investigated, a nearly equal number exhibited constant or, in some cases, increased calcification under moderately (600 ppm) or extremely (900 or 2850 ppm) elevated pCO2. The organisms' investigated in this study secrete various forms of CaCO3, which differ in crystallographic structure and therefore solubility: aragonite and high-Mg are generally more soluble than low-Mg calcite. We have employed powder x-ray diffraction, Raman spectroscopy, inductively-coupled-plasma mass-spectrometry, and scanning electron microscopy to quantify changes in the organisms' skeletal mineralogy (aragonite:calcite ratio) and Mg-content (MgCO3:CaCO3 ratio) that occurred in response to the prescribed reductions in seawater CaCO3 saturation state. We will compare calcification and mineralogical response patterns amongst the organisms to elucidate the role of mineral lability in driving species-specific responses to CO2-induced ocean acidification.

  4. Ages and stable-isotope compositions of secondary calcite and opal in drill cores from Tertiary volcanic rocks of the Yucca Mountain area, Nevada

    USGS Publications Warehouse

    Szabo, B. J.; Kyser, T.K.

    1990-01-01

    Stable-isotope compositions of fracture- and cavity-filling calcite from the unsaturated zone of three drill cores at Yucca Mountain Tertiary volcanic complex indicate that the water from which the minerals precipitated was probably meteoric in origin. A decrease in 18O in the calcite with depth is interpreted as being due to the increase in temperature in drill holes corresponding to an estimated average geothermal gradient of 34?? per kilometer. A few of the calcite samples and all of the opal samples yielded uranium-series ages older than 400 000 yr, although most of the calcite samples yielded ages between 26 000 and 310 000 yr. The stable-isotope and uranium-series dates from precipitated calcite and opal of this reconnaissance study suggest a complex history of fluid movement through the volcanic pile, and episodes of fracture filling predominantly from meteoric water during at least the past 400 000 yr. -Authors

  5. Giant calcite concretions in aeolian dune sandstones; sedimentological and architectural controls on diagenetic heterogeneity, mid-Cretaceous Iberian Desert System, Spain

    NASA Astrophysics Data System (ADS)

    Arribas, Maria Eugenia; Rodríguez-López, Juan Pedro; Meléndez, Nieves; Soria, Ana Rosa; de Boer, Poppe L.

    2012-01-01

    Aeolian dune sandstones of the Iberian erg system (Cretaceous, Spain) host giant calcite concretions that constitute heterogeneities of diagenetic origin within a potential aeolian reservoir. The giant calcite concretions developed in large-scale aeolian dune foresets, at the transition between aeolian dune toeset and damp interdune elements, and in medium-scale superimposed aeolian dune sets. The chemical composition of the giant concretions is very homogeneous. They formed during early burial by low Mg-calcite precipitation from meteoric pore waters. Carbonate components with yellow/orange luminescence form the nuclei of the poikilotopic calcite cement. These cements postdate earlier diagenetic features, characterized by early mechanical compaction, Fe-oxide cements and clay rims around windblown quartz grains resulting from the redistribution of aeolian dust over the grain surfaces. The intergranular volume (IGV) in friable aeolian sandstone ranges from 7.3 to 15.3%, whereas in cemented aeolian sandstone it is 18.6 to 25.3%. The giant-calcite concretions developed during early diagenesis under the influence of meteoric waters associated with the groundwater flow of the desert basin, although local (e.g. activity of fluid flow through extensional faults) and/or other regional controls (e.g. variations of the phreatic level associated with a variable water influx to the erg system and varying sea level) could have favoured the local development of giant-calcite concretions. The spatial distribution pattern of carbonate grains and the main bounding surfaces determined the spatial distribution of the concretions. In particular, the geometry of the giant calcite concretions is closely associated with main bounding aeolian surfaces. Thus, interdune, superimposition and reactivation surfaces exerted a control on the concretion geometries ranging from flat and tabular ones (e.g. bounded by interdunes) to wedge-shaped concretions at the dune foresets (e.g. bounded by

  6. Intrinsic versus extrinsic controls on the development of calcite dendrite bushes, Shuzhishi Spring, Rehai geothermal area, Tengchong, Yunnan Province, China

    NASA Astrophysics Data System (ADS)

    Jones, Brian; Peng, Xiaotong

    2012-04-01

    In the Rehai geothermal area, located near Tengchong, there is an old succession of crystalline calcite that formed from a spring that is no longer active. The thin-bedded succession, exposed on the south bank of Zaotang River, is formed of three-dimensional dendrite bushes that are up to 6 cm high and 3 cm in diameter with multiple levels of branching. Bedding is defined by color, which ranges from white to gray to almost black and locally accentuated by differential weathering that highlights the branching motif of the dendrites. The succession developed through repeated tripartite growth cycles that involved: Phase I that was characterized by rapid vertical growth of the dendrite bushes with ever-increasing branching; Phase II that developed once growth of the dendrites had almost or totally ceased, and involved an initial phase of etching that was followed by the precipitation of various secondary minerals (sheet calcite, trigonal calcite crystals, hexagonal calcite crystals, hexagonal plates formed of Ca and P, Mn precipitates, Si-Mg reticulate coatings, opal-CT lepispheres) on the branches of the calcite dendrites, and Phase III that involved deposition of detrital quartz, feldspar, clay, and calcite on top of the dendrite bushes. The tripartite growth cycle is attributed primarily to aperiodic cycles in the CO2 content of the spring water that was controlled by subsurface igneous activity rather than climatic controls. High CO2 coupled with rapid CO2 degassing triggered growth of the dendrite bushes. As CO2 levels waned, saturation levels in the spring water decreased and calcite dendrite growth ceased and precipitation of the secondary minerals took place, possibly in the microcosms of microbial mats. Deposition of the detrital sediment was probably related to surface runoff that was triggered by periods of high rainfall. Critically, this study shows that intrinsic factors rather than extrinsic factors (e.g., climate) were the prime control on the

  7. 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

  8. Review of recent transgenic studies on abiotic stress tolerance and future molecular breeding in potato.

    PubMed

    Kikuchi, Akira; Huynh, Huu Duc; Endo, Tsukasa; Watanabe, Kazuo

    2015-03-01

    Global warming has become a major issue within the last decade. Traditional breeding programs for potato have focused on increasing productivity and quality and disease resistance, thus, modern cultivars have limited tolerance of abiotic stresses. The introgression of abiotic stress tolerance into modern cultivars is essential work for the future. Recently, many studies have investigated abiotic stress using transgenic techniques. This manuscript focuses on the study of abiotic stress, in particular drought, salinity and low temperature, during this century. Dividing studies into these three stress categories for this review was difficult. Thus, based on the study title and the transgene property, transgenic studies were classified into five categories in this review; oxidative scavengers, transcriptional factors, and above three abiotic categories. The review focuses on studies that investigate confer of stress tolerance and the identification of responsible factors, including wild relatives. From a practical application perspective, further evaluation of transgenic potato with abiotic stress tolerance is required. Although potato plants, including wild species, have a large potential for abiotic stress tolerance, exploration of the factors responsible for conferring this tolerance is still developing. Molecular breeding, including genetic engineering and conventional breeding using DNA markers, is expected to develop in the future.

  9. 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

  10. Strain rate dependent calcite microfabric evolution - an experiment carried out by nature

    NASA Astrophysics Data System (ADS)

    Rogowitz, A.; Huet, B.; Grasemann, B.; Habler, G.

    2013-12-01

    The deformation behaviour of calcite has been studied extensively in a number of experiments. Different strain rates and pressure and temperature conditions have been used to investigate a wide range of deformation regimes. However, a direct comparison with natural fault rocks remains difficult because of extreme differences between experimental and natural strain rates. A secondary shear zone (flanking structure) developed in almost pure calcite marble on Syros (Greece). Due to rotation of an elliptical inclusion (crack) a heterogeneous strain field in the surrounding area occurred resulting in different strain domains and the formation of the flanking structure. Assuming that deformation was active continuously during the development of the flanking structure, the different strain domains correspond to different strain-rate domains. The outcrop thus represents the final state of a natural experiment and gives us a great opportunity to get natural constraints on strain rate dependent deformation behaviour of calcite. Comparing the microfabrics in the 1 to 2.5 cm thick shear zone and the surrounding host rocks, which formed under the same metamorphic conditions but with different strain rates, is the central focus of this study. Due to the extreme variation in strain and strain rate, different microstructures and textures can be observed corresponding to different deformation mechanisms. With increasing strain rate we observe a change in dominant deformation mechanism from dislocation glide to dislocation creep and finally diffusion creep. Additionally, a change from subgrain rotation (SGR) to bulging (BLG) recrystallization can be observed in the dislocation creep regime. Textures and the degree of intracrystalline deformation have been measured by electron back scatter diffraction (EBSD). At all strain rates clear CPOs developed leading to the assumption that calcite preferentially deforms within the dislocation creep field. However, we can also find clear

  11. A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

    USGS Publications Warehouse

    Davis, J.A.; Fuller, C.C.; Cook, A.D.

    1987-01-01

    The rate of Cd2+ sorption by calcite was determined as a function of pH and Mg2+ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO3. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca2+ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd2+ sorption decrease with increasing pH or with increasing Mg2+. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer. A model is presented which is consistent with the rates of Cd2+ sorption and Ca2+ isotopic exchange. In the model, the first step in Cd2+ sorption involves a fast adsorption reaction that is followed by diffusion of Cd2+ into a surface layer of hydrated CaCO3 that overlies crystalline calcite. Desorption of Cd2+ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO3, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution. ?? 1987.

  12. Exploring strategies to remove contaminants from subsurface plumes: iron-bearing materials and calcite

    NASA Astrophysics Data System (ADS)

    Lawter, A.; Qafoku, N. P.; Garcia, W.; Lee, B.; Freedman, V. L.

    2017-12-01

    At the Hanford site in eastern Washington, depending on the particular waste site, radionuclide (Tc99/I129) laden liquid waste was not of a sufficient volume to carry the contamination through the vadose zone to the groundwater. Contaminants are therefore retained in the vadose zone, which represents a continuous source of these contaminants to groundwater through flux created by precipitation recharge. Deployment of treatment technologies in the vadose zone that will intercept flow from vadose zone recharge and sequester contaminants is needed for future groundwater protection. In this study, first we tested zero valent iron (ZVI) and sulfur modified iron (SMI) to determine the feasibility of using these materials to intercept Tc migrating from the vadose zone into the groundwater. Secondly, this study focused on testing the ZVI and SMI in conjunction with several potential amendments needed for capture of additional contaminants present (e.g., IO3) to immobilize contaminants both individually and combined. Previous testing has shown removal of IO3 by incorporation into calcite; these experiments test the effect of ZVI/SMI on the efficiency of the removal of IO3 by calcite and vice versa. Preliminary results have shown strong removal of high Tc concentrations (i.e., 22 ppm or 44 ppm) at solid to solution ratios of 1 g to 100 mL, but when the solid and the Tc concentration was scaled down to more field relevant conditions (i.e., 0.42 ppm), the Tc removal was slower and the amount of Tc removed (per gram of Fe solid) was decreased. In some tests, results indicated that there is no interference from IO3 on Tc removal, but presence of ZVI/SMI has a negative impact on the removal of IO3 by calcite incorporation, likely due to the fast reduction of iodate to iodide by the ZVI/SMI (iodide is usually not incorporated into calcite).

  13. Lab-Scale Study of the Calcium Carbonate Dissolution and Deposition by Marine Cyanobacterium Phormidium subcapitatum

    NASA Technical Reports Server (NTRS)

    Karakis, S. G.; Dragoeva, E. G.; Lavrenyuk, T. I.; Rogochiy, A.; Gerasimenko, L. M.; McKay, D. S.; Brown, I. I.

    2006-01-01

    Suggestions that calcification in marine organisms changes in response to global variations in seawater chemistry continue to be advanced (Wilkinson, 1979; Degens et al. 1985; Kazmierczak et al. 1986; R. Riding 1992). However, the effect of [Na+] on calcification in marine cyanobacteria has not been discussed in detail although [Na+] fluctuations reflect both temperature and sea-level fluctuations. The goal of these lab-scale studies therefore was to study the effect of environmental pH and [Na+] on CaCO3 deposition and dissolution by marine cyanobacterium Phormidium subcapitatum. Marine cyanobacterium P. subcapitatum has been cultivated in ASN-III medium. [Ca2+] fluctuations were monitored with Ca(2+) probe. Na(+) concentrations were determined by the initial solution chemistry. It was found that the balance between CaCO3 dissolution and precipitation induced by P. subcapitatum grown in neutral ASN III medium is very close to zero. No CaCO3 precipitation induced by cyanobacterial growth occurred. Growth of P. subcapitatum in alkaline ASN III medium, however, was accompanied by significant oscillations in free Ca(2+) concentration within a Na(+) concentration range of 50-400 mM. Calcium carbonate precipitation occurred during the log phase of P. subcapitatum growth while carbonate dissolution was typical for the stationary phase of P. subcapitatum growth. The highest CaCO3 deposition was observed in the range of Na(+) concentrations between 200-400 mM. Alkaline pH also induced the clamping of P. subcapitatum filaments, which appeared to have a strong affinity to envelop particles of chemically deposited CaCO3 followed by enlargement of those particles size. EDS analysis revealed the presence of Mg-rich carbonate (or magnesium calcite) in the solution containing 10-100 mM Na(+); calcite in the solution containing 200 mM Na(+); and aragonite in the solution containing with 400 mM Na(+). Typical present-day seawater contains xxmM Na(+). Early (Archean) seawater was

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

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Domagal-Goldman, Shawn D.; Segura, Antígona; Claire, Mark W.

    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. Onmore » 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.« less

  15. Application of kinetic models to the design of a calcite permeable reactive barrier (PRB) for fluoride remediation.

    PubMed

    Cai, Qianqian; Turner, Brett D; Sheng, Daichao; Sloan, Scott

    2018-03-01

    The kinetics of fluoride sorption by calcite in the presence of metal ions (Co, Mn, Cd and Ba) have been investigated and modelled using the intra-particle diffusion (IPD), pseudo-second order (PSO), and the Hill 4 and Hill 5 kinetic models. Model comparison using the Akaike Information Criterion (AIC), the Schwarz Bayseian Information Criterion (BIC) and the Bayes Factor allows direct comparison of model results irrespective of the number of model parameters. Information Criterion results indicate "very strong" evidence that the Hill 5 model was the best fitting model for all observed data due to its ability to fit sigmoidal data, with confidence contour analysis showing the model parameters were well constrained by the data. Kinetic results were used to determine the thickness of a calcite permeable reactive barrier required to achieve up to 99.9% fluoride removal at a groundwater flow of 0.1 m.day -1 . Fluoride removal half-life (t 0.5 ) values were found to increase in the order Ba ≈ stonedust (a 99% pure natural calcite) < Cd < Co < Mn. A barrier width of 0.97 ± 0.02 m was found to be required for the fluoride/calcite (stonedust) only system when using no factor of safety, whilst in the presence of Mn and Co, the width increased to 2.76 ± 0.28 and 19.83 ± 0.37 m respectively. In comparison, the PSO model predicted a required barrier thickness of ∼46.0, 62.6 & 50.3 m respectively for the fluoride/calcite, Mn and Co systems under the same conditions. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

  16. Abiotic dechlorination in rock matrices impacted by long-term exposure to TCE.

    PubMed

    Schaefer, Charles E; Towne, Rachael M; Lippincott, David R; Lacombe, Pierre J; Bishop, Michael E; Dong, Hailiang

    2015-01-01

    Field and laboratory tests were performed to evaluate the abiotic reaction of trichloroethene (TCE) in sedimentary rock matrices. Hydraulically conductive fractures, and the rock directly adjacent to the hydraulically conductive fractures, within a historically contaminated TCE bedrock aquifer were used as the basis for this study. These results were compared to previous work using rock that had not been exposed to TCE (Schaefer et al., 2013) to assess the impact of long-term TCE exposure on the abiotic dechlorination reaction, as the longevity of these reactions after long-term exposure to TCE was hitherto unknown. Results showed that potential abiotic TCE degradation products, including ethane, ethene, and acetylene, were present in the conductive fractures. Using minimally disturbed slices of rock core at and near the fracture faces, laboratory testing on the rocks confirmed that abiotic dechlorination reactions between the rock matrix and TCE were occurring. Abiotic daughter products measured in the laboratory under controlled conditions were consistent with those measured in the conductive fractures, except that propane also was observed as a daughter product. TCE degradation measured in the laboratory was well described by a first order rate constant through the 118-d study. Observed bulk first-order TCE degradation rate constants within the rock matrix were 1.3×10(-8) s(-1). These results clearly show that abiotic dechlorination of TCE is occurring within the rock matrix, despite decades of exposure to TCE. Furthermore, these observed rates of TCE dechlorination are expected to have a substantial impact on TCE migration and uptake/release from rock matrices. Copyright © 2014 Elsevier Ltd. All rights reserved.

  17. WRKY Proteins: Signaling and Regulation of Expression during Abiotic Stress Responses

    PubMed Central

    Banerjee, Aditya

    2015-01-01

    WRKY proteins are emerging players in plant signaling and have been thoroughly reported to play important roles in plants under biotic stress like pathogen attack. However, recent advances in this field do reveal the enormous significance of these proteins in eliciting responses induced by abiotic stresses. WRKY proteins act as major transcription factors, either as positive or negative regulators. Specific WRKY factors which help in the expression of a cluster of stress-responsive genes are being targeted and genetically modified to induce improved abiotic stress tolerance in plants. The knowledge regarding the signaling cascade leading to the activation of the WRKY proteins, their interaction with other proteins of the signaling pathway, and the downstream genes activated by them are altogether vital for justified targeting of the WRKY genes. WRKY proteins have also been considered to generate tolerance against multiple abiotic stresses with possible roles in mediating a cross talk between abiotic and biotic stress responses. In this review, we have reckoned the diverse signaling pattern and biological functions of WRKY proteins throughout the plant kingdom along with the growing prospects in this field of research. PMID:25879071

  18. Unraveling the role of fungal symbionts in plant abiotic stress tolerance

    PubMed Central

    Singh, Lamabam Peter

    2011-01-01

    Fungal symbionts have been found to be associated with every plant studied in the natural ecosystem, where they colonize and reside entirely or partially in the internal tissues of their host plant. Fungal endophytes can express/form a range of different lifestyle/relationships with different host including symbiotic, mutualistic, commensalistic and parasitic in response to host genotype and environmental factors. In mutualistic association fungal endophyte can enhance growth, increase reproductive success and confer biotic and abiotic stress tolerance to its host plant. Since abiotic stress such as, drought, high soil salinity, heat, cold, oxidative stress and heavy metal toxicity is the common adverse environmental conditions that affect and limit crop productivity worldwide. It may be a promising alternative strategy to exploit fungal endophytes to overcome the limitations to crop production brought by abiotic stress. There is an increasing interest in developing the potential biotechnological applications of fungal endophytes for improving plant stress tolerance and sustainable production of food crops. Here we have described the fungal symbioses, fungal symbionts and their role in abiotic stress tolerance. A putative mechanism of stress tolerance by symbionts has also been covered. PMID:21512319

  19. Nitrogen fertility and abiotic stresses management in cotton crop: a review.

    PubMed

    Khan, Aziz; Tan, Daniel Kean Yuen; Afridi, Muhammad Zahir; Luo, Honghai; Tung, Shahbaz Atta; Ajab, Mir; Fahad, Shah

    2017-06-01

    This review outlines nitrogen (N) responses in crop production and potential management decisions to ameliorate abiotic stresses for better crop production. N is a primary constituent of the nucleotides and proteins that are essential for life. Production and application of N fertilizers consume huge amounts of energy, and excess is detrimental to the environment. Therefore, increasing plant N use efficiency (NUE) is important for the development of sustainable agriculture. NUE has a key role in crop yield and can be enhanced by controlling loss of fertilizers by application of humic acid and natural polymers (hydrogels), having high water-holding capacity which can improve plant performance under field conditions. Abiotic stresses such as waterlogging, drought, heat, and salinity are the major limitations for successful crop production. Therefore, integrated management approaches such as addition of aminoethoxyvinylglycine (AVG), the film antitranspirant (di-1-p-menthene and pinolene) nutrients, hydrogels, and phytohormones may provide novel approaches to improve plant tolerance against abiotic stress-induced damage. Moreover, for plant breeders and molecular biologists, it is a challenge to develop cotton cultivars that can tolerate plant abiotic stresses while having high potential NUE for the future.

  20. WRKY proteins: signaling and regulation of expression during abiotic stress responses.

    PubMed

    Banerjee, Aditya; Roychoudhury, Aryadeep

    2015-01-01

    WRKY proteins are emerging players in plant signaling and have been thoroughly reported to play important roles in plants under biotic stress like pathogen attack. However, recent advances in this field do reveal the enormous significance of these proteins in eliciting responses induced by abiotic stresses. WRKY proteins act as major transcription factors, either as positive or negative regulators. Specific WRKY factors which help in the expression of a cluster of stress-responsive genes are being targeted and genetically modified to induce improved abiotic stress tolerance in plants. The knowledge regarding the signaling cascade leading to the activation of the WRKY proteins, their interaction with other proteins of the signaling pathway, and the downstream genes activated by them are altogether vital for justified targeting of the WRKY genes. WRKY proteins have also been considered to generate tolerance against multiple abiotic stresses with possible roles in mediating a cross talk between abiotic and biotic stress responses. In this review, we have reckoned the diverse signaling pattern and biological functions of WRKY proteins throughout the plant kingdom along with the growing prospects in this field of research.

  1. 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.

  2. Characteristics of biogenic calcite in the prismatic layer of a pearl oyster, Pinctada fucata.

    PubMed

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

    2010-10-01

    The fine structure of the calcite prism in the outer layer of a pearl oyster, Pinctada fucata, has been investigated using various electron beam techniques, in order to understand its characteristics and growth mechanism including the role of intracrystalline organic substances. As the calcite prismatic layer grows thicker, sinuous boundaries develop to divide the prism into a number of domains. The crystal misorientation between the adjacent domains is several to more than ten degrees. The component of the misorientation is mainly the rotation about the c-axis. There is no continuous organic membrane at the boundaries. Furthermore, the crystal orientation inside the domains changes gradually, as indicated by the electron back-scattered diffraction (EBSD) in a scanning electron microscope (SEM). Transmission electron microscopy (TEM) examination revealed that the domain consists of sub-grains of a few hundred nanometers divided by small-angle grain boundaries, which are probably the origin of the gradual change of the crystal orientation inside the domains. Spherular Fresnel contrasts were often observed at the small-angle grain boundaries, in defocused TEM images. Electron energy-loss spectroscopy (EELS) indicated the spherules are organic macromolecules, suggesting that incorporation of organic macromolecules during the crystal growth forms the sub-grain structure of the calcite prism.

  3. On-line Raman spectroscopy of calcite and malachite during irradiation with swift heavy ions

    NASA Astrophysics Data System (ADS)

    Dedera, Sebastian; Burchard, Michael; Glasmacher, Ulrich A.; Schöppner, Nicole; Trautmann, Christina; Severin, Daniel; Romanenko, Anton; Hubert, Christian

    2015-12-01

    A new on-line Raman System, which was installed at the M3-beamline at the UNILAC, GSI Helmholtzzentrum für Schwerionenforschung Darmstadt was used for first "in situ" spectroscopic measurements. Calcite and malachite samples were irradiated in steps between 1 × 109 and 1 × 1012 ions/cm2 with Au ions (calcite) and Xe ions (malachite) at an energy of 4.8 MeV/u. After irradiation, calcite revealed a new Raman band at 437 cm-1 and change of the full width at half maximum for the 1087 cm-1 Raman band. The Raman bands of malachite change significantly with increasing fluence. Up to a fluence of 7 × 1010 ions/cm2, all existing bands decrease in intensity. Between 8 × 1010 and 1 × 1011 ions/cm2 a broad Cu2O band between 110 and 220 cm-1 occurs, which superimposes the pre-existing Raman bands. Additionally, a new broad band between 1000 and 1750 cm-1 is formed, which is interpreted as a carbon coating. In contrast to the Cu2O band, the carbon band vanished when further irradiating the sample. The installations as well as first in situ measurements at room temperature are presented.

  4. Phytoplankton responses to temperature increases are constrained by abiotic conditions and community composition.

    PubMed

    Striebel, Maren; Schabhüttl, Stefanie; Hodapp, Dorothee; Hingsamer, Peter; Hillebrand, Helmut

    2016-11-01

    Effects of temperature changes on phytoplankton communities seem to be highly context-specific, but few studies have analyzed whether this context specificity depends on differences in the abiotic conditions or in species composition between studies. We present an experiment that allows disentangling the contribution of abiotic and biotic differences in shaping the response to two aspects of temperature change: permanent increase of mean temperature versus pulse disturbance in form of a heat wave. We used natural communities from six different sites of a floodplain system as well as artificially mixed communities from laboratory cultures and grew both, artificial and natural communities, in water from the six different floodplain lakes (sites). All 12 contexts (2 communities × 6 sites) were first exposed to three different temperature levels (12, 18, 24 °C, respectively) and afterward to temperature pulses (4 °C increase for 7 h day(-1)). Temperature-dependent changes in biomass and community composition depended on the initial composition of phytoplankton communities. Abiotic conditions had a major effect on biomass of phytoplankton communities exposed to different temperature conditions, however, the effect of biotic and abiotic conditions together was even more pronounced. Additionally, phytoplankton community responses to pulse temperature effects depended on the warming history. By disentangling abiotic and biotic effects, our study shows that temperature-dependent effects on phytoplankton communities depend on both, biotic and abiotic constraints.

  5. Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

    NASA Astrophysics Data System (ADS)

    Immenhauser, A.; Buhl, D.; Richter, D.; Niedermayr, A.; Riechelmann, D.; Dietzel, M.; Schulte, U.

    2010-08-01

    The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ 26Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ 26Mg values of loess-derived soil above the cave (-1.0 ± 0.5‰), soil water (-1.2 ± 0.5‰), the carbonate hostrock (-3.8 ± 0.5‰), dripwater in the cave (-1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; -4.3 ± 0.6‰), cave loam (-0.6 ± 0.1‰) and runoff water (-1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000ln αMg-cc-Mg(aq) = -2.4‰. A similar Mg-isotope fractionation (1000ln αMg-cc-Mg(aq) ≈ -2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, 26Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg 2+ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for

  6. The interaction between abiotic photodegradation and microbial decomposition under ultraviolet radiation.

    PubMed

    Wang, Jing; Liu, Lingli; Wang, Xin; Chen, Yiwei

    2015-05-01

    Elevated ultraviolet (UV) radiation has been demonstrated to stimulate litter decomposition. Despite years of research, it is still not fully understood whether the acceleration in litter degradation is primarily attributed to abiotic photodegradation or the combined effects of abiotic photodegradation and microbial decomposition. In this study, we used meta-analysis to synthesize photodegradation studies and compared the effects of UV radiation on litter decomposition between abiotic and biotic conditions. We also conducted a microcosm experiment to assess the effects of UV radiation on litter biodegradability and microbial activity. Overall, our meta-analysis found that under abiotic photodegradation, UV radiation reduced the remaining litter mass by 1.44% (95% CI: 0.85% to 2.08%), did not affect the remaining lignin and increased the dissolved organic carbon (DOC) concentration by 14.01% (1.49-23.67%). Under combined abiotic photodegradation and microbial decomposition, UV radiation reduced the remaining litter mass and lignin by 1.60% (0.04-3.58%) and 16.07% (9.27-24.23%), respectively, but did not alter DOC concentration. UV radiation had no significant impact on soil microbial biomass carbon (MBC), but it reduced microbial respiration by 44.91% (2.26-78.62%) and altered the composition of the microbial community. In addition, UV radiation reduced nitrogen (N) immobilization by 19.44% (4.77-37.92%). Our microcosm experiment further indicated that DOC concentration and the amount of respired C in UV-treated litter increased with UV exposure time, suggesting that longer UV exposure resulted in greater biodegradability. Overall, our study suggested that UV exposure could increase litter biodegradability by increasing the microbial accessibility of lignin, as well as the labile carbon supply to microbes. However, the remaining litter mass was not different between the abiotic and biotic conditions, most likely because the positive effect of UV radiation on litter

  7. Identification of spectrally similar materials using the USGS Tetracorder algorithm: The calcite-epidote-chlorite problem

    USGS Publications Warehouse

    Dalton, J.B.; Bove, D.J.; Mladinich, C.S.; Rockwell, B.W.

    2004-01-01

    A scheme to discriminate and identify materials having overlapping spectral absorption features has been developed and tested based on the U.S. Geological Survey (USGS) Tetracorder system. The scheme has been applied to remotely sensed imaging spectroscopy data acquired by the Airborne Visible and Infrared Imaging Spectrometer (AVIRIS) instrument. This approach was used to identify the minerals calcite, epidote, and chlorite in the upper Animas River watershed, Colorado. The study was motivated by the need to characterize the distribution of calcite in the watershed and assess its acid-neutralizing potential with regard to acidic mine drainage. Identification of these three minerals is difficult because their diagnostic spectral features are all centered at 2.3 ??m, and have similar shapes and widths. Previous studies overestimated calcite abundance as a result of these spectral overlaps. The use of a reference library containing synthetic mixtures of the three minerals in varying proportions was found to simplify the task of identifying these minerals when used in conjunction with a rule-based expert system. Some inaccuracies in the mineral distribution maps remain, however, due to the influence of a fourth spectral component, sericite, which exhibits spectral absorption features at 2.2 and 2.4 ??m that overlap the 2.3-??m absorption features of the other three minerals. Whereas the endmember minerals calcite, epidote, chlorite, and sericite can be identified by the method presented here, discrepancies occur in areas where all four occur together as intimate mixtures. It is expected that future work will be able to reduce these discrepancies by including reference mixtures containing sericite. ?? 2004 Elsevier Inc. All rights reserved.

  8. 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 range. Because of the relatively high temperature sensitivity suggested by these results and by Bottinga's calculations, and the pressure independence of isotope fractionation, ??(Cc-Gr) may provide a very good thermometer for high-grade marbles. Comparison of this field calibration for ??(Cc-Gr) vs temperature with results from other terranes supports the utility of ??(Cc-Gr) for geothermometry and suggests that graphite is much more sluggish to exchange than calcite, that exchange between calcite and graphite occurs at temperatures as low as 300??C, and that equilibrium may normally be attained only when peak metamorphic temperatures are greater than 500-600??C. Because 13C exchange is an unavoidable metamorphic process at temperatures above 300??C, high values of ??13C(Gr) in moderate- to high-grade carbonate-bearing rocks do not provide a sufficient criterion to infer an abiogenic origin for the graphite. ?? 1981.

  9. Tracing the incorporation of carbon into benthic foraminiferal calcite following the Deepwater Horizon event.

    PubMed

    Schwing, Patrick T; Chanton, Jeffrey P; Romero, Isabel C; Hollander, David J; Goddard, Ethan A; Brooks, Gregg R; Larson, Rebekka A

    2018-06-01

    Following the Deepwater Horizon (DWH) event in 2010, hydrocarbons were deposited on the continental slope in the northeastern Gulf of Mexico through marine oil snow sedimentation and flocculent accumulation (MOSSFA). The objective of this study was to test the hypothesis that benthic foraminiferal δ 13 C would record this depositional event. From December 2010 to August 2014, a time-series of sediment cores was collected at two impacted sites and one control site in the northeastern Gulf of Mexico. Short-lived radioisotopes ( 210 Pb and 234 Th) were employed to establish the pre-DWH, DWH, and post-DWH intervals. Benthic foraminifera (Cibicidoides spp. and Uvigerina spp.) were isolated from these intervals for δ 13 C measurement. A modest (0.2-0.4‰), but persistent δ 13 C depletion in the DWH intervals of impacted sites was observed over a two-year period. This difference was significantly beyond the pre-DWH (background) variability and demonstrated that benthic foraminiferal calcite recorded the depositional event. The longevity of the depletion in the δ 13 C record suggested that benthic foraminifera may have recorded the change in organic matter caused by MOSSFA from 2010 to 2012. These findings have implications for assessing the subsurface spatial distribution of the DWH MOSSFA event. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Ab initio study of single-crystalline and polycrystalline elastic properties of Mg-substituted calcite crystals.

    PubMed

    Zhu, L-F; Friák, M; Lymperakis, L; Titrian, H; Aydin, U; Janus, A M; Fabritius, H-O; Ziegler, A; Nikolov, S; Hemzalová, P; Raabe, D; Neugebauer, J

    2013-04-01

    We employ ab initio calculations and investigate the single-crystalline elastic properties of (Ca,Mg)CO3 crystals covering the whole range of concentrations from pure calcite CaCO3 to pure magnesite MgCO3. Studying different distributions of Ca and Mg atoms within 30-atom supercells, our theoretical results show that the energetically most favorable configurations are characterized by elastic constants that nearly monotonously increase with the Mg content. Based on the first principles-derived single-crystalline elastic anisotropy, the integral elastic response of (Ca,Mg)CO3 polycrystals is determined employing a mean-field self-consistent homogenization method. As in case of single-crystalline elastic properties, the computed polycrystalline elastic parameters sensitively depend on the chemical composition and show a significant stiffening impact of Mg atoms on calcite crystals in agreement with the experimental findings. Our analysis also shows that it is not advantageous to use a higher-scale two-phase mix of stoichiometric calcite and magnesite instead of substituting Ca atoms by Mg ones on the atomic scale. Such two-phase composites are not significantly thermodynamically favorable and do not provide any strong additional stiffening effect. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Adjustment errors of sunstones in the first step of sky-polarimetric Viking navigation: studies with dichroic cordierite/ tourmaline and birefringent calcite crystals

    PubMed Central

    Száz, Dénes; Farkas, Alexandra; Blahó, Miklós; Barta, András; Egri, Ádám; Kretzer, Balázs; Hegedüs, Tibor; Jäger, Zoltán; Horváth, Gábor

    2016-01-01

    According to an old but still unproven theory, Viking navigators analysed the skylight polarization with dichroic cordierite or tourmaline, or birefringent calcite sunstones in cloudy/foggy weather. Combining these sunstones with their sun-dial, they could determine the position of the occluded sun, from which the geographical northern direction could be guessed. In psychophysical laboratory experiments, we studied the accuracy of the first step of this sky-polarimetric Viking navigation. We measured the adjustment error e of rotatable cordierite, tourmaline and calcite crystals when the task was to determine the direction of polarization of white light as a function of the degree of linear polarization p. From the obtained error functions e(p), the thresholds p* above which the first step can still function (i.e. when the intensity change seen through the rotating analyser can be sensed) were derived. Cordierite is about twice as reliable as tourmaline. Calcite sunstones have smaller adjustment errors if the navigator looks for that orientation of the crystal where the intensity difference between the two spots seen in the crystal is maximal, rather than minimal. For higher p (greater than pcrit) of incident light, the adjustment errors of calcite are larger than those of the dichroic cordierite (pcrit=20%) and tourmaline (pcrit=45%), while for lower p (less than pcrit) calcite usually has lower adjustment errors than dichroic sunstones. We showed that real calcite crystals are not as ideal sunstones as it was believed earlier, because they usually contain scratches, impurities and crystal defects which increase considerably their adjustment errors. Thus, cordierite and tourmaline can also be at least as good sunstones as calcite. Using the psychophysical e(p) functions and the patterns of the degree of skylight polarization measured by full-sky imaging polarimetry, we computed how accurately the northern direction can be determined with the use of the Viking sun

  12. Kinetics of abiotic nitrous oxide production via oxidation of hydroxylamine by particulate metals in seawater

    NASA Astrophysics Data System (ADS)

    Cavazos, A. R.; Taillefert, M.; Glass, J. B.

    2016-12-01

    The oceans are a significant of nitrous oxide (N2O) to the atmosphere. Current models of global oceanic N2­O flux focus on microbial N2O cycling and often ignore abiotic reactions, such as the thermodynamically favorable oxidation of the nitrification intermediate hydroxylamine (NH2OH) by Mn(IV) or Fe(III). At circumneutral pH, NH2OH oxidation is more thermodynamically favorable via Mn(IV) than Fe(III) reduction. We characterized the kinetics of NH2OH oxidation in synthetic ocean water at pH 5.1-8.8 using microsensor electrodes to measure real-time N2O production. N2O production rates and yield were greater when NH2OH was oxidized by Mn(IV) than Fe(III). Accordingly, the reduction of Mn(IV) was first order with respect to NH2OH whereas the reduction of Fe(III) was zero order with respect to NH2OH. Interestingly, the order of the reaction with respect to Mn(IV) appears to be negative whereas the reaction is second order with respect to Fe(III). The inverse order with respect to Mn(IV) may be due to the aggregation of particles in seawater, which decreases their surface area and changes their reactivity. Finally, the reaction is first order with respect to protons with Fe(III) as the oxidant but zero order with Mn(IV). The stronger effect of the pH on the reaction with Fe(III) as the oxidant compared to Mn(IV) reflects the stoichiometry of these two reactions, as each mole of N2O produced by Fe(III) reduction consumes eight protons while each mole of N2O produced with Mn(IV) as the oxidant requires only four protons. Our data show that abiotic NH2OH oxidation by Mn(IV) or Fe(III) particles may represent a significant source of N2O in seawater. These findings suggest that abiotic N2O production in marine waters may be significant in areas of the oceans where particulate metals originating from aerosols, dust, or rivers may react with NH2OH released from ammonia-oxidizing microorganisms.

  13. Pb 2+–Calcite Interactions under Far-from-Equilibrium Conditions: Formation of Micropyramids and Pseudomorphic Growth of Cerussite

    DOE PAGES

    Yuan, Ke; De Andrade, Vincent; Feng, Zhange; ...

    2018-01-04

    The presence of impurity ions is known to significantly influence mineral surface morphology during crystal growth from aqueous solution, but knowledge on impurity ion-mineral interactions during dissolution under far-from equilibrium conditions remains limited. Here we show that calcite (CaCO 3) exhibits a rich array of dissolution features in the presence of Pb. During the initial stage, calcite exhibits non-classical surface features characterized as micro pyramids developed spontaneously in acidic Pb-bearing solutions. Subsequent pseudomorphic growth of cerussite (PbCO 3) was observed, where nucleation occurred entirely within a pore space created by dissolution at the calcite/substrate interface. Uneven growth rates yielded amore » cerussite shell made of lath- or dendritic-shaped crystals. The cerussite phase was separated from the calcite by pores of less than 200 nm under transmission X-ray microscopy, consistent with the interface-coupled dissolution-precipitation mechanism. These results show that impurity metal ions exert significant control over the microscale dissolution features found on mineral surfaces and provide new insights into interpreting and designing micro structures observed in naturally-occurring and synthetic carbonate minerals by dissolution. In addition, heterogeneous micro-environments created in transport limited reactions under pore spaces may lead to unusual growth forms during crystal nucleation and precipitation.« less

  14. Sm-Nd in marine carbonates and phosphates - Implications for Nd isotopes in seawater and crustal ages

    NASA Technical Reports Server (NTRS)

    Shaw, H. F.; Wasserburg, G. J.

    1985-01-01

    The possibility of establishing a record of variations in the isotopic composition of Nd in seawater over geologic time is explored. To construct such a record, a phase must be identified which incorporated Nd with the same isotopic composition as seawater at the time of its formation, preserves that composition, and which is relatively common in sediments. To evaluate the suitability of carbonates and phosphates, the Rb, Sr, Sm, and Nd concentrations and the Nd and Sr isotopic composition of a variety of modern and ancient marine calcite, aragonite, and apatite samples have been measured and the results are presented and discussed.

  15. Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades

    USGS Publications Warehouse

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

    2000-01-01

    The crystallization of calcium carbonate minerals plays an integral role in the water chemistry of terrestrial ecosystems. Humic substances, which are ubiquitous in natural waters, have been shown to reduce or inhibit calcite crystal growth in experiments. The purpose of this study is to quantify and understand the kinetic effects of hydrophobic organic acids isolated from the Florida Everglades and a fulvic acid from Lake Fryxell, Antarctica, on the crystal growth of calcite (CaCO3). Highly reproducible calcite growth experiments were performed in a sealed reactor at constant pH, temperature, supersaturation (?? = 4.5), P(CO2) (10-3.5atm), and ionic strength (0.1 M) with various concentrations of organic acids. Higher plant-derived aquatic hydrophobic acids from the Everglades were more effective growth inhibitors than microbially derived fulvic acid from Lake Fryxell. Organic acid aromaticity correlated strongly with growth inhibition. Molecular weight and heteroatom content correlated well with growth inhibition, whereas carboxyl content and aliphatic nature did not. Copyright (C) 1999 Elsevier Science Ltd.

  16. Angle-dependent rotation of calcite in elliptically polarized light

    NASA Astrophysics Data System (ADS)

    Herne, Catherine M.; Cartwright, Natalie A.; Cattani, Matthew T.; Tracy, Lucas A.

    2017-08-01

    Calcite crystals trapped in an elliptically polarized laser field exhibit intriguing rotational motion. In this paper, we show measurements of the angle-dependent motion, and discuss how the motion of birefringent calcite can be used to develop a reliable and efficient process for determining the polarization ellipticity and orientation of a laser mode. The crystals experience torque in two ways: from the transfer of spin angular momentum (SAM) from the circular polarization component of the light, and from a torque due to the linear polarization component of the light that acts to align the optic axis of the crystal with the polarization axis of the light. These torques alternatingly compete with and amplify each other, creating an oscillating rotational crystal velocity. We model the behavior as a rigid body in an angle-dependent torque. We experimentally demonstrate the dependence of the rotational velocity on the angular orientation of the crystal by placing the crystals in a sample solution in our trapping region, and observing their behavior under different polarization modes. Measurements are made by acquiring information simultaneously from a quadrant photodiode collecting the driving light after it passes through the sample region, and by imaging the crystal motion onto a camera. We finish by illustrating how to use this model to predict the ellipticity of a laser mode from rotational motion of birefringent crystals.

  17. Sulfur in foraminiferal calcite as a potential proxy for seawater carbonate ion concentration

    NASA Astrophysics Data System (ADS)

    van Dijk, I.; de Nooijer, L. J.; Boer, W.; Reichart, G.-J.

    2017-07-01

    Sulfur (S) incorporation in foraminiferal shells is hypothesized to change with carbonate ion concentration [CO32-], due to substitution of sulfate for carbonate ions in the calcite crystal lattice. Hence S/Ca values of foraminiferal carbonate shells are expected to reflect sea water carbonate chemistry. To generate a proxy calibration linking the incorporation of S into foraminiferal calcite to carbonate chemistry, we cultured juvenile clones of the larger benthic species Amphistegina gibbosa and Sorites marginalis over a 350-1200 ppm range of pCO2 values, corresponding to a range in [CO32-] of 93 to 211 μmol/kg. We also investigated the potential effect of salinity on S incorporation by culturing juvenile Amphistegina lessonii over a large salinity gradient (25-45). Results show S/CaCALCITE is not impacted by salinity, but increases with increasing pCO2 (and thus decreasing [CO32-] and pH), indicating S incorporation may be used as a proxy for [CO32-]. Higher S incorporation in high-Mg species S. marginalis suggests a superimposed biomineralization effect on the incorporation of S. Microprobe imaging reveals co-occurring banding of Mg and S in Amphistegina lessonii, which is in line with a strong biological control and might explain higher S incorporation in high Mg species. Provided a species-specific calibration is available, foraminiferal S/Ca values might add a valuable new tool for reconstructing past ocean carbonate chemistry.

  18. 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

  19. 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.

  20. 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

  1. Sorption kinetics of TNT and RDX in anaerobic freshwater and marine sediments: Batch studies.

    PubMed

    Ariyarathna, Thivanka; Vlahos, Penny; Tobias, Craig; Smith, Richard

    2016-01-01

    Examination of the partitioning of explosives onto sediment in marine environments is critical to predict the toxicological impacts of worldwide explosive-contaminated sites adjacent to estuaries, wetlands, and the coastal ocean. Marine sediments have been identified as sites of enhanced munitions removal, yet most studies addressing these interactions focus on soils and freshwater sediments. The present study measured the kinetics of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) sorption onto 2 marine sediments of varying grain sizes (silt vs sand) and organic carbon (OC) content. Abiotic sediment sorption tests were performed at 23 °C, 15 °C, and 4 °C by spiking TNT and RDX solutions directly into anaerobic sediment slurries. Marine sediments showed significantly higher compound uptake rates (0.30-0.80 h(-1) ) than freshwater silt (0.0046-0.0065 h(-1) ) for both compounds, probably because of lower compound solubilities and a higher pH in marine systems. Equilibrium partition constants are on the same order of magnitude for marine silt (1.1-2.0 L kg(-1) sediment) and freshwater silt (1.4-3.1 L kg(-1) sediment) but lower for marine sand (0.72-0.92 L kg(-1) sediment). Total organic carbon content in marine sediments varied linearly with equilibrium partition constants for TNT and was moderately linear for RDX. Uptake rates and equilibrium constants of explosives are inversely correlated to temperature regardless of sediment type because of kinetic barriers associated with low temperatures. © 2015 SETAC.

  2. Geochemistry of volcanogenic clayey marine sediments from the Hazar-Maden Basin (Eastern Turkey)

    NASA Astrophysics Data System (ADS)

    Akkoca, Dicle Bal; Kürüm, Sevcan; Huff, Warren D.

    2013-12-01

    The Hazar-Madeıı Basin sediments were deposited along the southern branch of the Neotethys Ocean margin during Late Maastrichtian-Middle Eocene times. X-ray powder diffraction (XRD), ICP-AES, ICP-MS and scanning electron microscopy (SEM) were performed on samples of the Upper Maastrichtian-Middle Eocene Hazar Group and the Middle Eocene Maden Complex from the Hazar-Maden Basin to investigate the main effects of depositional envi- ronmental parameters in three sections belonging to deeper marine (slope), proximal arc volcanic (Mastarhill and Yukaribag sections) and shallow platform marine (Sebken section) settings. Marine sediments contain clay minerals (smectite, smectite/chlorite, chlorite, illite, interstratified illite/smectite, illite/chlorite, palygorskite), clinoptilolite, quartz, feldspar, calcite, dolomite, opal-CT and hematite. The clays are dominated by iron-rich smectites. La, Zr and Th concentrations are high in the shallow marginal Sebken section where the terrestrial detrital contribution is significant, while Sc and Co are more dominant in the deeper marine (slope) Yukaribag section, which is represented by basic-type volcanism and a higher contribution of hydrothermal phases. In a chondrite-normalized REE diagram, the negative Eu anomaly in samples from Sebken, the section which was deposited in a shallow marine environment, is less significant than that of the other two sections indicating the presence of a high terrestrial contribution in that part of the basin. A decrease in LREE v/HREEiV and Lajv/Ybv, LaiV/Sin v ratios from Sebken to Mastarhill and the Yukaribag sections indi- cates deepening of the basin and an increasing contribution of volcanism in that direction.

  3. Calcite raft geochemistry as a hydrological proxy for Holocene aquifer conditions in Hoyo Negro and Ich Balam (Sac Actun Cave System), Quintana Roo, Mexico

    NASA Astrophysics Data System (ADS)

    Kovacs, Shawn E.; Reinhardt, Eduard G.; Chatters, James C.; Rissolo, Dominique; Schwarcz, Henry P.; Collins, Shawn V.; Kim, Sang-Tae; Nava Blank, Alberto; Luna Erreguerena, Pilar

    2017-11-01

    Two cores from calcite rafts deposits located in Cenote Ich Balam and Hoyo Negro were dated and analyzed for 87Sr/86Sr, δ18O, δ13C, Sr/Ca and Cl/Ca. The geochemical records show changing aquifer salinity spanning the last ∼ 8.5 cal kyrs BP and interrelationships with Holocene climate trends (wet and dry periods). During the wet mid-Holocene, the salinity of the meteoric Water Mass (WM; at 7.8-8.3 cal kyrs BP) was relatively high at 1.5-2.7 ppt and then became less saline (1.0-1.5 ppt) during the last ∼ 7000 yrs as climate became progressively drier. High salinity of the meteoric WM during the wet mid-Holocene is attributed to increased turbulent mixing between the meteoric and underlying marine WM. Increased precipitation, in terms of amount, frequency, and intensity (e.g. hurricanes) causes higher flow of meteoric water towards the coast and mixing at the halocline, a phenomenon recorded with recent instrumental monitoring of the aquifer. Conversely, during dry periods reduced precipitation and flow in the meteoric WM would result in lower salinity. Karst properties and Holocene sea-level rise also seem to have an effect on the aquifer. When the regionally extensive network of shallow cave passages (∼ 10-12 m water depth) are flooded at ∼ 8000 cal yrs BP, there is a rapid shift in salinity. This study demonstrates that calcite raft deposits can be used as paleo-environmental recorders documenting the effects of sea level and climate change on aquifer condition.

  4. Aragonite-Calcite Inversion During Biogenic Carbonate Sampling: Considerations for Interpreting Isotopic Measurements in Paleoclimate Studies

    NASA Astrophysics Data System (ADS)

    Waite, A. J.; Swart, P. K.

    2011-12-01

    As aragonite is the metastable polymorph of calcium carbonate, it lends itself to monotropic inversion to the more stable polymorph, calcite. This inversion is possible through an increase in the temperature and pressure conditions to which the sample is exposed and, although first noted nearly a century ago, has been primarily discussed in the context of sample roasting prior to analyses in paleoclimatological studies. Over the last several decades, however, researchers have found evidence to suggest that the friction associated with the sampling of biogenic carbonates via milling/drilling also induces inversion. Furthermore, this inversion may be associated with a shift in measured oxygen isotopic values and ultimately have significant implications for the interpretation of paleoclimatic reconstructions. Despite this, the isotopic heterogeneity of biogenic aragonite skeletons makes the effects of inversion challenging to test and the subject remains underrepresented in the literature. Here we present a first order study into the effects of milling on both the mineralogy and isotopic compositions measured in sclerosponges, corals, and molluscs. X-Ray diffraction analysis of samples hand ground with a mortar and pestle reveal 100% aragonitic skeletons. Conversely, samples milled with a computerized micromill show measurable inversion to calcite. On average, percent inversion of aragonite to calcite for individual specimens was 15% for sclerosponges, 16% for corals, and 9% for molluscs. Isotopic data from these specimens show that the higher the percentage of aragonite inverted to calcite, the more depleted the measured oxygen isotopic values. In the largest of the datasets (sclerosponges), it is evident that the range of oxygen isotope values from milled samples (-0.02 to +0.84%) exceeds the range in values for those samples which were hand ground and showed no inversion (+0.53 to +0.90%). This, coupled with the strong correlation between the two variables

  5. Area and percent of forest affected by abiotic agents beyond reference conditions

    Treesearch

    2012-01-01

    Criterion 3, Indicator 16, of the Montréal Process Criteria and Indicators for the Conservation and Sustainable Management of Temperate and Boreal Forests was designed to assess the impact of abiotic agents upon forests (Montréal Process Working Group 2007). Various abiotic agents, both natural and human-induced, can change forest structure and species composition....

  6. Persistent Organic Pollutants in Biotic and Abiotic Components of Antarctic Pristine Environment

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Laxmikant; Chauhan, Abhishek; Ranjan, Anuj; Jindal, Tanu

    2018-02-01

    Over the past decades, research in Antarctica has built a new understanding of Antarctica, its past, present and future. Human activities and long-range pollutants are increasing on the Antarctic continent. Research on persistent organic pollutants (POPs) has been carried out internationally by several countries having their permanent research stations to explain the impact of an ever increasing range of POPs in Antarctic ecosystem. POPs have been detected in Antarctica despite its geographical isolation and almost complete absence of human settlements. The presence of POPs in different abiotic (atmosphere, water bodies, sediments, soil, sea ice) and biotic components (mosses, lichens, krill, penguins, skua, etc.) in Antarctica has been studied and documented around for decades and has either been banned or strictly regulated but is still found in the environment. This review focuses on recent research pertaining to sources and occurrence of POPs in Antarctic lake water, soil, sediment, lichen, mosses and other Antarctic marine community. This review also proposes to summarize the current state of research on POPs in Antarctica environment and draw the earliest conclusions on possible significance of POPs in Antarctica based on presently available information from related Antarctic environment.

  7. Persistent Organic Pollutants in Biotic and Abiotic Components of Antarctic Pristine Environment

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Laxmikant; Chauhan, Abhishek; Ranjan, Anuj; Jindal, Tanu

    2018-05-01

    Over the past decades, research in Antarctica has built a new understanding of Antarctica, its past, present and future. Human activities and long-range pollutants are increasing on the Antarctic continent. Research on persistent organic pollutants (POPs) has been carried out internationally by several countries having their permanent research stations to explain the impact of an ever increasing range of POPs in Antarctic ecosystem. POPs have been detected in Antarctica despite its geographical isolation and almost complete absence of human settlements. The presence of POPs in different abiotic (atmosphere, water bodies, sediments, soil, sea ice) and biotic components (mosses, lichens, krill, penguins, skua, etc.) in Antarctica has been studied and documented around for decades and has either been banned or strictly regulated but is still found in the environment. This review focuses on recent research pertaining to sources and occurrence of POPs in Antarctic lake water, soil, sediment, lichen, mosses and other Antarctic marine community. This review also proposes to summarize the current state of research on POPs in Antarctica environment and draw the earliest conclusions on possible significance of POPs in Antarctica based on presently available information from related Antarctic environment.

  8. 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

  9. 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.

  10. Aragonite→calcite transformation studied by EPR of Mn 2+ ions

    NASA Astrophysics Data System (ADS)

    Lech, J.; Śl|zak, A.

    1989-05-01

    The irreversible transformation aragonite→calcite has been studied both at different fixed heating rates (5, 10, 15 and 20 K/min) and at different fixed temperatures. Apparent progression rates of the transformation were observed above 685 K. At 730 K the transformation became sudden and violent. Time developments of the transformation at fixed temperatures have been discussed in terms of Avrami-Lichti's approach to transitions involving nucleation processes.

  11. 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

  12. U-Pb Dating of Calcite to Constrain Basinal Brine Flux Events: An Example from the Upper Midwest USA

    NASA Astrophysics Data System (ADS)

    Rasbury, T.; Luczaj, J.

    2017-12-01

    Calcite forms in a variety of settings and can be the product of surface to deep basinal fluids. As such, this mineral can uniquely record details of the fluids responsible for its formation. The forms of calcium carbonates and their stratigraphic relationships from the thin section to the regional scale give important insights on pulses of fluids. A fundamental question is the age of such fluid pulses. While calcite excludes uranium (U) from its crystal structure, some is incorporated and depending on the U/Pb ratio, this provides an opportunity for radiometric dating. Calcite crystals of various sizes and crystal habits are found in Paleozoic carbonate rocks throughout the region from the western Michigan basin to the upper Mississippi valley. These are typically associated with Mississippi Valley-type (MVT) mineralization, including galena, sphalerite, and iron sulfides, but typically post-date the main MVT event. We have analyzed a variety of these calcites and find multiple generations of calcite, separated by tens of millions of years. The initial Pb isotope ratios are similar to the isotope ratios of nearby galena, strongly suggesting a genetic relationship. Our oldest ages are 200 Ma, and we find ages ranging into the Cenozoic. Based on the Paleozoic-hosted galena Pb-isotope isoscapes from the region, the fluids may have been sourced from both the Michigan and Illinois basins. An important and unanswered question is what would cause significant fluid movement out of the basins substantially after Appalachian orogenesis. Noble gas data from brines in the Michigan Basin have a mantle component and have been suggested to be responsible for recognized elevated temperatures across the basin (Ma et al., 2009). Multiple thermal events during the Paleozoic and Mesozoic eras may have an internal heat source related to reactivation of faults of the Keweenawan Rift system below the Michigan Basin. Perhaps a mantle heat source from below episodically fluxes into the

  13. Jet-Suspended, Calcite-Ballasted Cyanobacterial Waterwarts in a Desert Spring

    NASA Technical Reports Server (NTRS)

    Pichel-Garcia, Ferran; Wade, Bman D.; Farmer, Jack D.

    2002-01-01

    We describe a population of colonial cyanobacteria (waterwarts) that develops as the dominant primary producer in a bottom-fed, warm spring in the Cuatro Cienegas karstic region of the Mexican Chihuahuan Desert. The centimeter-sized waterwarts were suspended within a central, conically shaped, 6-m deep well by upwelling waters. Waterwarts were built by an unicellular cyanobacterium and supported a community of epiphytic filamentous cyanobacteria and diatoms but were free of heterotrophic bacteria inside. Sequence analysis of genes revealed that this cyanobacterium is only distantly related to several strains of other unicellular teria Cyanothece, Waterwarts contained orderly arrangements of mineral made up of microcrystalline low-magnesium calcite with high levels of strontium and sulfur. Waterwarts were 95.9% (v/v) glycan, 2.8% cells, and 1.3% mineral grains and had a buoyant density of 1.034 kg/L. An analysis of the hydrological properties of the spring well and the waterwarts demonstrated that both large colony size and the presence of controlled amounts of mineral ballast are required to prevent the population from being washed out of the well. The unique hydrological characteristics of the spring have likely selected for both traits. The mechanisms by which controlled nucleation of extracellular calcite is achieved remain to be explored.

  14. Calcitic microlenses as part of the photoreceptor system in brittlestars

    NASA Astrophysics Data System (ADS)

    Aizenberg, Joanna; Tkachenko, Alexei; Weiner, Steve; Addadi, Lia; Hendler, Gordon

    2001-08-01

    Photosensitivity in most echinoderms has been attributed to `diffuse' dermal receptors. Here we report that certain single calcite crystals used by brittlestars for skeletal construction are also a component of specialized photosensory organs, conceivably with the function of a compound eye. The analysis of arm ossicles in Ophiocoma showed that in light-sensitive species, the periphery of the labyrinthic calcitic skeleton extends into a regular array of spherical microstructures that have a characteristic double-lens design. These structures are absent in light-indifferent species. Photolithographic experiments in which a photoresist film was illuminated through the lens array showed selective exposure of the photoresist under the lens centres. These results provide experimental evidence that the microlenses are optical elements that guide and focus the light inside the tissue. The estimated focal distance (4-7µm below the lenses) coincides with the location of nerve bundles-the presumed primary photoreceptors. The lens array is designed to minimize spherical aberration and birefringence and to detect light from a particular direction. The optical performance is further optimized by phototropic chromatophores that regulate the dose of illumination reaching the receptors. These structures represent an example of a multifunctional biomaterial that fulfills both mechanical and optical functions.

  15. 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.

  16. Experiments on the abiotic amplification of optical activity

    NASA Technical Reports Server (NTRS)

    Bonner, W. A.; Blair, N. E.; Dirbas, F. M.

    1981-01-01

    Experiments concerning the physical mechanisms for the abiotic generation and chemical mechanisms for the amplification of optical activity in biological compounds are reviewed. Attention is given to experiments involving the determination of the differential adsorption of racemic amino acids on d- and l-quartz, the asymmetric photolysis of racemic amino acids by circularly polarized light, and the asymmetric radiolysis of solid amino acids by longitudinally polarized electrons, and the enantiomeric enrichments thus obtained are noted. Further experiments on the amplification of the chirality in the polymerization of D, L-amino acid mixtures and the hydrolysis of D-, L-, and D, L-polypeptides are discussed. It is suggested that a repetitive cycle of partial polymerization-hydrolyses may account for the abiotic genesis of optically enriched polypeptides on the primitive earth.

  17. Rapid changes in water hardness and alkalinity: Calcite formation is lethal to Daphnia magna.

    PubMed

    Bogart, Sarah J; Woodman, Samuel; Steinkey, Dylan; Meays, Cindy; Pyle, Greg G

    2016-07-15

    There is growing concern that freshwater ecosystems may be negatively affected by ever-increasing anthropogenic inputs of extremely hard, highly alkaline effluent containing large quantities of Ca(2+), Mg(2+), CO3(2-), and HCO3(-) ions. In this study, the toxicity of rapid and extreme shifts in water hardness (38-600mg/L as CaCO3) and alkalinity (30-420mg/L as CaCO3) to Daphnia magna was tested, both independently and in combination. Within these ranges, where no precipitation event occurred, shifts in water hardness and/or alkalinity were not toxic to D. magna. In contrast, 98-100% of D. magna died within 96h after exposure to 600mg/L as CaCO3 water hardness and 420mg/L as CaCO3 alkalinity (LT50 of 60h with a 95% CI of 54.2-66.0h). In this treatment, a CaCO3 (calcite) precipitate formed in the water column which was ingested by and thoroughly coated the D. magna. Calcite collected from a mining impacted stream contained embedded organisms, suggesting field streams may also experience similar conditions and possibly increased mortality as observed in the lab tests. Although further investigation is required to determine the exact fate of aquatic organisms exposed to rapid calcite precipitation in the field, we caution that negative effects may occur more quickly or at lower concentrations of water hardness and alkalinity in which we observed effects in D. magna, because some species, such as aquatic insects, are more sensitive than cladocerans to changes in ionic strength. Our results provide evidence that both calcite precipitation and the major ion balance of waters should be managed in industrially affected ecosystems and we support the development of a hardness+alkalinity guideline for the protection of aquatic life. Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.

  18. Microbial bio-mineralization processes in hydrothermal travertine: the case study of two active travertine systems (Tuscany, Italy).

    NASA Astrophysics Data System (ADS)

    Barilaro, Federica; Bontognali, Tomaso R. R.; Mc Kenzie, Judith A.; Vasconcelos, Crisogono

    2015-04-01

    ). The nano-globules, that represent the first stage of precipitation, coalesce and organize in rods. The assemblage of these rods gives rise to triangular-like morphologies that, gradually, evolve to form well developed calcite crystals, substituting/replacing the organic matter. The presence of EPS, microbs, and calcite mineral phase suggest that biological activity and degradation of organic matter may play a fundamental role in the travertine formation. Acicular crystals of aragonite, nucleated also on organic compound and characterized by the lack of nano-globules, surround the calcite crystals aggregates. The precipitation of aragonite may suggest a change in micro-environmental conditions that involve a predominantly abiotic mechanism of precipitation. Gypsum crystals were mainly individuated in the upper zone of microbial mats and filamentous organic structures connected to the crystals have been observed. A biologically induced process is also claimed for the identified framboidal pyrite related to possible sulphate reducing bacteria. These observations suggest that biological activities are crucial in travertine precipitation. Travertine precipitation is not only related to abiotic parameters of calcium equilibrium, such us physicochemical carbon dioxid degassing and elevated temperature of the hydrothermal water. This study 1) demonstrates that organomineralization processes are not only exclusive of marine carbonate and tufa and 2) confirms the importance of micro- and nano-scale investigation to discriminate between biotic versus abiotic origin of the precipitates.

  19. Hydrogen peroxide priming modulates abiotic oxidative stress tolerance: insights from ROS detoxification and scavenging

    PubMed Central

    Hossain, Mohammad A.; Bhattacharjee, Soumen; Armin, Saed-Moucheshi; Qian, Pingping; Xin, Wang; Li, Hong-Yu; Burritt, David J.; Fujita, Masayuki; Tran, Lam-Son P.

    2015-01-01

    Plants are constantly challenged by various abiotic stresses that negatively affect growth and productivity worldwide. During the course of their evolution, plants have developed sophisticated mechanisms to recognize external signals allowing them to respond appropriately to environmental conditions, although the degree of adjustability or tolerance to specific stresses differs from species to species. Overproduction of reactive oxygen species (ROS; hydrogen peroxide, H2O2; superoxide, O2⋅-; hydroxyl radical, OH⋅ and singlet oxygen, 1O2) is enhanced under abiotic and/or biotic stresses, which can cause oxidative damage to plant macromolecules and cell structures, leading to inhibition of plant growth and development, or to death. Among the various ROS, freely diffusible and relatively long-lived H2O2 acts as a central player in stress signal transduction pathways. These pathways can then activate multiple acclamatory responses that reinforce resistance to various abiotic and biotic stressors. To utilize H2O2 as a signaling molecule, non-toxic levels must be maintained in a delicate balancing act between H2O2 production and scavenging. Several recent studies have demonstrated that the H2O2-priming can enhance abiotic stress tolerance by modulating ROS detoxification and by regulating multiple stress-responsive pathways and gene expression. Despite the importance of the H2O2-priming, little is known about how this process improves the tolerance of plants to stress. Understanding the mechanisms of H2O2-priming-induced abiotic stress tolerance will be valuable for identifying biotechnological strategies to improve abiotic stress tolerance in crop plants. This review is an overview of our current knowledge of the possible mechanisms associated with H2O2-induced abiotic oxidative stress tolerance in plants, with special reference to antioxidant metabolism. PMID:26136756

  20. Stability of Basalt plus Anhydrite plus Calcite at HP-HT: Implications for Venus, the Earth and Mars

    NASA Technical Reports Server (NTRS)

    Martin, A. M.; Righter, K.; Treiman, A. H.

    2010-01-01

    "Canali" observed at Venus surface by Magellan are evidence for very long melt flows, but their composition and origin remain uncertain. The hypothesis of water-rich flow is not reasonable regarding the temperature at Venus surface. The length of these channels could not be explained by a silicate melt composition but more likely, by a carbonate-sulfate melt which has a much lower viscosity (Kargel et al 1994). One hypothesis is that calcite CaCO3 and anhydrite CaSO4 which are alteration products of basalts melted during meteorite impacts. A famous example recorded on the Earth (Chicxulub) produced melt and gas rich in carbon and sulfur. Calcite and sulfate evaporites are also present on Mars surface, associated with basalts. An impact on these materials might release C- and S-rich melt or fluid. Another type of planetary phenomenon (affecting only the Earth) might provoke a high pressure destabilization of basalt+anhydrite+calcite. Very high contents of C and S are measured in some Earth s magmas, either dissolved or in the form of crystals (Luhr 2008). As shown by the high H content and high fO2 of primary igneous anhydrite-bearing lavas, the high S content in their source may be explained by subduction of an anhydrite-bearing oceanic crust, either directly (by melting followed by eruption) or indirectly (by release of S-rich melt or fluid that metasomatize the mantle) . Calcite is a major product of oceanic sedimentation and alteration of the crust. Therefore, sulfate- and calcite-rich material may be subducted to high pressures and high temperatures (HP-HT) and release S- and C-rich melts or fluids which could influence the composition of subduction zone lavas or gases. Both phenomena - meteorite impact and subduction - imply HP-HT conditions - although the P-T-time paths are different. Some HP experimental/theoretical studies have been performed on basalt/eclogite, calcite and anhydrite separately or on a combination of two. In this study we performed piston

  1. Arsenic uptake by gypsum and calcite: Modelling and probing by neutron and X-ray scattering

    NASA Astrophysics Data System (ADS)

    Fernández-Martínez, A.; Román-Ross, G.; Cuello, G. J.; Turrillas, X.; Charlet, L.; Johnson, M. R.; Bardelli, F.

    2006-11-01

    Uptaking of contaminants by solid phases is relevant to many issues in environmental science as this process can remove them from solutions and retard their transport into the hydrosphere. Here we report on two structural studies performed on As-doped gypsum (CaSO 4 2H 2O) and calcite (CaCO 3), using neutron (D20-ILL) and X-ray (ID11-ESRF) diffraction data and EXAFS (BM8-ESRF). The aim of this study is to determine whether As gets into the bulk of gypsum and calcite structures or is simply adsorbed on the surface. Different mechanisms of substitution are used as hypotheses. The combined Rietveld analysis of neutron and X-ray diffraction data shows an expansion of the unit cell volume proportional to the As concentration within the samples. DFT-based simulations confirm the increase of the unit cell volume proportional to the amount of carbonate or sulphate groups substituted. Interpolation of the experimental Rietveld data allows us to distinguish As substituted within the structure from that adsorbed on the surface of both minerals. Results obtained by EXAFS analysis from calcite samples show good agreement with the hypothesis of replacement of As into the C crystallographic site.

  2. Hydrocarbon-water interactions during brine migration: Evidence from hydrocarbon inclusions in calcite cements from Danish North Sea oil fields

    USGS Publications Warehouse

    Jensenius, J.; Burruss, R.C.

    1990-01-01

    Crude oils in primary and secondary fluid inclusions in calcite from fractures in seven offshore oil fields associated with diapiric salt structures in the Danish sector of the North Sea were analyzed by capillary column gas chromatography and compared with crude oils produced from the same reservoirs. Oils from fluid inclusions in all fields show evidence of biodegradation (decreased n-C17/pristane and n-C18/phytane ratios and loss of n-C7, 2-methyl hexane, and 3-methyl hexane relative to methyl cyclohexane) and water washing (absence of benzene and depletion of toluene). Some oils in inclusions are extremely enriched in C6 and C7 cyclic alkanes suggesting that these samples contain hydrocarbons exsolved from ascending, hotter formation waters. Compared to inclusion oils the produced oils are less biodegraded, but are water washed, indicating that both types of oil interacted with large volumes of formation water. The carbon isotopic composition of the calcite host of the fluid inclusions in the Dagmar and Skjold fields is as light as -16.5%. PDB and the sulfur isotopic composition of pyrite in and adjacent to the calcite veins in the Skjold field is as light as -39.6%. CDT, indicating that biodegradation of the oils was a source of some of the carbon in the calcite and sulfate reduction was the source of sulfur for the pyrite. The evidence for microbial degradation of petroleum is consistent with present-day reservoir temperatures (65??-96??C) but is not consistent with previous estimates of the temperatures of calcite vein filling (95??-130??C) which are much higher than the temperatures of known occurrences of biodegraded oil. ?? 1990.

  3. Hydrocarbon-water interactions during brine migration: Evidence from hydrocarbon inclusions in calcite cements from Danish North Sea oil fields

    NASA Astrophysics Data System (ADS)

    Jensenius, Jørgen; Burruss, Robert C.

    1990-03-01

    Crude oils in primary and secondary fluid inclusions in calcite from fractures in seven offshore oil fields associated with diapiric salt structures in the Danish sector of the North Sea were analyzed by capillary column gas chromatography and compared with crude oils produced from the same reservoirs. Oils from fluid inclusions in all fields show evidence of biodegradation (decreased n- C17/pristane and n- C18/phytane ratios and loss of n-C 7, 2-methyl hexane, and 3-methyl hexane relative to methyl cyclohexane) and water washing (absence of benzene and depletion of toluene). Some oils in inclusions are extremely enriched in C 6 and C 7 cyclic alkanes suggesting that these samples contain hydrocarbons exsolved from ascending, hotter formation waters. Compared to inclusion oils the produced oils are less biodegraded, but are water washed, indicating that both types of oil interacted with large volumes of formation water. The carbon isotopic composition of the calcite host of the fluid inclusions in the Dagmar and Skjold fields is as light as -16.5%. PDB and the sulfur isotopic composition of pyrite in and adjacent to the calcite veins in the Skjold field is as light as -39.6%. CDT, indicating that biodegradation of the oils was a source of some of the carbon in the calcite and sulfate reduction was the source of sulfur for the pyrite. The evidence for microbial degradation of petroleum is consistent with present-day reservoir temperatures (65°-96°C) but is not consistent with previous estimates of the temperatures of calcite vein filling (95°-130°C) which are much higher than the temperatures of known occurrences of biodegraded oil.

  4. Photoinduced synthesis of single-digit micrometer-size spheroidal calcite composites in the presence of partially hydrolyzed poly(vinyl alcohol)

    NASA Astrophysics Data System (ADS)

    Nishio, Takashi; Naka, Kensuke

    2015-06-01

    Photoinduced crystallization of calcium carbonate (CaCO3), which was based on the photodecarboxylation of ketoprofen (KP, 2-(3-benzoylphyenyl)propionic acid) under alkaline conditions of pH 8.4 and 10 was studied for preparation of CaCO3 composite particles in single-digit micrometer-sizes. In this method, a homogeneous solution comprising KP, calcium chloride, ammonia, and partially hydrolyzed poly(vinyl alcohol) (PVAPS, degree of saponification: 86.5-89.0 mol%) was used as a precursor solution and was exposed to ultraviolet (UV) irradiation for different time periods. After the UV irradiation for 50 min, calcite spheroids in single-digit micrometer-sizes were obtained as major products at pH 8.4. The obtained calcite spheroids contained organic components of about 10 wt%. The comparison of the characteristics of the CaCO3 obtained at pH 8.4 and 10 suggests that the nucleation and crystallization of both vaterite and calcite continuously took place in a moderated supersaturation owing to the CO2 hydration equilibrium as long as the photodecarboxylation of KP continued. Consequently, the aggregation-based crystal growth in the presence of PVAPS seemed to enable the formation of the spheroidal composites of calcite in single-digit micrometer-sizes.

  5. The Ascorbate-glutathione-α-tocopherol Triad in Abiotic Stress Response

    PubMed Central

    Szarka, András; Tomasskovics, Bálint; Bánhegyi, Gábor

    2012-01-01

    The life of any living organism can be defined as a hurdle due to different kind of stresses. As with all living organisms, plants are exposed to various abiotic stresses, such as drought, salinity, extreme temperatures and chemical toxicity. These primary stresses are often interconnected, and lead to the overproduction of reactive oxygen species (ROS) in plants, which are highly reactive and toxic and cause damage to proteins, lipids, carbohydrates and DNA, which ultimately results in oxidative stress. Stress-induced ROS accumulation is counteracted by enzymatic antioxidant systems and non-enzymatic low molecular weight metabolites, such as ascorbate, glutathione and α-tocopherol. The above mentioned low molecular weight antioxidants are also capable of chelating metal ions, reducing thus their catalytic activity to form ROS and also scavenge them. Hence, in plant cells, this triad of low molecular weight antioxidants (ascorbate, glutathione and α-tocopherol) form an important part of abiotic stress response. In this work we are presenting a review of abiotic stress responses connected to these antioxidants. PMID:22605990

  6. Environmental science. Rethinking the marine carbon cycle: factoring in the multifarious lifestyles of microbes.

    PubMed

    Worden, Alexandra Z; Follows, Michael J; Giovannoni, Stephen J; Wilken, Susanne; Zimmerman, Amy E; Keeling, Patrick J

    2015-02-13

    The profound influence of marine plankton on the global carbon cycle has been recognized for decades, particularly for photosynthetic microbes that form the base of ocean food chains. However, a comprehensive model of the carbon cycle is challenged by unicellular eukaryotes (protists) having evolved complex behavioral strategies and organismal interactions that extend far beyond photosynthetic lifestyles. As is also true for multicellular eukaryotes, these strategies and their associated physiological changes are difficult to deduce from genome sequences or gene repertoires—a problem compounded by numerous unknown function proteins. Here, we explore protistan trophic modes in marine food webs and broader biogeochemical influences. We also evaluate approaches that could resolve their activities, link them to biotic and abiotic factors, and integrate them into an ecosystems biology framework. Copyright © 2015, American Association for the Advancement of Science.

  7. 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

  8. Sulphate partitioning into calcite: Experimental verification of pH control and application to seasonality in speleothems

    NASA Astrophysics Data System (ADS)

    Wynn, Peter M.; Fairchild, Ian J.; Borsato, Andrea; Spötl, Christoph; Hartland, Adam; Baker, Andy; Frisia, Silvia; Baldini, James U. L.

    2018-04-01

    Carbonate-associated sulphate (CAS) is a useful carrier of palaeoenvironmental information throughout the geologic record, particularly through its stable isotope composition. However, a paucity of experimental data restricts quantitative understanding of sulphate incorporation into carbonates, and consequently CAS concentrations and their diagenetic modifications are rarely interpreted. However, in the case of calcite speleothems, the remarkably high-resolution CAS records which are obtainable via modern microanalytical techniques represent a potentially invaluable source of palaeoenvironmental information. Here, we describe the results of controlled experiments of sulphate co-precipitation with calcite in freshwater solutions where pH, saturation state, and sulphate concentration were varied independently of each other. Solution pH is confirmed as the principal control on sulphate incorporation into calcite. The relative efficiency of incorporation was calculated as a partition coefficient DSO4 = (mSO4/mCO3)solid/(mSO4/mCO3)solution. High crystal growth rates (driven by either pH or saturation state) encouraged higher values of DSO4 because of an increasing concentration of defect sites on crystal surfaces. At low growth rates, DSO4 was reduced due to an inferred competition between sulphate and bicarbonate at the calcite surface. These experimental results are applied to understand the incorporation of sulphate into speleothem calcite. The experimentally determined pH-dependence suggests that strong seasonal variations in cave air PCO2 could account for annual cycles in sulphate concentration observed in stalagmites. Our new experimentally determined values of DSO4 were compared with DSO4 values calculated from speleothem-drip water monitoring from two caves within the Austrian and Italian Alps. At Obir cave, Austria, DSO4 (×105) varies between 11.1 (winter) and 9.0 (summer) and the corresponding figures for Ernesto cave, Italy, are 15.4 (winter) and 14

  9. Abiotic drivers of Chihuahuan Desert plant communities

    Treesearch

    Laura Marie Ladwig

    2014-01-01

    Within grasslands, precipitation, fire, nitrogen (N) addition, and extreme temperatures influence community composition and ecosystem function. The differential influences of these abiotic factors on Chihuahuan Desert grassland communities was examined within the Sevilleta National Wildlife Refuge, located in central New Mexico, U.S.A. Although fire is a natural...

  10. New Environmentalconditions Responsible for the amount of mg Incorporated in Biogenic Carbonates

    NASA Astrophysics Data System (ADS)

    Zuddas, P.; Cherchi, A.; DeGiudici, G. B.; Buosi, C.

    2012-12-01

    The composition of carbonate minerals formed in past and present oceans is assumed to be significantly controlled by temperature and seawater composition. Several kinetic laboratory investigations have suggested that the temperature is kinetically responsible for the amount of Mg incorporated in both abiotic and biogenic calcites and that variation of kinetic reaction mechanism resulting from the temperature changes are correlated with the variable amount of Mg incorporated in calcites. These results explain why in present-day marine carbonates low-Mg calcite cements are mainly associated with cool water while high-Mg carbonates are dominantly found in warm-water environments. An apparent inverse relationship between the global average paleo-temperature and the Mg/Ca ratio is however observed in the past formed marine carbonate. This apparent contradiction has been interpreted as resulting from a possible changing in the relative seawater geochemical cycles of these cations. Recent monitoring of costal areas in presence of heavy metals and CO2 released from industrial polluted area reveals the presence of porcelanaceous miliolids infested by microscopic boring microflora (cyanobacteria, algae and fungi). Here, benthonic foraminifera have Mg/Ca molar ratio by one order of magnitude higher when compared to the average value of the same genus living under uncontaminated environments. A similar behaviour has been found for Zn, Cd and Pb. In these contaminated environments, temperature and average major seawater composition remain constant, while PCO2 partial pressure (estimated by pH and alkalinity using the ion pairing model) is 3-5 times higher than the average for the open sea nearby. Geochemical models predicts that CO2 increase is affecting carbonate saturation state of surface water in the twenty-first century indicating that calcareous organisms may have difficulty calcifying leading to production of weaker skeletons and greater vulnerability to erosion. The

  11. Functionalization of biomineral reinforcement in crustacean cuticle: Calcite orientation in the partes incisivae of the mandibles of Porcellio scaber and the supralittoral species Tylos europaeus (Oniscidea, Isopoda).

    PubMed

    Huber, Julia; Griesshaber, Erika; Nindiyasari, Fitriana; Schmahl, Wolfgang W; Ziegler, Andreas

    2015-05-01

    In arthropods the cuticle forms an exoskeleton with its physical and chemical properties adapted to functions of distinct skeletal elements. The cuticle of the partes incisivae (PI) in mandibles of terrestrial isopods is a composite of chitin-protein fibrils/fibres and minerals. It consists of an unmineralized tip, a middle region with organic fibrils reinforced mainly with amorphous calcium phosphate and a base region mineralized with amorphous calcium carbonate and calcite. In this study we extend our work on the structure and material properties of the incisive cuticle employing electron backscatter diffraction (EBSD), and investigate calcite orientation patterns in the PI of two terrestrial isopod species from different habitats. We trace small-scale differences in texture sharpness and calcite microstructure, and compare calcite organization and orientation patterns in the PI with those in the tergites of the same isopod species. We observe that in the PI calcite orientation, the degree of crystal alignment, and mode of crystalline domain assemblage is highly varied within short length scales. This contrasts to calcite organization in the tergite cuticle, where calcite has only one specific texture pattern. Such a large range in the variation of calcite organization has not been observed in other carbonate biological hard tissues, such as shells and teeth, where one specific texture and microstructure prevails. Thus, the investigated isopod species are able to control crystallization of the amorphous carbonate precursor in a differential way, most probably related to the function of the individual skeletal element and the animals' behavior. Copyright © 2015 Elsevier Inc. All rights reserved.

  12. Origin of Abiotic Methane in Submarine Hydrothermal Systems

    NASA Astrophysics Data System (ADS)

    Seewald, J. S.; German, C. R.; Grozeva, N. G.; Klein, F.; McDermott, J. M.; Ono, S.; Reeves, E. P.; Wang, D. T.

    2018-05-01

    Results of recent investigations into the chemical and isotopic composition of actively venting submarine hydrothermal fluids and volatile species trapped in fluid inclusions will be discussed in the context of processes responsible for abiotic CH4 formation.

  13. Abiotic Stress Responses and Microbe-Mediated Mitigation in Plants: The Omics Strategies

    PubMed Central

    Meena, Kamlesh K.; Sorty, Ajay M.; Bitla, Utkarsh M.; Choudhary, Khushboo; Gupta, Priyanka; Pareek, Ashwani; Singh, Dhananjaya P.; Prabha, Ratna; Sahu, Pramod K.; Gupta, Vijai K.; Singh, Harikesh B.; Krishanani, Kishor K.; Minhas, Paramjit S.

    2017-01-01

    Abiotic stresses are the foremost limiting factors for agricultural productivity. Crop plants need to cope up adverse external pressure created by environmental and edaphic conditions with their intrinsic biological mechanisms, failing which their growth, development, and productivity suffer. Microorganisms, the most natural inhabitants of diverse environments exhibit enormous metabolic capabilities to mitigate abiotic stresses. Since microbial interactions with plants are an integral part of the living ecosystem, they are believed to be the natural partners that modulate local and systemic mechanisms in plants to offer defense under adverse external conditions. Plant-microbe interactions comprise complex mechanisms within the plant cellular system. Biochemical, molecular and physiological studies are paving the way in understanding the complex but integrated cellular processes. Under the continuous pressure of increasing climatic alterations, it now becomes more imperative to define and interpret plant-microbe relationships in terms of protection against abiotic stresses. At the same time, it also becomes essential to generate deeper insights into the stress-mitigating mechanisms in crop plants for their translation in higher productivity. Multi-omics approaches comprising genomics, transcriptomics, proteomics, metabolomics and phenomics integrate studies on the interaction of plants with microbes and their external environment and generate multi-layered information that can answer what is happening in real-time within the cells. Integration, analysis and decipherization of the big-data can lead to a massive outcome that has significant chance for implementation in the fields. This review summarizes abiotic stresses responses in plants in-terms of biochemical and molecular mechanisms followed by the microbe-mediated stress mitigation phenomenon. We describe the role of multi-omics approaches in generating multi-pronged information to provide a better understanding

  14. Abiotic Stress Responses and Microbe-Mediated Mitigation in Plants: The Omics Strategies.

    PubMed

    Meena, Kamlesh K; Sorty, Ajay M; Bitla, Utkarsh M; Choudhary, Khushboo; Gupta, Priyanka; Pareek, Ashwani; Singh, Dhananjaya P; Prabha, Ratna; Sahu, Pramod K; Gupta, Vijai K; Singh, Harikesh B; Krishanani, Kishor K; Minhas, Paramjit S

    2017-01-01

    Abiotic stresses are the foremost limiting factors for agricultural productivity. Crop plants need to cope up adverse external pressure created by environmental and edaphic conditions with their intrinsic biological mechanisms, failing which their growth, development, and productivity suffer. Microorganisms, the most natural inhabitants of diverse environments exhibit enormous metabolic capabilities to mitigate abiotic stresses. Since microbial interactions with plants are an integral part of the living ecosystem, they are believed to be the natural partners that modulate local and systemic mechanisms in plants to offer defense under adverse external conditions. Plant-microbe interactions comprise complex mechanisms within the plant cellular system. Biochemical, molecular and physiological studies are paving the way in understanding the complex but integrated cellular processes. Under the continuous pressure of increasing climatic alterations, it now becomes more imperative to define and interpret plant-microbe relationships in terms of protection against abiotic stresses. At the same time, it also becomes essential to generate deeper insights into the stress-mitigating mechanisms in crop plants for their translation in higher productivity. Multi-omics approaches comprising genomics, transcriptomics, proteomics, metabolomics and phenomics integrate studies on the interaction of plants with microbes and their external environment and generate multi-layered information that can answer what is happening in real-time within the cells. Integration, analysis and decipherization of the big-data can lead to a massive outcome that has significant chance for implementation in the fields. This review summarizes abiotic stresses responses in plants in-terms of biochemical and molecular mechanisms followed by the microbe-mediated stress mitigation phenomenon. We describe the role of multi-omics approaches in generating multi-pronged information to provide a better understanding

  15. Hydrodynamic control of inorganic calcite precipitation in Huanglong Ravine, China: Field measurements and theoretical prediction of deposition rates

    NASA Astrophysics Data System (ADS)

    Zaihua, Liu; Svensson, U.; Dreybrodt, W.; Daoxian, Yuan; Buhmann, D.

    1995-08-01

    Hydrochemical and hydrodynamical investigations are presented to explain tufa deposition rates along the flow path of the Huanglong Ravine, located in northwestern Sichuan province, China, on an altitude of about 3400 m asl. Due to outgassing of CO 2 the mainly spring-fed stream exhibits, along a valley of 3.5 km, calcite precipitation rates up to a few mm/year. We have carried out in situ experiments to measure calcite deposition rates at rimstone dams, inside of pools and in the stream-bed. Simultaneously, the downstream evolution of water chemistry was investigated at nine locations with respect to Ca 2+, Mg 2+, Na +, Cl -, SO 42-, and alkalinity. Temperature, pH, and conductivity were measured in situ, while total hardness, Ca T, and alkalinity have been determined immediately after sampling, performing standard titration methods. The water turned out to be of an almost pure CaMgHCO 3 type. The degassing of CO 2 causes high supersaturation with respect to calcite and due to calcite precipitation the Ca 2+ concentration decreases from 6·10 -3 mole/1 upstream down to 2.5·10 -3 mole/1 at the lower course. Small rectangular shaped tablets of pure marble were mounted under different flow regimes, i.e., at the dam sites with fast water flow as well as inside pools with still water. After the substrate samples had stayed in the water for a period of a few days, the deposition rates were measured by weight increase, up to several tens of milligrams. Although there were no differences in hydrochemistry, deposition rates in fast flowing water were higher by as much as a factor of four compared to still water, indicating a strong influence of hydrodynamics. While upstream rates amounted up to 5 mm/year, lower rates of about 1 mm/year were observed downstream. Inspection of the marble substrate surfaces by EDAX and SEM (scanning electron microscope) revealed authigeneously grown calcite crystals of about 10 μm. Their shape and habit are indicative of a chemically

  16. Microbial Surface Colonization and Biofilm Development in Marine Environments

    PubMed Central

    2015-01-01

    SUMMARY Biotic and abiotic surfaces in marine waters are rapidly colonized by microorganisms. Surface colonization and subsequent biofilm formation and development provide numerous advantages to these organisms and support critical ecological and biogeochemical functions in the changing marine environment. Microbial surface association also contributes to deleterious effects such as biofouling, biocorrosion, and the persistence and transmission of harmful or pathogenic microorganisms and their genetic determinants. The processes and mechanisms of colonization as well as key players among the surface-associated microbiota have been studied for several decades. Accumulating evidence indicates that specific cell-surface, cell-cell, and interpopulation interactions shape the composition, structure, spatiotemporal dynamics, and functions of surface-associated microbial communities. Several key microbial processes and mechanisms, including (i) surface, population, and community sensing and signaling, (ii) intraspecies and interspecies communication and interaction, and (iii) the regulatory balance between cooperation and competition, have been identified as critical for the microbial surface association lifestyle. In this review, recent progress in the study of marine microbial surface colonization and biofilm development is synthesized and discussed. Major gaps in our knowledge remain. We pose questions for targeted investigation of surface-specific community-level microbial features, answers to which would advance our understanding of surface-associated microbial community ecology and the biogeochemical functions of these communities at levels from molecular mechanistic details through systems biological integration. PMID:26700108

  17. Adjustment errors of sunstones in the first step of sky-polarimetric Viking navigation: studies with dichroic cordierite/ tourmaline and birefringent calcite crystals.

    PubMed

    Száz, Dénes; Farkas, Alexandra; Blahó, Miklós; Barta, András; Egri, Ádám; Kretzer, Balázs; Hegedüs, Tibor; Jäger, Zoltán; Horváth, Gábor

    2016-01-01

    According to an old but still unproven theory, Viking navigators analysed the skylight polarization with dichroic cordierite or tourmaline, or birefringent calcite sunstones in cloudy/foggy weather. Combining these sunstones with their sun-dial, they could determine the position of the occluded sun, from which the geographical northern direction could be guessed. In psychophysical laboratory experiments, we studied the accuracy of the first step of this sky-polarimetric Viking navigation. We measured the adjustment error e of rotatable cordierite, tourmaline and calcite crystals when the task was to determine the direction of polarization of white light as a function of the degree of linear polarization p. From the obtained error functions e(p), the thresholds p* above which the first step can still function (i.e. when the intensity change seen through the rotating analyser can be sensed) were derived. Cordierite is about twice as reliable as tourmaline. Calcite sunstones have smaller adjustment errors if the navigator looks for that orientation of the crystal where the intensity difference between the two spots seen in the crystal is maximal, rather than minimal. For higher p (greater than p crit) of incident light, the adjustment errors of calcite are larger than those of the dichroic cordierite (p crit=20%) and tourmaline (p crit=45%), while for lower p (less than p crit) calcite usually has lower adjustment errors than dichroic sunstones. We showed that real calcite crystals are not as ideal sunstones as it was believed earlier, because they usually contain scratches, impurities and crystal defects which increase considerably their adjustment errors. Thus, cordierite and tourmaline can also be at least as good sunstones as calcite. Using the psychophysical e(p) functions and the patterns of the degree of skylight polarization measured by full-sky imaging polarimetry, we computed how accurately the northern direction can be determined with the use of the Viking

  18. Ningaloo Reef: Shallow Marine Habitats Mapped Using a Hyperspectral Sensor

    PubMed Central

    Kobryn, Halina T.; Wouters, Kristin; Beckley, Lynnath E.; Heege, Thomas

    2013-01-01

    Research, monitoring and management of large marine protected areas require detailed and up-to-date habitat maps. Ningaloo Marine Park (including the Muiron Islands) in north-western Australia (stretching across three degrees of latitude) was mapped to 20 m depth using HyMap airborne hyperspectral imagery (125 bands) at 3.5 m resolution across the 762 km2 of reef environment between the shoreline and reef slope. The imagery was corrected for atmospheric, air-water interface and water column influences to retrieve bottom reflectance and bathymetry using the physics-based Modular Inversion and Processing System. Using field-validated, image-derived spectra from a representative range of cover types, the classification combined a semi-automated, pixel-based approach with fuzzy logic and derivative techniques. Five thematic classification levels for benthic cover (with probability maps) were generated with varying degrees of detail, ranging from a basic one with three classes (biotic, abiotic and mixed) to the most detailed with 46 classes. The latter consisted of all abiotic and biotic seabed components and hard coral growth forms in dominant or mixed states. The overall accuracy of mapping for the most detailed maps was 70% for the highest classification level. Macro-algal communities formed most of the benthic cover, while hard and soft corals represented only about 7% of the mapped area (58.6 km2). Dense tabulate coral was the largest coral mosaic type (37% of all corals) and the rest of the corals were a mix of tabulate, digitate, massive and soft corals. Our results show that for this shallow, fringing reef environment situated in the arid tropics, hyperspectral remote sensing techniques can offer an efficient and cost-effective approach to mapping and monitoring reef habitats over large, remote and inaccessible areas. PMID:23922921

  19. The evolution of Carbon isotopes in calcite in the presence of cyanobacteria

    NASA Astrophysics Data System (ADS)

    Grimm, Christian; Mavromatis, Vasileios; Pokrovsky, Oleg S.; Oelkers, Eric H.

    2016-04-01

    Stable isotopic compositions in carbonates are widely used as indicators of environmental conditions prevailing during mineral formation. This reconstruction is substantially based on the assumption that there is no change in the mineral composition over geological time. However, recent experimental studies have shown that carbon and magnesium isotopes in hydrous Mg-carbonates undergo continuous re-equilibration with the ambient solution even after mineral precipitation stopped ([1] and [2], respectively). To verify whether this holds true for anhydrous Ca-bearing carbonates which readily form at earth's surface environments, a series of batch system calcite precipitation experiments were performed in the presence of actively growing cyanobacteria Synechococcus sp. The bacteria were grown at ambient temperature in a BG11 culture medium (SIGMA C3061) and continuous stirring, air-bubbling and illumination. Calcite precipitation was initiated by the addition of 8.5mM CaCl2 and 0-50 mM NaHCO3 or NaHCO3-Na2CO3 mixtures. The presence of cyanobacteria is on one hand promoting CaCO3 formation due to increasing pH resulting from photosynthesis. On the other hand, actively growing cyanobacteria drastically change carbon isotope signature of the aqueous fluid phase by preferably incorporating the lighter 12C isotope into biomass [1]. This study explores the effect of continuously changing carbon isotope compositions in dissolved inorganic carbon (DIC) on precipitated calcite which is in chemical equilibrium with the ambient fluid phase. [1] Mavromatis et al. (2015). The continuous re-equilibration of carbon isotope compositions of hydrous Mg-carbonates in the presence of cyanobacteria. Chem. Geol. 404, 41-51 [2] Mavromatis et al. (2012). Magnesium isotope fractionation during hydrous magnesium carbonate precipitation with and without cyanobacteria. Geochim. Cosmochim. Acta 76, 161-174

  20. Novel NAC Transcription Factor TaNAC67 Confers Enhanced Multi-Abiotic Stress Tolerances in Arabidopsis

    PubMed Central

    Mao, Xinguo; Chen, Shuangshuang; Li, Ang; Zhai, Chaochao; Jing, Ruilian

    2014-01-01

    Abiotic stresses are major environmental factors that affect agricultural productivity worldwide. NAC transcription factors play pivotal roles in abiotic stress signaling in plants. As a staple crop, wheat production is severely constrained by abiotic stresses whereas only a few NAC transcription factors have been characterized functionally. To promote the application of NAC genes in wheat improvement by biotechnology, a novel NAC gene designated TaNAC67 was characterized in common wheat. To determine its role, transgenic Arabidopsis overexpressing TaNAC67-GFP controlled by the CaMV-35S promoter was generated and subjected to various abiotic stresses for morphological and physiological assays. Gene expression showed that TaNAC67 was involved in response to drought, salt, cold and ABA treatments. Localization assays revealed that TaNAC67 localized in the nucleus. Morphological analysis indicated the transgenics had enhanced tolerances to drought, salt and freezing stresses, simultaneously supported by enhanced expression of multiple abiotic stress responsive genes and improved physiological traits, including strengthened cell membrane stability, retention of higher chlorophyll contents and Na+ efflux rates, improved photosynthetic potential, and enhanced water retention capability. Overexpression of TaNAC67 resulted in pronounced enhanced tolerances to drought, salt and freezing stresses, therefore it has potential for utilization in transgenic breeding to improve abiotic stress tolerance in crops. PMID:24427285

  1. Potential for Ureolytically Driven Calcite Precipitation to Remediate Strontium-90 at the Hanford 100-N Area

    NASA Astrophysics Data System (ADS)

    Fujita, Y.; Taylor, J. L.; Wendt, L.; Reed, D.; Smith, R. W.

    2009-12-01

    A groundwater plume of Strontium-90 at the 100-N Springs Area of the U. S. Department of Energy’s Hanford Reservation in Washington is discharging into the Columbia River. Previous pump and treat activities to remove the 90Sr were ineffective and consequently discontinued; immobilization of the contaminant in situ is preferable, but no proven methods to accomplish this objective currently exist. This study was a preliminary assessment of the feasibility at the 100-N Area of a novel in situ remediation approach for 90Sr, where microbial urea hydrolysis is used to drive the precipitation of calcite and the co-precipitation of strontium in the calcite. Water quality data from the 100-N site indicated that geochemical conditions at the site were conducive to stable calcite precipitation, and groundwater and sediment samples from the site were examined to assess the urea hydrolyzing capabilities of the native microbial populations. Estimated average numbers of ureolytic organisms in the groundwater, determined using cultivation-based tests (Most Probable Number) for urease activity, ranged from 72 to 1,100 cells mL-1. Estimated numbers of ureC gene targets in the water samples, as determined by quantitative polymerase chain reaction (qPCR) assays, ranged from 850 to 17,600 copies mL-1; the ureC gene codes for the catalytic subunit of urease. In the sediment samples, ureC gene targets ranged from non-detectable to 925,000 copies g-1 of sediment. For both water and sediment, the number of ureolytic cells (estimated by qPCR) generally amounted to < 5% of the total microbial cell numbers. Nevertheless, estimates of in situ ureolysis rates using trace levels of 14C-labeled urea added to the groundwater and sediment samples in the laboratory indicate that significant urea hydrolyzing activity exists in the 100-N subsurface. Normalizing the measured urea hydrolysis rates to 1 L of in situ pore space resulted in hydrolysis rates on the order of 9.5 nmol L-1 hr-1 and 170 to 2

  2. Calcite production by Coccolithophores in the South East Pacific Ocean: from desert to jungle

    NASA Astrophysics Data System (ADS)

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

    2007-09-01

    BIOSOPE cruise achieved an oceanographic transect from the Marquise Islands to the Peru-Chili upwelling (PCU) via the centre of the South Pacific Gyre (SPG). Water samples from 6 depths in the euphotic zone were collected at 20 stations. The concentrations of suspended calcite particles, coccolithophores cells and detached coccoliths were estimated together with size and weight using an automatic polarizing microscope, a digital camera, and a collection of softwares performing morphometry and pattern recognition. Some of these softwares are new and described here for the first time. The coccolithophores standing stocks are usually low and reach maxima west of the PCU. The coccoliths of Emiliania huxleyi, Gephyrocapsa spp. and Crenalithus spp. (Order Isochrysidales) represent 50% of all the suspended calcite particles detected in the size range 0.1-46 μm (21% of PIC in term of the calcite weight). The latter species are found to grow preferentially in the Chlorophyll maximum zone. In the SPG their maximum concentrations was found to occur between 150 and 200 m, which is very deep for these taxa. The weight and size of coccoliths and coccospheres are correlated. Large and heavy coccoliths and coccospheres are found in the regions with relative higher fertility in the Marquises Island and in the PCU. Small and light coccoliths and coccospheres are found west of the PCU. This distribution may correspond to that of the concentration of calcium and carbonate ions.

  3. Occurrence and genesis of Quaternary microbialitic tufa at Hammam Al Ali, Oman

    NASA Astrophysics Data System (ADS)

    Khalaf, Fikry I.

    2017-05-01

    Remnants of late Quaternary microbialitic tufa occurs within a shallow depression in the Hammam Al Ali hot spring area, which is located approximately 14.5 km to the southwest of Muscat, Oman. The tufa precipitated from hot spring water supersaturated with respect to calcium carbonate and is mostly of a porous phytogenic type, with occasional detrital and stromatolitic types. Microscopic and nanoscopic examination revealed that the tufa deposits developed through two successive processes of calcite precipitation, biotic and abiotic, preceded by limited precipitation of unstable aragonite. It is suggested that biologically mediated precipitation results in the construction of incomplete skeletal calcite crystals. The latter provide a base for classical physiochemical precipitation and, eventually, the development of complete sparry calcite crystals. The initiation of dendritic calcite crystals in the stromatolitic tufa as incomplete biogenic skeletal crystals and their characteristic growth pattern indicates that the tufa represents a clear example of hot spring calcitic microbialite.

  4. Polyamines and abiotic stress in plants: a complex relationship Frontiers in Plant Science

    Treesearch

    Rakesh Minocha; Rajtilak Majumdar; Subhash C. Minocha

    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...

  5. Calcite phase determination of CaCO3 nanoparticles synthesized by one step drying method

    NASA Astrophysics Data System (ADS)

    Sulimai, N. H.; Rani, Rozina Abdul; Khusaimi, Z.; Abdullah, S.; Salifairus, M. J.; Alrokayan, Salman; Khan, Haseeb; Rusop, M.

    2018-05-01

    Calcium Carbonate (CaCO3) is a type of carbonic salt. It exist naturally as white odourless solid and may also be synthesized by chemical reactions. This work studies one-step precipitation of CaCO3 that was prepared by novel method of one-step precipitation method. The method was then proceeded by different types of drying. The first type is by normal drying in oven whereas the second type is with the presence of hydrothermal influence. From the results, precipitated CaCO3 dried by normal drying method produces CaCO3 with two polymorphs present; calcite and vaterite. Normal drying at 500°C has no vaterite phase left. Drying by hydrothermal precipitated CaCO3 has Nitrogen (N) left on the surfaces of the precipitated CaCO3. This work successfully identified calcite phase in the precipitated CaCO3.

  6. 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.

  7. 3D visualization of additive occlusion and tunable full-spectrum fluorescence in calcite

    PubMed Central

    Green, David C.; Ihli, Johannes; Thornton, Paul D.; Holden, Mark A.; Marzec, Bartosz; Kim, Yi-Yeoun; Kulak, Alex N.; Levenstein, Mark A.; Tang, Chiu; Lynch, Christophe; Webb, Stephen E. D.; Tynan, Christopher J.; Meldrum, Fiona C.

    2016-01-01

    From biomineralization to synthesis, organic additives provide an effective means of controlling crystallization processes. There is growing evidence that these additives are often occluded within the crystal lattice. This promises an elegant means of creating nanocomposites and tuning physical properties. Here we use the incorporation of sulfonated fluorescent dyes to gain new understanding of additive occlusion in calcite (CaCO3), and to link morphological changes to occlusion mechanisms. We demonstrate that these additives are incorporated within specific zones, as defined by the growth conditions, and show how occlusion can govern changes in crystal shape. Fluorescence spectroscopy and lifetime imaging microscopy also show that the dyes experience unique local environments within different zones. Our strategy is then extended to simultaneously incorporate mixtures of dyes, whose fluorescence cascade creates calcite nanoparticles that fluoresce white. This offers a simple strategy for generating biocompatible and stable fluorescent nanoparticles whose output can be tuned as required. PMID:27857076

  8. 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. Copyright © 2011 Elsevier Ltd. All rights reserved.

  9. Recent sediment remolding on a deep shelf, Ross Sea: implications for radiocarbon dating of Antarctic marine sediments

    NASA Astrophysics Data System (ADS)

    Domack, Eugene W.; Taviani, Marco; Rodriguez, Anthonio

    1999-11-01

    Coarse, bioclastic rich sands have been widely reported from the banks of the Antarctic continental shelf but their origin is still poorly known. We report on a suite of coarse sediments recovered from the top of the Mawson Bank in the northwestern Ross Sea. Radiocarbon ages of biogenic calcite, for modern and apparently late Pleistocene deposits, range from 1085±45 to 20,895±250 yr B.P.. Discovery of soft tissue (Ascidian) preserved as an incrustation on a pebble at 2 m depth indicates aggregation of the sediment within several months or a year of core recovery. Radiocarbon ages of acid insoluble organic matter (aiom) are less than those of the foraminifera calcite. The aiom ages are also reversed in sequence, indicating reworking of the sediment during deposition. These observations and a review of recently published literature suggest that much of the bank top sediment in Antarctica is presently undergoing remobilization, under the influence of strong currents and/or icebergs even under interglacical (high-stand) sea levels. These observations point out the need for careful, integrated studies on high latitude marine sediment cores before resultant "ages" alone are used as the foundation for paleoglacial reconstructions.

  10. Do positive interactions increase with abiotic stress? A test from a semi-arid steppe.

    PubMed Central

    Maestre, Fernando T; Cortina, Jordi

    2004-01-01

    Theoretical models predict that the relative importance of facilitation and competition may vary inversely across gradients of abiotic stress. However, these predictions have not been thoroughly tested in the field, especially in semi-arid environments. In this study, we evaluated how the net effect of the tussock grass Stipa tenacissima on the shrub Pistacia lentiscus varied across a gradient of abiotic stress in semi-arid Mediterranean steppes. We fitted the relationship between accumulated rainfall and the relative neighbour index (our measures of abiotic stress and of the net effect of S. tenacissima on P. lentiscus, respectively), which varied across this gradient, to a quadratic model. Competitive interactions dominated at both extremes of the gradient. Our results do not support established theory. Instead, they suggest that a shift from facilitation to competition under high abiotic stress conditions is likely to occur when the levels of the most limiting resource are so low that the benefits provided by the facilitator cannot overcome its own resource uptake. PMID:15504009

  11. Meteoric calcite cementation: diagenetic response to relative fall in sea-level and effect on porosity and permeability, Las Negras area, southeastern Spain

    NASA Astrophysics Data System (ADS)

    Li, Zhaoqi; Goldstein, Robert H.; Franseen, Evan K.

    2017-03-01

    A dolomitized Upper Miocene carbonate system in southeast Spain contains extensive upper and lower zones of calcite cementation that cut across the stratigraphy. Cement textures including isopachous and circumgranular, which are consistent with phreatic-zone cementation. Cements in the upper cemented zone are non-luminescent, whereas those in the lower cemented zone exhibit multiple bands of luminescent and non-luminescent cements. In the upper cemented zone, isotopic data show two meteoric calcite lines (MCL) with mean δ18O at - 5.1‰ and - 5.8‰ VPDB, whereas no clear MCL is defined in the lower cemented zone where mean δ18O for calcite cement is at - 6.7‰ VPDB. δ13C values in both cement zones are predominantly negative, ranging from - 10 to + 2‰ VPDB, suggestive of carbon from soil gas or decayed organics. Measurements of Tm ice in primary fluid inclusions yield a mode of 0.0 °C in both zones, indicating calcite cementation from fresh water. These two zones define the positions of two different paleo-water tables that formed during a relative sea-level fall and erosional downcutting during the Plio-Pleistocene. The upper cemented zone pre-dated the lower cemented zone on the basis of known relative sea-level history. Meteoric calcite cementation reduced porosity and permeability, but measured values are inconsistent with simple filling of open pore space. Each texture, boundstone, grainstone, packstone, wackestone, produces a different relationship between percent calcite cement and porosity/permeability. Distribution of cements may be predictable on the basis of known sea-level history, and the effect of the cementation can be incorporated into subsurface geomodels by defining surfaces of rock boundaries that separate cemented zones from uncemented zones, and applying texture-specific relationships among cementation, porosity and permeability.

  12. Abiotic stress responses in plants: roles of calmodulin-regulated proteins.

    PubMed

    Virdi, Amardeep S; Singh, Supreet; Singh, Prabhjeet

    2015-01-01

    Intracellular changes in calcium ions (Ca(2+)) in response to different biotic and abiotic stimuli are detected by various sensor proteins in the plant cell. Calmodulin (CaM) is one of the most extensively studied Ca(2+)-sensing proteins and has been shown to be involved in transduction of Ca(2+) signals. After interacting with Ca(2+), CaM undergoes conformational change and influences the activities of a diverse range of CaM-binding proteins. A number of CaM-binding proteins have also been implicated in stress responses in plants, highlighting the central role played by CaM in adaptation to adverse environmental conditions. Stress adaptation in plants is a highly complex and multigenic response. Identification and characterization of CaM-modulated proteins in relation to different abiotic stresses could, therefore, prove to be essential for a deeper understanding of the molecular mechanisms involved in abiotic stress tolerance in plants. Various studies have revealed involvement of CaM in regulation of metal ions uptake, generation of reactive oxygen species and modulation of transcription factors such as CAMTA3, GTL1, and WRKY39. Activities of several kinases and phosphatases have also been shown to be modulated by CaM, thus providing further versatility to stress-associated signal transduction pathways. The results obtained from contemporary studies are consistent with the proposed role of CaM as an integrator of different stress signaling pathways, which allows plants to maintain homeostasis between different cellular processes. In this review, we have attempted to present the current state of understanding of the role of CaM in modulating different stress-regulated proteins and its implications in augmenting abiotic stress tolerance in plants.

  13. Genetic diversity and temporal variation of the marine Synechococcus community in the subtropical coastal waters of Hong Kong.

    PubMed

    Jing, Hongmei; Zhang, Rui; Pointing, Stephen B; Liu, Hongbin; Qian, Peiyuan

    2009-03-01

    The phylogenetic diversity of the marine Synechococcus community in the subtropical coastal waters of Hong Kong, China, was examined through intergenic transcribed spacer clone libraries. All the sequences obtained fell within both marine cluster A (MC-A) and B (MC-B), with MC-A phylotypes dominating throughout the year. Distinct phylogenetic lineages specific to Hong Kong waters were detected from both MC-A and MC-B. The highest Synechococcus community diversity occurred in December, but the highest Synechococcus abundance occurred in August. On the other hand, both the abundance and diversity of Synechococcus showed a minimum in February. The remarkable seasonal variations of Synechococcus diversity observed were likely the result of the changes of hydrographic condition modulated by monsoons. Principal component analysis revealed that the in situ abiotic water characteristics, especially salinity and water turbidity, explained much of the variability of the marine Synechococcus population diversity in Hong Kong coastal waters. In addition, the temporal changes of Synechococcus abundance were largely driven by water temperature.

  14. Stable Carbon Isotopic Signatures of Abiotic Organics from Hydrothermal Synthesis Experiments

    NASA Technical Reports Server (NTRS)

    Stern, Jennifer C.; Summers, David P.; Kubo, Mike; Yassar, Saima

    2006-01-01

    Stable carbon isotopes can be powerful biogeochemical markers in the study of life's origins. Biogenic carbon fixation produces organics that are depleted in C-13 by about -20 to -30%0. Less attention has been paid to the isotopic signatures of abiotic processes. The possibility of abiotic processes producing organics with morphologies and isotopic signatures in the biogenic range has been at the center of recent debate over the Earth's earliest microfossils. The abiotic synthesis of organic compounds in hydrothermal environments is one possible source of endogenous organic matter to the prebiotic earth. Simulated hydrothermal settings have been shown to synthesize, among other things, single chain amphiphiles and simple lipids from a mix of CO, CO2, and H2. A key characteristic of these amphiphilic molecules is the ability to self-assemble in aqueous phases into more organized structures called vesicles, which form a selectively permeable boundary and serve the function of containing and concentrating other organic molecules. The ability to form cell like structures also makes these compounds more likely to be mistaken for biogenic. Hydrothermal simulation experiments were conducted from oxalic or formic acid in water at 175 C for 72 hr. The molecular and isotopic composition of the products of these reactions were determined and compared to biogenic fractionations . Preliminary results indicate isotopic fractionation during abiotic hydrocarbon synthesis in hydrothermal environments is on par with biological carbon fixation.

  15. Sorption-desorption of cadmium in aqueous palygorskite, sepiolite, and calcite suspensions: isotherm hysteresis.

    PubMed

    Shirvani, Mehran; Kalbasi, Mahmoud; Shariatmadari, Hosein; Nourbakhsh, Farshid; Najafi, Bijan

    2006-12-01

    Sorption isotherms have been widely used to assess the heavy metal retention characteristics of soil particles. Desorption behavior of the retained metals, however, usually differ from that of sorption, leading to a lack of coincidence in the experimentally obtained sorption and desorption isotherms. In this study, we examine the nonsingularity of cadmium (Cd) sorption-desorption isotherms, to check the possible hysteresis and reversibility phenomena, in aqueous palygorskite, sepiolite and calcite systems. Sorption of Cd was carried out using a 24-h batch equilibration experiment with eight different Cd solution concentrations, equivalent to 20-100% of maximum sorption capacity of each mineral. Immediately after sorption, desorption took place using successive dilution method with five consecutive desorption steps. Both Cd sorption and desorption data were adequately described by Freundlich equation (0.81Calcite showed much smaller hysteresis compared to the other two silicate clays at low Cd surface load, but its hysteresis indices significantly increased, and exceeded that of palygorskite, as the amount of Cd in the systems increased. The average amount of Cd released after five desorption steps, was 13.8%, 2.2% and 3.6% for the palygorskite, sepiolite and calcite, respectively, indicating that a large portion of Cd was irreversibly retained by the minerals.

  16. Capillarity creates single-crystal calcite nanowires from amorphous calcium carbonate.

    PubMed

    Kim, Yi-Yeoun; Hetherington, Nicola B J; Noel, Elizabeth H; Kröger, Roland; Charnock, John M; Christenson, Hugo K; Meldrum, Fiona C

    2011-12-23

    Single-crystal calcite nanowires are formed by crystallization of morphologically equivalent amorphous calcium carbonate (ACC) particles within the pores of track etch membranes. The polyaspartic acid stabilized ACC is drawn into the membrane pores by capillary action, and the single-crystal nature of the nanowires is attributed to the limited contact of the intramembrane ACC particle with the bulk solution. The reaction environment then supports transformation to a single-crystal product. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Structural analysis of the industrial grade calcite

    NASA Astrophysics Data System (ADS)

    Shah, Rajiv P.; Raval, Kamlesh G.

    2017-05-01

    The chemical, optical and structural characterization of the industrial grade Calcite by EDAX, FT-IR and XRD. EDAX is a widely used technique to analyze the chemical components in a material, FT-IR stands for Fourier Transform Infra-Red, the preferred method of infrared spectroscopy. The resultant spectrum represents the molecular absorption and transmission, creating a molecular fingerprint of the sample, The atomic planes of a crystal cause an incident beam of X-rays to interfere with one another as they leave the crystal. The phenomenon is called X ray diffraction.(XRD). Data analysis of EDAX, FT-IR and XRD has been carried out with help of various instruments and software and find out the results of the these industrial grade materials which are mostly used in ceramics industries

  18. Fabrication of B-type carbonate apatite blocks by the phosphorization of free-molding gypsum-calcite composite.

    PubMed

    Zaman, Chowdury Tanira; Takeuchi, Akari; Matsuya, Shigeki; Zaman, Q H M Shawket; Ishikawa, Kunio

    2008-09-01

    B-type carbonate apatite (CO3Ap) block may be an ideal artificial bone substitute because it is closer in chemical composition to bone mineral. In the present study, the feasibility to fabricate CO3Ap blocks was investigated using compositional transformation, which was based on the dissolution-precipitation reaction of a gypsum-calcite composite with free-molding behavior. For the compositional change, or phosphorization, gypsum-calcite composites of varying CaCO3 contents were immersed in 1 mol/L (NH4)3PO4 aqueous solution at 100 degrees C for 24 hours. No macroscopic changes were found after the treatment, whereas microscopic change was observed at SEM level. X-ray diffraction, Fourier transform infrared spectroscopy and CHN analysis indicated that the composites were B-type CO3Ap containing approximately 6-7 wt% of CO3, a value similar to that of biological bone apatite. Diametral tensile strength of the CO3Ap block was approximately 1-3 MPa. Based on the results obtained, it was therefore concluded that gypsum-calcite was a good candidate for the fabrication of CO3Ap blocks, coupled with the advantage that the composite can be molded to any shape by virtue of the setting property of gypsum.

  19. Trace-element partition coefficients in the calcite-water system and their paleoclimatic significance in cave studies

    NASA Astrophysics Data System (ADS)

    Gascoyne, Melvyn

    1983-02-01

    Speleothems (stalactites, stalagmites) formed in limestone caves have been found to contain much information on the timing and intensity of past climates, from analysis of their U, Th, 13C and 18O contents. Because the incorporation of certain trace elements (e.g., Mg, Mn and Zn) in calcite is known to be temperature-dependent, it may be possible to use variations in trace-metal content of fossil speleothems as an alternative paleotem-perature indicator. Using specially developed ion-exchange sampling techniques, analysis of trace-metal content of seepage water and associated fresh calcite deposits in caves in Vancouver Island and Jamaica shows that Mg is distributed between phases in a consistent manner within the temperature regimes of the caves (7° and 23°C, respectively). Average values of the distribution coefficient for Mg are respectively 0.017 and 0.045 at these temperatures. These results indicate that the Mg content of calcite varies directly with temperature and in a sufficiently pronounced manner that a 1°C rise in depositional temperature of a speleothem containing 500 ppm Mg, at ˜10°C, would be seen as an increase of ˜35ppm Mg — a readily determinable shift. Other factors affecting Mg content of a speleothem are considered.

  20. Ocean chemistry controls trends in foraminiferal mineralogy

    NASA Astrophysics Data System (ADS)

    de Nooijer, Lennart; van Dijk, Inge; Reichart, Gert-Jan

    2014-05-01

    Foraminifera are unicellular marine protists of which many produce a calcium carbonate shell of either aragonite or calcite. Since they are responsible for a large part of open ocean calcium carbonate precipitation, it is necessary to understand their response to changes in ocean chemistry. On geological time scales, the ratio of Mg over Ca in seawater played an important role in controlling marine aragonite versus calcite mineralogy. Here we reconstructed occurrences of aragonite and low- and high-Mg calcite producing foraminifera through the Phanerozoic. We discovered a two-step impact of seawater chemistry and mass extinction events on the evolution of foraminifera. Seawater Mg to Ca ratios favor production of either calcite, or of high magnesium carbonate and aragonite shells. However, mass extinction events controlled the timing of shifts in dominance from one mineralogy to the other. This observation suggests that ongoing ocean acidification may have important consequences for foraminiferal calcification. Although reduced carbonate saturation state increases dissolution rates of high-Mg calcite and aragonite compared to low-Mg calcite, the current high Mg/Ca of the ocean kinetically favors precipitation of high-Mg calcite and aragonite. Contrary to the differential effects of dissolution, we argue that ongoing ocean acidification is likely to particularly impact calcite producers (e.g. planktonic foraminifera, coccolithophores) compared to those precipitating high-Mg calcite and aragonite (e.g. corals).

  1. The Role of Tomato WRKY Genes in Plant Responses to Combined Abiotic and Biotic Stresses

    PubMed Central

    Bai, Yuling; Sunarti, Sri; Kissoudis, Christos; Visser, Richard G. F.; van der Linden, C. G.

    2018-01-01

    In the field, plants constantly face a plethora of abiotic and biotic stresses that can impart detrimental effects on plants. In response to multiple stresses, plants can rapidly reprogram their transcriptome through a tightly regulated and highly dynamic regulatory network where WRKY transcription factors can act as activators or repressors. WRKY transcription factors have diverse biological functions in plants, but most notably are key players in plant responses to biotic and abiotic stresses. In tomato there are 83 WRKY genes identified. Here we review recent progress on functions of these tomato WRKY genes and their homologs in other plant species, such as Arabidopsis and rice, with a special focus on their involvement in responses to abiotic and biotic stresses. In particular, we highlight WRKY genes that play a role in plant responses to a combination of abiotic and biotic stresses.

  2. Strain localization in ultramylonitic calcite marbles by dislocation creep-accommodated grain boundary sliding

    NASA Astrophysics Data System (ADS)

    Rogowitz, Anna; Grasemann, Bernhard; Clancy White, Joseph

    2015-04-01

    Strain localization in monomineralic rocks is often associated with brittle precursors, resulting in stress and strain concentration, followed by grain size reduction and activation of grain-size-sensitive deformation mechanisms such as diffusion creep, grain boundary sliding and cataclastic flow. The aforementioned mechanisms typically tend to produce a random crystallographic orientation or a decrease in intensity of a pre-existing texture. However, reports of fine grained polycrystalline materials showing a preferred crystallographic orientation indicate a need for subsequent grain re-organization by either static annealing or the activation of additional deformation mechanisms in conjunction with grain boundary sliding. We present observations from an almost pure calcite marble layer from Syros Island (Cyclades, Greece) deformed in lower greenschist facies conditions. The presence of a crack (i.e. cross-cutting element) that rotated during shear resulted in the formation of a flanking structure. At the location of maximum displacement (120 cm) along the cross-cutting element, the marble is extremely fine grained (3 µm) leading to anticipation of deformation by grain-size-sensitive mechanisms. Detailed microstructural analysis of the highly strained (80 < gamma < 1000) calcite ultramylonite by optical microscopy, electron backscatter diffraction and scanning transmission electron microscopy show that recrystallization by bulging results in small, strain-free grains. The change in grain size appears to be concomitant with increased activity of independent grain boundary sliding as indicated by a random misorientation angle distribution. At the same time, dislocation multiplication through Frank-Read sources produces high mean dislocation density (~ 5x10^13 m^-2) as well as a weak primary CPO; the latter all argue that grain boundary sliding was accommodated by dislocation activity. Theoretical and experimental determined relationships (paleowattmeter

  3. Strain rate dependent activation of slip systems in calcite marbles from Syros (Cyclades, Greece)

    NASA Astrophysics Data System (ADS)

    Rogowitz, Anna; Grasemann, Bernhard; Morales, Luiz F. G.; Huet, Benjamin; White, Joseph C.

    2017-04-01

    The activation of certain slip systems in calcite has been experimentally proven to be highly temperature dependent, but also the strain rate plays an important role on the activation of the dominant slip system. In this study, observations from a flanking structure (i.e. shear zone) that developed under lower greenschist-facies conditions, in an almost pure calcite marble (Syros Island, Greece) are presented. The shear zone is characterized by a strain gradient from the slightly deformed tips (γ ˜ 50) to the highly strained centre (γ up to 1000) while the host rock is moderately deformed (γ ˜ 3). During the shear zone development, the strain gradient coincided with a strain rate gradient with strain rate varying from 10-13 to 10-9 s-1. The studied outcrop thus represents the final state of a natural experiment and gives us a great opportunity to get natural constraints on strain rate dependent mechanical behaviour in a calcite marble. Detailed microstructural analyses have been performed via optical microscopy, electron microscopy, electron backscatter diffraction mapping and transmission electron microscopy, on samples from the highly strained shear zone and the host rock. The analyses show that the calcite microfabric varies depending on position within the shear zone, indicating activation of different deformation, recrystallization mechanisms and slip systems at different strain rates. Up to strain rates of ˜10-10 s-1 the marble deformed exclusively within the dislocation creep field, showing a change in recrystallization mechanism and dominant active slip system. While the marble preferentially recrystallized by grain boundary migration at relatively low strain rates (˜10-13 s-1), subgrain rotation recrystallization seems to be the dominant mechanism at higher strain rates (˜10-12 to 10-10 s-1). At higher strain rates (˜10-9 s-1), the recrystallization mechanism is bulging, resulting in the development of an extremely fine grained ultramylonite

  4. Geochemical distinctions between igneous carbonate, calcite cements, and limestone xenoliths (Polino carbonatite, Italy): spatially resolved LAICPMS analyses

    NASA Astrophysics Data System (ADS)

    Rosatelli, G.; Wall, F.; Stoppa, F.; Brilli, M.

    2010-11-01

    Petrography-controlled laser ablation inductively coupled plasma mass spectrometry (LAICPMS) analyses of carbonate in fresh shallow level sub-volcanic Polino monticellite calcio-carbonatite tuffisite have been performed to assess the geochemical differences between fresh igneous, epigenetic carbonates and sedimentary accidental fragments. Igneous calcite has consistently high LREE/HREE ratios (La/Yb N , 15-130) due to high LREE (ΣLREE, 425-1,269 ppm). Secondary calcite cements are characterized by progressively lower and more variable trace element contents, with lower LREE/HREE ratios. A distinguishing geochemical feature is progressively increasing negative Ce anomalies observed through coarse secondary calcite that can be related to the surface environment processes. The limestone accidental fragments in the tuffisite have trace element contents almost two orders of magnitude lower than igneous carbonate and low LREE (ΣLREE < 9.5 ppm) with low LREE/HREE fractionation (La/Yb N ratios < 18). The stable isotope composition of different carbonate types is consistent with their formation in different environments. The tuffisitization processes during diatreme formation under high CO2-OH fugacity conditions may account for the differences noted in the igneous carbonates.

  5. The dissolution of calcite in CO2-saturated solutions at 25°C and 1 atmosphere total pressure

    USGS Publications Warehouse

    Plummer, Niel; Wigley, T.M.L.

    1976-01-01

    The dissolution of Iceland spar in CO2-saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.

  6. Coupled biotic-abiotic oxidation of organic matter by biogenic MnO_{2}

    NASA Astrophysics Data System (ADS)

    Gonzalez, Julia; Peña, Jasquelin

    2016-04-01

    Some reactive soil minerals are strongly implicated in stabilising organic matter. However, others can play an active role in the oxidation of organic molecules. In natural systems, layer-type manganese oxide minerals (MnO2) typically occur as biomineral assemblages consisting of mineral particles and microbial biomass. Both the mineral and biological fractions of the assemblage can be powerful oxidants of organic C. The biological compartment relies on a set of enzymes to drive oxidative transformations of reduced C-substrates, whereas MnO2 minerals are strong, less specific abiotic oxidants that are assumed to rely on interfacial interactions between C-substrates and the mineral surface. This project aims to understand the coupling between microbial C mineralization and abiotic C oxidation mediated by MnO2 in bacterial-MnO2 assemblages. Specifically, under conditions of high C turnover, microbial respiration can significantly alter local pH, dissolved oxygen and pool of available reductants, which may modify rates and mechanism of C oxidation by biotic and abiotic components. We first investigated changes in the solution chemistry of Pseudomonas putida suspensions exposed to varying concentrations of glucose, chosen to represent readily bioavailable substrates in soils. Glucose concentrations tested ranged between 0 and 5.5mM and changes in pH, dissolved oxygen and dissolved organic and inorganic carbon were tracked over 48h. We then combined literature review and wet-chemical experiments to compile the pH dependence of rates of organic substrate oxidation by MnO2, including glucose. Our results demonstrate a strong pH dependence for these abiotic reactions. In assemblages of P. putida - MnO2, kinetic limitations for abiotic C oxidation by MnO2 are overcome by changes in biogeochemical conditions that result from bacterial C metabolism. When extrapolated to a soil solution confronted to an input of fresh dissolved organic matter, bacterial C metabolism of the

  7. Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

    USGS Publications Warehouse

    Balci, N.; Shanks, Wayne C.; Mayer, B.; Mandernack, K.W.

    2007-01-01

    To better understand reaction pathways of pyrite oxidation and biogeochemical controls on ??18O and ??34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)aq as an oxidant with varying ??18OH2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ???2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ???2.7. The ??34SSO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (???-0.7???) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (??18 OSO4 s(-) H2 O) of ???3.5??? was determined for the anaerobic (biological and abiotic) experiments. This measured ??18 OSO42 - s(-) H2

  8. Site-specific 15N isotopic signatures of abiotically produced N2O

    NASA Astrophysics Data System (ADS)

    Heil, Jannis; Wolf, Benjamin; Brüggemann, Nicolas; Emmenegger, Lukas; Tuzson, Béla; Vereecken, Harry; Mohn, Joachim

    2014-08-01

    Efficient nitrous oxide (N2O) mitigation strategies require the identification of the main source and sink processes and their contribution to total soil N2O production. Several abiotic reactions of nitrification intermediates leading to N2O production are known, but their contribution to total N2O production in soils is uncertain. As the site preference (SP) of 15N in N2O is a promising tool to give more insight into N2O production processes, we investigated the SP of N2O produced by different abiotic reactions in a laboratory study. All reactions involved the nitrification intermediate hydroxylamine (NH2OH) in combination with nitrite (NO2-), Fe3+, Fe2+ and Cu2+, reactants commonly or potentially found in soils, at different concentrations and pH values. N2O production and its four main isotopic species (14N14N16O, 15N14N16O, 14N15N16O, and 14N14N18O) were quantified simultaneously and online at high temporal resolution using quantum cascade laser absorption spectroscopy. Thereby, our study presents the first continuous analysis of δ18O in N2O. The experiments revealed the possibility of purely abiotic reactions over a wide range of acidity (pH 3-8) by different mechanisms. All studied abiotic pathways produced N2O with a characteristic SP in the range of 34-35‰, unaffected by process conditions and remaining constant over the course of the experiments. These findings reflect the benefit of continuous N2O isotopic analysis by laser spectroscopy, contribute new information to the challenging source partitioning of N2O emissions from soils, and emphasize the potentially significant role of coupled biotic-abiotic reactions in soils.

  9. The Arabidopsis PLAT domain protein1 is critically involved in abiotic stress tolerance.

    PubMed

    Hyun, Tae Kyung; van der Graaff, Eric; Albacete, Alfonso; Eom, Seung Hee; Großkinsky, Dominik K; Böhm, Hannah; Janschek, Ursula; Rim, Yeonggil; Ali, Walid Wahid; Kim, Soo Young; Roitsch, Thomas

    2014-01-01

    Despite the completion of the Arabidopsis genome sequence, for only a relatively low percentage of the encoded proteins experimental evidence concerning their function is available. Plant proteins that harbour a single PLAT (Polycystin, Lipoxygenase, Alpha-toxin and Triacylglycerol lipase) domain and belong to the PLAT-plant-stress protein family are ubiquitously present in monocot and dicots. However, the function of PLAT-plant-stress proteins is still poorly understood. Therefore, we have assessed the function of the uncharacterised Arabidopsis PLAT-plant-stress family members through a combination of functional genetic and physiological approaches. PLAT1 overexpression conferred increased abiotic stress tolerance, including cold, drought and salt stress, while loss-of-function resulted in opposite effects on abiotic stress tolerance. Strikingly, PLAT1 promoted growth under non-stressed conditions. Abiotic stress treatments induced PLAT1 expression and caused expansion of its expression domain. The ABF/ABRE transcription factors, which are positive mediators of abscisic acid signalling, activate PLAT1 promoter activity in transactivation assays and directly bind to the ABRE elements located in this promoter in electrophoretic mobility shift assays. This suggests that PLAT1 represents a novel downstream target of the abscisic acid signalling pathway. Thus, we showed that PLAT1 critically functions as positive regulator of abiotic stress tolerance, but also is involved in regulating plant growth, and thereby assigned a function to this previously uncharacterised PLAT domain protein. The functional data obtained for PLAT1 support that PLAT-plant-stress proteins in general could be promising targets for improving abiotic stress tolerance without yield penalty.

  10. The Arabidopsis PLAT Domain Protein1 Is Critically Involved in Abiotic Stress Tolerance

    PubMed Central

    Eom, Seung Hee; Großkinsky, Dominik K.; Böhm, Hannah; Janschek, Ursula; Rim, Yeonggil; Ali, Walid Wahid; Kim, Soo Young; Roitsch, Thomas

    2014-01-01

    Despite the completion of the Arabidopsis genome sequence, for only a relatively low percentage of the encoded proteins experimental evidence concerning their function is available. Plant proteins that harbour a single PLAT (Polycystin, Lipoxygenase, Alpha-toxin and Triacylglycerol lipase) domain and belong to the PLAT-plant-stress protein family are ubiquitously present in monocot and dicots. However, the function of PLAT-plant-stress proteins is still poorly understood. Therefore, we have assessed the function of the uncharacterised Arabidopsis PLAT-plant-stress family members through a combination of functional genetic and physiological approaches. PLAT1 overexpression conferred increased abiotic stress tolerance, including cold, drought and salt stress, while loss-of-function resulted in opposite effects on abiotic stress tolerance. Strikingly, PLAT1 promoted growth under non-stressed conditions. Abiotic stress treatments induced PLAT1 expression and caused expansion of its expression domain. The ABF/ABRE transcription factors, which are positive mediators of abscisic acid signalling, activate PLAT1 promoter activity in transactivation assays and directly bind to the ABRE elements located in this promoter in electrophoretic mobility shift assays. This suggests that PLAT1 represents a novel downstream target of the abscisic acid signalling pathway. Thus, we showed that PLAT1 critically functions as positive regulator of abiotic stress tolerance, but also is involved in regulating plant growth, and thereby assigned a function to this previously uncharacterised PLAT domain protein. The functional data obtained for PLAT1 support that PLAT-plant-stress proteins in general could be promising targets for improving abiotic stress tolerance without yield penalty. PMID:25396746

  11. 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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Magnet-Facilitated Selection of Electrogenic Bacteria from Marine Sediment

    PubMed Central

    Kiseleva, Larisa; Briliute, Justina; Khilyas, Irina V.; Simpson, David J. W.; Fedorovich, Viacheslav; Cohen, M.; Goryanin, Igor

    2015-01-01

    Some bacteria can carry out anaerobic respiration by depositing electrons on external materials, such as electrodes, thereby creating an electrical current. Into the anode chamber of microbial fuel cells (MFCs) having abiotic air-cathodes we inoculated microorganisms cultured from a magnetic particle-enriched portion of a marine tidal sediment, reasoning that since some external electron acceptors are ferromagnetic, electrogenic bacteria should be found in their vicinity. Two MFCs, one inoculated with a mixed bacterial culture and the other with an axenic culture of a helical bacterium isolated from the magnetic particle enrichment, termed strain HJ, were operated for 65 d. Both MFCs produced power, with production from the mixed culture MFC exceeding that of strain HJ. Strain HJ was identified as a Thalassospira sp. by transmission electron microscopic analysis and 16S rRNA gene comparisons. An MFC inoculated with strain HJ and operated in open circuit produced 47% and 57% of the maximal power produced from MFCs inoculated with the known electrogen Geobacter daltonii and the magnetotactic bacterium Desulfamplus magnetomortis, respectively. Further investigation will be needed to determine whether bacterial populations associated with magnetic particles within marine sediments are enriched for electrogens. PMID:26504814

  13. Magnet-Facilitated Selection of Electrogenic Bacteria from Marine Sediment.

    PubMed

    Kiseleva, Larisa; Briliute, Justina; Khilyas, Irina V; Simpson, David J W; Fedorovich, Viacheslav; Cohen, M; Goryanin, Igor

    2015-01-01

    Some bacteria can carry out anaerobic respiration by depositing electrons on external materials, such as electrodes, thereby creating an electrical current. Into the anode chamber of microbial fuel cells (MFCs) having abiotic air-cathodes we inoculated microorganisms cultured from a magnetic particle-enriched portion of a marine tidal sediment, reasoning that since some external electron acceptors are ferromagnetic, electrogenic bacteria should be found in their vicinity. Two MFCs, one inoculated with a mixed bacterial culture and the other with an axenic culture of a helical bacterium isolated from the magnetic particle enrichment, termed strain HJ, were operated for 65 d. Both MFCs produced power, with production from the mixed culture MFC exceeding that of strain HJ. Strain HJ was identified as a Thalassospira sp. by transmission electron microscopic analysis and 16S rRNA gene comparisons. An MFC inoculated with strain HJ and operated in open circuit produced 47% and 57% of the maximal power produced from MFCs inoculated with the known electrogen Geobacter daltonii and the magnetotactic bacterium Desulfamplus magnetomortis, respectively. Further investigation will be needed to determine whether bacterial populations associated with magnetic particles within marine sediments are enriched for electrogens.

  14. Relationships between biotic and abiotic factors and regeneration of chestnut oak, white oak, and northern red oak

    Treesearch

    Songlin Fei; Kim C. Steiner; James C. Finley; Marc E. McDill

    2003-01-01

    A series of substantial field surveys of 38 mixed-oak stands in central Pennsylvania were carried out during 1996-2000. All the stands were surveyed 1 year prior to harvest, and 16 stands have been surveyed 1 year after harvest. Three abiotic factors at stand scale, four abiotic factors at plot scale, and two biotic factors and one abiotic factor at subplot scale was...

  15. Abiotic stress responses in plants: roles of calmodulin-regulated proteins

    PubMed Central

    Virdi, Amardeep S.; Singh, Supreet; Singh, Prabhjeet

    2015-01-01

    Intracellular changes in calcium ions (Ca2+) in response to different biotic and abiotic stimuli are detected by various sensor proteins in the plant cell. Calmodulin (CaM) is one of the most extensively studied Ca2+-sensing proteins and has been shown to be involved in transduction of Ca2+ signals. After interacting with Ca2+, CaM undergoes conformational change and influences the activities of a diverse range of CaM-binding proteins. A number of CaM-binding proteins have also been implicated in stress responses in plants, highlighting the central role played by CaM in adaptation to adverse environmental conditions. Stress adaptation in plants is a highly complex and multigenic response. Identification and characterization of CaM-modulated proteins in relation to different abiotic stresses could, therefore, prove to be essential for a deeper understanding of the molecular mechanisms involved in abiotic stress tolerance in plants. Various studies have revealed involvement of CaM in regulation of metal ions uptake, generation of reactive oxygen species and modulation of transcription factors such as CAMTA3, GTL1, and WRKY39. Activities of several kinases and phosphatases have also been shown to be modulated by CaM, thus providing further versatility to stress-associated signal transduction pathways. The results obtained from contemporary studies are consistent with the proposed role of CaM as an integrator of different stress signaling pathways, which allows plants to maintain homeostasis between different cellular processes. In this review, we have attempted to present the current state of understanding of the role of CaM in modulating different stress-regulated proteins and its implications in augmenting abiotic stress tolerance in plants. PMID:26528296

  16. The Second Skin: Ecological Role of Epibiotic Biofilms on Marine Organisms

    PubMed Central

    Wahl, Martin; Goecke, Franz; Labes, Antje; Dobretsov, Sergey; Weinberger, Florian

    2012-01-01

    In the aquatic environment, biofilms on solid surfaces are omnipresent. The outer body surface of marine organisms often represents a highly active interface between host and biofilm. Since biofilms on living surfaces have the capacity to affect the fluxes of information, energy, and matter across the host’s body surface, they have an important ecological potential to modulate the abiotic and biotic interactions of the host. Here we review existing evidence how marine epibiotic biofilms affect their hosts’ ecology by altering the properties of and processes across its outer surfaces. Biofilms have a huge potential to reduce its host’s access to light, gases, and/or nutrients and modulate the host’s interaction with further foulers, consumers, or pathogens. These effects of epibiotic biofilms may intensely interact with environmental conditions. The quality of a biofilm’s impact on the host may vary from detrimental to beneficial according to the identity of the epibiotic partners, the type of interaction considered, and prevailing environmental conditions. The review concludes with some unresolved but important questions and future perspectives. PMID:22936927

  17. Abiotic CO2 reduction during geologic carbon sequestration facilitated by Fe(II)-bearing minerals

    NASA Astrophysics Data System (ADS)

    Nielsen, L. C.; Maher, K.; Bird, D. K.; Brown, G. E.; Thomas, B.; Johnson, N. C.; Rosenbauer, R. J.

    2012-12-01

    Redox reactions involving subsurface minerals and fluids and can lead to the abiotic generation of hydrocarbons from CO2 under certain conditions. Depleted oil reservoirs and saline aquifers targeted for geologic carbon sequestration (GCS) can contain significant quantities of minerals such as ferrous chlorite, which could facilitate the abiotic reduction of carbon dioxide to n-carboxylic acids, hydrocarbons, and amorphous carbon (C0). If such reactions occur, the injection of supercritical CO2 (scCO2) could significantly alter the oxidation state of the reservoir and cause extensive reorganization of the stable mineral assemblage via dissolution and reprecipitation reactions. Naturally occurring iron oxide minerals such as magnetite are known to catalyze CO2 reduction, resulting in the synthesis of organic compounds. Magnetite is thermodynamically stable in Fe(II) chlorite-bearing mineral assemblages typical of some reservoir formations. Thermodynamic calculations demonstrate that GCS reservoirs buffered by the chlorite-kaolinite-carbonate(siderite/magnesite)-quartz assemblage favor the reduction of CO2 to n-carboxylic acids, hydrocarbons, and C0, although the extent of abiotic CO2 reduction may be kinetically limited. To investigate the rates of abiotic CO2 reduction in the presence of magnetite, we performed batch abiotic CO2 reduction experiments using a Dickson-type rocking hydrothermal apparatus at temperatures (373 K) and pressures (100 bar) within the range of conditions relevant to GCS. Blank experiments containing CO2 and H2 were used to rule out the possibility of catalytic activity of the experimental apparatus. Reaction of brine-suspended magnetite nanoparticles with scCO2 at H2 partial pressures typical of reservoir rocks - up to 100 and 0.1 bars respectively - was used to investigate the kinetics of magnetite-catalyzed abiotic CO2 reduction. Later experiments introducing ferrous chlorite (ripidolite) were carried out to determine the potential for

  18. Abiotic dechlorination of chlorinated ethenes in natural clayey soils: Impacts of mineralogy and temperature

    NASA Astrophysics Data System (ADS)

    Schaefer, Charles E.; Ho, Paul; Gurr, Christopher; Berns, Erin; Werth, Charles

    2017-11-01

    Laboratory batch experiments were performed to assess the impacts of temperature and mineralogy on the abiotic dechlorination of tetrachloroethene (PCE) or trichloroethene (TCE) due to the presence of ferrous minerals in natural aquifer clayey soils under anaerobic conditions. A combination of x-ray diffraction (XRD), magnetic susceptibility, and ferrous mineral content were used to characterize each of the 3 natural soils tested in this study, and dechlorination at temperatures ranging from 20 to 55 °C were examined. Results showed that abiotic dechlorination occurred in all 3 soils examined, yielding reduced gas abiotic dechlorination products acetylene, butane, ethene, and/or propane. Bulk first-order dechlorination rate constants (kbulk), scaled to the soil:water ratio expected for in situ conditions, ranged from 2.0 × 10- 5 day- 1 at 20 °C, to 32 × 10- 5 day- 1 at 55 °C in the soil with the greatest ferrous mineral content. For the generation of acetylene and ethene from PCE, the reaction was well described by Arrhenius kinetics, with an activation energy of 91 kJ/mol. For the generation of coupling products butane and propane, the Arrhenius equation did not provide a satisfactory description of the data, likely owing to the complex reaction mechanisms associated with these products and/or diffusional mass transfer processes associated with the ferrous minerals likely responsible for these coupling reactions. Although the data set was too limited to determine a definitive correlation, the two soils with elevated ferrous mineral contents had elevated abiotic dechlorination rate constants, while the one soil with a low ferrous mineral content had a relatively low abiotic dechlorination rate constant. Overall, results suggest intrinsic abiotic dechlorination rates may be an important long-term natural attenuation component in site conceptual models for clays that have the appropriate iron mineralogy.

  19. An Overview of Marine Biodiversity in United States Waters

    PubMed Central

    Fautin, Daphne; Dalton, Penelope; Incze, Lewis S.; Leong, Jo-Ann C.; Pautzke, Clarence; Rosenberg, Andrew; Sandifer, Paul; Sedberry, George; Tunnell, John W.; Abbott, Isabella; Brainard, Russell E.; Brodeur, Melissa; Eldredge, Lucius G.; Feldman, Michael; Moretzsohn, Fabio; Vroom, Peter S.; Wainstein, Michelle; Wolff, Nicholas

    2010-01-01

    Marine biodiversity of the United States (U.S.) is extensively documented, but data assembled by the United States National Committee for the Census of Marine Life demonstrate that even the most complete taxonomic inventories are based on records scattered in space and time. The best-known taxa are those of commercial importance. Body size is directly correlated with knowledge of a species, and knowledge also diminishes with distance from shore and depth. Measures of biodiversity other than species diversity, such as ecosystem and genetic diversity, are poorly documented. Threats to marine biodiversity in the U.S. are the same as those for most of the world: overexploitation of living resources; reduced water quality; coastal development; shipping; invasive species; rising temperature and concentrations of carbon dioxide in the surface ocean, and other changes that may be consequences of global change, including shifting currents; increased number and size of hypoxic or anoxic areas; and increased number and duration of harmful algal blooms. More information must be obtained through field and laboratory research and monitoring that involve innovative sampling techniques (such as genetics and acoustics), but data that already exist must be made accessible. And all data must have a temporal component so trends can be identified. As data are compiled, techniques must be developed to make certain that scales are compatible, to combine and reconcile data collected for various purposes with disparate gear, and to automate taxonomic changes. Information on biotic and abiotic elements of the environment must be interactively linked. Impediments to assembling existing data and collecting new data on marine biodiversity include logistical problems as well as shortages in finances and taxonomic expertise. PMID:20689852

  20. An overview of marine biodiversity in United States waters

    USGS Publications Warehouse

    Fautin, Daphne G.; Delton, Penelope; Incze, Lewis S.; Leong, Jo-Ann C.; Pautzke, Clarence; Rosenberg, Andrew A.; Sandifer, Paul; Sedberry, George R.; Tunnell, John W.; Abbott, Isabella; Brainard, Russell E.; Brodeur, Melissa; Eldredge, Lucius G.; Feldman, Michael; Moretzsohn, Fabio; Vroom, Peter S.; Wainstein, Michelle; Wolff, Nicholas

    2010-01-01

    Marine biodiversity of the United States (U.S.) is extensively documented, but data assembled by the United States National Committee for the Census of Marine Life demonstrate that even the most complete taxonomic inventories are based on records scattered in space and time. The best-known taxa are those of commercial importance. Body size is directly correlated with knowledge of a species, and knowledge also diminishes with distance from shore and depth. Measures of biodiversity other than species diversity, such as ecosystem and genetic diversity, are poorly documented. Threats to marine biodiversity in the U.S. are the same as those for most of the world: overexploitation of living resources; reduced water quality; coastal development; shipping; invasive species; rising temperature and concentrations of carbon dioxide in the surface ocean, and other changes that may be consequences of global change, including shifting currents; increased number and size of hypoxic or anoxic areas; and increased number and duration of harmful algal blooms. More information must be obtained through field and laboratory research and monitoring that involve innovative sampling techniques (such as genetics and acoustics), but data that already exist must be made accessible. And all data must have a temporal component so trends can be identified. As data are compiled, techniques must be developed to make certain that scales are compatible, to combine and reconcile data collected for various purposes with disparate gear, and to automate taxonomic changes. Information on biotic and abiotic elements of the environment must be interactively linked. Impediments to assembling existing data and collecting new data on marine biodiversity include logistical problems as well as shortages in finances and taxonomic expertise.

  1. An overview of marine biodiversity in United States waters.

    PubMed

    Fautin, Daphne; Dalton, Penelope; Incze, Lewis S; Leong, Jo-Ann C; Pautzke, Clarence; Rosenberg, Andrew; Sandifer, Paul; Sedberry, George; Tunnell, John W; Abbott, Isabella; Brainard, Russell E; Brodeur, Melissa; Eldredge, Lucius G; Feldman, Michael; Moretzsohn, Fabio; Vroom, Peter S; Wainstein, Michelle; Wolff, Nicholas

    2010-08-02

    Marine biodiversity of the United States (U.S.) is extensively documented, but data assembled by the United States National Committee for the Census of Marine Life demonstrate that even the most complete taxonomic inventories are based on records scattered in space and time. The best-known taxa are those of commercial importance. Body size is directly correlated with knowledge of a species, and knowledge also diminishes with distance from shore and depth. Measures of biodiversity other than species diversity, such as ecosystem and genetic diversity, are poorly documented. Threats to marine biodiversity in the U.S. are the same as those for most of the world: overexploitation of living resources; reduced water quality; coastal development; shipping; invasive species; rising temperature and concentrations of carbon dioxide in the surface ocean, and other changes that may be consequences of global change, including shifting currents; increased number and size of hypoxic or anoxic areas; and increased number and duration of harmful algal blooms. More information must be obtained through field and laboratory research and monitoring that involve innovative sampling techniques (such as genetics and acoustics), but data that already exist must be made accessible. And all data must have a temporal component so trends can be identified. As data are compiled, techniques must be developed to make certain that scales are compatible, to combine and reconcile data collected for various purposes with disparate gear, and to automate taxonomic changes. Information on biotic and abiotic elements of the environment must be interactively linked. Impediments to assembling existing data and collecting new data on marine biodiversity include logistical problems as well as shortages in finances and taxonomic expertise.

  2. Characterization of Shock Effects in Calcite by Raman Spectroscopy: Results of Experiments

    NASA Technical Reports Server (NTRS)

    Bell, M. S.

    2016-01-01

    Carbonates comprise approx. 20% by volume of present day Earth's sedimentary rocks and store most of the terrestrial CO2 inventory. Some of the oldest meta-sedimentary rocks found on Earth contain abundant carbonate from which impact-induced release of CO2 could have played a role in the formation and evolution of the atmosphere. Carbonates are also present in the target materials for approx. 30% of all terrestrial impact structures including large impacts such as Chicxulub which happened to occur at a location with extraordinarily thick platform carbonate 3-6 km deep. The impact release of CO2 from carbonates can cause global warming as a result of the well-known greenhouse effect and have subsequent effects on climate and biota. Therefore, the shock behavior of calcite is important in understanding the Cretaceous-Paleogene event and other impacts with carbonate-bearing sediments in their target(s) such as Mars and some asteroids. A comprehensive survey utilizing a variety of techniques to characterize the effects manifest in Calcite (Iceland Spar) experimentally shocked to 60.8 GPa has been completed. Results of analysis by Raman Spectroscopy are reported here.

  3. Chalk-calcite-microfluidic experiments: construction and flooding of microsystems with reactive fluids

    NASA Astrophysics Data System (ADS)

    Neuville, Amélie; Thuy Luu, Thi; Dysthe, Dag Kristian; Vinningland, Jan Ludvig; Hiorth, Aksel

    2015-04-01

    Direct in situ observation of the pore structure changes that occur when chalk is flooded with brines could resolve many of the open questions that remain about the interactions between mineralogical alterations and oil-liberating mechanisms. Experiments on core scale and field tests that have been carried out the last decade have clearly shown that water chemistry affects the final oil recovery. However, there is generally no consensus in the scientific community of why additional oil is released. In this work, our aim is to focus on in-situ observations of single phase flow and interactions at the pore scale. To do so, we create several types of custom-made microsystems with chalk and calcite crystals. We then do experiments with reacting fluids in these microsystems. During these experiments, we realize in-situ observations (geometrical characteristics, reaction rate) using microsopy techniques (white light vertical/phase shift interferometric microscopy, and classical microscopy), and show how they vary as function as the water chemistry. In simple systems made of calcite, we obtain reactive rates that are coherent with the litterature and with numerical simulations based on Lattice-Boltzmann methods.

  4. Bacterial bio-mediated calcite precipitation for monumental stones conservation: methods of evaluation.

    PubMed

    Tiano, P; Biagiotti, L; Mastromei, G

    1999-05-01

    The weathering of monumental stones is a complex process inserted in the more general 'matter transformation cycle' operated by physical, chemical and biological factors. The consequence of these combined actions is a loss of cohesion with dwindling and scaling of stone material and the induction of a progressive mineral matrix dissolution. In the case of calcareous stones, calcite leaching increases the material porosity and decreases its mechanical features with a general weakening of the superficial structural strength. Attempts to stop, or at least to slow down, deterioration of monumental stones has been made by conservative treatments with both inorganic or organic products. More recent studies show a new approach to hinder these phenomena by inducing a bio-mediated precipitation of calcite directly inside the stone porosity. This can be achieved either through the application of organic matrix macromolecules extracted from sea shells or of living bacteria. The effectiveness of the treatment using calcinogenic bacteria has been evaluated with laboratory tests specifically developed to evaluate the parameters such as : porosity, superficial strength and chromatic changes, influenced by the treatment itself. The results obtained seem to indicate that this type of treatment might not be suitable for monumental stone conservation.

  5. Induction of abiotic stress tolerance in plants by endophytic microbes.

    PubMed

    Lata, R; Chowdhury, S; Gond, S K; White, J F

    2018-04-01

    Endophytes are micro-organisms including bacteria and fungi that survive within healthy plant tissues and promote plant growth under stress. This review focuses on the potential of endophytic microbes that induce abiotic stress tolerance in plants. How endophytes promote plant growth under stressful conditions, like drought and heat, high salinity and poor nutrient availability will be discussed. The molecular mechanisms for increasing stress tolerance in plants by endophytes include induction of plant stress genes as well as biomolecules like reactive oxygen species scavengers. This review may help in the development of biotechnological applications of endophytic microbes in plant growth promotion and crop improvement under abiotic stress conditions. Increasing human populations demand more crop yield for food security while crop production is adversely affected by abiotic stresses like drought, salinity and high temperature. Development of stress tolerance in plants is a strategy to cope with the negative effects of adverse environmental conditions. Endophytes are well recognized for plant growth promotion and production of natural compounds. The property of endophytes to induce stress tolerance in plants can be applied to increase crop yields. With this review, we intend to promote application of endophytes in biotechnology and genetic engineering for the development of stress-tolerant plants. © 2018 The Society for Applied Microbiology.

  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. Cortex proliferation in the root is a protective mechanism against abiotic stress.

    PubMed

    Cui, Hongchang

    2015-01-01

    Although as an organ the root plays a pivotal role in nutrient and water uptake as well anchorage, individual cell types function distinctly. Cortex is regarded as the least differentiated cell type in the root, but little is known about its role in plant growth and physiology. In recent studies, we found that cortex proliferation can be induced by oxidative stress. Since all types of abiotic stress lead to oxidative stress, this finding suggests a role for cortex in coping with abiotic stress. This hypothesis was tested in this study using the spy mutant, which has an extra layer of cortex in the root. Interestingly, the spy mutant was shown to be hypersensitive to salt and oxidizing reagent applied to the leaves, but it was as tolerant as the wild type to these compounds in the soil. This result lends support to the notion that cortex has a protective role against abiotic stress arising from the soil.

  8. Microbial Surface Colonization and Biofilm Development in Marine Environments.

    PubMed

    Dang, Hongyue; Lovell, Charles R

    2016-03-01

    Biotic and abiotic surfaces in marine waters are rapidly colonized by microorganisms. Surface colonization and subsequent biofilm formation and development provide numerous advantages to these organisms and support critical ecological and biogeochemical functions in the changing marine environment. Microbial surface association also contributes to deleterious effects such as biofouling, biocorrosion, and the persistence and transmission of harmful or pathogenic microorganisms and their genetic determinants. The processes and mechanisms of colonization as well as key players among the surface-associated microbiota have been studied for several decades. Accumulating evidence indicates that specific cell-surface, cell-cell, and interpopulation interactions shape the composition, structure, spatiotemporal dynamics, and functions of surface-associated microbial communities. Several key microbial processes and mechanisms, including (i) surface, population, and community sensing and signaling, (ii) intraspecies and interspecies communication and interaction, and (iii) the regulatory balance between cooperation and competition, have been identified as critical for the microbial surface association lifestyle. In this review, recent progress in the study of marine microbial surface colonization and biofilm development is synthesized and discussed. Major gaps in our knowledge remain. We pose questions for targeted investigation of surface-specific community-level microbial features, answers to which would advance our understanding of surface-associated microbial community ecology and the biogeochemical functions of these communities at levels from molecular mechanistic details through systems biological integration. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

  9. Controls of ionic strength and macromolecule chemistry on calcite nucleation: Salinity and ion hydration as levers for regulating biomineralization

    NASA Astrophysics Data System (ADS)

    Dove, P. M.; Giuffre, A. J.; Mergelsberg, S. T.; Han, N.; De Yoreo, J. J.

    2016-12-01

    Organisms form shells and skeletons with remarkable fidelity by controlling the timing and placement of the minerals that nucleate and subsequently grow. An extensive effort has identified features of the organic matrix that regulate this process. Recent measurements from our group show the energy barrier to nucleation onto polysaccharide (PS) substrates is dependent upon hydrophilicity through functional group chemistry and suggest that free energy of the macromolecule-liquid interface influences where and when mineral nucleation occurs (Giuffre et al., 2013, PNAS). The importance of interfacial free energy in regulating nucleation raises the question of whether local changes in salinity or electrolyte composition can be tuned to further modulate the onset of calcite nucleation. Using alginate (negatively charged by carboxyl groups) and chitosan (small positive charge by amine groups), the rate of calcite nucleation was measured at controlled supersaturations and pH as a function of NaCl concentration (65-600 mM). Analyses of the data show the thermodynamic barrier to calcite nucleation onto both types of PS increases with ionic strength. The evidence suggests this effect arises from an increasing concentration of solvated ions at the PS-water interface while also increasing the hydrophilic character of that interface; thus decreasing the substrate-liquid interfacial free energy. To test this explanation, a second group of nucleation experiments used a suite of electrolytes (alkali chlorides for alginate and sodium halides for chitosan) while holding ionic strength constant. Indeed, the nucleation barriers for calcite formation are electrolyte-specific and correlated with the hydration free energy of the ion. This suggests solvated electrolyte ions indirectly regulate calcite nucleation onto substrates through their competition with the substrate for water thereby influencing net interfacial free energy. These effects are consistent with the long

  10. Biotic and abiotic transformations of methyl tertiary butyl ether (MTBE).

    PubMed

    Fischer, Axel; Oehm, Claudia; Selle, Michael; Werner, Peter

    2005-11-01

    Methyl tertiary butyl ether (MTBE) is a fuel additive which is used all over the world. In recent years it has often been found in groundwater, mainly in the USA, but also in Europe. Although MTBE seems to be a minor toxic, it affects the taste and odour of water at concentrations of < 30 microg/L. Although MTBE is often a recalcitrant compound, it is known that many ethers can be degraded by abiotic means. The aim of this study was to examine biotic and abiotic transformations of MTBE with respect to the particular conditions of a contaminated site (former refinery) in Leuna, Germany. Groundwater samples from wells of a contaminated site were used for aerobic and anaerobic degradation experiments. The abiotic degradation experiment (hydrolysis) was conducted employing an ion-exchange resin and MTBE solutions in distilled water. MTBE, tertiary butyl formate (TBF) and tertiary butyl alcohol (TBA) were measured by a gas chromatograph with flame ionisation detector (FID). Aldehydes and organic acids were respectively analysed by a gas chromatograph with electron capture detector (ECD) and high-performance ion chromatography (HPIC). Under aerobic conditions, MTBE was degraded in laboratory experiments. Only 4 of a total of 30 anaerobic experiments exhibited degradation, and the process was very slow. In no cases were metabolites detected, but a few degradation products (TBF, TBA and formic acid) were found on the site, possibly due to the lower temperatures in groundwater. The abiotic degradation of MTBE with an ion-exchange resin as a catalyst at pH 3.5 was much faster than hydrolysis in diluted hydrochloric acid (pH 1.0). Although the aerobic degradation of MTBE in the environment seems to be possible, the specific conditions responsible are widely unknown. Successful aerobic degradation only seems to take place if there is a lack of other utilisable compounds. However, MTBE is often accompanied by other fuel compounds on contaminated sites and anaerobic conditions

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

    DOE PAGES

    Ihli, Johannes; Clark, Jesse N.; Côté, Alexander S.; ...

    2016-06-15

    Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. In this study, we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO 3) 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 generatedmore » 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. In conclusion, 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.« less

  12. 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

  13. Emerging trends in the functional genomics of the abiotic stress response in crop plants.

    PubMed

    Vij, Shubha; Tyagi, Akhilesh K

    2007-05-01

    Plants are exposed to different abiotic stresses, such as water deficit, high temperature, salinity, cold, heavy metals and mechanical wounding, under field conditions. It is estimated that such stress conditions can potentially reduce the yield of crop plants by more than 50%. Investigations of the physiological, biochemical and molecular aspects of stress tolerance have been conducted to unravel the intrinsic mechanisms developed during evolution to mitigate against stress by plants. Before the advent of the genomics era, researchers primarily used a gene-by-gene approach to decipher the function of the genes involved in the abiotic stress response. However, abiotic stress tolerance is a complex trait and, although large numbers of genes have been identified to be involved in the abiotic stress response, there remain large gaps in our understanding of the trait. The availability of the genome sequences of certain important plant species has enabled the use of strategies, such as genome-wide expression profiling, to identify the genes associated with the stress response, followed by the verification of gene function by the analysis of mutants and transgenics. Certain components of both abscisic acid-dependent and -independent cascades involved in the stress response have already been identified. Information originating from the genome-wide analysis of abiotic stress tolerance will help to provide an insight into the stress-responsive network(s), and may allow the modification of this network to reduce the loss caused by stress and to increase agricultural productivity.

  14. A NAP-Family Histone Chaperone Functions in Abiotic Stress Response and Adaptation1[OPEN

    PubMed Central

    Pareek, Ashwani; Singla-Pareek, Sneh Lata

    2016-01-01

    Modulation of gene expression is one of the most significant molecular mechanisms of abiotic stress response in plants. Via altering DNA accessibility, histone chaperones affect the transcriptional competence of genomic loci. However, in contrast to other factors affecting chromatin dynamics, the role of plant histone chaperones in abiotic stress response and adaptation remains elusive. Here, we studied the physiological function of a stress-responsive putative rice (Oryza sativa) histone chaperone of the NAP superfamily: OsNAPL6. We show that OsNAPL6 is a nuclear-localized H3/H4 histone chaperone capable of assembling a nucleosome-like structure. Utilizing overexpression and knockdown approaches, we found a positive correlation between OsNAPL6 expression levels and adaptation to multiple abiotic stresses. Results of comparative transcriptome profiling and promoter-recruitment studies indicate that OsNAPL6 functions during stress response via modulation of expression of various genes involved in diverse functions. For instance, we show that OsNAPL6 is recruited to OsRad51 promoter, activating its expression and leading to more efficient DNA repair and abrogation of programmed cell death under salinity and genotoxic stress conditions. These results suggest that the histone chaperone OsNAPL6 may serve a regulatory role in abiotic stress physiology possibly via modulating nucleosome dynamics at various stress-associated genomic loci. Taken together, our findings establish a hitherto unknown link between histone chaperones and abiotic stress response in plants. PMID:27342307

  15. Comparison of rates of ureolysis between Sporosarcina pasteurii and an indigenous groundwater community under conditions required to precipitate large volumes of calcite

    NASA Astrophysics Data System (ADS)

    Tobler, Dominique J.; Cuthbert, Mark O.; Greswell, Richard B.; Riley, Michael S.; Renshaw, Joanna C.; Handley-Sidhu, Stephanie; Phoenix, Vernon R.

    2011-06-01

    Ureolysis-driven calcite precipitation has potential to seal porosity and fracture networks in rocks thus preventing groundwater flow and contaminant transport. In this study urea hydrolysis and calcite precipitation rates for the model bacterium Sporosarcina pasteurii were compared with those of indigenous groundwater communities under conditions required to precipitate large volumes of calcite (up to 50 g L -1). We conducted microcosm experiments in oxic artificial and anoxic natural groundwaters (collected from the Permo-Triassic sandstone aquifer at Birmingham, UK) that were inoculated with aerobically grown S. pasteurii. The rate constants for urea hydrolysis, kurea, ranged between 0.06 and 3.29 d -1 and were only affected by inoculum density. Higher Ca 2+ concentration (50-500 mM Ca 2+) as well as differences in fO 2 did not inhibit the ureolytic activity of S. pasteurii and did not significantly impact kurea. These results demonstrate that S. pasteurii has potential to improve calcite precipitation in both oxic and anoxic groundwaters, especially if indigenous communities lack ureolytic activity. Urea hydrolysis by indigenous groundwater communities was investigated in anoxic, natural groundwaters amended with urea and CaCl 2. A notable increase in ureolysis rates was measured only when these communities were stimulated with dilute nutrients (with best results from blackstrap molasses). Furthermore, there was a considerable lag time (12-20 days) before ureolysis and calcite precipitation began. Calculated ureolysis rate constants, kurea, ranged between 0.03 and 0.05 d -1 and were similar to kurea values produced by S. pasteurii at low inoculum densities. Overall, this comparative study revealed that the growth of ureolytic microorganisms present within groundwaters can easily be stimulated to enhance rates of urea hydrolysis in the subsurface, and thus can be used to induce calcite precipitation in these environments. The time required for urea hydrolysis to

  16. Abscisic Acid and abiotic stress signaling.

    PubMed

    Tuteja, Narendra

    2007-05-01

    Abiotic stress is severe environmental stress, which impairs crop production on irrigated land worldwide. Overall, the susceptibility or tolerance to the stress in plants is a coordinated action of multiple stress responsive genes, which also cross-talk with other components of stress signal transduction pathways. Plant responses to abiotic stress can be determined by the severity of the stress and by the metabolic status of the plant. Abscisic acid (ABA) is a phytohormone critical for plant growth and development and plays an important role in integrating various stress signals and controlling downstream stress responses. Plants have to adjust ABA levels constantly in responce to changing physiological and environmental conditions. To date, the mechanisms for fine-tuning of ABA levels remain elusive. The mechanisms by which plants respond to stress include both ABA-dependent and ABA-independent processes. Various transcription factors such as DREB2A/2B, AREB1, RD22BP1 and MYC/MYB are known to regulate the ABA-responsive gene expression through interacting with their corrosponding cis-acting elements such as DRE/CRT, ABRE and MYCRS/MYBRS, respectively. Understanding these mechanisms is important to improve stress tolerance in crops plants. This article first describes the general pathway for plant stress response followed by roles of ABA and transcription factors in stress tolerance including the regulation of ABA biosynthesis.

  17. Abscisic Acid and Abiotic Stress Signaling

    PubMed Central

    2007-01-01

    Abiotic stress is severe environmental stress, which impairs crop production on irrigated land worldwide. Overall, the susceptibility or tolerance to the stress in plants is a coordinated action of multiple stress responsive genes, which also cross-talk with other components of stress signal transduction pathways. Plant responses to abiotic stress can be determined by the severity of the stress and by the metabolic status of the plant. Abscisic acid (ABA) is a phytohormone critical for plant growth and development and plays an important role in integrating various stress signals and controlling downstream stress responses. Plants have to adjust ABA levels constantly in responce to changing physiological and environmental conditions. To date, the mechanisms for fine-tuning of ABA levels remain elusive. The mechanisms by which plants respond to stress include both ABA-dependent and ABA-independent processes. Various transcription factors such as DREB2A/2B, AREB1, RD22BP1 and MYC/MYB are known to regulate the ABA-responsive gene expression through interacting with their corrosponding cis-acting elements such as DRE/CRT, ABRE and MYCRS/MYBRS, respectively. Understanding these mechanisms is important to improve stress tolerance in crops plants. This article first describes the general pathway for plant stress response followed by roles of ABA and transcription factors in stress tolerance including the regulation of ABA biosynthesis. PMID:19516981

  18. 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...

  19. The radiogenic and stable Sr isotope geochemistry of basalt weathering in Iceland: Role of hydrothermal calcite and implications for long-term climate regulation

    NASA Astrophysics Data System (ADS)

    Andrews, M. Grace; Jacobson, Andrew D.

    2017-10-01

    Several studies have examined the geochemistry of Icelandic rivers to quantify the relationship between basalt weathering and long-term climate regulation. Recent research has suggested that the chemical weathering of hydrothermal and metamorphic calcite contributes significant quantities of HCO3- to the Icelandic riverine flux (Jacobson et al., 2015). Because the HCO3- derives from volcanic CO2 that was sequestered in mineral form prior to atmospheric injection, the strength of the basalt weathering feedback occurring in Iceland may be lower than previously realized. To test these hypotheses, we analyzed the radiogenic and stable Sr isotope composition (87Sr/86Sr and δ88/86Sr) of the same suite of water, rock, and mineral samples as examined in Jacobson et al. (2015), and we developed a simple model of the long-term C cycle that considers the transformation of volcanic CO2 to HCO3- during subsurface silicate weathering, which is a precursor to hydrothermal calcite formation. Interpretations based on 87Sr/86Sr and Ca/Sr ratios suggest that conservative, three-component mixing between basalt, calcite, and atmospheric deposition adequately explains river geochemistry. On average, the δ88/86Sr values of glacial and non-glacial rivers (0.414‰ and 0.388‰, respectively) are generally higher than those for basalt (0.276‰); however, calcite δ88/86Sr values (0.347‰) are also higher than those for basalt and span the range of riverine values. Thus, riverine δ88/86Sr values are also consistent three-component mixing between basalt, calcite, and atmospheric deposition. Isotopic fractionation is not required to explain riverine trends. Finally, model equations for the long-term C cycle demonstrate that subsurface silicate weathering reduces the magnitude of the volcanic CO2 degassing flux, which in turn causes the atmosphere to stabilize at lower pCO2 values compared to the case where no subsurface silicate weathering occurs. However, the proportion of the net

  20. Analysis of Cell Wall-Related Genes in Organs of Medicago sativa L. under Different Abiotic Stresses.

    PubMed

    Behr, Marc; Legay, Sylvain; Hausman, Jean-Francois; Guerriero, Gea

    2015-07-16

    Abiotic constraints are a source of concern in agriculture, because they can have a strong impact on plant growth and development, thereby affecting crop yield. The response of plants to abiotic constraints varies depending on the type of stress, on the species and on the organs. Although many studies have addressed different aspects of the plant response to abiotic stresses, only a handful has focused on the role of the cell wall. A targeted approach has been used here to study the expression of cell wall-related genes in different organs of alfalfa plants subjected for four days to three different abiotic stress treatments, namely salt, cold and heat stress. Genes involved in different steps of cell wall formation (cellulose biosynthesis, monolignol biosynthesis and polymerization) have been analyzed in different organs of Medicago sativa L. Prior to this analysis, an in silico classification of dirigent/dirigent-like proteins and class III peroxidases has been performed in Medicago truncatula and M. sativa. The final goal of this study is to infer and compare the expression patterns of cell wall-related genes in response to different abiotic stressors in the organs of an important legume crop.

  1. Analysis of Cell Wall-Related Genes in Organs of Medicago sativa L. under Different Abiotic Stresses

    PubMed Central

    Behr, Marc; Legay, Sylvain; Hausman, Jean-Francois; Guerriero, Gea

    2015-01-01

    Abiotic constraints are a source of concern in agriculture, because they can have a strong impact on plant growth and development, thereby affecting crop yield. The response of plants to abiotic constraints varies depending on the type of stress, on the species and on the organs. Although many studies have addressed different aspects of the plant response to abiotic stresses, only a handful has focused on the role of the cell wall. A targeted approach has been used here to study the expression of cell wall-related genes in different organs of alfalfa plants subjected for four days to three different abiotic stress treatments, namely salt, cold and heat stress. Genes involved in different steps of cell wall formation (cellulose biosynthesis, monolignol biosynthesis and polymerization) have been analyzed in different organs of Medicago sativa L. Prior to this analysis, an in silico classification of dirigent/dirigent-like proteins and class III peroxidases has been performed in Medicago truncatula and M. sativa. The final goal of this study is to infer and compare the expression patterns of cell wall-related genes in response to different abiotic stressors in the organs of an important legume crop. PMID:26193255

  2. The Stable Isotope Fractionation of Abiotic Reactions: A Benchmark in the Detection of Life

    NASA Technical Reports Server (NTRS)

    Summers, David P.

    2003-01-01

    One very important tool in the analysis of biogenic, and potentially biogenic, samples is the study of their stable isotope distributions. The isotope distribution of a sample depends on the process(es) that created it. One important application of the analysis of C & N stable isotope ratios has been in the determination of whether organic matter in a sample is of biological origin or was produced abiotically. For example, the delta C-13 of organic material found embedded in phosphate grains was cited as a critical part of the evidence for life in 3.8 billion year old samples. The importance of such analysis in establishing biogenicity was highlighted again by the role this issue played in the recent debate over the validity of what had been accepted as the Earth s earliest microfossils. These kinds of analysis imply a comparison with the fractionation that one would have seen if the organic material had been produced by alternative, abiotic, pathways. Could abiotic reactions account for the same level of fractionation? Additionally, since the fractionation can vary between different abiotic reactions, understanding their fractionations can be important in distinguishing what reactions may have been significant in the formation of different abiological samples (such as extraterrestrial samples). There is however, a scarcity of data on the fractionation of carbon and nitrogen by abiotic reactions. In order to interpret properly what the stable isotope ratios of samples tell us about their biotic or abiotic nature, more needs to be known about how abiotic reactions fractionate C and N. Carbon isotope fractionations have been studied for a few abiotic processes. These studies presumed the presence of a reducing atmosphere, focusing on reactions involving spark discharge, W photolysis of reducing gas mixtures, and cyanide polymerization in the presence of ammonia. They did find that the initial products showed a depletion in I3C with values in the range of a few per

  3. Calcite precipitation on glass substrates and active stalagmites in Katerloch Cave (Austria): Constraints from environmental monitoring

    NASA Astrophysics Data System (ADS)

    Sakoparnig, Marlene; Boch, Ronny; Wang, Xianfeng; Lin, Ke; Spötl, Christoph; Leis, Albrecht; Gollowitsch, Anna; Dietzel, Martin

    2016-04-01

    Located near Graz at the SE-rim of the Alps Katerloch is well-known for its impressive dripstone decoration, e.g. several metres tall and relatively fast growing (0.2-0.7 mm/yr on average) candle-stick-type stalagmites. In the course of an ongoing multi-annual and partially high-resolution cave monitoring program we study modern (active) sites of carbonate deposition focusing on the site-specific growth dynamics and connection of modern regional and cave environmental conditions with petrographic, chemical and stable isotopic information captured in the speleothems. Fresh calcite precipitates on artificial (glass) substrates underneath active drip sites were collected continuously from 2006 to 2014 (eight years!). The samples (up to 7 mm thick) represent cave sections of different temperature and drip sites of partially different characteristics (e.g. drip rate). We also recovered short drill cores (up to 3 cm length, 1 cm diameter) from the top of active stalagmites probably representing the last decades to centuries of calcite crystallization. Moreover, an actively growing stalagmite (K10) comprising both modern and past calcite deposition was collected. 238U-234U-230Th dating using MC-ICP-MS of K10 (71 cm long) revealed several distinct growth intervals (separated by growth interruptions) starting at 129.1 ±1.2 kyr BP (Last Interglacial) up to now, mostly reflecting warm and humid climate intervals. High-resolution (100 μm) isotope profiles micromilled from the multi-annual modern calcite precipitates on artificial substrates revealed low δ13C values of -12.8 to -8.3 ‰ (VPDB) and relatively high δ18O of -6.9 to -4.9 ‰Ṫhe δ18O curves from all collection sites (different growth rate) record a pronounced decrease during their most recent growth period most likely corresponding to a significant decrease towards lower oxygen isotope values observed in drip waters collected in the year 2014 compared with samples from 2005 to 2007. Drip water δ2H /δ18O

  4. Comparison of the Abiotic Preferences of Macroinvertebrates in Tropical River Basins

    PubMed Central

    Everaert, Gert; De Neve, Jan; Boets, Pieter; Dominguez-Granda, Luis; Mereta, Seid Tiku; Ambelu, Argaw; Hoang, Thu Huong; Goethals, Peter L. M.; Thas, Olivier

    2014-01-01

    We assessed and compared abiotic preferences of aquatic macroinvertebrates in three river basins located in Ecuador, Ethiopia and Vietnam. Upon using logistic regression models we analyzed the relationship between the probability of occurrence of five macroinvertebrate families, ranging from pollution tolerant to pollution sensitive, (Chironomidae, Baetidae, Hydroptilidae, Libellulidae and Leptophlebiidae) and physical-chemical water quality conditions. Within the investigated physical-chemical ranges, nine out of twenty-five interaction effects were significant. Our analyses suggested river basin dependent associations between the macroinvertebrate families and the corresponding physical-chemical conditions. It was found that pollution tolerant families showed no clear abiotic preference and occurred at most sampling locations, i.e. Chironomidae were present in 91%, 84% and 93% of the samples taken in Ecuador, Ethiopia and Vietnam. Pollution sensitive families were strongly associated with dissolved oxygen and stream velocity, e.g. Leptophlebiidae were only present in 48%, 2% and 18% of the samples in Ecuador, Ethiopia and Vietnam. Despite some limitations in the study design, we concluded that associations between macroinvertebrates and abiotic conditions can be river basin-specific and hence are not automatically transferable across river basins in the tropics. PMID:25279673

  5. A Central Role for Thiols in Plant Tolerance to Abiotic Stress

    PubMed Central

    Zagorchev, Lyuben; Seal, Charlotte E.; Kranner, Ilse; Odjakova, Mariela

    2013-01-01

    Abiotic stress poses major problems to agriculture and increasing efforts are being made to understand plant stress response and tolerance mechanisms and to develop new tools that underpin successful agriculture. However, the molecular mechanisms of plant stress tolerance are not fully understood, and the data available is incomplete and sometimes contradictory. Here, we review the significance of protein and non-protein thiol compounds in relation to plant tolerance of abiotic stress. First, the roles of the amino acids cysteine and methionine, are discussed, followed by an extensive discussion of the low-molecular-weight tripeptide, thiol glutathione, which plays a central part in plant stress response and oxidative signalling and of glutathione-related enzymes, including those involved in the biosynthesis of non-protein thiol compounds. Special attention is given to the glutathione redox state, to phytochelatins and to the role of glutathione in the regulation of the cell cycle. The protein thiol section focuses on glutaredoxins and thioredoxins, proteins with oxidoreductase activity, which are involved in protein glutathionylation. The review concludes with a brief overview of and future perspectives for the involvement of plant thiols in abiotic stress tolerance. PMID:23549272

  6. Comparison of the abiotic preferences of macroinvertebrates in tropical river basins.

    PubMed

    Everaert, Gert; De Neve, Jan; Boets, Pieter; Dominguez-Granda, Luis; Mereta, Seid Tiku; Ambelu, Argaw; Hoang, Thu Huong; Goethals, Peter L M; Thas, Olivier

    2014-01-01

    We assessed and compared abiotic preferences of aquatic macroinvertebrates in three river basins located in Ecuador, Ethiopia and Vietnam. Upon using logistic regression models we analyzed the relationship between the probability of occurrence of five macroinvertebrate families, ranging from pollution tolerant to pollution sensitive, (Chironomidae, Baetidae, Hydroptilidae, Libellulidae and Leptophlebiidae) and physical-chemical water quality conditions. Within the investigated physical-chemical ranges, nine out of twenty-five interaction effects were significant. Our analyses suggested river basin dependent associations between the macroinvertebrate families and the corresponding physical-chemical conditions. It was found that pollution tolerant families showed no clear abiotic preference and occurred at most sampling locations, i.e. Chironomidae were present in 91%, 84% and 93% of the samples taken in Ecuador, Ethiopia and Vietnam. Pollution sensitive families were strongly associated with dissolved oxygen and stream velocity, e.g. Leptophlebiidae were only present in 48%, 2% and 18% of the samples in Ecuador, Ethiopia and Vietnam. Despite some limitations in the study design, we concluded that associations between macroinvertebrates and abiotic conditions can be river basin-specific and hence are not automatically transferable across river basins in the tropics.

  7. Inhibition of phosphorus sorption on calcite by dairy manure-sourced DOC.

    PubMed

    Weyers, Eva; Strawn, Daniel G; Peak, Derek; Baker, Leslie L

    2017-10-01

    In confined animal feeding operations, such as dairies, manure is amended to soils at high rates leading to increases in P and organic matter in the soils. Phosphorus reacts with soil-Ca to form Ca-P minerals, which controls P availability for leaching and transport through the watershed. In this research, the effects of manure sourced dissolved organic matter (DOM) on P sorption on calcite were measured at different reaction times and concentrations. Reactions were monitored in 1% and 10% manure-to-water extract solutions spiked with P. When manure-DOM was present, a significant reduction in P sorption occurred (2-90% absolute decrease) compared to samples without manure-DOM. The greatest decrease occurred in the samples reacted in the 10% manure solution. XANES spectroscopic analysis showed that at 1% manure solution, a Ca-P phase similar to hydroxyapatite formed. In the calcite samples reacted in the 10% manure solution, K-edge XANES spectroscopy revealed that P occurred as a Ca-Mg-P phase instead of the less soluble hydroxyapatite-like phase. Results from this study suggest that in manure-amended calcareous soils, increased DOM from manure will decrease P sorption capacity and increase the overall P concentration in solution, which will increase the mobility of P and subsequently pose greater risks for impairment of surface water quality. Copyright © 2017 Elsevier Ltd. All rights reserved.

  8. Biomimetic synthesis of calcite films by a polymer-induced liquid-precursor (PILP) process. 1. Influence and incorporation of magnesium

    NASA Astrophysics Data System (ADS)

    Cheng, Xingguo; Varona, Philip L.; Olszta, Matthew J.; Gower, Laurie B.

    2007-09-01

    Magnesium-bearing calcium carbonate films have been synthesized via a polymer-induced liquid-precursor (PILP) mineralization process. A variety of morphological features of biominerals can be mimicked with this PILP process; therefore, our group has proposed that this crystallization system can be used as an effective in vitro model system for examining mechanistic issues related to biomineralization. Here, the effect of the Mg 2+/Ca 2+ ratio on the rate of transformation of the amorphous precursor films was investigated using polarized optical microscopy (POM), and the final crystalline structure and composition were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), inductively coupled plasma spectroscopy (ICP) and energy dispersive spectroscopy (EDS). The entrapment of high levels of magnesium in the deposited precursor films had a pronounced inhibitory effect on the amorphous to crystalline transformation, and furthermore, influenced the polycrystalline nature of the film. The magnesium content incorporated within the calcite lattice (8-26%) resembles the range found in biologically formed high magnesium-bearing calcite, while much lower levels were formed via the conventional solution crystallization process. The formation of non-equilibrium morphologies and similar compositions of magnesium-bearing calcite via the PILP process further supports our hypothesis that the PILP process may play a fundamental role in the formation of calcitic biominerals in nature. In the realm of biomimetic engineering, the PILP process may also establish itself as a new method to produce thin ceramic films with variable compositions under ambient conditions.

  9. Temperature Dependence of the Structural Parameters in the Transformation of Aragonite to Calcite, as Determined from In Situ Synchrotron Powder X-ray-Diffratction Data

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Antao, Sytle M.; Hassan, Ishmael; West Indies)

    The temperature dependency of the crystal structure and the polymorphic transition of CaCO{sub 3} from aragonite to calcite were studied using Rietveld structure refinement and high-temperature in situ synchrotron powder X-ray-diffraction data at ambient pressure, P. The orthorhombic metastable aragonite at room P, space group Pmcn, transforms to trigonal calcite, space group R{bar 3}c, at about T{sub c} = 468 C. This transformation occurs rapidly; it starts at about 420 C and is completed by 500 C, an 80 C interval that took about 10 minutes using a heating rate of 8 C/min. Structurally, from aragonite to calcite, the distributionmore » of the Ca atom changes from approximately hexagonal to cubic close-packing. A 5.76% discontinuous increase in volume accompanies the reconstructive first-order transition. Besides the change in coordination of the Ca atom from nine to six from aragonite to calcite, the CO{sub 3} groups change by a 30{sup o} rotation across the transition.« less

  10. Changes in abiotic influences on seed plants and ferns during 18 years of primary succession on Puerto Rican landslides

    Treesearch

    Lawrence R. Walker; Aaron B. Shiels; Peter J. Bellingham; Ashley D. Sparrow; Ned Fetcher; Fred H. Landau; Deborah J. Lodge

    2013-01-01

    Abiotic variables are critical drivers of succession in most primary seres, but how their influence on biota changes over time is rarely examined. Landslides provide good model systems for examining abiotic influences because they are spatially and temporally heterogeneous habitats with distinct abiotic and biotic gradients and post-landslide erosion. In an 18-year...

  11. Transcriptomic Profiling of the Maize (Zea mays L.) Leaf Response to Abiotic Stresses at the Seedling Stage.

    PubMed

    Li, Pengcheng; Cao, Wei; Fang, Huimin; Xu, Shuhui; Yin, Shuangyi; Zhang, Yingying; Lin, Dezhou; Wang, Jianan; Chen, Yufei; Xu, Chenwu; Yang, Zefeng

    2017-01-01

    Abiotic stresses, including drought, salinity, heat, and cold, negatively affect maize ( Zea mays L.) development and productivity. To elucidate the molecular mechanisms of resistance to abiotic stresses in maize, RNA-seq was used for global transcriptome profiling of B73 seedling leaves exposed to drought, salinity, heat, and cold stress. A total of 5,330 differentially expressed genes (DEGs) were detected in differential comparisons between the control and each stressed sample, with 1,661, 2,019, 2,346, and 1,841 DEGs being identified in comparisons of the control with salinity, drought, heat, and cold stress, respectively. Functional annotations of DEGs suggested that the stress response was mediated by pathways involving hormone metabolism and signaling, transcription factors (TFs), very-long-chain fatty acid biosynthesis and lipid signaling, among others. Of the obtained DEGs (5,330), 167 genes are common to these four abiotic stresses, including 10 up-regulated TFs (five ERFs, two NACs, one ARF, one MYB, and one HD-ZIP) and two down-regulated TFs (one b-ZIP and one MYB-related), which suggested that common mechanisms may be initiated in response to different abiotic stresses in maize. This study contributes to a better understanding of the molecular mechanisms of maize leaf responses to abiotic stresses and could be useful for developing maize cultivars resistant to abiotic stresses.

  12. Abiotic stress QTL in lettuce crop–wild hybrids: comparing greenhouse and field experiments

    PubMed Central

    Hartman, Yorike; Hooftman, Danny A P; Uwimana, Brigitte; Schranz, M Eric; van de Wiel, Clemens C M; Smulders, Marinus J M; Visser, Richard G F; Michelmore, Richard W; van Tienderen, Peter H

    2014-01-01

    The development of stress-tolerant crops is an increasingly important goal of current crop breeding. A higher abiotic stress tolerance could increase the probability of introgression of genes from crops to wild relatives. This is particularly relevant to the discussion on the risks of new GM crops that may be engineered to increase abiotic stress resistance. We investigated abiotic stress QTL in greenhouse and field experiments in which we subjected recombinant inbred lines from a cross between cultivated Lactuca sativa cv. Salinas and its wild relative L. serriola to drought, low nutrients, salt stress, and aboveground competition. Aboveground biomass at the end of the rosette stage was used as a proxy for the performance of plants under a particular stress. We detected a mosaic of abiotic stress QTL over the entire genome with little overlap between QTL from different stresses. The two QTL clusters that were identified reflected general growth rather than specific stress responses and colocated with clusters found in earlier studies for leaf shape and flowering time. Genetic correlations across treatments were often higher among different stress treatments within the same experiment (greenhouse or field), than among the same type of stress applied in different experiments. Moreover, the effects of the field stress treatments were more correlated with those of the greenhouse competition treatments than to those of the other greenhouse stress experiments, suggesting that competition rather than abiotic stress is a major factor in the field. In conclusion, the introgression risk of stress tolerance (trans-)genes under field conditions cannot easily be predicted based on genomic background selection patterns from controlled QTL experiments in greenhouses, especially field data will be needed to assess potential (negative) ecological effects of introgression of these transgenes into wild relatives. PMID:25360276

  13. Understanding the Interaction of Peptides and Proteins with Abiotic Surfaces: Towards Water-Free Biologics

    DTIC Science & Technology

    2018-02-03

    peptides immobilized on abiotic surfaces depends upon a) the chemical and physical nature of the abiotic surface; b) the physicochemical properties of... dependent model of protein aggregation, aggregation proceeds only after a lag phase in which the concentration of energetically unfavorable nuclei reaches...time dependent kinetics or dynamics at such interfaces. This paper focuses on these three most important advantages of SFG and reviews some of the

  14. 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.

  15. 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.

  16. 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

  17. Massive production of abiotic methane during subduction evidenced in metamorphosed ophicarbonates from the Italian Alps

    PubMed Central

    Vitale Brovarone, Alberto; Martinez, Isabelle; Elmaleh, Agnès; Compagnoni, Roberto; Chaduteau, Carine; Ferraris, Cristiano; Esteve, Imène

    2017-01-01

    Alteration of ultramafic rocks plays a major role in the production of hydrocarbons and organic compounds via abiotic processes on Earth and beyond and contributes to the redistribution of C between solid and fluid reservoirs over geological cycles. Abiotic methanogenesis in ultramafic rocks is well documented at shallow conditions, whereas natural evidence at greater depths is scarce. Here we provide evidence for intense high-pressure abiotic methanogenesis by reduction of subducted ophicarbonates. Protracted (≥0.5–1 Ma), probably episodic infiltration of reduced fluids in the ophicarbonates and methanogenesis occurred from at least ∼40 km depth to ∼15–20 km depth. Textural, petrological and isotopic data indicate that methane reached saturation triggering the precipitation of graphitic C accompanied by dissolution of the precursor antigorite. Continuous infiltration of external reducing fluids caused additional methane production by interaction with the newly formed graphite. Alteration of high-pressure carbonate-bearing ultramafic rocks may represent an important source of abiotic methane, with strong implications for the mobility of deep C reservoirs. PMID:28223715

  18. Hydroxyapatite coatings for marble protection: Optimization of calcite covering and acid resistance

    NASA Astrophysics Data System (ADS)

    Graziani, Gabriela; Sassoni, Enrico; Franzoni, Elisa; Scherer, George W.

    2016-04-01

    Hydroxyapatite (HAP) has a much lower dissolution rate and solubility than calcite, especially in an acidic environment, so it has been proposed for the protection of marble against acidic rain corrosion. Promising results were obtained, but further optimization is necessary as the treated layer is often incomplete, cracked and/or porous. In this paper, several parameters were investigated to obtain a coherent, uncracked layer, and to avoid the formation of metastable, soluble phases instead of HAP: the role of the pH of the starting solution; the effect of organic and inorganic additions, and in particular that of ethanol, as it is reported to adsorb on calcite, hence possibly favoring the growth of the HAP layer. Finally, a double application of the treatment was tested. Results were compared to those obtained with ammonium oxalate treatment, widely investigated for marble protection. Results indicate that adding small amounts of ethanol to the formulation remarkably increases the acid resistance of treated samples, and yields better coverage of the surface without crack formation. The effectiveness of the treatment is further enhanced when a second treatment is applied. The efficacy of ethanol-doped DAP mixtures was found to be remarkably higher than that of ammonium oxalate based treatments.

  19. Biotic and abiotic factors predicting the global distribution and population density of an invasive large mammal

    PubMed Central

    Lewis, Jesse S.; Farnsworth, Matthew L.; Burdett, Chris L.; Theobald, David M.; Gray, Miranda; Miller, Ryan S.

    2017-01-01

    Biotic and abiotic factors are increasingly acknowledged to synergistically shape broad-scale species distributions. However, the relative importance of biotic and abiotic factors in predicting species distributions is unclear. In particular, biotic factors, such as predation and vegetation, including those resulting from anthropogenic land-use change, are underrepresented in species distribution modeling, but could improve model predictions. Using generalized linear models and model selection techniques, we used 129 estimates of population density of wild pigs (Sus scrofa) from 5 continents to evaluate the relative importance, magnitude, and direction of biotic and abiotic factors in predicting population density of an invasive large mammal with a global distribution. Incorporating diverse biotic factors, including agriculture, vegetation cover, and large carnivore richness, into species distribution modeling substantially improved model fit and predictions. Abiotic factors, including precipitation and potential evapotranspiration, were also important predictors. The predictive map of population density revealed wide-ranging potential for an invasive large mammal to expand its distribution globally. This information can be used to proactively create conservation/management plans to control future invasions. Our study demonstrates that the ongoing paradigm shift, which recognizes that both biotic and abiotic factors shape species distributions across broad scales, can be advanced by incorporating diverse biotic factors. PMID:28276519

  20. Are karrikins involved in plant abiotic stress responses?

    PubMed

    Li, Weiqiang; Tran, Lam-Son Phan

    2015-09-01

    Recent reports have shown that strigolactones play a positive role in plant responses to drought and salt stress through MAX2 (More Axillary Growth 2). Increasing evidence suggests that MAX2 is also involved in karrikin signaling, raising the question whether karrikins play any role in plant adaptation to abiotic stresses. Copyright © 2015 Elsevier Ltd. All rights reserved.