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Sample records for biogenic calcite crystals

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

    Science.gov (United States)

    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.

  2. Transformation and Crystallization Energetics of Synthetic and Biogenic Amorphous Calcium Carbonate

    Energy Technology Data Exchange (ETDEWEB)

    Radha, A. V. [Peter A. Rock Thermochemistry Lab. and Nanomaterials in the Environment, Agriculture, and Technology Organized Research Unit (NEAT ORU), Univ. of California, Davis, CA (United States); Forbes, Tori Z. [Peter A. Rock Thermochemistry Lab. and Nanomaterials in the Environment, Agriculture, and Technology Organized Research Unit (NEAT ORU), Univ. of California, Davis, CA (United States); Killian, Christopher E. [Univ. of Wisconsin, Madison, WI (United States); Gilbert, P.U.P.A [Univ. of Wisconsin, Madison, WI (United States); Navrotsky, Alexandra [Peter A. Rock Thermochemistry Lab. and Nanomaterials in the Environment, Agriculture, and Technology Organized Research Unit (NEAT ORU), Univ. of California, Davis, CA (United States)

    2010-01-01

    Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC → less metastable hydrated ACC→anhydrous ACC ~ biogenic anhydrous ACC→vaterite → aragonite → calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO₂ sequestration.

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

    Science.gov (United States)

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

    2013-08-07

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

  4. Quantitative laboratory measurements of biogeochemical processes controlling biogenic calcite carbon sequestration.

    Energy Technology Data Exchange (ETDEWEB)

    Zendejas, Frank; Lane, Todd W.; Lane, Pamela D.

    2011-01-01

    The purpose of this LDRD was to generate data that could be used to populate and thereby reduce the uncertainty in global carbon cycle models. These efforts were focused on developing a system for determining the dissolution rate of biogenic calcite under oceanic pressure and temperature conditions and on carrying out a digital transcriptomic analysis of gene expression in response to changes in pCO2, and the consequent acidification of the growth medium.

  5. Biogenic processes in crystalline bedrock fractures indicated by carbon isotope signatures of secondary calcite

    International Nuclear Information System (INIS)

    Sahlstedt, Elina; Karhu, Juha A.; Pitkänen, Petteri; Whitehouse, Martin

    2016-01-01

    34–54 m showed evidence of localized methanotrophic activity seen as anomalously 13 C depleted calcite, having δ 13 C values as low as −53.8‰. At depths of ∼60–400 m, positive δ 13 C values of up to +31.6‰ in late-stage calcite of Group 1–2 indicated methanogenesis. In comparison, high CH 4 concentrations in present day groundwaters are found at depths of >300 m. One sample at a depth of 111 m showed a transition from methanogenetic conditions (calcite bearing methanogenetic signature) to sulfate reducing (precipitation of pyrite on calcite surface), however, the timing of this transition is so far unclear. The results from this study gives indications of the complex nature of sulfur and carbon cycling in fractured crystalline environments and highlights the usefulness of in situ stable isotope analysis. - Highlights: • The carbon isotope variation in fracture calcite was measured in situ. • The δ 13 C values were used to investigate carbon sources and cycling in fractured rock. • Information on biogenic processes in the paleogroundwaters was gained.

  6. Biogenic Crystal and New Materials

    International Nuclear Information System (INIS)

    Bigi, A.; Falini, G.; Gazzano, M.; Roveri, N.; Ripamonti, A.; CNR, Bologna

    1998-01-01

    Organism use inorganic compounds to form inorganic-organic structured composites, with remarkable properties and functions. The target of many laboratory experiments is the natural processes simulation, in order to understand the molecular recognition process between the nucleation sites on the macromolecular matrix and the ions on the growing crystal nuclei. The understanding of biological phenomena opens new routes to the design of new materials or to the improvement of ceramics, polymers, semiconductors and composites [it

  7. Assessing the potential for using biogenic calcites as dosemeters for luminescence dating

    International Nuclear Information System (INIS)

    Duller, G.A.T.; Penkman, K.E.H.; Wintle, A.G.

    2009-01-01

    Calcium carbonate emits an intense thermoluminescence (TL) signal and previous work has explored the potential of using this signal to date both inorganic carbonates such as limestones and stalagmites and biogenic calcite produced by marine organisms. Luminescence analysis of biogenic calcites directly dates the secretion of the mineral by the organism and is therefore not reliant upon exposure of the sample to daylight. A method is outlined for using the TL signals from slug plates, from the Limacidae family, and opercula from the snail Bithynia tentaculata to construct a single-aliquot regenerative-dose growth curve. Analysis of slug plates from a number of Quaternary sites show that the equivalent dose (D e ) of a late Holocene sample is close to zero and that the D e increases with age over the last 500 ka. The TL signal from snail opercula is shown to increase up to doses over 4000 Gy. Replicate measurements from 16 opercula from a site ∼220 ka show a broad distribution. Potential causes of this scatter are discussed along with recommendations about how it could be reduced. The major challenge which remains to be solved before slug plates or snail opercula could be used to calculate ages is to develop methods for calculating the dose rate received during burial.

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

    Science.gov (United States)

    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

  9. Controls on the precipitation of barite (BaSO 4) crystals in calcite travertine at Twitya Spring, a warm sulphur spring in Canada's Northwest Territories

    Science.gov (United States)

    Bonny, Sandy M.; Jones, Brian

    2008-01-01

    Twitya Spring discharges warm (24 °C), anoxic, sulphide-, calcium- (65 ppm) and barium- (≥ 0.78 ppm) rich spring water to a steep flow path that is inhabited by streamer and mat-forming microbes ( Thiothrix, Beggiatoa, Oscillatoria, Spirulina, diatoms, rod shaped bacteria). Oxidation and CO 2 degassing drive precipitation of elemental sulphur, barite, opaline silica, and calcite. A mound of travertine at the base of the flow path, dominantly composed of bedded barium-enriched crystallographic and noncrystallographic dendritic calcite crystals and calcite cements, hosts three types of barite crystals: type 1 (T1) intergrown tabular crystals that formed in solution, type 2 (T2) tabular and rhombic crystals that nucleated on calcite, and type 3 (T3) subhedral and anhedral microcrystals that nucleated on microbial cell surfaces and in microbial extracellular polymeric substances. The formation and distribution of T1, T2, and T3 barite in the Twitya Spring flow path are controlled by physiochemical gradients, calcite precipitation rates, and adsorption of barium to microbial biomass, all of which vary seasonally and episodically at Twitya Spring. The complex physiochemical and biological controls on barite formation at Twitya Spring both suggest that the classification of biogenic or inorganic sedimentary barite on the basis of crystal size and morphology may be oversimplified. There is also the potential that primary and authigenic barite crystals hosted in carbonates may yield information about the microbial ecology and ambient physiochemistry of their depositional environments.

  10. Biogenic calcite particles from microalgae—Coccoliths as a potential raw material

    Science.gov (United States)

    Chairopoulou, Makrina Artemis; Vučak, Marijan; Posten, Clemens; Teipel, Ulrich

    2017-01-01

    Synthetic calcite (CaCO3) particles are found in a broad range of applications. The geometry of particles produced from limestone or precipitation are versatile but limited to basic shapes. The microalga Emiliania huxleyi produces micro‐structured calcite platelets, called coccoliths. This article presents the results of an application‐orientated study, which includes characteristic values also used in the calcite industry for particle evaluation. It is demonstrated that coccoliths are significantly different from all industrial particles produced so far. Coccoliths are porous particles, mainly consisted of calcium carbonate, with further elements such as Mg, Si, Sr, and Fe often embedded in their structure. Their structure is extremely sophisticated, while the overall particle morphology and particle size distribution are homogeneous. This study gives a first inside into the potential of these exceptional objects and may set further impulses for their utilization in specific calcite particle applications. PMID:28701909

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

    Science.gov (United States)

    Murai, Rie

    2013-01-01

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

  12. Galacturonomannan and Golgi-derived membrane linked to growth and shaping of biogenic calcite

    Science.gov (United States)

    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.

  13. High surface area calcite

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  15. Morphological changes of calcite single crystals induced by graphene-biomolecule adducts

    Science.gov (United States)

    Calvaresi, Matteo; Di Giosia, Matteo; Ianiro, Alessandro; Valle, Francesco; Fermani, Simona; Polishchuk, Iryna; Pokroy, Boaz; Falini, Giuseppe

    2017-01-01

    Calcite has the capability to interact with a wide variety of molecules. This usually induces changes in shape and morphology of crystals. Here, this process was investigated using sheets of graphene-biomolecule adducts. They were prepared and made dispersible in water through the exfoliation of graphite by tip sonication in the presence tryptophan or N-acetyl-D-glucosamine. The crystallization of calcium carbonate in the presence of these additives was obtained by the vapor diffusion method and only calcite formed. The analysis of the microscopic observations showed that the graphene-biomolecule adducts affected shape and morphology of rhombohedral {10.4} faced calcite crystals, due to their stabilization of additional {hk.0} faces. The only presence of the biomolecule affected minimally shape and morphology of calcite crystals, highlighting the key role of the graphene sheets as 2D support for the adsorption of the biomolecules.

  16. Investigating the Basis of Biogenic Calcium Carbonate Formation from an Amorphous Precursor: Nature of the Transformation to Calcite on Hydroxyl Functionalized Surfaces

    Science.gov (United States)

    Wang, D.; Lee, J. R.; Talley, C. E.; Murphy, K. E.; Han, T. Y.; Deyoreo, J. J.; Dove, P. M.

    2006-12-01

    Calcium carbonate biominerals are particularly significant because of their direct role in regulating the global carbon cycle, as well as their ubiquitous occurrence across earth environments. Biogenic carbonates are further distinguished by their broad phlyogenetic distribution; hence it has been suggested that unrelated eukaryotes must have used similar biochemical strategies to control mineralization. Recent studies have shown that an amorphous calcium carbonate (ACC) phase potentially plays a key role in the initial formation of carbonate minerals and in "shaping" them into complex morphologies widely seen in biominerals. Echinoderms, mollusks, and possibly many other organisms use ACC as a precursor phase that is first nucleated in cellularly controlled environments such as vesicles and subsequently transforms into a fully crystalline material. Recent studies on sea urchin embryos have shown that during transformation ACC develops short range that resembles calcite before fully crystallizing and serve as inspiration for our studies in synthetic systems. Self-assembled monolayers (SAM) on gold and silver have been used as simple model systems that approximate biological surfaces. Many studies have shown that thiol monolayers with hydroxyl termination stabilize a transitory ACC film that with prolonged exposure to aqueous solution transforms into calcite nucleated on {104} faces. Using Near Edge X-ray Absorption Fine Structure (NEXAFS) we studied SAM/mineral interactions with well ordered mercaptophenol monolayers showed that when these films are first exposed to calcium carbonate solutions, they become disordered and remain so after subsequent deposition of an ACC over-layer. Yet calcite nucleates and grows from the surface bound ACC with predominantly {104} orientation, which suggests a dynamic structural relationship between the SAMs and the mineral phase. While the monolayer/mineral phase interaction has been characterized, the mechanism for nucleating

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

    Science.gov (United States)

    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

  18. Crystallization of biogenic hydrous amorphous silica

    Science.gov (United States)

    Kyono, A.; Yokooji, M.; Chiba, T.; Tamura, T.; Tuji, A.

    2017-12-01

    Diatom, Nitzschia cf. frustulum, collected from Lake Yogo, Siga prefecture, Japan was cultured in laboratory. Organic components of the diatom cell were removed by washing with acetone and sodium hypochlorite. The remaining frustules were studied by SEM-EDX, FTIR spectroscopy, and synchrotron X-ray diffraction. The results showed that the spindle-shaped morphology of diatom frustule was composed of hydrous amorphous silica. Pressure induced phase transformation of the diatom frustule was investigated by in situ Raman spectroscopic analysis. With exposure to 0.3 GPa at 100 oC, Raman band corresponding to quartz occurred at ν = 465 cm-1. In addition, Raman bands known as a characteristic Raman pattern of moganite was also observed at 501 cm-1. From the integral ratio of Raman bands, the moganite content in the probed area was estimated to be approximately 50 wt%. With the pressure and temperature effect, the initial morphology of diatom frustule was completely lost and totally changed to a characteristic spherical particle with a diameter of about 2 mm. With keeping the compression of 5.7 GPa at 100 oC, a Raman band assignable to coesite appeared at 538 cm-1. That is, with the compression and heating, the hydrous amorphous silica can be readily crystallized into quartz, moganite, and coesite. The first-principles calculations revealed that a disiloxane molecule stabilized in a trans configuration is twisted 60o and changed into the cis configuration with a close approach of water molecule. It is therefore a reasonable assumption that during crystallization of hydrous amorphous silica, the Si-O-Si bridging unit with the cis configuration would survive as a structural defect and then crystallized into moganite by keeping the geometry. This hypothesis is adaptable to the phase transformation from hydrous amorphous silica to coesite as well, because coesite has the four-membered rings and easily formed from the hydrous amorphous silica under high pressure and high

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

    Science.gov (United States)

    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.

  20. Amelogenin processing by MMP-20 prevents protein occlusion inside calcite crystals.

    Science.gov (United States)

    Bromley, Keith M; Lakshminarayanan, Rajamani; Thompson, Mitchell; Lokappa, Sowmya B; Gallon, Victoria A; Cho, Kang R; Qiu, S Roger; Moradian-Oldak, Janet

    2012-10-03

    Calcite crystals were grown in the presence of full-length amelogenin and during its proteolysis by recombinant human matrix metalloproteinase 20 (rhMMP-20). Recombinant porcine amelogenin (rP172) altered the shape of calcite crystals by inhibiting the growth of steps on the {104} faces and became occluded inside the crystals. Upon co-addition of rhMMP-20, the majority of the protein was digested resulting in a truncated amelogenin lacking the C-terminal segment. In rP172-rhMMP-20 samples, the occlusion of amelogenin into the calcite crystals was drastically decreased. Truncated amelogenin (rP147) and the 25-residue C-terminal domain produced crystals with regular shape and less occluded organic material. Removal of the C-terminal diminished the affinity of amelogenin to the crystals and therefore prevented occlusion. We hypothesize that HAP and calcite interact with amelogenin in a similar manner. In the case of each material, full-length amelogenin binds most strongly, truncated amelogenin binds weakly and the C-terminus alone has the weakest interaction. Regarding enamel crystal growth, the prevention of occlusion into maturing enamel crystals might be a major benefit resulting from the selective cleavage of amelogenin at the C-terminus by MMP-20. Our data have important implications for understanding the hypomineralized enamel phenotype in cases of amelogenesis imperfecta resulting from MMP-20 mutations and will contribute to the design of enamel inspired biomaterials.

  1. The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite.

    Science.gov (United States)

    Rodriguez-Blanco, Juan Diego; Shaw, Samuel; Benning, Liane G

    2011-01-01

    The kinetics and mechanisms of nanoparticulate amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite, were studied at a range of environmentally relevant temperatures (7.5-25 °C) using synchrotron-based in situ time-resolved Energy Dispersive X-ray Diffraction (ED-XRD) in conjunction with high-resolution electron microscopy, ex situ X-ray diffraction and infrared spectroscopy. The crystallization process occurs in two stages; firstly, the particles of ACC rapidly dehydrate and crystallize to form individual particles of vaterite; secondly, the vaterite transforms to calcite via a dissolution and reprecipitation mechanism with the reaction rate controlled by the surface area of calcite. The second stage of the reaction is approximately 10 times slower than the first. Activation energies of calcite nucleation and crystallization are 73±10 and 66±2 kJ mol(-1), respectively. A model to calculate the degree of calcite crystallization from ACC at environmentally relevant temperatures (7.5-40 °C) is also presented.

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

    Science.gov (United States)

    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.

  3. Formation of star-shaped calcite crystals with Mg 2+ inorganic mineralizer without organic template

    Science.gov (United States)

    Zhu, Liying; Zhao, Qingrui; Zheng, Xiuwen; Xie, Yi

    2006-04-01

    Star-shaped calcite crystals with 3¯m symmetry were obtained in the mixed solvent of ethanol and H 2O (4:1 vol%) using Mg 2+ as grow mineralizer without any organic template under the solvothermal condition. The crystals branched to the six directions perpendicular to the c-axis. In the process, Mg 2+ takes an important influence on such novel morphology via entering the crystal lattice of calcite to absorb the special plane and change the general growth habit. The aqueous solvent is favorable to form aragonite, while the presence of alcohol promotes the formation of calcite, the thermodynamically stable phase. The products were characterized by the techniques of XRD, SEM, SAED, IR and ICP. The formation process was also primarily studied.

  4. Arsenic uptake in bacterial calcite

    Energy Technology Data Exchange (ETDEWEB)

    Catelani, Tiziano; Perito, Brunella; Bellucci, Francesco; Lee, Sang Soo; Fenter, Paul; Newville, Matthew G.; 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 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 c 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.

  5. Arsenic uptake in bacterial calcite

    Science.gov (United States)

    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.

  6. Capillarity creates single-crystal calcite nanowires from amorphous calcium carbonate.

    Science.gov (United States)

    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.

  7. Transformation of amorphous calcium carbonate to rod-like single crystal calcite via "copying" collagen template.

    Science.gov (United States)

    Xue, Zhonghui; Hu, Binbin; Dai, Shuxi; Du, Zuliang

    2015-10-01

    Collagen Langmuir films were prepared by spreading the solution of collagen over deionized water, CaCl2 solution and Ca(HCO3)2 solution. Resultant collagen Langmuir monolayers were then compressed to a lateral pressure of 10 mN/m and held there for different duration, allowing the crystallization of CaCO3. The effect of crystallization time on the phase composition and microstructure of CaCO3 was investigated. It was found that amorphous calcium carbonate (ACC) was obtained at a crystallization time of 6 h. The amorphous CaCO3 was transformed to rod-like single crystal calcite crystals at an extended crystallization time of 12 h and 24 h, via "copying" the symmetry and dimensionalities of collagen fibers. Resultant calcite crystallites were well oriented along the longitudinal axis of collagen fibers. The ordered surface structure of collagen fibers and electrostatic interactions played key roles in tuning the oriented nucleation and growth of the calcite crystallites. The mineralized collagen possessing both desired mechanical properties of collagen fiber and good biocompatibility of calcium carbonate may be assembled into an ideal biomaterial for bone implants. Copyright © 2015. Published by Elsevier B.V.

  8. Microstructure and thermal change of texture of calcite crystals in ostrich eggshell Struthio camelus

    International Nuclear Information System (INIS)

    Heredia, A.; Rodriguez-Hernandez, A.G.; Lozano, L.F.; Pena-Rico, M.A.; Velazquez, R.; Basiuk, V.A.; Bucio, L.

    2005-01-01

    Eggshell from ostrich Struthio camelus, pristine and thermally treated in the range from room temperature to 550 deg. C, was investigated with low vacuum scanning electron microscopy (LVSEM), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray powder diffractometry (XRD). Different zones of the eggshell were analysed, including the protein-related, non-crystalline, inner organic membrane. After the high-temperature treatment (>500 deg. C), only crystallised calcite phase was found showing two main textures depending on the shell zone and the treatment temperature. In the crystal layer of the untreated samples, nanosized calcite crystals are organized with their c crystallographic axes highly aligned normal to eggshell surface (a very sharp gaussian angular distribution, σ=0.14, was obtained by using the Rietveld method to model the preferred orientation function in the X-ray powder diffraction pattern). Elemental analysis revealed more Mg 2+ in the crystal layer than in cone layer of the eggshell. A high nitrogen content in the organic membrane is associated to a proteinaceous phase. The cone and palisade layers are composed of needle-shaped calcite crystals, which are more crystallized than in the crystal layer and in average with their c crystallographic axes oriented in all directions except for the one perpendicular to the eggshell surface. Due to the complex structure and the amorphous/crystal phase interactions, the heating at about 500 deg. C texturizes the crystals orienting them mainly along the c-axes normal to the inner eggshell surface

  9. Morphology of calcite crystals in clast coatings from four soils in the Mojave desert region

    Science.gov (United States)

    Chadwick, Oliver A.; Sowers, Janet M.; Amundson, Ronald G.

    1989-01-01

    Pedogenic calcite-crystal coatings on clasts were examined in four soils along an altitudinal gradient on Kyle Canyon alluvium in southern Nevada. Clast coatings were studied rather than matrix carbonate to avoid the effects of soil matrix on crystallization. Six crystal sizes and shapes were recognized and distinguished. Equant micrite was the dominant crystal form with similar abundance at all elevations. The distributions of five categories of spar and microspar appear to be influenced by altitudinally induced changes in effective moisture. In the drier, lower elevation soils, crystals were equant or parallel prismatic with irregular, interlocking boundaries while in the more moist, higher elevation soils they were randomly oriented, euhedral, prismatic, and fibrous. There was little support for the supposition that Mg(+2) substitution or increased (Mg + Ca)/HCO3 ratios in the precipitating solution produced crystal elongation.

  10. Flux Growth and Crystal Structure Refinement of Calcite Type Borate GaBO3

    Directory of Open Access Journals (Sweden)

    Shichao Wang

    2015-05-01

    Full Text Available A single crystal of gallium borate, GaBO3, 4 × 4 × 0.2 mm3 in size has been grown by spontaneous crystallization with a molten flux based on a Bi2O3-3B2O3 solvent. From single crystal X-ray diffraction measurement, GaBO3 was found to crystallize in the trigonal calcite type, space group R-3c, with cell dimensions a = 4.56590(10 and c = 14.1764(4 Å, Z = 6. Layers of distorted [GaO6] octahedra are interleaved by layers of triangular planar [BO3] unites. The transmission spectrum on a single crystal indicated that the band gap of GaBO3 is 3.62 eV.

  11. In Vitro Calcite Crystal Morphology Is Modulated by Otoconial Proteins Otolin-1 and Otoconin-90

    Science.gov (United States)

    Moreland, K. Trent; Hong, Mina; Lu, Wenfu; Rowley, Christopher W.; Ornitz, David M.; De Yoreo, James J.; Thalmann, Ruediger

    2014-01-01

    Otoconia are formed embryonically and are instrumental in detecting linear acceleration and gravity. Degeneration and fragmentation of otoconia in elderly patients leads to imbalance resulting in higher frequency of falls that are positively correlated with the incidence of bone fractures and death. In this work we investigate the roles otoconial proteins Otolin-1 and Otoconin 90 (OC90) perform in the formation of otoconia. We demonstrate by rotary shadowing and atomic force microscopy (AFM) experiments that Otolin-1 forms homomeric protein complexes and self-assembled networks supporting the hypothesis that Otolin-1 serves as a scaffold protein of otoconia. Our calcium carbonate crystal growth data demonstrate that Otolin-1 and OC90 modulate in vitro calcite crystal morphology but neither protein is sufficient to produce the shape of otoconia. Coadministration of these proteins produces synergistic effects on crystal morphology that contribute to morphology resembling otoconia. PMID:24748133

  12. Calcite biomineralization in coccoliths: Evidence from atomic force microscopy (AFM)

    DEFF Research Database (Denmark)

    Henriksen, Karen; Stipp, S.L.S.

    2002-01-01

    geochemistry, crystal orientation, coccolith function, biomineralization, biological calcite, atomic force microscopy......geochemistry, crystal orientation, coccolith function, biomineralization, biological calcite, atomic force microscopy...

  13. A Novel Acidic Matrix Protein, PfN44, Stabilizes Magnesium Calcite to Inhibit the Crystallization of Aragonite*

    Science.gov (United States)

    Pan, Cong; Fang, Dong; Xu, Guangrui; Liang, Jian; Zhang, Guiyou; Wang, Hongzhong; Xie, Liping; Zhang, Rongqing

    2014-01-01

    Magnesium is widely used to control calcium carbonate deposition in the shell of pearl oysters. Matrix proteins in the shell are responsible for nucleation and growth of calcium carbonate crystals. However, there is no direct evidence supporting a connection between matrix proteins and magnesium. Here, we identified a novel acidic matrix protein named PfN44 that affected aragonite formation in the shell of the pearl oyster Pinctada fucata. Using immunogold labeling assays, we found PfN44 in both the nacreous and prismatic layers. In shell repair, PfN44 was repressed, whereas other matrix proteins were up-regulated. Disturbing the function of PfN44 by RNAi led to the deposition of porous nacreous tablets with overgrowth of crystals in the nacreous layer. By in vitro circular dichroism spectra and fluorescence quenching, we found that PfN44 bound to both calcium and magnesium with a stronger affinity for magnesium. During in vitro calcium carbonate crystallization and calcification of amorphous calcium carbonate, PfN44 regulated the magnesium content of crystalline carbonate polymorphs and stabilized magnesium calcite to inhibit aragonite deposition. Taken together, our results suggested that by stabilizing magnesium calcite to inhibit aragonite deposition, PfN44 participated in P. fucata shell formation. These observations extend our understanding of the connections between matrix proteins and magnesium. PMID:24302723

  14. Smaller Calcite Lattice Deformation Caused by Occluded Organic Material in Coccoliths than in Mollusk Shell

    DEFF Research Database (Denmark)

    Froelich, Simon; Sørensen, H.O.; Hakim, S.S.

    2015-01-01

    The growth and nucleation of biominerals are directed and affected by associated biological molecules. In this paper, we investigate the influence of occluded biomolecules on biogenic calcite from the coccolithophorid Pleurochrysis carterae and from chalk, a rock composed predominantly of fossil....... Two heating cycles allow us to differentiate the effects of thermal agitation and organic molecules. Single peak analysis and Rietveld refinement were combined to show significant differences resulting from the occluded biomolecules on the mineral phase in biogenic calcite in the mollusk shell....... This suggests that the interaction between biomolecules and calcite is not as tight in the coccoliths as in the shell. Although the shape of chalk has been preserved over millions of years, no major influence on the crystal lattice was observed in the chalk samples....

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

    Science.gov (United States)

    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

  16. Evolution and the Calcite Eye Lens

    OpenAIRE

    Williams, Vernon L.

    2013-01-01

    Calcite is a uniaxial, birefringent crystal, which in its optically transparent form, has been used for animal eye lenses, the trilobite being one such animal. Because of the calcite birefringence there is a difficulty in using calcite as a lens. When the propagation direction of incoming light is not exactly on the c-axis, the mages blur. In this paper, calcite blurring is evaluated, and the non-blurring by a crystallin eye lens is compared to a calcite one.

  17. High-Magnesian Calcite Mesocrystals : A Coordination Chemistry Approach

    NARCIS (Netherlands)

    Lenders, Jos J. M.; Dey, Archan; Bomans, Paul H. H.; Spielmann, Jan; Hendrix, Marco M. R. M.; de With, Gijsbertus; Meldrum, Fiona C.; Harder, Sjoerd; Sommerdijk, Nico A. J. M.

    2012-01-01

    While biogenic calcites frequently contain appreciable levels of magnesium, the pathways leading to such high concentrations remain unclear. The production of high-magnesian calcites in vitro is highly challenging, because Mg-free aragonite, rather than calcite, is the favored product in the

  18. Morphology Controls on Calcite Recrystallization.

    Science.gov (United States)

    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).

  19. Hydro-gel environment and solution additives modify calcite growth mechanism to an accretion process of amorphous nanospheres

    Science.gov (United States)

    Gal, A.; Kahil, K.; Habraken, W.; Gur, D.; Fratzl, P.; Addadi, L.; Weiner, S.

    2013-12-01

    Various biominerals form via the transformation of a transient amorphous precursor phase into a mature crystalline phase. The mature biominerals usually exhibit morphology reminiscent of aggregated nanoparticles. Although these observations suggest an accretion-based growth process consisting on nanoparticles, the key factors that control the accretion process are unknown. We investigated the transformation of solid amorphous calcium carbonate (ACC) into calcite. When plant cystoliths, a biogenic stable ACC phase, are transformed into calcite in vitro by immersion in water, calcite crystals grow in two distinct steps (Gal et al., Angewandte Chemie, 2013). First, rhombohedral crystals grow that show flat facets as expected from ion-by-ion growth. These crystals then grow by the aggregation and crystallization of the original ACC nanospheres leading to a surface morphology dominated by aggregated spheres. The transformation process occurs within an organic hydro-gel that originates from inside the cystoliths. We tested the importance of the gel phase to the transformation process by transforming synthetic ACC into calcite inside various gels. In all the investigated systems: in gelatin, agarose, and pectin gels, calcite crystals grew that showed the nanosphere aggregation morphology. In additional experiments we demonstrated that also other additives, such as phosphate ions and biogenic macromolecules, that slow down ACC dissolution and calcite precipitation from ions can induce the accretion process dominance (see figure attached). These experiments show that although in solution the dominant process is dissolution to ions of the ACC and crystal growth by ion-by-ion mechanism, the presence of an additive that slows the ion-mediated processes makes the ACC nanospheres stable long enough to interact with the crystal surface. As a result, the metastable ACC nanospheres undergo secondary nucleation on the crystal surface without dissolving. These experiments highlight

  20. Interactions of Eu(III) with biogenic CaCO{sub 3} studied with TRLFS

    Energy Technology Data Exchange (ETDEWEB)

    Johnstone, Erik V.; Schmidt, Moritz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Surface Processes; Cherkouk, Andrea [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Biogeochemistry

    2016-07-01

    The interactions of Eu(III) with CaCO{sub 3} arising from biogenic origin was investigated by Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS). Biologically-induced precipitation via ureolysis was studied with the bacteria Sporosarcina pasteurii in the presence of Eu(III). Biomineralization occurred forming mixed phases of vaterite and calcite after one day that transformed over two weeks to pure calcite. Eu(III) was quantitatively removed from solution during mineral formation. TRLFS results show that after one day the Eu{sup 3+} is located in the vaterite phase. After one week, the Eu{sup 3+} was found primarily in the vaterite, despite calcite now being the predominant mineral, and a transition species was also formed. In the calcite two incorporated Eu{sup 3+} species were present: one substitutes at the Ca{sup 2+} site in the crystal lattice and the other is speculated to be associated with the organicmineral matrix.

  1. Crystal and fine structural transformation of Heat-treated biogenic manganese oxide

    Czech Academy of Sciences Publication Activity Database

    Kimura, N.; Hashimoto, H.; Miyata, N.; Nishina, Y.; Kusano, Y.; Ikeda, Y.; Nakanishi, Y.; Fujii, T.; Šafařík, Ivo; Šafaříková, Miroslava; Takada, J.

    2013-01-01

    Roč. 60, č. 3 (2013), s. 92-98 ISSN 0532-8799 R&D Projects: GA MŠk(CZ) LH11111 Institutional support: RVO:67179843 Keywords : microorganisms * biogenic manganese oxides * phase transitions * nano-sheets * microstructures Subject RIV: EH - Ecology, Behaviour

  2. Composite Magnetite and Protein Containing CaCO3 Crystals. External Manipulation and Vaterite → Calcite Recrystallization-Mediated Release Performance.

    Science.gov (United States)

    Sergeeva, Alena; Sergeev, Roman; Lengert, Ekaterina; Zakharevich, Andrey; Parakhonskiy, Bogdan; Gorin, Dmitry; Sergeev, Sergey; Volodkin, Dmitry

    2015-09-30

    Biocompatibility and high loading capacity of mesoporous CaCO3 vaterite crystals give an option to utilize the polycrystals for a wide range of (bio)applications. Formation and transformations of calcium carbonate polymorphs have been studied for decades, aimed at both basic and applied research interests. Here, composite multilayer-coated calcium carbonate polycrystals containing Fe3O4 magnetite nanoparticles and model protein lysozyme are fabricated. The structure of the composite polycrystals and vaterite → calcite recrystallization kinetics are studied. The recrystallization results in release of both loaded protein and Fe3O4 nanoparticles (magnetic manipulation is thus lost). Fe3O4 nanoparticles enhance the recrystallization that can be induced by reduction of the local pH with citric acid and reduction of the polycrystal crystallinity. Oppositely, the layer-by-layer assembled poly(allylamine hydrochloride)/poly(sodium styrenesulfonate) polyelectrolyte coating significantly inhibits the vaterite → calcite recrystallization (from hours to days) most likely due to suppression of the ion exchange giving an option to easily tune the release kinetics for a wide time scale, for example, for prolonged release. Moreover, the recrystallization of the coated crystals results in formulation of multilayer capsules keeping the feature of external manipulation. This study can help to design multifunctional microstructures with tailor-made characteristics for loading and controlled release as well as for external manipulation.

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

    Science.gov (United States)

    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

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

    NARCIS (Netherlands)

    Wolthers, M.; Nehrke, G.; Gustafsson, J.P.; Van Cappellen, P.

    2012-01-01

    Until recently the influence of solution stoichiometry on calcite crystal growth kinetics has attracted little attention, despite the fact that in most aqueous environments calcite precipitates from non-stoichiometric solution. In order to account for the dependence of the calcite crystal growth

  5. Elastic constants of calcite

    Science.gov (United States)

    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.

  6. Speleothems from Mawsmai and Krem Phyllut caves, Meghalaya, India: some evidences on biogenic activities

    Science.gov (United States)

    Baskar, Sushmitha; Baskar, R.; Lee, Natuschka; Theophilus, P. K.

    2009-05-01

    The Mawsmai cave and Krem Phyllut caves, East Khasi hills, Meghalaya, India has so far not yet attracted the attention of geomicrobiologists. Observations and hypotheses on the possible influence of identified microorganisms for speleothem formations in Meghalaya are reported for the first time. XRD studies identified calcite in speleothems and gypsum in cave wall deposits as the dominant minerals. SEM-EDAX showed interesting microfabric features showing strong resemblance with fossilised bacteria, calcified filaments, needle calcite and numerous nano scale calcite crystals, highly weathered and disintegrated crystals of calcite, that point towards a significant microbial influence in its genesis. Thin section petrography showed laminated stromatolitic features. The microorganisms identified by conventional isolation and further evaluation of isolates by molecular techniques include Bacillus cereus, Bacillus mycoides, Bacillus licheniformis, Micrococcus luteus, and Actinomycetes. Microscopic observations also showed unidentifiable cocci and four unidentifiable strains of CaSO4 (gypsum) precipitating bacteria. Experimental studies confirmed that these bacteria are able to precipitate calcium minerals (calcite, gypsum, minor amounts of dolomite) in the laboratory. These results allow us to postulate that species like these may contribute to active biogenic influence in the cave formations at Meghalaya.

  7. Intracrystalline deformation of calcite

    NARCIS (Netherlands)

    Bresser, J.H.P. de

    1991-01-01

    It is well established from observations on natural calcite tectonites that intracrystalline plastic mechanisms are important during the deformation of calcite rocks in nature. In this thesis, new data are presented on fundamental aspects of deformation behaviour of calcite under conditions where

  8. Crystal defects induced by chitin and chitinolytic enzymes in the prismatic layer of Pinctada fucata.

    Science.gov (United States)

    Kintsu, Hiroyuki; Okumura, Taiga; Negishi, Lumi; Ifuku, Shinsuke; Kogure, Toshihiro; Sakuda, Shohei; Suzuki, Michio

    2017-07-22

    Biomineralization, in which organisms create biogenic hard tissues, with hardness or flexibility enhanced by organic-inorganic interaction is an interesting and attractive focus for application of biomimetic functional materials. Calcites in the prismatic layer of Pinctada fucata are tougher than abiotic calcites due to small crystal defects. However, the molecular mechanism of the defect formation remains unclear. Here, chitin and two chitinolytic enzymes, chitinase and chitobiase, were identified as organic matrices related to for the formation of small crystal defects in the prismatic layer. Experiments with a chitinase inhibitor in vivo showed chitinase is necessary to form the prismatic layer. Analysis of calcite crystals, which were synthesized in a chitin hydrogel treated with chitinolytic enzymes, by electron microscopy and X-ray diffraction showed that crystal defects became larger as chitin was more degraded. These results suggest that interactions between chitin and calcium carbonate increase as chitin is thinner. Copyright © 2017. Published by Elsevier Inc.

  9. Fracture calcites at Olkiluoto. Evidence from quaternary infills for palaeohydrogeology

    International Nuclear Information System (INIS)

    Gehoer, S.; Kaerki, A.; Taikina-aho, O.; Karhu, J.; Loefman, J.; Pitkaenen, P.; Ruotsalainen, P.

    2002-02-01

    Recently formed secondary minerals, predominantly calcite, occur in varying amounts as fracture infills, and the calcite types, their chemical compositions and isotope ratios reflect the compositions and physicochemical factors of the groundwater system in which they were formed. Fluid inclusions trapped in calcites give direct evidence of trapping temperatures and past salinities and of the chemical compositions of the palaeo fluids. A wide range of mineralogical and geochemical examinations were carried out within the EQUIP project to examine features of this kind. The fracture calcites at the Olkiluoto site are of various origins and represent several textural types. The exact number of calcite-producing events is unknown, but the duration of the period that was appropriate for the precipitation of low temperature calcite is estimated to have exceeded 1000 Ma. Thus the number of genetically related calcite units is assumed to be considerable. This study was focused on the petrogenesis of calcites crystallized in fractures of high water conductivity during the latest stages of geological evolution. The majority of these late stage calcites form physically homogeneous, scaly layers, and in a few cases thin layers composed of idiomorphic crystals. Chemically these are almost stoichiometric calcites (CaCO 3 ). The MnO content may exceed 1%, while the amounts of other elements present are minor, although the trace element concentrations, particularly those of large ionic trace elements, can be used as distinguishing features for the recognition of individual precipitates representing different calcite generations. Evidence from fluid inclusions, or more correctly from the absence of these in the late stage calcites, can be interpreted as an indication of slow rates of crystallization under cool conditions. Many chemical variables, e.g. oxygen isotope ratios, demonstrate an equilibrium between the latest calcites and water similar to the present groundwater. Older

  10. Fracture calcites at Olkiluoto. Evidence from quaternary infills for palaeohydrogeology

    Energy Technology Data Exchange (ETDEWEB)

    Gehoer, S.; Kaerki, A.; Taikina-aho, O. [Kivitieto Oy (Finland); Karhu, J. [Helsinki Univ. (Finland); Loefman, J. [VTT Processes, Espoo (Finland); Pitkaenen, P. [VTT Building and Transport, Espoo (Finland); Ruotsalainen, P. [TUKES, Helsinki (Finland)

    2002-02-01

    Recently formed secondary minerals, predominantly calcite, occur in varying amounts as fracture infills, and the calcite types, their chemical compositions and isotope ratios reflect the compositions and physicochemical factors of the groundwater system in which they were formed. Fluid inclusions trapped in calcites give direct evidence of trapping temperatures and past salinities and of the chemical compositions of the palaeo fluids. A wide range of mineralogical and geochemical examinations were carried out within the EQUIP project to examine features of this kind. The fracture calcites at the Olkiluoto site are of various origins and represent several textural types. The exact number of calcite-producing events is unknown, but the duration of the period that was appropriate for the precipitation of low temperature calcite is estimated to have exceeded 1000 Ma. Thus the number of genetically related calcite units is assumed to be considerable. This study was focused on the petrogenesis of calcites crystallized in fractures of high water conductivity during the latest stages of geological evolution. The majority of these late stage calcites form physically homogeneous, scaly layers, and in a few cases thin layers composed of idiomorphic crystals. Chemically these are almost stoichiometric calcites (CaCO{sub 3}). The MnO content may exceed 1%, while the amounts of other elements present are minor, although the trace element concentrations, particularly those of large ionic trace elements, can be used as distinguishing features for the recognition of individual precipitates representing different calcite generations. Evidence from fluid inclusions, or more correctly from the absence of these in the late stage calcites, can be interpreted as an indication of slow rates of crystallization under cool conditions. Many chemical variables, e.g. oxygen isotope ratios, demonstrate an equilibrium between the latest calcites and water similar to the present groundwater. Older

  11. Stable isotope (C, O) and monovalent cation fractionation upon synthesis of carbonate-bearing hydroxyl apatite (CHAP) via calcite transformation

    Science.gov (United States)

    Böttcher, Michael E.; Schmiedinger, Iris; Wacker, Ulrike; Conrad, Anika C.; Grathoff, Georg; Schmidt, Burkhard; Bahlo, Rainer; Gehlken, Peer-L.; Fiebig, Jens

    2016-04-01

    Carbonate-bearing hydroxyl-apatite (CHAP) is of fundamental and applied interest to the (bio)geochemical, paleontological, medical and material science communities, since it forms the basic mineral phase in human and animal teeth and bones. In addition, it is found in non-biogenic phosphate deposits. The stable isotope and foreign element composition of biogenic CHAP is widely used to estimate the formation conditions. This requires careful experimental calibration under well-defined boundary conditions. Within the DFG project EXCALIBOR, synthesis of carbonate-bearing hydroxyapatite was conducted via the transformation of synthetic calcite powder in aqueous solution as a function of time, pH, and temperature using batch-type experiments. The aqueous solution was analyzed for the carbon isotope composition of dissolved inorganic carbonate (gas irmMS), the oxygen isotope composition of water (LCRDS), and the cationic composition. The solid was characterized by powder X-ray diffraction, micro Raman and FTIR spectroscopy, SEM-EDX, elemental analysis (EA, ICP-OES) and gas irmMS. Temperature was found to significantly impact the transformation rate of calcite to CHAP. Upon complete transformation, CHAP was found to contain up to 5% dwt carbonate, depending on the solution composition (e.g., pH), both incorporated on the A and B type position of the crystal lattice. The oxygen isotope fractionation between water and CHAP decreased with increasing temperature with a tentative slope shallower than those reported in the literature for apatite, calcite or aragonite. In addition, the presence of dissolved NH4+, K+ or Na+ in aqueous solution led to partial incorporation into the CHAP lattice. How these distortions of the crystal lattice may impact stable isotope discrimination is subject of future investigations.

  12. Diagenetic alteration in low-Mg calcite from macrofossils

    DEFF Research Database (Denmark)

    Ullmann, Clemens Vinzenz; Korte, Christoph

    2015-01-01

    microscopy) and chemical (trace element abundances, isotopic ratios) screening techniques used to assess the alteration degree of low-Mg calcite macrofossils and summarize the findings on diagenetic trends observed for elemental and isotopic systems in such materials. For a robust evaluation...... of the preservation state of biogenic calcite, it is advisable to combine a set of complementary techniques. Absolute limiting values of element and isotope ratios for discarding diagenetically altered materials cannot be universally applied, but should rather be evaluated on a case to case basis. The evaluation can...

  13. Recombinant production of a shell matrix protein in Escherichia coli and its application to the biomimetic synthesis of spherulitic calcite crystals.

    Science.gov (United States)

    Song, Wooho; Bahn, So Yeong; Cha, Hyung Joon; Pack, Seung Pil; Choi, Yoo Seong

    2016-05-01

    To overcome the limited production capability of shell matrix proteins and efficiently conduct in vitro CaCO3 biomineralization studies, a putative recombinant shell matrix protein was prepared and characterized. A glycine-rich protein (GRP_BA) was found in Pinctada fucata as a putative shell matrix protein (NCBI reference sequence; BAA20465). It was genetically redesigned for the production in Escherichia coli. The recombinant protein was obtained in a 400 ml shake-flask culture at approx. 30 mg l(-1) with a purity of >95 %. It efficiently formed a complex with Ca(2+). Ca(2+)-induced agglomeration was like other calcification-related proteins. Spherulitic calcite micro-particles, 20-30 µm diam. with rosette- and sphere-like structures were synthesized in the presence of the recombinant shell protein, which could be formed by stacking and/or aggregation of calcite nanograins and the bound protein. Recombinant production of a shell matrix protein could overcome potential difficulties associated with the limited amount of protein available for biomineralization studies and provide opportunities to fabricate biominerals in practical aspects.

  14. Effect of Mica and Hematite (001) Surfaces on the Precipitation of Calcite

    OpenAIRE

    Huifang Xu; Mo Zhou; Yihang Fang; H. Henry Teng

    2018-01-01

    The substrate effect of mica and hematite on the nucleation and crystallization of calcite was investigated using scanning electron microscope (SEM), X-ray diffraction (XRD), and electron backscatter diffraction (EBSD) methods. On mica, we found, in the absence of Mg2+, the substrates’ (001) surfaces with hexagonal and pseudo-hexagonal two-dimensional (2-D) structure can affect the orientation of calcite nucleation with calcite (001) ~// mica (001) and calcite (010) ~// mica (010) to be the m...

  15. Simulation of Calcite Calcination

    Directory of Open Access Journals (Sweden)

    A. G. Коzhevnikov

    2006-01-01

    Full Text Available Mathematical modeling and experimental investigation results of heat transfer in the case of calcite calcinations in regenerative shaft furnaces are given in the paper. Influence of heating gas temperature, calcined material fragment size and desired final product output on the duration of calcite calcination has been studied. It has been shown that with the given percentage of final product output and permissible changes in heating gas temperature in the furnace it is the fraction size of the calcined material that greatly determines such parameter as a process duration.

  16. Grain coarsening of calcite: Fundamental mechanisms and biogenic inhibition

    DEFF Research Database (Denmark)

    Schultz, Logan Nicholas

    coarsening – small grains coarsen by aggregation at high temperatures, followed by Ostwald ripening. Alginate, a model for the acidic polysaccharides produced by coccolithiphores, inhibited coarsening at a steady rate. A Pseudomonas aeruginosa biofilm preserved particles for at least 60 days before...

  17. Interaction of alcohols with the calcite surface.

    Science.gov (United States)

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

    2015-02-07

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

  18. Role of Fungi in the Biomineralization of Calcite

    Directory of Open Access Journals (Sweden)

    Saskia Bindschedler

    2016-05-01

    Full Text Available In the field of microbial biomineralization, much of the scientific attention is focused on processes carried out by prokaryotes, in particular bacteria, even though fungi are also known to be involved in biogeochemical cycles in numerous ways. They are traditionally recognized as key players in organic matter recycling, as nutrient suppliers via mineral weathering, as well as large producers of organic acids such as oxalic acid for instance, an activity leading to the genesis of various metal complexes such as metal-oxalate. Their implications in the transformation of various mineral and metallic compounds has been widely acknowledged during the last decade, however, currently, their contribution to the genesis of a common biomineral, calcite, needs to be more thoroughly documented. Calcite is observed in many ecosystems and plays an essential role in the biogeochemical cycles of both carbon (C and calcium (Ca. It may be physicochemical or biogenic in origin and numerous organisms have been recognized to control or induce its biomineralization. While fungi have often been suspected of being involved in this process in terrestrial environments, only scarce information supports this hypothesis in natural settings. As a result, calcite biomineralization by microbes is still largely attributed to bacteria at present. However, in some terrestrial environments there are particular calcitic habits that have been described as being fungal in origin. In addition to this, several studies dealing with axenic cultures of fungi have demonstrated the ability of fungi to produce calcite. Examples of fungal biomineralization range from induced to organomineralization processes. More examples of calcite biomineralization related to direct fungal activity, or at least to their presence, have been described within the last decade. However, the peculiar mechanisms leading to calcite biomineralization by fungi remain incompletely understood and more research is

  19. Carbon isotope fractionation between amorphous calcium carbonate and calcite in earthworm-produced calcium carbonate

    International Nuclear Information System (INIS)

    Versteegh, E.A.A.; Black, S.; Hodson, M.E.

    2017-01-01

    In this study we investigate carbon isotope fractionation during the crystallization of biogenic calcium carbonate. Several species of earthworm including Lumbricus terrestris secrete CaCO 3 . Initially a milky fluid comprising micro-spherules of amorphous CaCO 3 (ACC) is secreted into pouches of the earthworm calciferous gland. The micro-spherules coalesce and crystalize to form millimetre scale granules, largely comprising calcite. These are secreted into the earthworm intestine and from there into the soil. L. terrestris were cultured for 28 days in two different soils, moistened with three different mineral waters at 10, 16 and 20 °C. The milky fluid in the calciferous glands, granules in the pouches of the calciferous glands and granules excreted into the soil were collected and analysed by FTIR spectroscopy to determine the form of CaCO 3 present and by IRMS to determine δ 13 C values. The milky fluid was ACC. Granules removed from the pouches and soil were largely calcite; the granules removed from the pouches contained more residual ACC than those recovered from the soil. The δ 13 C values of milky fluid and pouch granules became significantly more negative with increasing temperature (p ≤ 0.001). For samples from each temperature treatment, δ 13 C values became significantly (p ≤ 0.001) more negative from the milky fluid to the pouch granules to the soil granules (−13.77, −14.69 and −15.00 respectively at 10 °C; −14.37, −15.07 and −15.18 respectively at 16 °C and −14.89, −15.41 and −15.65 respectively at 20 °C). Fractionation of C isotopes occurred as the ACC recrystallized to form calcite with the fractionation factor ε calcite-ACC  = −1.20 ± 0.52‰. This is consistent with the crystallization involving dissolution and reprecipitation rather than a solid state rearrangement. Although C isotopic fractionation has previously been described between different species of dissolved inorganic carbon and

  20. Mineralogical-Chemical Characteristics of Calcite from Zletovo, Sasa and Buchim Deposits

    International Nuclear Information System (INIS)

    Shijakova-lvanova, Tena; Paneva-Zajkova, Vesna; Donova, Ilinka

    2006-01-01

    The paper presents mineralogical-chemical characteristics, dependence between some elements and concentration of some calcite elements of Zletovo, Sasa and Buchim deposits. Calcite from Sasa, Zletovo and Buchim occurs in rhombohedral crystals of different size. The colour is white, but in Buchim it is white, pink, and yellow. Their twinning is very common. Chemical composition of calcite was determined by AES-ICP. Results show that in calcite from Buchim the concentration of Ba is much higher in pink calcite from than in white or yellow. The concentration of Zn and Ph is the lowest in white calcite. The calcite from Zletovo contains much higher concentrations of Pb, Zn, Sr, but calcite of Buchim which is pink contains higher amounts of Ba and Co. The concentrations of CaO, MgO, and MnO in all calcite simples are approximately equal. Concentration of all other elements in calcite of Sasa, Zletovo and Buchim is approximately equal. TG and DTA curves out on all simples were recorded.The decompositions of the samples of calcite starts at different temperature and it is not finish until 1000 o C. (Author)

  1. Ion beam modifications of defect sub-structure of calcite cleavages

    Indian Academy of Sciences (India)

    WINTEC

    ment effectively causes local heating and increase the concentration of CO. –. 3. 2 ions formed on subsequent thermal stimulation. Thus, ion bombardment of calcite crystal surfaces in- troduce lattice defects and modify surface morphology. The electrical and mechanical properties of calcite sur- face are drastically modified ...

  2. Interactions of U(VI), Nd, and Th(IV) at the Calcite-solution interface

    International Nuclear Information System (INIS)

    Carroll, S.A.; Dran, J.C.

    1992-01-01

    The interactions of U(VI), Nd, and Th(IV) at the calcite-solution interface at controlled pCO 2 (g) have been investigated by Rutherford backscattering (RBS), scanning electron microscopy (SEM) and energy dispersive (EDS) analyses of reacted calcite. Uranium precipitation at the calcite-solution interface was observed only for those experiments in which the initial [U(VI)] was greater than the solubility of rutherfordine, UO 2 CO 3 (s). At pH 8.0, flat radial uranium and calcium zoned precipitates form at the mineral-solution interface. At pH 4.3, uranium forms an anastomosing precipitate throughout the calcite surface. RBS analyses confirmed the SEM analyses showing that uranium forms a solid phase within the calcite surface, but formation of an uranium-calcium solid solution at depth is limited. In sharp contrast to U(VI), Nd is concentrated in the solid phase as individual neodymium-calcium carbonate crystals. Calcite and pure orthorhombic neodymium carbonate crystals dissolve at the expense of the formation of a more stable neodymium-calcium solid solution. In the presence of calcite, a thorium-calcium solid solution forms by exchanging Th for Ca in the calcite structure. Thorium precipitates in two linear trends which intersect each other at approximately 105deg C and 75deg C, parallel to calcite rhombohedral cleavage faces. (orig.)

  3. Coprecipitation of cadmium with calcite

    International Nuclear Information System (INIS)

    Fujino, Osamu; Kumagai, Tetsu; Shigematsu, Tsunenobu; Matsui, Masakazu

    1976-01-01

    The distribution of cadmium between precipitates of calcite and saturated aqueous solution was measured at 25 0 C to understand the distribution of cadmium in the bivalves. Calcite was precipitated from calcium bicarbonate solution by the gradual release of carbon dioxide. The cadmium ions were coprecipitated in calcite, obeying the logarithmic distribution law. The apparent distribution coefficient was decreased as α, α'-dipyridyl increased, but the true distribution coefficient was found to be an almost constant value, 560. This value is fairly close to the ratio of solubility product constants K sub(calcite)/K sub(CdCO 3 ), 890. This suggests that the deviation of the present solid solution from ideality is not very large. (auth.)

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

    Science.gov (United States)

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

    2016-02-01

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

  5. Biotic control of skeletal growth by scleractinian corals in aragonite-calcite seas.

    Directory of Open Access Journals (Sweden)

    Tomihiko Higuchi

    Full Text Available 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.

  6. Stable calcium isotope composition of a pedogenic carbonate in forested ecosystem: the case of the needle fibre calcite (NFC).

    Science.gov (United States)

    Milliere, Laure; Verrecchia, Eric; Gussone, Nikolaus

    2014-05-01

    Calcium (Ca), carbon (C) and oxygen (O) are important elements in terrestrial environment, as their biogeochemical cycles are directly related to the storage of atmospheric carbon. Nevertheless, contrarily to C and O, Ca isotope composition has been only poorly studied in the terrestrial carbonates. Needle Fibre Calcite (NFC) is one of the most common pedogenic carbonates, unless its origin is still under debate. Recent studies explain its formation by precipitation inside fungal hyphae. Due to this possible biogenic origin, NFC can be considered as a potential bridge between the biochemistry (precipitation inside organic structure) and geochemistry (pedogenic carbonate related to soil conditions) of the Ca. Thus, the study of the Ca isotope composition of NFC seem to be of first interest in order to shed light on the behaviour of Ca in terrestrial environment, especially when precipitation of secondary carbonates is involved. The sampling site is situated in the Swiss Jura Mountains and has been chosen due to a previous complete study of the C and O isotope composition of NFC in relation to the ecosystem, which represent a good precondition for the understanding of the NFC Ca isotope signatures in this context. In this study, the implication of the fungi in the origin of NFC is investigated, by comparing the Ca isotope composition of NFC and a purely physicochemical calcite cement (LCC), both precipitated in the same environment. The δ44Ca signature of NFC and LCC crystals were used to determine possible differences of the precipitation rate during their formation. NFC and LCC have similar δ18O composition and are supposed to precipitate at the same temperature (Milliere et al., 2011a). Thus the study of Ca isotope composition of NFC seems to demonstrate that the elongated shape of the calcite needle can be explained by different precipitation processes than the rhombohedric calcite crystals precipitated in the same environment; and more precisely, the specific

  7. Calcite Dissolution Kinetics

    Science.gov (United States)

    Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.

    2016-12-01

    A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations 500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics of dissolution. The interplay of mineral

  8. Evaluation of Various Synthesis Methods for Calcite-Precipitated Calcium Carbonate (PCC) Formation

    Energy Technology Data Exchange (ETDEWEB)

    Ramakrishna, Chilakala [Hanil Cement Corporation, Danyang (Korea, Republic of); Thenepalli, Thriveni; Ahn, Ji Whan [Korea Institute of Geoscience and Mineral Resources, Daejeon (Korea, Republic of)

    2017-06-15

    This review paper evaluates different kinds of synthesis methods for calcite precipitated calcium carbonates by using different materials. The various processing routes of calcite with different compositions are reported and the possible optimum conditions required to synthesize a desired particle sizes of calcite are predicted. This paper mainly focuses on that the calcite morphology and size of the particles by carbonation process using loop reactors. In this regard, we have investigated various parameters such as CO{sub 2} flow rate, Ca (OH){sub 2} concentration, temperature, pH effect, reaction time and loop reactor mechanism with orifice diameter. The research results illustrate the formation of well-defined and pure calcite crystals with controlled crystal growth and particle size, without additives or organic solvents. The crystal growth and particle size can be controlled, and smaller sizes are obtained by decreasing the Ca (OH){sub 2} concentration and increasing the CO{sub 2} flow rate at lower temperatures with suitable pH. The crystal structure of obtained calcite was characterized by using X-ray diffraction method and the morphology by scanning electron microscope (SEM). The result of x-ray diffraction recognized that the calcite phase of calcium carbonate was the dominating crystalline structure.

  9. Evaluation of Various Synthesis Methods for Calcite-Precipitated Calcium Carbonate (PCC) Formation

    International Nuclear Information System (INIS)

    Ramakrishna, Chilakala; Thenepalli, Thriveni; Ahn, Ji Whan

    2017-01-01

    This review paper evaluates different kinds of synthesis methods for calcite precipitated calcium carbonates by using different materials. The various processing routes of calcite with different compositions are reported and the possible optimum conditions required to synthesize a desired particle sizes of calcite are predicted. This paper mainly focuses on that the calcite morphology and size of the particles by carbonation process using loop reactors. In this regard, we have investigated various parameters such as CO 2 flow rate, Ca (OH) 2 concentration, temperature, pH effect, reaction time and loop reactor mechanism with orifice diameter. The research results illustrate the formation of well-defined and pure calcite crystals with controlled crystal growth and particle size, without additives or organic solvents. The crystal growth and particle size can be controlled, and smaller sizes are obtained by decreasing the Ca (OH) 2 concentration and increasing the CO 2 flow rate at lower temperatures with suitable pH. The crystal structure of obtained calcite was characterized by using X-ray diffraction method and the morphology by scanning electron microscope (SEM). The result of x-ray diffraction recognized that the calcite phase of calcium carbonate was the dominating crystalline structure.

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

    Science.gov (United States)

    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

  11. X-ray scattering of calcite thin films deposited by atomic layer deposition: Studies in air and in calcite saturated water solution

    International Nuclear Information System (INIS)

    Wang, Peng; Hudak, Michael R.; Lerner, Allan; Grubbs, Robert K.; Wang, Shanmin; Zhang, Zhan; Karapetrova, Evguenia; Hickmott, Donald; Majewski, Jaroslaw

    2014-01-01

    Carbonates are one of the most abundant groups of minerals in earth systems and are important in many geological settings and industrial processes. Calcite (CaCO 3 ) thin films produced by atomic layer deposition offer a method to evaluate the surficial properties of carbonates as well as interactions at the carbonate–fluid interface. Using synchrotron X-ray reflectivity and X-ray diffraction, these films are observed to be porous, polycrystalline, and have crystallites oriented with the major (104) calcite cleavage plane parallel to the surface of the z-cut single crystal quartz substrate. An Al 2 O 3 buffer layer, present between quartz and the calcite film, does not affect the as-deposited film, but does influence how the films reorganize in contact with fluid. Without a buffer layer, calcite reorients its crystallites to have populations of (006) and (030) parallel to the substrate, while those with an Al 2 O 3 buffer layer become more amorphous. Amorphous films may represent an analog to amorphous calcium carbonate and provide insights into that material's thermophysical behavior. Due to a higher percentage of pore spaces available for fluid infiltration, films deposited at higher temperature make the calcite thin films more susceptible to amorphization. These films are chemically similar, but structurally dissimilar to bulk natural calcite. Nevertheless, they can be a complementary system to traditional single crystal X-ray surface scattering studies on carbonates, particularly for important but less common minerals, to evaluate mineral–fluid interfacial interactions. - Highlights: • Atomic layer deposition (ALD) used to produce calcite films. • Calcite film orientation and crystallinity depend on ALD parameters. • ALD calcite films can be both crystalline and amorphous. • Interaction of water with films can re-orient or amorphize the films. • ALD calcite films may be useful to study carbonate–fluid interfacial interactions

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

    Science.gov (United States)

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

    2011-03-01

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

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

    Science.gov (United States)

    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.

  14. Application of calcite Mg partitioning functions to the reconstruction of paleocean Mg/Ca

    Science.gov (United States)

    Hasiuk, Franciszek J.; Lohmann, Kyger C.

    2010-12-01

    Calcite Mg/Ca is usually assumed to vary linearly with solution Mg/Ca, that a constant partition coefficient describes the relationship between these two ratios. Numerous published empirical datasets suggests that this relationship is better described by a power function. We provide a compilation of these literature data for biotic and abiotic calcite in the form of Calcite Mg/Ca = F(Solution Mg/Ca) H, where F and H are empirically determined fitting parameters describing the slope and deviation from linearity, respectively, of the function. This is equivalent to Freundlich sorption behavior controlling Mg incorporation in calcite. Using a power function, instead of a partition coefficient, lowers Phanerozoic seawater Mg/Ca estimates based on echinoderm skeletal material by, on average, 0.5 mol/mol from previous estimates. These functions can also be used to model the primary skeletal calcite Mg/Ca of numerous calcite phases through geologic time. Such modeling suggests that the Mg/Ca of all calcite precipitated from seawater has varied through the Phanerozoic in response to changing seawater Mg/Ca and that the overall range in Mg/Ca measured among various calcite phases would be greatest when seawater Mg/Ca was also high (e.g., "aragonite seas") and lowest when seawater Mg/Ca was low (e.g., "calcite seas"). It follows that, during times of "calcite seas" when the seawater Mg/Ca is presumed to have been lower, deposition of calcite with low Mg contents would have resulted in a depressed drive for diagenetic stabilization of shelfal carbonate and, in turn, lead to greater preservation of crystal and skeletal microfabrics and primary chemistries in biotic and abiotic calcites.

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

    Science.gov (United States)

    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

  16. Interactions between cadmium and calcite

    NARCIS (Netherlands)

    van der Weijden, R.D.

    1995-01-01

    The thesis is composed of five chapters, some of which have been published or have been accepted for publication. The contents in some of the chapters may therefore slightly overlap, also because the subjects are closely related. The first two chapters focus mostly on the sorption of Cd on calcite,

  17. Biogenic Emission Sources

    Science.gov (United States)

    Biogenic emissions sources come from natural sources and need to accounted for in photochemical grid models. They are computed using a model which utilizes spatial information on vegetation and land use.

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

    Science.gov (United States)

    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.

  19. Paleotransport of lanthanides and strontium recorded in calcite compositions from tuffs at Yucca Mountain, Nevada, USA

    International Nuclear Information System (INIS)

    Vaniman, D.T.; Chipera, S.J.

    1996-01-01

    Secondary calcite occurs in both saturated and unsaturated hydrologic zones (SZ and UZ, respectively) in the tuffs at Yucca Mountain, Nevada, USA. In the upper UZ, the major constituents of the calcite crystal structure (C, O) have surface origins. At greater depth there is a open-quotes barren zone,close quotes straddling the water table, where calcite is rare and mixing of surface and subsurface sources may occur. Deep in the SZ, distinctive Mn calcites reflect deep sources, including Ca released as analcime or albite formed and carbonates derived from underlying Paleozoic rocks. In the UZ and in the barren zone, above the deep Mn calcites, variations in calcite lanthanide chemistry can be used to distinguish rhyolitic from quartz-latitic sources. Lanthanide ratios and Sr contents of calcites record the chemical evolution of waters flowing through the UZ and upper SZ. Variations in calcite chemistry in the UZ and in the barren zone show that (1) Sr, which is readily exchanged with clays or zeolites, is essentially removed from some flowpaths that are in contact with these minerals and (2) traces of Mn oxides found in the tuffs have a significant effect of groundwater chemistry in the UZ and in the barren zone by removing almost all Ce from solution (evidenced by characteristic Ce depletions in calcite throughout this zone). Extreme Ce removal may be a result of Ce oxidation (Ce 3+ → Ce 4+ ) at the surfaces of some Mn oxides, particularly rancieite. Higher Sr contents and lack of Ce depletions in the deeper Mn calcites reflect different ages, origins, and transport systems. The calcite record of lanthanide and Sr transport in the UZ shows that minor minerals (clays and zeolites) and even trace minerals (Mn oxides) will affect the compositions of groundwaters that flow over distances greater than a few tens of meters. 43 refs., 8 figs., 4 tabs

  20. Biogenic hardparts: Difficult archives of the geological past (Invited)

    Science.gov (United States)

    Immenhauser, A.; Schone, B. R.; Hoffmann, R.; Niedermayr, A.

    2013-12-01

    Biomineralized exo- or endoskeletons of fossil marine invertebrates are widespread and diverse components of the Phanerozoic rock record of Earth's past and present oceans. Exoskeletons serve as protection against environmental pressure or predators, whilst endoskeletons can act as support or serve as an attachment for muscles and ligaments and hence as a mechanism for transmitting muscular forces. Biogenic hard parts represent sophisticated products resulting from the hierarchical interaction of inorganic minerals (95%) and macromolecular organic matrices, forming commonly less than 5%. The significance of many biogenic carbonate archives lies in the time-resolved growth patterns and their ability to record ambient environmental conditions in the form of multiple geochemical properties (multi-proxy archives) that have been widely used to assess past oceanic seawater properties. Here, we compile and review published work dealing with crystallization pathways of skeletal hard parts secreted by mollusks (i.e., bivalves and cephalopods) as well as brachiopods as widely used archives of ancient neritic epeiric settings. Bivalves and cephalopods (e.g., extinct ammonoids and belemnites and extant Sepia, Nautilus and Spirula) all form accretionary calcitic, aragonitic or vateritic skeletal hard parts. Despite the fact that mollusks and brachiopods form part of very different branches of the animal phylogenetic tree, their biomineralization strategies are surprisingly similar. Our main focus lies in a critical assessment of the complex pathways of ions and aquo-complexes from their source (seawater) to the final product (biomineral). We do this as an attempt to critically test the commonly held hypothesis that many fossil hard parts precipitated (under favorable conditions and pending subsequent diagenetic alteration) in equilibrium with seawater. Two main observations stand out: (1) the present knowledge on pathways and mechanisms (e.g., ion channel trans-membrane or

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

    Science.gov (United States)

    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.

  2. What concentration of actinides can be packed into calcite? Hints from rare earth element (REE) composition

    International Nuclear Information System (INIS)

    Christiansen, J.; Stipp, S.L.S.; Waight, T.; Baker, J.A.

    2005-01-01

    Full text of publication follows: For reliable modelling of actinide mobility in the event of spent fuel repository failure, we need data describing the uptake capacity of the minerals likely to find themselves in the transport path. Calcite (CaCO 3 ) is a common secondary mineral in fractures and pore fillings, especially downstream from degrading concrete facilities, so it is a likely candidate for incorporation. Investigations made under ACTAF, a 5. Framework EURATOM integrated project, as well as some other research studies, have shown that actinides are successfully incorporated as substituting ions within the calcite mineral structure. The question remaining, is how much can calcite take up. Geologists routinely use relative concentrations of rare Earth elements (REE's), the lanthanides, for interpreting rock genesis and history. One can also adopt them as analogues for the radioactive elements because their f-orbital electron configuration makes them behave very much like actinides. We collected and analysed a suite of 70 calcite samples from a great number of possible formation environments, geological ages and geographical locations, for the purpose of finding the range and maximum of total f-orbital substitution possible in calcite, under natural conditions. We analysed them using Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICP-MS). The maximum concentration found was about 5 x 10 -3 mole/kg total REE in a sample that had a geological history of formation where REE fluids played a role. Over the whole suite, total REE ranged from less than 10 -4 moles/kg for limestone samples formed from biogenic calcite where REE-enriched fluids would have played a negligible role. Thus, in natural calcite, REE's are present and all evidence points to a structural incorporation within the mineral rather than as a separate REE-rich phase. These data compare favourably with mole fractions from calcite grown synthetically, where as much as 6 x 10 -3

  3. Principles of calcite dissolution in human and artificial otoconia.

    Directory of Open Access Journals (Sweden)

    Leif Erik Walther

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

  4. Shock-induced devolatilization of calcite

    Science.gov (United States)

    Boslough, M. B.; Ahrens, T. J.; Vizgirda, J.; Becker, R. H.; Epstein, S.

    1982-01-01

    Experimental measurements of the release adiabats by Vizgirda (1981) indicate that substantial vaporization takes place upon release from shock pressures of 37 GPa for calcite and 14 GPa for aragonite. The present investigation includes the first controlled partial vaporization experiments on calcite. The experiments were conducted to test the predictions of the release adiabat experiments. The quantities of the gaseous species produced from shocked calcite and their carbon and oxygen isotopic compositions were determined, and the shock-induced effect on the Mn(2+) electron spin resonance spectrum in the shock-recovered calcite was observed. On the basis of the obtained results, it is concluded that shock stresses at the 17-18 GPa level give rise to volatilization of 0.03-0.3 (mole) percent of calcite to CO2 and CO. The devolatilization of calcite occurs at low pressure at significantly lower entropy densities than predicted on the basis of thermodynamic continuum models.

  5. Rearrangement of porous CaO aggregates during calcite decomposition in vacuum

    International Nuclear Information System (INIS)

    Beruto, D.; Barco, L.; Searcy, A.W.

    1983-01-01

    High-resolution SEM photographs, N 2 adsorption isotherms, Hg porosimetry, and micrometer measurements were used to characterize CaO particle shapes and pore-size distributions that result when calcite crystals are decomposed in vacuum at 686 0 C. The surface area of the CaO produced from large calcite crystals is constant at 116 + or - 4 m 2 /g independent of the extent of reaction. The volume occupied by a CaO aggregate is approx. = 98 + or - 2% that of the original calcite crystal. The approx. = 54% total porosity is comprised of 42% pores of approx. = 5 nm cross section and 12% pores of approx. = 10 μm cross section. The duplex pore structure is formed by a diffusionless repacking of CaO particles that initially form with a more uniform distribution of particles and pores

  6. Fluid inclusion studies of calcite veins from Yucca Mountain, Nevada, Tuffs: Environment of formation

    International Nuclear Information System (INIS)

    Roedder, E.; Whelan, J.F.; Vaniman, D.T.

    1994-01-01

    Calcite vein and vug fillings at four depths (130-314m), all above the present water table in USW G-1 bore hole at Yucca Mountain, Nevada, contain primary fluid inclusions with variable vapor/liquid raitos: Most of these inclusions are either full of liquid or full of vapor. The liquid-filled inclusions show that most of the host calcite crystallized from fluids at 2 vapor phase at ''<100 degrees C''. Our new studies reveal the additional presence of major methane in the vapor-filled inclusion, indicating even lower temperatures of trapping, perhaps at near-surface temperatures. They also show that the host calcite crystals grew from a flowing film of water on the walls of fractures open to the atmosphere, the vapor-filled inclusions representing bubbles that exsolved from this film onto the crystal surface

  7. Fluid inclusion studies of calcite veins from Yucca Mountain, Nevada, Tuffs: Environment of formation

    International Nuclear Information System (INIS)

    Roedder, E.; Whelan, J.F.; Vaniman, D.T.

    1994-01-01

    Calcite vein and vug fillings at fourth depths (130-314m), all above the present water table in USW G-1 bore hole at Yucca Mountain, Nevada, contain primary fluid inclusions with variable vapor/liquid ratios: most of these inclusions are either full of liquid or full of vapor. The liquid-filled inclusions show that most of the host calcite crystallized from fluids at 2 vapor phase at open-quotes 100 degrees Cclose quotes. Our new studies reveal the additional presence of major methane in the vapor-filled inclusion, indicating even lower temperatures of trapping, perhaps at near-surface temperatures. They also show that the host calcite crystals grew from a flowing film of water on the walls of fractures open to the atmosphere, the vapor-filled inclusions representing bubbles that exsolved from this film onto the crystal surface

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

    Science.gov (United States)

    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.

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

    Directory of Open Access Journals (Sweden)

    C. Neal

    2001-01-01

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

  10. Mechanism of Calcite Co-Orientation in the Sea Urchin Tooth

    Energy Technology Data Exchange (ETDEWEB)

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

    2009-12-01

    Sea urchin teeth are remarkable and complex calcite structures, continuously growing at the forming end and self-sharpening at the mature grinding tip. The calcite (CaCO{sub 3}) crystals of tooth components, plates, fibers, and a high-Mg polycrystalline matrix, have highly co-oriented crystallographic axes. This ability to co-orient calcite in a mineralized structure is shared by all echinoderms. However, the physico-chemical mechanism by which calcite crystals become co-oriented in echinoderms remains enigmatic. Here, we show differences in calcite c-axis orientations in the tooth of the purple sea urchin (Strongylocentrotus purpuratus), using high-resolution X-ray photoelectron emission spectromicroscopy (X-PEEM) and microbeam X-ray diffraction ({mu}XRD). All plates share one crystal orientation, propagated through pillar bridges, while fibers and polycrystalline matrix share another orientation. Furthermore, in the forming end of the tooth, we observe that CaCO{sub 3} is present as amorphous calcium carbonate (ACC). We demonstrate that co-orientation of the nanoparticles in the polycrystalline matrix occurs via solid-state secondary nucleation, propagating out from the previously formed fibers and plates, into the amorphous precursor nanoparticles. Because amorphous precursors were observed in diverse biominerals, solid-state secondary nucleation is likely to be a general mechanism for the co-orientation of biomineral components in organisms from different phyla.

  11. Microbially Induced Calcite Precipitation Employing Environmental Isolates

    Directory of Open Access Journals (Sweden)

    Gunjo Kim

    2016-06-01

    Full Text Available 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.

  12. Elastic properties of anisotropic synthetic calcite-muscovite aggregates

    Science.gov (United States)

    Almqvist, Bjarne S. G.; Burlini, Luigi; Mainprice, David; Hirt, Ann M.

    2010-08-01

    A set of synthetic aggregates, containing mixtures of calcite and muscovite, were compacted with varying uniaxial loads ranging from 20 MPa up to 400 MPa. Their elastic properties have been measured using compressional and shear waves in confining hydrostatic pressures up to 475 MPa. Measured seismic velocities are shown to depend on 1) the ratio of calcite to muscovite, 2) the uniaxial load used during sample manufacturing, and 3) the porosity amount prior to velocity measurements. The matrix framework may also affect the seismic velocities, but this effect is not easily quantifiable. In general, measured seismic velocities decrease with increasing muscovite content and porosity. Elastic properties have been calculated based on texture measurements, which were obtained by neutron diffraction. The calculated velocities are based on the calcite and muscovite single crystal elastic tensors, their orientation distribution functions, and their modal fractions. A large discrepancy is apparent between calculated and measured velocities, where the former always overestimate the actual velocities. Shear waves display less of a difference between calculated and measured values, than do compressional waves, indicating that waves propagating by shearing are less affected by sample porosity and matrix framework. A better agreement between measured and calculated seismic velocities arises when the initial porosity is taken into account, using a differential effective medium model. Seismic anisotropy is evident from both measured and calculated velocities, and is low for samples containing pure calcite, but becomes prominent as the muscovite concentration increases. The intensity of anisotropy further depends on the uniaxial load used during sample compaction and the initial porosity.

  13. Mg isotope fractionation in biogenic carbonates of deep-sea coral, benthic foraminifera, and hermatypic coral.

    Science.gov (United States)

    Yoshimura, Toshihiro; Tanimizu, Masaharu; Inoue, Mayuri; Suzuki, Atsushi; Iwasaki, Nozomu; Kawahata, Hodaka

    2011-11-01

    High-precision Mg isotope measurements by multiple collector inductively coupled plasma mass spectrometry were applied for determinations of magnesium isotopic fractionation of biogenic calcium carbonates from seawater with a rapid Mg purification technique. The mean δ(26)Mg values of scleractinian corals, giant clam, benthic foraminifera, and calcite deep-sea corals were -0.87‰, -2.57‰, -2.34‰, and -2.43‰, suggesting preferential precipitation of light Mg isotopes to produce carbonate skeleton in biomineralization. Mg isotope fractionation in deep-sea coral, which has high Mg calcite skeleton, showed a clear temperature (T) dependence from 2.5 °C to 19.5 °C: 1,000 × ln(α) = -2.63 (±0.076) + 0.0138 (±0.0051) × T(R(2) = 0.82, p coral. Since the precipitation rates of deep-sea coral and benthic foraminifera are several orders of magnitude different, the results suggest that kinetic isotope fractionation may not be a major controlling factor for high-Mg calcite. The Mg isotope fractionation factors and the slope of temperature dependence from deep-sea corals and benthic foraminifera are similar to that for an inorganically precipitated calcite speleothem. Taking into account element partitioning and the calcification rate of biogenic CaCO(3), the similarity among inorganic minerals, deep-sea corals, and benthic foraminiferas may indicate a strong mineralogical control on Mg isotope fractionation for high-Mg calcite. On the other hand, δ(26)Mg in hermatypic corals composed of aragonite has been comparable with previous data on biogenic aragonite of coral, sclerosponges, and scaphopad, regardless of species differences of samples.

  14. Phase transitions in biogenic amorphous calcium carbonate.

    Science.gov (United States)

    Gong, Yutao U T; Killian, Christopher E; Olson, Ian C; Appathurai, Narayana P; Amasino, Audra L; Martin, Michael C; Holt, Liam J; Wilt, Fred H; Gilbert, P U P A

    2012-04-17

    Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC · H(2)O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC · H(2)O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC · H(2)O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC · H(2)O in vitro.

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

    Science.gov (United States)

    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.

  16. crystal

    Science.gov (United States)

    Yu, Yi; Huang, Yisheng; Zhang, Lizhen; Lin, Zhoubin; Sun, Shijia; Wang, Guofu

    2014-07-01

    A Nd3+:Na2La4(WO4)7 crystal with dimensions of ϕ 17 × 30 mm3 was grown by the Czochralski method. The thermal expansion coefficients of Nd3+:Na2La4(WO4)7 crystal are 1.32 × 10-5 K-1 along c-axis and 1.23 × 10-5 K-1 along a-axis, respectively. The spectroscopic characteristics of Nd3+:Na2La4(WO4)7 crystal were investigated. The Judd-Ofelt theory was applied to calculate the spectral parameters. The absorption cross sections at 805 nm are 2.17 × 10-20 cm2 with a full width at half maximum (FWHM) of 15 nm for π-polarization, and 2.29 × 10-20 cm2 with a FWHM of 14 nm for σ-polarization. The emission cross sections are 3.19 × 10-20 cm2 for σ-polarization and 2.67 × 10-20 cm2 for π-polarization at 1,064 nm. The fluorescence quantum efficiency is 67 %. The quasi-cw laser of Nd3+:Na2La4(WO4)7 crystal was performed. The maximum output power is 80 mW. The slope efficiency is 7.12 %. The results suggest Nd3+:Na2La4(WO4)7 crystal as a promising laser crystal fit for laser diode pumping.

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

    Science.gov (United States)

    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

  18. 3D visualization of additive occlusion and tunable full-spectrum fluorescence in calcite

    Science.gov (United States)

    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.

    2016-11-01

    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.

  19. Impact of amorphous precursor phases on magnesium isotope signatures of Mg-calcite

    Science.gov (United States)

    Mavromatis, Vasileios; Purgstaller, Bettina; Dietzel, Martin; Buhl, Dieter; Immenhauser, Adrian; Schott, Jacques

    2017-04-01

    Various marine calcifiers form exoskeletons via an amorphous calcium carbonate (ACC) precursor phase and magnesium plays an important role in the temporary stabilization of this metastable phase. Thus, the use of Mg isotope ratios of marine biogenic carbonates as a proxy to reconstruct past seawater chemistry calls for a detailed understanding of the mechanisms controlling Mg isotope signatures during the formation and transformation of ACC to the final crystalline carbonate mineral. For this purpose we have investigated the Mg isotope fractionation between (Ca,Mg)CO3 solids and aqueous fluids at 25 °C and pH = 8.3 during (i) the direct precipitation of crystalline Mg-calcite and (ii) the formation of Mg-rich ACC (Mg-ACC) and its transformation to Mg-calcite. The outcome documents that the small Mg isotope fractionation between Mg-ACC and reactive fluid (ΔMg26ACC-fluid = - 1.0 ± 0.1 ‰) is not preserved during the transformation of the ACCs into Mg-calcite. Following a pronounced isotopic shift accompanying the transformation of Mg-ACC into Mg-calcite, Δ26Mgcalcite-fluid progressively decreases with reaction progress from ∼ - 3.0 ‰ to - 3.6 ‰, reflecting both the approach of isotopic equilibrium and the increase of calcite Mg content (to near 20 mol % Mg). In contrast the crystalline Mg-calcite precipitated directly from the reacting fluid, i.e. lacking a discernable formation of an amorphous precursor, exhibits only small temporal variations in Δ26Mgcalcite-fluid which overall is affected by the precipitation kinetics. The values found in this study at the onset of Mg-ACC precipitation for Mg isotope fractionation between Mg-ACC and the fluid (ΔMg26ACC-fluid = - 1.0 ‰) and between Mg-ACC and Mg2+(aq) (Δ (aq) 26Mg ACC-Mg2+ = + 2.0 ‰) are consistent with the formation of a hydrated Ca nanoporous solid accommodating Mg bicarbonate/carbonate species in combination with hydrated magnesium. This material crossed by percolating channels filled with the

  20. Biogenic Emission Inventory System (BEIS)

    Science.gov (United States)

    Biogenic Emission Inventory System (BEIS) estimates volatile organic compound (VOC) emissions from vegetation and nitric oxide (NO) emission from soils. Recent BEIS development has been restricted to the SMOKE system

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

    Science.gov (United States)

    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.

  2. Interaction of europium and nickel with calcite studied by Rutherford Backscattering Spectrometry and Time-Resolved Laser Fluorescence Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sabau, A. [Agence Nationale pour la gestion des Déchets RAdioactifs, 1-7 rue J. Monnet, Parc de la Croix Blanche, 92298 Châtenay-Malabry Cedex (France); Université de Nice Sophia Antipolis, Ecosystèmes Côtiers Marins et Réponses aux Stress (ECOMERS), 28 avenue Valrose, 06108 Nice Cedex 2 (France); Pipon, Y., E-mail: pipon@ipnl.in2p3.fr [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); Institut Universitaire de Technologie (IUT) Lyon-1, Université Claude Bernard Lyon 1, 69 622 Villeurbanne Cedex (France); Toulhoat, N. [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); CEA/DEN, Saclay, 91191 Gif sur Yvette (France); Lomenech, C. [Université de Nice Sophia Antipolis, Ecosystèmes Côtiers Marins et Réponses aux Stress (ECOMERS), 28 avenue Valrose, 06108 Nice Cedex 2 (France); Jordan, N. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (IRE) (Germany); Moncoffre, N. [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); Barkleit, A. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (IRE) (Germany); and others

    2014-08-01

    This study aims at elucidating the mechanisms regulating the interaction of Eu and Ni with calcite (CaCO{sub 3}). Calcite powders or single crystals (some mm sized) were put into contact with Eu or Ni solutions at concentrations ranging from 10{sup −3} to 10{sup −5} mol L{sup −1} for Eu and 10{sup −3} mol L{sup −1} for Ni. The sorption durations ranged from 1 week to 1 month. Rutherford Backscattering Spectrometry (RBS) well adapted to discriminate incorporation processes such as: (i) adsorption or co precipitation at the mineral surfaces or, (ii) incorporation into the mineral structure (through diffusion for instance), has been carried out. Moreover, using the fluorescence properties of europium, the results have been compared to those obtained by Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) on calcite powders. For the single crystals, complementary SEM observations of the mineral surfaces at low voltage were also performed. Results showed that Ni accumulates at the calcite surface whereas Eu is also incorporated at a greater depth. Eu seems therefore to be incorporated into two different states in calcite: (i) heterogeneous surface accumulation and (ii) incorporation at depth greater than 160 nm after 1 month of sorption. Ni was found to accumulate at the surface of calcite without incorporation.

  3. Confocal Raman microscope mapping as a tool to describe different mineral and organic phases at high spatial resolution within marine biogenic carbonates: case study on Nerita undata (Gastropoda, Neritopsina

    Directory of Open Access Journals (Sweden)

    J. Nouet

    2011-12-01

    Full Text Available Marine biogenic carbonates formed by invertebrates (e.g. corals and mollusks represent complex composites of one or more mineral phases and organic molecules. This complexity ranges from the macroscopic structures observed with the naked eye down to sub micrometric structures only revealed by micro analytical techniques. Understanding to what extent and how organisms can control the formation of these structures requires that the mineral and organic phases can be identified and their spatial distribution related. Here we demonstrate the capability of confocal Raman microscopy applied to cross sections of a shell of Nerita undata to describe the distribution of calcite and aragonite including their crystallographic orientation with high lateral resolution (~300 nm. Moreover, spatial distribution of functional groups of organic compounds can be simultaneously acquired, allowing to specifically relate them to the observed microstructures. The data presented in this case study highlights the possible new contributions of this method to the description of modalities of Nerita undata shell formation, and what could be expected of its application to other marine biogenic carbonates. Localization of areas of interest would also allow further investigations using more localized methods, such as TEM that would provide complementary information on the relation between organic molecules and crystal lattice.

  4. Confocal Raman microscope mapping as a tool to describe different mineral and organic phases at high spatial resolution within marine biogenic carbonates: case study on Nerita undata (Gastropoda, Neritopsina)

    Science.gov (United States)

    Nehrke, G.; Nouet, J.

    2011-12-01

    Marine biogenic carbonates formed by invertebrates (e.g. corals and mollusks) represent complex composites of one or more mineral phases and organic molecules. This complexity ranges from the macroscopic structures observed with the naked eye down to sub micrometric structures only revealed by micro analytical techniques. Understanding to what extent and how organisms can control the formation of these structures requires that the mineral and organic phases can be identified and their spatial distribution related. Here we demonstrate the capability of confocal Raman microscopy applied to cross sections of a shell of Nerita undata to describe the distribution of calcite and aragonite including their crystallographic orientation with high lateral resolution (~300 nm). Moreover, spatial distribution of functional groups of organic compounds can be simultaneously acquired, allowing to specifically relate them to the observed microstructures. The data presented in this case study highlights the possible new contributions of this method to the description of modalities of Nerita undata shell formation, and what could be expected of its application to other marine biogenic carbonates. Localization of areas of interest would also allow further investigations using more localized methods, such as TEM that would provide complementary information on the relation between organic molecules and crystal lattice.

  5. Unusual biogenic calcite structures in two shallow lakes, James Ross Island, Antarctica

    Czech Academy of Sciences Publication Activity Database

    Elster, Josef; Nedbalová, Linda; Vodrážka, R.; Láska, K.; Haloda, J.; Komárek, Jiří

    2016-01-01

    Roč. 13, č. 2 (2016), s. 535-549 ISSN 1726-4170 R&D Projects: GA MŠk ME 945 Institutional support: RVO:67985939 Keywords : James Ross Island * cyanobacteria * microalgae Subject RIV: EH - Ecology, Behaviour Impact factor: 3.851, year: 2016

  6. Calcite Biohybrids as Microenvironment for Stem Cells

    Directory of Open Access Journals (Sweden)

    Razi Vago

    2012-04-01

    Full Text Available A new type of composite 3D biomaterial that provides extracellular cues that govern the differentiation processes of mesenchymal stem cells (MSCs has been developed. In the present study, we evaluated the chondrogenecity of a biohybrid composed of a calcium carbonate scaffold in its calcite polymorph and hyaluronic acid (HA. The source of the calcite scaffolding is an exoskeleton of a sea barnacle Tetraclita rifotincta (T. rifotincta, Pilsbry (1916. The combination of a calcium carbonate-based bioactive scaffold with a natural polymeric hydrogel is designed to mimic the organic-mineral composite of developing bone by providing a fine-tuned microenvironment. The results indicate that the calcite-HA interface creates a suitable microenvironment for the chondrogenic differentiation of MSCs, and therefore, the biohybrid may provide a tool for tissue-engineered cartilage.

  7. Ion microprobe assessment of the heterogeneity of Mg/Ca, Sr/Ca and Mn/Ca ratios in Pecten maximus and Mytilus edulis (bivalvia shell calcite precipitated at constant temperature

    Directory of Open Access Journals (Sweden)

    P. S. Freitas

    2009-07-01

    Full Text Available Small-scale heterogeneity of biogenic carbonate elemental composition can be a significant source of error in the accurate use of element/Ca ratios as geochemical proxies. In this study ion microprobe (SIMS profiles showed significant small-scale variability of Mg/Ca, Sr/Ca and Mn/Ca ratios in new shell calcite of the marine bivalves Pecten maximus and Mytilus edulis that was precipitated during a constant-temperature culturing experiment. Elevated Mg/Ca, Sr/Ca and Mn/Ca ratios were found to be associated with the deposition of elaborate shell features, i.e. a shell surface stria in P. maximus and surface shell disturbance marks in both species, the latter a common occurrence in bivalve shells. In both species the observed small-scale elemental heterogeneity most likely was not controlled by variable transport of ions to the extra-pallial fluid, but by factors such as the influence of shell organic content and/or crystal size and orientation, the latter reflecting conditions at the shell crystal-solution interface. In the mid and innermost regions of the P. maximus shell the lack of significant small-scale variation of Mg/Ca ratios, which is consistent with growth at constant temperature, suggest a potential application as a palaeotemperature proxy. Cross-growth band element/Ca ratio profiles in the interior of bivalve shells may provide more promising palaeo-environmental tools than sampling from the outer region of bivalve shells.

  8. Hydropower's Biogenic Carbon Footprint.

    Science.gov (United States)

    Scherer, Laura; Pfister, Stephan

    2016-01-01

    Global warming is accelerating and the world urgently needs a shift to clean and renewable energy. Hydropower is currently the largest renewable source of electricity, but its contribution to climate change mitigation is not yet fully understood. Hydroelectric reservoirs are a source of biogenic greenhouse gases and in individual cases can reach the same emission rates as thermal power plants. Little is known about the severity of their emissions at the global scale. Here we show that the carbon footprint of hydropower is far higher than previously assumed, with a global average of 173 kg CO2 and 2.95 kg CH4 emitted per MWh of electricity produced. This results in a combined average carbon footprint of 273 kg CO2e/MWh when using the global warming potential over a time horizon of 100 years (GWP100). Nonetheless, this is still below that of fossil energy sources without the use of carbon capture and sequestration technologies. We identified the dams most promising for capturing methane for use as alternative energy source. The spread among the ~1500 hydropower plants analysed in this study is large and highlights the importance of case-by-case examinations.

  9. Hydropower's Biogenic Carbon Footprint.

    Directory of Open Access Journals (Sweden)

    Laura Scherer

    Full Text Available Global warming is accelerating and the world urgently needs a shift to clean and renewable energy. Hydropower is currently the largest renewable source of electricity, but its contribution to climate change mitigation is not yet fully understood. Hydroelectric reservoirs are a source of biogenic greenhouse gases and in individual cases can reach the same emission rates as thermal power plants. Little is known about the severity of their emissions at the global scale. Here we show that the carbon footprint of hydropower is far higher than previously assumed, with a global average of 173 kg CO2 and 2.95 kg CH4 emitted per MWh of electricity produced. This results in a combined average carbon footprint of 273 kg CO2e/MWh when using the global warming potential over a time horizon of 100 years (GWP100. Nonetheless, this is still below that of fossil energy sources without the use of carbon capture and sequestration technologies. We identified the dams most promising for capturing methane for use as alternative energy source. The spread among the ~1500 hydropower plants analysed in this study is large and highlights the importance of case-by-case examinations.

  10. Stable isotopes in pedogenic calcite: Can the positive linear covariant trends be used to quantify paleo-evaporation rates?

    Science.gov (United States)

    Gröcke, D.; Ufnar, D.; Beddows, P. A.

    2007-12-01

    Paleoclimatological models suggest enhanced evaporation rates in subtropical regions during greenhouse- world conditions. Laboratory evaporation experiments show that calcites precipitated from variably saturated solutions yield a positive linear covariant trend (PLCT) in δ18O vs δ13C values. This investigation experimentally quantifies calcite PLCT so that δ13C of subtropical paleosol calcretes may be used as a regional proxy of paleo-evaporation rates. A series of powdered CaCO3 samples with δ18O and δ13C values of -19.6‰ and -37.2‰ VPDB respectively were dissolved in deionized water in a pressure sealed container; it also contained separate vials of calcite reacted with HCl to generate a range of pCO2 environments, thus simulating a soil atmosphere. The variable pCO2 conditions simulate expected soil atmosphere pCO2 conditions in a calcrete horizon during alternative phases of calcite dissolution and precipitation. After 24 hrs, the solutions were placed in an open beaker in an incubator at 36°C and allowed to evaporate. Aliquots of 100 μL were removed at 24 hr intervals and the time of calcite crystal nucleation was also noted. Water analyses yielded δ18O enrichments ranging from an initial value of -4.8‰ VSMOW to a range of +10.0‰ to +14.8‰ VSMOW after an evaporation period of 75 hrs. The most enriched water values were attained from the solutions formed under lower pCO2 conditions (more enriched calcite δ18O, δ13C). The array of calcite δ18O vs δ13C values fall upon a PLCT that projects from a theoretical meteoric calcite line (MCL) calculated from the incubation temperature and deionized water δ18O and δ13C values. The precipitated calcite δ18O values range from the MCL value of -8.8‰ VPDB to +0.5‰ VPDB. The higher pCO2 waters precipitated calcite very early during evaporation, and thus the δ18O and δ13C calcite values are slightly enriched relative to the theoretical MCL. The lower pCO2 conditions precipitated calcite late in

  11. Acidization of shales with calcite cemented fractures

    Science.gov (United States)

    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

  12. Modelling how incorporation of divalent cations affects calcite wettability-implications for biomineralisation and oil recovery

    Science.gov (United States)

    Andersson, M. P.; Dideriksen, K.; Sakuma, H.; Stipp, S. L. S.

    2016-06-01

    Using density functional theory and geochemical speciation modelling, we predicted how solid-fluid interfacial energy is changed, when divalent cations substitute into a calcite surface. The effect on wettability can be dramatic. Trace metal uptake can impact organic compound adsorption, with effects for example, on the ability of organisms to control crystal growth and our ability to predict the wettability of pore surfaces. Wettability influences how easily an organic phase can be removed from a surface, either organic compounds from contaminated soil or crude oil from a reservoir. In our simulations, transition metals substituted exothermically into calcite and more favourably into sites at the surface than in the bulk, meaning that surface properties are more strongly affected than results from bulk experiments imply. As a result of divalent cation substitution, calcite-fluid interfacial energy is significantly altered, enough to change macroscopic contact angle by tens of degrees. Substitution of Sr, Ba and Pb makes surfaces more hydrophobic. With substitution of Mg and the transition metals, calcite becomes more hydrophilic, weakening organic compound adsorption. For biomineralisation, this provides a switch for turning on and off the activity of organic crystal growth inhibitors, thereby controlling the shape of the associated mineral phase.

  13. Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

    Science.gov (United States)

    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…

  14. Mechanisms of metasomatism in the calcite-pitchblende system: 2. Replacement of pitchblende by calcite

    International Nuclear Information System (INIS)

    Dymkov, Yu.M.

    1996-01-01

    The principal mechanisms of the nasturan replacement by calcite -intrametasomatism, frontal metasomatism, dispersive metasomatism, and transformative metasomatism - are discussed in terms of G.L. Pospelov's (1973) concept. The main chemical condition required by the process is an oxidized environment, in which the tetravalent uranium of pitchblende or transitional reduced phases (coffinite) oxidizes to yield readily soluble uranyl compounds. The latter are replaced by calcite

  15. Sealing process with calcite in the Nojima active fault zone revealed from isotope analysis of calcite

    International Nuclear Information System (INIS)

    Arai, Takashi; Tsukahara, Hiroaki; Morikiyo, Toshiro

    2003-01-01

    The Nojima fault appeared on the surface in the northern part of Awaji Island, central Japan as a result of the Hyogo-ken Nanbu earthquake (1995, M=7.2). Active fault drilling was performed by the Disaster Prevention Research Institute (DPRI), Kyoto University, and core samples were retrieved from 1410 to 1710 m, which were composed of intact and fractured granodiorites. We obtained calcite samples and gas samples from the vein in marginal fracture and non-fracture zones. We analyzed the carbon and oxygen isotope ratios of calcite and carbon dioxide to investigate the characteristic isotope ratios of fluids in the active fault zone, to estimate the origins of fluids, and to determine the sealing process of fractures. The analyzed values of carbon and oxygen isotope ratios of calcite were -10.3 to -7.2 per mille, 18 to 23 per mille, respectively, and carbon isotope ratios of CO 2 were -21 to -17 per mille. If carbon isotope ratios of calcite were at equilibrium with those of CO 2 , the precipitation temperature of calcite is calculated to be 30 to 50 deg C. This temperature is consistent with the present temperature of the depth where drilling cores were retrieved. Oxygen isotope ratios of H 2 O that, precipitated calcite were calculated to be -1.8 to -5.5 per mille. These values indicate calcite were precipitated from mixed fluids of sea water and meteoric water. Therefore, the marginal fracture zone of the Nojima fault was sealed with calcite, which was generated from mixing of sea water and meteoric water in situ. (author)

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

    Science.gov (United States)

    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

  17. The role of silicate surfaces on calcite precipitation kinetics

    DEFF Research Database (Denmark)

    Stockmann, Gabrielle J.; Wolff-Boenisch, Domenik; Bovet, Nicolas Emile

    2014-01-01

    The aim of this study is to illuminate how calcite precipitation depends on the identity and structure of the growth substrate. Calcite was precipitated at 25°C from supersaturated aqueous solutions in the presence of seeds of either calcite or one of six silicate materials: augite, enstatite...

  18. Transformation of Strontium during formation of biogenic calcium carbonate

    Science.gov (United States)

    Ohnuki, T.; Kozai, N.; Sakamoto, F.; Yamashita, M.; Horiieke, T.; Utsunomiya, S.

    2016-12-01

    Some amounts of radionuclides contaminated water containing 90Sr generated in the Fukushima Daiichi Nuclear Power Plant were leaked to sea water in the port. One of the possible method to eliminate 90Sr is co-precipitated with biogenic carbonates minerals (CCM). Specific bacteria are known to form biogenic CCM in groundwater. In the present study, we have screened specific bacterium to form CCM in saline water, and studied transformation of Sr during biogenic CCM. A marine microbe of strain TK2d, which is screened from Tokyo bay to form CCM in saline solution, was grown in the medium solution contained urea and Sr. The concentratuion of Sr2+ in the solution was monitored by ICP-OES (ICP-OES; 720 Agilent Technologies, Inc., USA) during the formation of biogenic CCM. The precipitates were analyzed by SEM, TEM, and XAFS. When 1.0 mM Sr was dissolved in the medium solution, the concentration of Sr decreased up to 0.02 mM within 10 days, indicating that most of Sr in the solution was eliminated within 10 days. SEM and TEM analyses showed that needle shaped CCM containing Ca and Sr were formed. The CCM was not single crystalline, but poly-crystalline of calcite and aragonite. The elemental mapping showed that Sr was present at the same position of Ca, indicating that Sr was coprecipitated with Ca. The XANES analysis of Sr in the precipitates showed that the XANES spectrum was not the same as that of Sr coprecipitated with an abiotic Ca carbonates. Linear combination fitting of XANES spectra by those of SrCl2 and SrCO3 showed that both Sr2+ and SrCO3 were present in CCM. Longer contact time resulted in higher content of SrCO3, indicating that Sr was incorporated gradually with time into CCM structure. Thus, Sr was changed its chemical species from adsorbed one to the incorporated one in biogenic CCM in saline solution. This work was partially supported by a research grant from the Japan Science and Technology Agency, Japan (research grant No. 260502).

  19. The Crystal Hotel: A Microfluidic Approach to Biomimetic Crystallization.

    Science.gov (United States)

    Gong, Xiuqing; Wang, Yun-Wei; Ihli, Johannes; Kim, Yi-Yeoun; Li, Shunbo; Walshaw, Richard; Chen, Li; Meldrum, Fiona C

    2015-12-02

    A "crystal hotel" microfluidic device that allows crystal growth in confined volumes to be studied in situ is used to produce large calcite single crystals with predefined crystallographic orientation, microstructure, and shape by control of the detailed physical environment, flow, and surface chemistry. This general approach can be extended to form technologically important, nanopatterned single crystals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Variations in calcite growth kinetics with surface topography: molecular dynamics simulations and process-based growth kinetics modelling

    NARCIS (Netherlands)

    Wolthers, M.; Di Tommaso, D.; Du, Zhimei; de Leeuw, Nora H.

    2013-01-01

    It is generally accepted that cation dehydration is the rate-limiting step to crystal growth from aqueous solution. Here we employ classical molecular dynamics simulations to show that the water exchange frequency at structurally distinct calcium sites in the calcite surface varies by about two

  1. Calcite Supersaturation and Precipitation Kinetics in the Lower Colorado River, Ail-American Canal and East Highline Canal

    Science.gov (United States)

    Suarez, D. L.

    1983-06-01

    In situ pH determinations and analysis of major ions in solution indicated that the lower Colorado River is supersaturated with respect to calcite throughout the entire daily cycle, in both winter and summer. Although the ion activity product was 4 to 6 times greater than the calcite solubility product, there was no detectable precipitation. Chemical analyses of water samples taken along 350 km of the river and canals from Parker Dam to the Salton Sea also revealed no evidence of calcium carbonate precipitation despite the inflow of saline and highly supersaturated irrigation return flows. Laboratory kinetic studies indicated that calcite crystal growth rates with Colorado River water are about 30% of the rate for pure Ca-HCO3 waters and about 70% of that for synthetic Colorado River water. Calcite precipitation by crystal growth in the river is limited by the combination of short residence times and unavailability of reactive calcite. Critical supersaturation levels necessary for heterogeneous nucleation do not occur; a high suspended load limits algal photosynthesis and thus prevents large decreases in daytime H2CO3 levels.

  2. Magnesian calcite sorbent for carbon dioxide capture

    Energy Technology Data Exchange (ETDEWEB)

    Mabry, J.C.; Mondal, K. [Southern Illinois University, Carbondale, IL (United States)

    2011-07-01

    Magnesian calcite with controlled properties was synthesized for the removal of carbon dioxide. The results from characterization, reactivity and CO{sub 2} capture capacity for different synthesis conditions are reported. The magnesian calcite samples (CaCO{sub 3}:MgCO{sub 3}) were synthesized by the coprecipitation of specific amounts of commercially available CaO and MgO by carbon dioxide. Characterization was done with BET, SEM/EDS, particle size analysis and XRD. The capacity was measured using TGA cycles at 800 {sup o}C and compared for different preparation conditions. The effects of CaO, MgO and surfactant loading on the physical properties and carbonation activity were studied to determine the optimal synthesis condition. A long-term carbonation-calcination cycling test was conducted on the optimal sample. It was observed that the sample maintained its capacity to 86% of its original uptake even after 50 cycles.

  3. Anomalous inelastic neutron scattering from calcite

    International Nuclear Information System (INIS)

    Dove, M.T.; Harris, M.J.; Winkler, B.; Hagen, M.E.; Keele Univ.; Powell, B.M.; Steigenberger, U.

    1992-01-01

    Inelastic neutron scattering measurements on calcite (CaCO 3 ) in its low temperature phase have revealed the existence of an unusual column of inelastic scattering at the wavevector corresponding to the F point of the high temperature Brillouin zone. At the same wavevector there is also a transverse acoustic soft mode and the column of scattering ranges in energy from zero up to the soft mode. The intensity of the anomalous scattering increases rapidly with temperature, and is consistent with an Arrhenius relation of the form exp(-T * /T), where T * = 1035 K. We speculate that this scattering arises from thermal fluctuations of the calcite structure into a different ordered structure, which is related to an ordering instability at the F point. Evidence for this possibility has also been obtained from lattice energy calculations. (author)

  4. Interaction of alcohols with the calcite surface

    DEFF Research Database (Denmark)

    Bovet, Nicolas Emile; Yang, Mingjun; Javadi, Meshkat Sadat

    2015-01-01

    . Controlling their growth requires complex polysaccharides. Polysaccharide activity depends on the functionality of OH groups, so to simplify the system in order to get closer to a molecular level understanding, we investigated the interaction of OH from a suite of alcohols with clean, freshly cleaved calcite...... surfaces. X-ray photoelectron spectroscopy (XPS) provided binding energies and revealed the extent of surface coverage. Molecular dynamics (MD) simulations supplemented with information about molecule ordering, orientation and packing density. The results show that all alcohols studied bond...... with the calcite surface through the OH group, with their carbon chains sticking away in a standing-up orientation. Alcohol molecules are closely packed and form a well-ordered monolayer on the surface....

  5. High resolution electron backscatter diffraction (EBSD) data from calcite biominerals in recent gastropod shells.

    Science.gov (United States)

    Pérez-Huerta, Alberto; Dauphin, Yannicke; Cuif, Jean Pierre; Cusack, Maggie

    2011-04-01

    Electron backscatter diffraction (EBSD) is a microscopy technique that reveals in situ crystallographic information. Currently, it is widely used for the characterization of geological materials and in studies of biomineralization. Here, we analyze high resolution EBSD data from biogenic calcite in two mollusk taxa, Concholepas and Haliotis, previously used in the understanding of complex biomineralization and paleoenvironmental studies. Results indicate that Concholepas has less ordered prisms than in Haliotis, and that in Concholepas the level of order is not homogenous in different areas of the shell. Overall, the usefulness of data integration obtained from diffraction intensity and crystallographic orientation maps, and corresponding pole figures, is discussed as well as its application to similar studies. © 2010 Elsevier Ltd. All rights reserved.

  6. Sea Urchin Spine Calcite Forms via a Transient Amorphous Calcium Carbonate Phase

    Science.gov (United States)

    Politi, Yael; Arad, Talmon; Klein, Eugenia; Weiner, Steve; Addadi, Lia

    2004-11-01

    The skeletons of adult echinoderms comprise large single crystals of calcite with smooth convoluted fenestrated morphologies, raising many questions about how they form. By using water etching, infrared spectroscopy, electron diffraction, and environmental scanning electron microscopy, we show that sea urchin spine regeneration proceeds via the initial deposition of amorphous calcium carbonate. Because most echinoderms produce the same type of skeletal material, they probably all use this same mechanism. Deposition of transient amorphous phases as a strategy for producing single crystals with complex morphology may have interesting implications for the development of sophisticated materials.

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

    Science.gov (United States)

    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

  8. Tuning calcite morphology and growth acceleration by a rational design of highly stable protein-mimetics

    Science.gov (United States)

    Chen, Chun-Long; Qi, Jiahui; Tao, Jinhui; Zuckermann, Ronald N.; DeYoreo, James J.

    2014-01-01

    In nature, proteins play a significant role in biomineral formation. One of the ultimate goals of bioinspired materials science is to develop highly stable synthetic molecules that mimic the function of these natural proteins by controlling crystal formation. Here, we demonstrate that both the morphology and the degree of acceleration or inhibition observed during growth of calcite in the presence of peptoids can be rationally tuned by balancing the electrostatic and hydrophobic interactions, with hydrophobic interactions playing the dominant role. While either strong electrostatic or hydrophobic interactions inhibit growth and reduces expression of the {104} faces, correlations between peptoid-crystal binding energies and observed changes in calcite growth indicate moderate electrostatic interactions allow peptoids to weakly adsorb while moderate hydrophobic interactions cause disruption of surface-adsorbed water layers, leading to growth acceleration with retained expression of the {104} faces. This study provides fundamental principles for designing peptoids as crystallization promoters, and offers a straightforward screening method based on macroscopic crystal morphology. Because peptoids are sequence-specific, highly stable, and easily synthesized, peptoid-enhanced crystallization offers a broad range of potential applications. PMID:25189418

  9. Cryogenic and non-cryogenic pool calcites indicating permafrost and non-permafrost periods: a case study from the Herbstlabyrinth-Advent Cave system (Germany

    Directory of Open Access Journals (Sweden)

    D. K. Richter

    2010-11-01

    Full Text Available Weichselian cryogenic calcites collected in what is referred to as the Rätselhalle of the Herbstlabyrinth-Advent Cave system are structurally classified as rhombohedral crystals and spherulitic aggregates. The carbon and oxygen isotopic composition of these precipitates (δ13C = +0.6 to −7.3‰ δ18O = −6.9 to −18.0‰ corresponds to those of known slowly precipitated cryogenic cave calcites under conditions of isotopic equilibrium between water and ice of Central European caves. The carbon and oxygen isotopic composition varies between different caves which is attributed to the effects of cave air ventilation before the freezing started.

    By petrographic and geochemical comparisons of Weichselian cryogenic calcite with recent to sub-recent precipitates as well as Weichselian non-cryogenic calcites of the same locality, a model for the precipitation of these calcites is proposed. While the recent and sub-recent pool-calcites isotopically match the composition of interglacial speleothems (stalagmites, etc., isotope ratios of Weichselian non-cryogenic pool-calcites reflect cooler conditions. Weichselian cryogenic calcites show a trend towards low δ18O values with higher carbon isotope ratios reflecting slow freezing of the precipitating solution. In essence, the isotope geochemistry of the Weichselian calcites reflects the climate history changing from overall initial permafrost conditions to permafrost-free and subsequently to renewed permafrost conditions. Judging from the data compiled here, the last permafrost stage in the Rätselhalle is followed by a warm period (interstadial and/or Holocene. During this warmer period, the cave ice melted and cryogenic and non-cryogenic Weichselian calcite precipitates were deposited on the cave ground or on fallen blocks, respectively.

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

    Science.gov (United States)

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

    2015-06-01

    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.

  11. Impact of trace metals on the water structure at the calcite surface

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  13. Biogenic Amines in Insect Antennae

    Directory of Open Access Journals (Sweden)

    Marianna I. Zhukovskaya

    2017-06-01

    Full Text Available Insect antenna is a multisensory organ, each modality of which can be modulated by biogenic amines. Octopamine (OA and its metabolic precursor tyramine (TA affect activity of antennal olfactory receptor neurons. There is some evidence that dopamine (DA modulates gustatory neurons. Serotonin can serve as a neurotransmitter in some afferent mechanosensory neurons and both as a neurotransmitter and neurohormone in efferent fibers targeted at the antennal vessel and mechanosensory organs. As a neurohormone, serotonin affects the generation of the transepithelial potential by sensillar accessory cells. Other possible targets of biogenic amines in insect antennae are hygro- and thermosensory neurons and epithelial cells. We suggest that the insect antenna is partially autonomous in the sense that biologically active substances entering its hemolymph may exert their effects and be cleared from this compartment without affecting other body parts.

  14. Carbonates in thrust faults: High temperature investigations into deformation processes in calcite-dolomite systems

    Science.gov (United States)

    Kushnir, A.; Kennedy, L.; Misra, S.; Benson, P.

    2012-04-01

    The role of dolomite on the strength and evolution of calcite-dolomite fold and thrust belts and nappes (as observed in the Canadian Rockies, the Swiss Alps, the Italian Apennines, and the Naukluft Nappe Complex) is largely unknown. Field investigations indicate that strain in natural systems is localized in calcite, resulting in a ductile response, while dolomite deforms in a dominantly brittle manner. To date, experimental studies on polymineralic carbonate systems are limited to homogeneous, fine-grained, calcite-dolomite composites of relatively low dolomite content. The effect of dolomite on limestone rheology, the onset of crystal-plastic deformation in dolomite in composites, and the potential for strain localization in composites have not yet been fully quantified. Constant displacement rate (3x10-4 s-1and 10-4 s-1), high confining pressure (300 MPa) and high temperature (750° C and 800° C) torsion experiments were conducted to address the role of dolomite on the strength of calcite-dolomite composites. Experiments were performed on samples produced by hot isostatic pressing (HIP) amalgams of a natural, pure dolomite and a reagent, pure calcite. We performed experiments on the following mixtures (given as dolomite%): 25%, 35%, 50%, and 75%. These synthetic HIP products eliminated concerns of mineralogical impurities and textural anomalies due to porosity, structural fabrics (e.g., foliation) and fossil content. The samples were deformed up to a maximum finite shear strain of 5.0 and the experimental set up was unvented to inhibit sample decarbonation. Mechanical data shows a considerable increase in sample yield strength with increasing dolomite content. Experimental products with low starting dolomite content (dol%: 25% and 35%) display macroscopic strain localization along compositionally defined foliation. Experimental products with high dolomite content (dol%: 50% and 75%) demonstrate no macroscopic foliation. Post-deformation microstructure analysis

  15. Rare Earth element (REE) incorporation in natural calcite. Upper limits for actinide uptake in a secondary phase

    International Nuclear Information System (INIS)

    Stipp, S.L.S.; Christensen, J.T.; Waight, T.E.; Lakshtanov, L.Z.; Baker, J.A.

    2006-01-01

    Secondary minerals have the potential to sequester escaped actinides in the event of a radioactive waste repository failure, but currently, data to define their maximum uptake capacity are generally lacking. To estimate a maximum limit for solid solution in calcite, we took advantage of the behavioural similarities of the 4f-orbital lanthanides with some of the 5f-orbital actinides and used rare Earth element (REE) concentration as an analogue. A suite of 65 calcite samples, mostly pure single crystals, was assembled from a range of geological settings, ages and locations and analysed by isotope dilution MC-ICP-MS (multiple-collector inductively-coupled plasma mass spectroscopy). All samples were shown to contain significant lanthanide concentrations. The highest were in calcite formed from hydrothermal solutions and from carbonatite magma. Maximum total mole fraction of REE was 4.72 x 10 -4 , which represents one substituted atom for about 2000 Ca sites. In comparison, synthetic calcite, precipitated at growth rates slow enough to insure solid solution formation, incorporated 7.5 x 10 -4 mole fraction Eu(III). For performance assessment, we propose that 7.5 mmole substitution/kg calcite should be considered the upper limit for actinide incorporation in secondary calcite. The largest source of uncertainty in this estimate results from extrapolating lanthanide data to actinides. However, the data offer confidence that for waters in the hydrothermal temperature range, such as in the near-field, or at groundwater temperatures, such as in the far-field, if calcite formation is favoured and actinides are present, those with behaviour like the trivalent lanthanides, especially Am 3+ and Cm 3+ , will be incorporated. REE are abundant and widely distributed, and they have remained in calcite for millions of years. Thus, one can be certain that incorporated actinides will also remain immobilised in calcite formed in fractures and pore spaces, as long as solution conditions

  16. Examination of TL and optical absorption in calcite's mineral

    International Nuclear Information System (INIS)

    Sabikoglu, I.; Can, N.

    2009-01-01

    Calcite which is a form of crystalline of the calcium carbonate composes parent material of chalk stone (limestone) and marble. Calcite which presents in various colors also in our country consists of yellow, blue, transparent and green colors. In this study, green calcite mineral which is taken from the region of Ayvalik, was examined of its thermoluminescence (TL) and optical absorption features in different doses. It has been obtained a large TL peak in 179 degree C and absorption peak in 550 mm.

  17. Origin of calcite in the glacigenic Virttaankangas complex

    Directory of Open Access Journals (Sweden)

    Nina M. Kortelainen

    2007-01-01

    Full Text Available Groundwaters of the glacigenic Virttaankangas complex in southern Finland are characterized by high pH values ranging up to 9.5. These values are significantly higher than those observed in silicate-rich shallow groundwater formations in crystalline bedrock areas. TheVirttaankangas sediments were discovered to contain small amounts of fine grained, dispersed calcite, which has a high tendency to increase the pH of local groundwaters. The primary goal of this study was to determine the mode of occurrence of calcite and to identifyits sources. The mineralogy of the glacigenic Virttaankangas complex was studied using material from 21 sediment drill cores. Fine-grained calcite is present in trace amounts (<< 1.4 % in the glaciofluvial and glaciolacustrine depositional units of the Virttaankangas complex. The topmost littoral sands were practically devoid of calcite. The isotope records of carbon and oxygen, the angular morphology of the grains and the uniform dispersion of calcite in the complex suggest a clastic origin for calcite, with no evidence for in-situ precipitation. In order to constrain the source of calcite, the isotopic composition of carbon and oxygen in five calcite samples was compared to the isotopic data from five carbonate rock erratics and eight crystalline bedrock samples from the region. Based on carbon and oxygen isotope ratios and chemical compositions, the dispersed calcite grains of the Virttaankangas complex appear to have been derived from the Mesoproterozoic Satakunta Formation, some 30 km NW from the Virttaankangas area. In sandstone, calcite is predominantly present as diagenetic cement in grain interspaces, concretions and interlayers. The source of detrital calcite was unexpected, as prior to this study the Satakunta sandstone hasnot been known to contain calcite.

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

    Science.gov (United States)

    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

  19. An investigation of the heterogeneous nucleation of calcite

    International Nuclear Information System (INIS)

    House, W.A.; Tutton, J.A.

    1982-01-01

    The heterogeneous precipitation kinetics of calcite from dilute calcium bicarbonate solutions onto pyrex glass seeds is investigated by using a modified form of the Davies and Jones equation. The rate constant is evaluated from experiments using calcite seeds and it is demonstrated that the growth rate does not increase in proportion to the increase in surface area accompanying precipitation. The number of heteronucleated particles is estimated by assuming a constant density of growth sites on the different calcite surfaces. A comparison is made between the specific surface areas of calcite obtained by the calcium-45 isotopic exchange method and other values. (orig.)

  20. Atom-resolved AFM imaging of calcite nanoparticles in water

    International Nuclear Information System (INIS)

    Imada, Hirotake; Kimura, Kenjiro; Onishi, Hiroshi

    2013-01-01

    Highlights: ► An advanced frequency-modulation AFM (FM-AFM) was applied for imaging particles. ► Atom-resolved topography of nano-sized particles of calcite was observed in water. ► Locally ordered structures were found and assigned to a (104) facet of calcite. ► A promising ability of FM-AFM was demonstrated in imaging nano-sized particles. - Abstract: The atom-resolved topography of calcite nanoparticles was observed in water using a frequency-modulation atomic force microscope. Locally ordered structures were found and assigned to a (104) facet of crystalline calcite

  1. Unconventional shallow biogenic gas systems

    Science.gov (United States)

    Shurr, G.W.; Ridgley, J.L.

    2002-01-01

    Unconventional shallow biogenic gas falls into two distinct systems that have different attributes. Early-generation systems have blanketlike geometries, and gas generation begins soon after deposition of reservoir and source rocks. Late-generation systems have ringlike geometries, and long time intervals separate deposition of reservoir and source rocks from gas generation. For both types of systems, the gas is dominantly methane and is associated with source rocks that are not thermally mature. Early-generation biogenic gas systems are typified by production from low-permeability Cretaceous rocks in the northern Great Plains of Alberta, Saskatchewan, and Montana. The main area of production is on the southeastern margin of the Alberta basin and the northwestern margin of the Williston basin. The huge volume of Cretaceous rocks has a generalized regional pattern of thick, non-marine, coarse clastics to the west and thinner, finer grained marine lithologies to the east. Reservoir rocks in the lower part tend to be finer grained and have lower porosity and permeability than those in the upper part. Similarly, source beds in the units have higher values of total organic carbon. Patterns of erosion, deposition, deformation, and production in both the upper and lower units are related to the geometry of lineament-bounded basement blocks. Geochemical studies show that gas and coproduced water are in equilibrium and that the fluids are relatively old, namely, as much as 66 Ma. Other examples of early-generation systems include Cretaceous clastic reservoirs on the southwestern margin of Williston basin and chalks on the eastern margin of the Denver basin. Late-generation biogenic gas systems have as an archetype the Devonian Antrim Shale on the northern margin of the Michigan basin. Reservoir rocks are fractured, organic-rich black shales that also serve as source rocks. Although fractures are important for production, the relationships to specific geologic structures are

  2. [Advances in researches of biogenic molluscicides].

    Science.gov (United States)

    Xue, Li; Jian-Rong, Dai; Yun-Tian, Xing

    2017-01-05

    Biogenic molluscicides refer to the use of plants, animals and micro-organisms or their metabolites, and synthesis biomimetic molluscicides to kill Oncomelania hupensis snails. With the rapid development of science and technology, new biogenic molluscicides are continuously emerging and the category also continues to expand. According to the molluscicidal active ingredient and sources, at present, the biogenic molluscicides with in-depth studies include plant-derived molluscicides, micro-organism molluscicides, microbial metabolite molluscicides and animal molluscicides. This paper reviews the advances in the researches of biogenic molluscicides in recent years.

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

    Science.gov (United States)

    Meyer, H. J.

    1984-05-01

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

  4. Framework for Assessing Biogenic CO2 Emissions from Stationary Sources

    Science.gov (United States)

    This revision of the 2011 report, Accounting Framework for Biogenic CO2 Emissions from Stationary Sources, evaluates biogenic CO2 emissions from stationary sources, including a detailed study of the scientific and technical issues associated with assessing biogenic carbon dioxide...

  5. Sorption and desorption of arsenate and arsenite on calcite

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt; Postma, Diederik Jan; Jakobsen, Rasmus

    2008-01-01

    The adsorption and desorption of arsenate (As(V)) and arsenite (As(111)) oil calcite was investigated in a series of batch experiments in calcite-equilibrated solutions. The solutions covered a broad range of pH, alkalinity, calcium concentration and ionic strength. The initial arsenic...

  6. Emission polarization study on quartz and calcite.

    Science.gov (United States)

    Vincent, R. K.

    1972-01-01

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

  7. Intolerance to dietary biogenic amines : a review

    NARCIS (Netherlands)

    Jansen, SC; van Dusseldorp, M; Bottema, KC; Dubois, AEJ

    Objective: To evaluate the scientific evidence for purported intolerance to dietary biogenic amines. Data Sources: MEDLINE was searched for articles in the English language published between January 1966 and August 2001. The keyword biogenic amin* was combined with hypersens*, allergen intoler*, and

  8. Intolerance to dietary biogenic amines: A review

    NARCIS (Netherlands)

    Jansen, S.C.; Dusseldorp, M. van; Bottema, K.C.; Dubois, A.E.J.

    2003-01-01

    Objective: To evaluate the scientific evidence for purported intolerance to dietary biogenic amines. Data Sources: MEDLINE was searched for articles in the English language published between January 1966 and August 2001. The keyword biogenic amin* was combined with hypersens*, allerg*, intoler*, and

  9. Assessment of the potential for dating secondary calcite and quartz in fault zones

    International Nuclear Information System (INIS)

    Morency, Maurice

    1982-03-01

    Calcite and quartz occur frequently as secondary minerals in faults. In many instances these minerals are not deformed. Calcite, for example, often exhibits an undisturbed fibrous habit or appears as euhedral crystals. Direct dating of euhedral crystals would provide a minimum age of the last movement along a fault, whereas dating of fibrous crystals would furnish the real age of the last movement. This information would be essential in the evaluation and selection of sites for both nuclear power reactors and nuclear waste disposal. In the Canadian context, to be successful, the technique should be able to date minerals as old as tens of millions of years. In this study both isotopic and radioactive damage techniques were considered. It was found that thermoluminescence, thermally stimulated current, and electron spin resonance offer possibilities. Recent electron spin resonance studies of ancient flints have yielded dates of several hundred million years. It is anticipated that in the near future a combination of the above techniques will be extensively used in the field of geochronology

  10. Calcite biomineralization by bacterial isolates from the recently discovered pristine karstic herrenberg cave.

    Science.gov (United States)

    Rusznyák, Anna; Akob, Denise M; Nietzsche, Sándor; Eusterhues, Karin; Totsche, Kai Uwe; Neu, Thomas R; Frosch, Torsten; Popp, Jürgen; Keiner, Robert; Geletneky, Jörn; Katzschmann, Lutz; Schulze, Ernst-Detlef; Küsel, Kirsten

    2012-02-01

    Karstic caves represent one of the most important subterranean carbon storages on Earth and provide windows into the subsurface. The recent discovery of the Herrenberg Cave, Germany, gave us the opportunity to investigate the diversity and potential role of bacteria in carbonate mineral formation. Calcite was the only mineral observed by Raman spectroscopy to precipitate as stalactites from seepage water. Bacterial cells were found on the surface and interior of stalactites by confocal laser scanning microscopy. Proteobacteria dominated the microbial communities inhabiting stalactites, representing more than 70% of total 16S rRNA gene clones. Proteobacteria formed 22 to 34% of the detected communities in fluvial sediments, and a large fraction of these bacteria were also metabolically active. A total of 9 isolates, belonging to the genera Arthrobacter, Flavobacterium, Pseudomonas, Rhodococcus, Serratia, and Stenotrophomonas, grew on alkaline carbonate-precipitating medium. Two cultures with the most intense precipitate formation, Arthrobacter sulfonivorans and Rhodococcus globerulus, grew as aggregates, produced extracellular polymeric substances (EPS), and formed mixtures of calcite, vaterite, and monohydrocalcite. R. globerulus formed idiomorphous crystals with rhombohedral morphology, whereas A. sulfonivorans formed xenomorphous globular crystals, evidence for taxon-specific crystal morphologies. The results of this study highlighted the importance of combining various techniques in order to understand the geomicrobiology of karstic caves, but further studies are needed to determine whether the mineralogical biosignatures found in nutrient-rich media can also be found in oligotrophic caves.

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

    NARCIS (Netherlands)

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

    2012-01-01

    Calcite–water interactions are important not only in carbon sequestration and the global carbon cycle, but also in contaminant behaviour in calcite-bearing host rock and in many industrial applications. Here we quantify the effect of variations in surface structure on calcite surface reactivity.

  12. Investigating the Physical Basis of Amorphous Precursor Transformation to Calcite Using Patterned Alkanethiol Surfaces

    Science.gov (United States)

    Wang, D.; Wallace, A.; Han, T. Y.; Lee, J. R.; Hailey, P. D.; de Yoreo, J. J.; Dove, P. M.

    2007-12-01

    Increasing evidence from X-ray Absorption Spectroscopy and Environmental Scanning Electron Microscopy (ESEM) studies of biominerals extracted from calcifying organisms show that amorphous calcium carbonate (ACC) plays a key role in the initial formation of carbonate minerals and in shaping them into complex morphologies. Echinoderms and possibly a wide variety of other organisms, use ACC as a precursor phase. The ACC is first formed within spatial and temporally controlled environments such as vesicles, followed by a subsequent onset of mineralization that transforms the precursor into a fully crystalline material. Recent studies on sea urchin embryos have shown that during this transformation, ACC develops short-range order that resembles calcite before fully crystallizing. While this "non-traditional" process is recognized, the mechanisms and factors that govern this transformation remain poorly understood. Of particular interest are the roles of water, and the functional group chemistry of surfaces and macromolecules within mineralization environments. To investigate these questions, we have developed an experimental approach using ESEM that allows us to control impurity concentration, surface functionality and water content through the degree of water condensation. Patterned self-assembled monolayers (SAM) of hydrophilic moieties with domains of approximately 25 microns in diameter are used to form an array of micro-reactors. ACC particles with known composition are then deposited on the patterns. Condensing water in the ESEM initializes the transformation of ACC to calcite. Our results show that in saturated water vapor, ACC swells, but no obvious faceting of the material occurs. It is only in bulk water, via dissolution/crystallization, where the calcite grown on carboxyl-terminated surfaces is found with the often-observed \\{013\\} nucleation face. We use this insight to understand the role of the different chemical moieties on ACC to calcite transformation

  13. Geometry of calcite cemented zones in shallow marine sandstones

    Energy Technology Data Exchange (ETDEWEB)

    Walderhaug, O.; Prestholm, E.; Oexnevad, I.E.I.

    1995-12-31

    In offshore oil production, tightly cemented calcite zones often form impermeable barriers to fluid flow an so adversely affect reservoir performance. Based on recent breakthroughs in the theory of the formation of calcite cemented zones, the project discussed in this paper was concerned with (1) Performing outcrop studies in order to increase the existing database on the geometry of calcite cemented zones, (2) Extending and refining methods of predicting the geometry of cored calcite cemented zones, and (3) Applying and illustrating the use of these methods by studying calcite cementation in shallow marine reservoir sandstones on the Norwegian shelf. The paper presents results from field work and applies these results and the criteria for recognizing geometrical forms of calcite cementation in cores to the Ula Formation of the Ula Field and the Rannoch Formation of the Gullfax Field. The results from the core and outcrop studies are integrated in a tentative identification key for cored calcite cemented zones. The work is part of PROFIT (Program for Research On Field oriented Improved recovery Technology), a research project conducted by RF - Rogaland Research in 1991-1994. 32 refs., 10 figs., 2 tabs.

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

    International Nuclear Information System (INIS)

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

    2000-01-01

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

  15. Strontium Incorporation into Calcite Generated by Bacterial Ureolysis

    International Nuclear Information System (INIS)

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

    2004-01-01

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

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

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  18. Biocementation of Concrete Pavements Using Microbially Induced Calcite Precipitation.

    Science.gov (United States)

    Jeong, Jin-Hoon; Jo, Yoon-Soo; Park, Chang-Seon; Kang, Chang-Ho; So, Jae-Seong

    2017-07-28

    In this study, the feasibility of introducing calcite-forming bacteria into concrete pavements to improve their mechanical performance was investigated. Lysinibacillus sphaericus WJ-8, which was isolated in a previous study and is capable of exhibiting high urease activity and calcite production, was used. When analyzed via scanning electron microscopy (SEM) and X-ray diffraction, WJ-8 showed a significant amount of calcite precipitation. The compressive strength of cement mortar mixed with WJ-8 cells and nutrient medium (urea with calcium lactate) increased by 10% compared with that of the controls. Energy dispersive x-ray spectroscopy analyses confirmed that the increase in strength was due to the calcite formed by the WJ-8 cells.

  19. Degeneration of biogenic superparamagnetic magnetite.

    Science.gov (United States)

    Li, Y-L; Pfiffner, S M; Dyar, M D; Vali, H; Konhauser, K; Cole, D R; Rondinone, A J; Phelps, T J

    2009-01-01

    Magnetite crystals precipitated as a consequence of Fe(III) reduction by Shewanella algae BrY after 265 h incubation and 5-year anaerobic storage were investigated with transmission electron microscopy, Mössbauer spectroscopy and X-ray diffraction. The magnetite crystals were typically superparamagnetic with an approximate size of 13 nm. The lattice constants of the 265 h and 5-year crystals are 8.4164A and 8.3774A, respectively. The Mössbauer spectra indicated that the 265 h magnetite had excess Fe(II) in its crystal-chemistry (Fe(3+) (1.990)Fe(2+) (1.015)O(4)) but the 5-year magnetite was Fe(II)-deficient in stoichiometry (Fe(3+) (2.388)Fe(2+) (0.419)O(4)). Such crystal-chemical changes may be indicative of the degeneration of superparamagnetic magnetite through the aqueous oxidization of Fe(II) anaerobically, and the concomitant oxidation of the organic phases (fatty acid methyl esters) that were present during the initial formation of the magnetite. The observation of a corona structure on the aged magnetite corroborates the anaerobic oxidation of Fe(II) on the outer layers of magnetite crystals. These results suggest that there may be a possible link between the enzymatic activity of the bacteria and the stability of Fe(II)-excess magnetite, which may help explain why stable nano-magnetite grains are seldom preserved in natural environments.

  20. Degeneration of Biogenic Superparamagnetic Magnetite

    Energy Technology Data Exchange (ETDEWEB)

    Li, Dr. Yi-Liang [University of Tennessee, Knoxville (UTK); Pfiffner, Susan M. [University of Tennessee, Knoxville (UTK); Dyar, Dr. M Darby [Mount Holyoke College; Vali, Dr. Hojatolah [McGill University, Montreal, Quebec; Konhauser, Dr, Kurt [University of Alberta; Cole, David R [ORNL; Rondinone, Adam Justin [ORNL; Phelps, Tommy Joe [ORNL

    2009-01-01

    ABSTRACT. Magnetite crystals precipitated as a consequence of Fe(III) reduction by Shewanella algae BrY after 265 hours incubation and 5-year storage were investigated with transmission electron microscopy, M ssbauer spectroscopy and X-ray diffraction. The magnetite crystals were typically superparamagnetic with an approximate size of 13 nm. The lattice constants of the 265 hour and 5-year crystals are 8.4164 and 8.3774 , respectively. The M ssbauer spectra indicated that the 265 hour magnetite had excess Fe(II) in its crystal-chemistry (Fe3+1.9901Fe2+ 1.0149O4) but the 5-year magnetite was Fe(II)-deficient in stoichiometry (Fe3+2.3875Fe2+0.4188O4). Such crystal-hemical changes may be indicative of the degeneration of superparamagnetic magnetite through the aqueous oxidization of Fe(II) anaerobically, and the concomitant oxidation of the organic phases(fatty acid methyl esters) that were present during the initial formation of the magnetite. The observation of a corona structure on the aged magnetite corroborates the oxidation of Fe(II) on the outer layers of magnetite crystals. These results suggest that there may be a possible link between the enzymatic activity of the bacteria and the stability of Fe(II)-excess magnetite, which may help explain why stable nano-magnetite grains are seldom preserved in natural environments.

  1. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    DEFF Research Database (Denmark)

    Madsen, Lene; Grahl-Madsen, Laila; Grøn, Christian

    1996-01-01

    The wettability of hydrocarbon reservoirs depends on how and to what extent the organic compounds are adsorbed onto the surfaces of calcite, quartz and clay. A model system of synthetic call cite, cyclohexane and the three probe molecules: benzoic acid, benzyl alcohol and benzylamine, have been...... of magnitude of Delta G degrees for the adsorption process implies the formation of a strong bond between the calcite surface and the adsorbate molecules. Copyright (C) 1996 Elsevier Science Ltd....

  2. Biogenic emissions modeling for Southeastern Texas

    Energy Technology Data Exchange (ETDEWEB)

    Estes, M.; Jacob, D.; Jarvie, J. [Texas Natural Resource Conservation Commission, Austin, TX (United States)] [and others

    1996-12-31

    The Texas Natural Resource Conservation Commission (TNRCC) modeling staff performed biogenic hydrocarbon emissions modeling in support of gridded photochemical modeling for ozone episodes in 1992 and 1993 for the Coastal Oxidant Assessment for Southeast Texas (COAST) modeling domain. This paper summarizes the results of the biogenic emissions modeling and compares preliminary photochemical modeling results to ambient air monitoring data collected during the 1993 COAST study. Biogenic emissions were estimated using BIOME, a gridded biogenic emissions model that uses region-specific land use and biomass density data, and plant species-specific emission factor data. Ambient air monitoring data were obtained by continuous automated gas chromatography at two sites, one-hour canister samples at 5 sites, and 24-hour canister samples at 13 other sites. The concentrations of Carbon Bond-IV species (as determined from urban airshed modeling) were compared to measured hydrocarbon concentrations. In this paper, we examined diurnal and seasonal variations, as well as spatial variations.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

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

    2012-04-01

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

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

    Science.gov (United States)

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Ke; De Andrade, Vincent; Feng, Zhange; Sturchio, Neil C. [Department; Lee, Sang Soo; Fenter, Paul

    2018-01-22

    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 (CaCO3) 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 (PbCO3) was observed, where nucleation occurred entirely within a pore space created by dissolution at the calcite/substrate interface. Uneven growth rates yielded a 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.

  7. Calcites from Ocean Crust Basalts: Reliable Proxy Archives?

    Science.gov (United States)

    Böhm, Florian; Eisenhauer, Anton

    2017-04-01

    Calcite cements in ocean crust basalts of the deep sea form from mixtures of cold seawater and warm hydrothermal fluids (about 0-70°C). These low temperature alteration (LTA) calcites have recently gained new interest as proxy recorders of seawater composition (Refs. 1-5). Recent LTA calcite reconstructions of the Sr/Ca and Mg/Ca evolution in ocean waters point to considerably lower Sr/Ca and Mg/Ca ratios during the Cretaceous and Paleogene than in the modern ocean. However, diagenetic alteration in contact with the basalt host rock may change the composition of the LTA calcites. For testing the reliability of LTA calcite records of seawater composition multi-proxy approaches are applied: oxygen isotopes indicate precipitation temperatures, strontium isotopes (87Sr/86Sr) and trace elements indicate influences from hydrothermal fluids. Additional information about the influence of basement rocks on LTA calcite composition can be derived from analyses of stable calcium and strontium isotopes (44/40Ca, 88/86Sr). We find low 44/40Ca values for DSDP and ODP sites where the 87Sr/86Sr ratios of LTA calcites indicate basement influence. On the other hand, for some sites the 87Sr/86Sr values inidicate precipitation from pristine seawater, while low 44/40Ca values indicate basement influence. All of these sites are either older than 50 Myr or show calcite precipitation temperatures >50°C. Sites that are younger than 25 Myr and had formation temperatures 50°C significantly higher 88/86Sr values were observed. The calcium isotope results indicate basement influence on LTA calcite composition at temperatures >10°C. Radiogenic strontium isotopes, in contrast, can be used as unequivocal basement influence indicators only at temperatures above 30°C. Below about 20°C 87Sr/86Sr ratios are no reliable indicators of basement influence. All LTA calcites of sites older than 50 Myr formed (or recrystallized) at temperatures >15°C. Low 44/40Ca values indicate that

  8. The Raman spectrum of CaCO{sub 3} polymorphs calcite and aragonite: A combined experimental and computational study

    Energy Technology Data Exchange (ETDEWEB)

    De La Pierre, Marco, E-mail: cedric.carteret@univ-lorraine.fr, E-mail: marco.delapierre@unito.it; Maschio, Lorenzo; Orlando, Roberto; Dovesi, Roberto [Dipartimento di Chimica, Università di Torino and NIS (Nanostructured Interfaces and Surfaces) Centre of Excellence, Via P. Giuria 7, 10125 Torino (Italy); Carteret, Cédric, E-mail: cedric.carteret@univ-lorraine.fr, E-mail: marco.delapierre@unito.it; André, Erwan [Laboratoire de Chimie Physique et Microbiologie pour l’Environnement (LCPME), UMR 7564, Université de Lorraine-CNRS, 405 rue de Vandoeuvre, 54601 Villers-lès-Nancy (France)

    2014-04-28

    Powder and single crystal Raman spectra of the two most common phases of calcium carbonate are calculated with ab initio techniques (using a “hybrid” functional and a Gaussian-type basis set) and measured both at 80 K and room temperature. Frequencies of the Raman modes are in very good agreement between calculations and experiments: the mean absolute deviation at 80 K is 4 and 8 cm{sup −1} for calcite and aragonite, respectively. As regards intensities, the agreement is in general good, although the computed values overestimate the measured ones in many cases. The combined analysis permits to identify almost all the fundamental experimental Raman peaks of the two compounds, with the exception of either modes with zero computed intensity or modes overlapping with more intense peaks. Additional peaks have been identified in both calcite and aragonite, which have been assigned to {sup 18}O satellite modes or overtones. The agreement between the computed and measured spectra is quite satisfactory; in particular, simulation permits to clearly distinguish between calcite and aragonite in the case of powder spectra, and among different polarization directions of each compound in the case of single crystal spectra.

  9. Biogenic magnetite as a primary remanence carrier in limestone deposits

    Science.gov (United States)

    Chang, Shih-Bin R.; Kirschvink, Joseph L.; Stolz, John F.

    1987-06-01

    Studies on the microbial communities and magnetic phases of samples collected from carbonate oozes at Sugarloaf Key, FL, U.S.A. and calcareous laminated sediments from Laguna Figueroa, Baja California, Mexico have revealed the existence of magnetotactic bacteria and ultrafine-grained single domain magnetite in both environments. Magnetotactic bacteria were identified by light and electron microscopy. The single domain magnetite was detected by coercivity spectra analysis with a SQUID magnetometer and examined under the transmission electron microscope. The similarity, in terms of size and shape, between the single domain magnetite found in these sediments and the magnetite observed in the bacterial magnetosome from enriched cultures indicates the ultrafine-grained magnetite in these two marine environments was biologically formed. These results, combined with the common occurrences of ultrafine-grained magnetite in limestone deposits detected rock magnetically, suggest biogenic magnetite may be present and contribute to the magnetic remanence in these rocks. Several Cambrian limestone samples, separately collected from Siberia, China, and Kazakhstan, were examined for the presence of bacterial magnetite. Samples from the Lower Cambrian Sinskian Formation at Siberia Platform were found to contain both a large amount of apparently bacterial magnetite particles and a very stable primary magnetic component. Post-Cambrian diagenesis does not seem to affect the microgranulometry of these apparently bacterial magnetite crystals or the magnetic remanence carried by them. Assessing the potential role of biogenic magnetite as a primary remanence carrier in other Phanerozoic limestone deposits ought to be further pursued.

  10. Light reflection control in biogenic micro-mirror by diamagnetic orientation.

    Science.gov (United States)

    Iwasaka, Masakazu; Mizukawa, Yuri

    2013-04-02

    As has become known, most materials, such as proteins and DNA, show orientation under strong magnetic fields. However, the critical threshold for the magnetic field of the magnetomechanical phenomena is still unknown. We demonstrate that a thin micro-mirror from a fish scale with high reflectivity exhibits a distinct magnetic response at 100 mT. A dramatic event under a magnetic field is the decrease of light scattering from guanine crystals as well as rapid rotation against the applied magnetic field. Enhancement of light scattering intensity is also observed when the three vectors of light incidence, magnetic field, and observation are orthogonally directed. The results indicate that biogenic guanine crystals have a large diamagnetic anisotropy along the surface parallel and normal directions. The micrometer to submicrometer scale of thin biogenic plates can act as a noninvasively, magnetically controlled micro-mirror for light irradiation control in the micrometer-scale region.

  11. Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    DePaolo, D.

    2010-10-15

    A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R{sub p}) to the gross forward precipitation rate (R{sub f}), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R{sub p} has been experimentally measured under varying conditions, but the magnitude of R{sub f} is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R{sub f} can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R{sub b} or k{sub b}), since at equilibrium R{sub f} = R{sub b}, and R{sub p} = 0. Hence it can be inferred that R{sub f} {approx} R{sub p} + R{sub b}. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R{sub p} (= R{sub f} - R{sub b}) << R{sub b}. For precipitation rates high enough that R{sub p} >> R{sub b}, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R{sub p} {approx} R{sub b} for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R{sub f} for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R{sub p

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

  14. On the formation and functions of high and very high magnesium calcites in the continuously growing teeth of the echinoderm Lytechinus variegatus: development of crystallinity and protein involvement.

    Science.gov (United States)

    Veis, Arthur; Stock, Stuart R; Alvares, Keith; Lux, Elizabeth

    2011-01-01

    Sea urchin teeth grow continuously and develop a complex mineralized structure consisting of spatially separate but crystallographically aligned first stage calcitic elements of high Mg content (5-15 mol% mineral). These become cemented together by epitaxially oriented second stage very high Mg calcite (30-40 mol% mineral). In the tooth plumula, ingressing preodontoblasts create layered cellular syncytia. Mineral deposits develop within membrane-bound compartments between cellular syncytial layers. We seek to understand how this complex tooth architecture is developed, how individual crystalline calcitic elements become crystallographically aligned, and how their Mg composition is regulated. Synchrotron microbeam X-ray scattering was performed on live, freshly dissected teeth. We observed that the initial diffracting crystals lie within independent syncytial spaces in the plumula. These diffraction patterns match those of mature tooth calcite. Thus, the spatially separate crystallites grow with the same crystallographic orientation seen in the mature tooth. Mineral-related proteins from regions with differing Mg contents were isolated, sequenced, and characterized. A tooth cDNA library was constructed, and selected matrix-related proteins were cloned. Antibodies were prepared and used for immunolocaliztion. Matrix-related proteins are acidic, phosphorylated, and associated with the syncytial membranes. Time-of-flight secondary ion mass spectroscopy of various crystal elements shows unique amino acid, Mg, and Ca ion distributions. High and very high Mg calcites differ in Asp content. Matrix-related proteins are phosphorylated. Very high Mg calcite is associated with Asp-rich protein, and it is restricted to the second stage mineral. Thus, the composition at each part of the tooth is related to architecture and function. Copyright © 2011 S. Karger AG, Basel.

  15. BIOGENIC AMINES CONTENT IN DIFFERENT WINE SAMPLES

    Directory of Open Access Journals (Sweden)

    Attila Kántor

    2015-02-01

    Full Text Available Twenty-five samples of different Slovak wines before and after filtration were analysed in order to determine the content of eight biogenic amines (tryptamine, phenylalanine, putrescine, cadaverine, histamine, tyramine, spermidine and spermine. The method involves extraction of biogenic amines from wine samples with used dansyl chloride. Ultra-high performance liquid chromatography (UHPLC was used for determination of biogenic amines equipped with a Rapid Resolution High Definition (RRHD, DAD detectors and Extend-C18 LC column (50 mm x 3.0 mm ID, 1.8 μm particle size. In this study the highest level of biogenic amine in all wine samples represent tryptamine (TRM with the highest content 170.9±5.3 mg/L in Pinot Blanc wine. Phenylalanine (PHE cadaverine (CAD, histamine (HIS and spermidine (SPD were not detected in all wines; mainly SPD was not detected in 16 wines, HIS not detected in 14 wines, PHE and CAD not detected in 2 wines. Tyramine (TYR, spermine (SPN and putrescine (PUT were detected in all wines, but PUT and SPN in very low concentration. The worst wine samples with high biogenic amine content were Saint Laurent (BF, Pinot Blanc (S and Pinot Noir (AF.

  16. Geochemical signatures of fluid paleo-transfer in fracture filling calcite from low permeability rock masses: examples taken from Bure's and Tournemire's site in France and northern Switzerland; Signatures geochimiques de paleocirculations aqueuses dans la calcite de remplissage de fracture de massifs argileux peu permeables et de leurs encaissants: exemples pris sur les sites de Bure, Tournemire et Suisse du nord

    Energy Technology Data Exchange (ETDEWEB)

    Lecocq, D

    2002-12-15

    Fractures in rock masses represent preferential path for fluid transfer and, as such, are the most efficient way for migration of radionuclides at a regional scale. The impact of fracturing on hydrogeological system is a major challenge for underground radioactive waste storage projects. In this context, geochemistry of fracture-filling calcite is used to better understand physical and chemical properties of palaeo-fluids. A new methodology has been developed to analyze Mg, Mn, Fe, Sr and Rare Earth Elements REE (La, Ce, Nd, Sm, Eu, Dy and Yb) in calcite by Secondary Ion Mass Spectrometry. Analyses of calcite crystals have been performed in fractures from Jurassic clays and limestones in France (Bure and Tournemire sites) and northern Switzerland (Mt Terri's tunnel and deep borehole). On each case, several geochemical signatures are observed, according to REE partitioning and Mn and Fe concentrations. In the Bure site, a dependence of calcite geochemistry from fracture host rock has been evidenced. On the other hand, speciation of REE in solution equilibrated with clayey or calcareous rocks at circum-neutral pH (7 to 8) is not significantly influenced by the media: speciation is dominated by carbonate species in both cases and phosphate complexes can modify heavy REE availability in relatively to light REE. These results point out that in fractures in clays, calcite crystallizes at equilibrium with a fluid expulsed during diagenesis from clay minerals, recording the effect of clays and accessory phases. In limestone fractures, calcite records a later event related to the past functioning of the present aquifer, and the fluid has reached equilibrium with the rock minerals. In secondary filling calcite from Toarcian Argilites faults close to Tournemire's tunnel, three successive generations of calcite are observed in an extensive fault, and a fourth in a compressive one. In Aalenian Opalinus Clays veins, comparison between existing isotopic data and Mn, Fe

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

    Science.gov (United States)

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

    2016-03-01

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

  18. The ABAG biogenic emissions inventory project

    Science.gov (United States)

    Carson-Henry, C. (Editor)

    1982-01-01

    The ability to identify the role of biogenic hydrocarbon emissions in contributing to overall ozone production in the Bay Area, and to identify the significance of that role, were investigated in a joint project of the Association of Bay Area Governments (ABAG) and NASA/Ames Research Center. Ozone, which is produced when nitrogen oxides and hydrocarbons combine in the presence of sunlight, is a primary factor in air quality planning. In investigating the role of biogenic emissions, this project employed a pre-existing land cover classification to define areal extent of land cover types. Emission factors were then derived for those cover types. The land cover data and emission factors were integrated into an existing geographic information system, where they were combined to form a Biogenic Hydrocarbon Emissions Inventory. The emissions inventory information was then integrated into an existing photochemical dispersion model.

  19. Biogenic scorodite crystallization by Acidianus sulfidivorans for arsenic removal

    NARCIS (Netherlands)

    Gonzalez-Contreras, P.A.; Weijma, J.; Weijden, van der R.D.; Buisman, C.J.N.

    2010-01-01

    Scorodite is an arsenic mineral with the chemical formula FeAsO4·2H2O. It is the most common natural arsenate associated with arsenic-bearing ore deposits. In the present study we show that the thermoacidophilic iron-oxidizing archaeon Acidianus sulfidivorans is able to precipitate scorodite in the

  20. Sulphate partitioning into calcite: Experimental verification of pH control and application to seasonality in speleothems

    Science.gov (United States)

    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

  1. Surface tension alteration on calcite, induced by ion substitution

    DEFF Research Database (Denmark)

    Sakuma, Hiroshi; Andersson, Martin Peter; Bechgaard, Klaus

    2014-01-01

    The interaction of water and organic molecules with mineral surfaces controls many processes in nature and industry. The thermodynamic property, surface tension, is usually determined from the contact angle between phases, but how does one understand the concept of surface tension at the nanoscale...... preferentially as ion pairs at solution-calcite interfaces. Mg2+ incorporation weakens organic molecule adhesion while strengthening water adsorption so Mg2+ substitution renders calcite more water wet. When Mg2+ replaces 10% of surface Ca2+, the contact angle changes dramatically, by 40 to 70, converting...

  2. TL studies of quaternary biogenic carbonate deposits of Saurashtra, Western India

    International Nuclear Information System (INIS)

    Patel, M.P.; Bhatt, Nilesh; Murthy, K.V.R.

    1992-01-01

    The quaternary biogenic carbonate deposits of Saurashtra, coastal as well as inland, comprise the beach rocks, miliolites and the stabilised sand dunes. The beach rocks contain the varieties of megafossils and broken shell fragments while the miliolites are granular made up of medium to fine grained, well sorted, abraded to finely abraded and even pelletised microfossils and shell fragments. The various constituents of the beach rocks and miliolites are cemented together by a fine calcite cement. The carbonate sand dunes contain relatively less amount of biogenic material and are rich in quartz. Age wise, the well consolidated beach rocks and miliolites are older (middle to later upper pleistocene) as compared to poorly consolidated coastal stabilised younger sand dunes (holocene). Chemically the former are rich in CaCO 3 while the latter are rich in SiO 2 . TL studies of the representative samples of beach rocks, miliolites and sand dunes clearly suggest that the glow curves of beach rocks and miliolites differ from that of sand dunes. Again, the existence of close similarity between the ATL/NTL curves for beach rocks and miliolites substantiate their close affinity in the field. (author). 14 refs., 2 tabs., 2 figs

  3. A new overall kinetic model describing calcite precipitation from brine-like solutions

    Science.gov (United States)

    Charara, M.; Lopez, O.; Zuddas, P.

    2005-12-01

    Future CO2 injections would modify strongly the physic and the chemistry of the brine aquifer hosts (i.e. temperature, chemical composition, PCO2 partial pressure etc...). Although many geological systems can be represented using thermodynamic concepts and principles, the factors governing their fate and evolution can only be understood if the kinetics and mechanisms of reactions are well known. One of the most important problems in the application of carbonate fluid-rock interactions is the function governing the variation on precipitation rate. A general rate law describing the calcite precipitation is: R=k,f(PCO2),g(I),h(T),φ(Π ai),φ([CO32-]) where R is the precipitation rate, k is the apparent kinetic constant of caclite crystal growth, PCO2 is the partial pressure of CO2 at equilibrium (from 30 to 3.104Pa), I is the fluid ionic strength (from 0.1 to 1 mol.kg-1), T is the temperature (from 5 to 60°C), ai is the activity of the specific brine constituents (accelerators, inhibitors, both organic and inorganic) and [CO32-] is the concentration in carbonate ion (from 100 to 400 mmol.kg-1) assumed to be the macroscopical variable governing the overall reaction. Based on parametric inversion of previous and new kinetic data, we established an empirical model describing the variation of calcite precipitation rate as a function of these multiset parameters and variables. The model robustness validation (square correlation coefficient of 0.95) was obtained by compairing experimental measured and calculated rates. We found that, despite temperature and fluid ionic strength rule the reaction kinetic mechanisms, the variation of PCO2 partial pressure enhances by three orders of magnitude the rate of calcite precipitation even in completly buffered brine-like conditions. Our results indicate that, in present day sedimentary basins, the main role played by PCO2 partial pressure is independent from the desequilibrium condition contrar to both temperature and ionic

  4. Shock Waves Trigger Fault Weakening in Calcite-bearing Rocks During Earthquakes

    Science.gov (United States)

    Spagnuolo, E.; Plumper, O.; Violay, M.; Cavallo, A.; Di Toro, G.

    2014-12-01

    The weakening mechanism of calcite-bearing rocks is still poorly understood though many major earthquakes stroke within carbonate sequences. Insights derive from the laboratory: in experiments performed on calcite-bearing gouges, up to 90% drop in friction is associated to grain size reduction to the nanoscale and the formation of crystal-plastic microstructures suggesting the activation of debated weakening mechanisms (e.g., grain boundary sliding and diffusion creep; nanopowder lubrication). Whatever the case, it is unclear how nanoparticles form and what their role is at the initiation of sliding. To investigate initial fault instability we sheared with a rotary shear apparatus SHIVA pre-cut ring-shaped solid cylinders (50/30 mm ext/int diameter) of Carrara marble (99.9% CaCO3). Rock cylinders were slid for few millimetres(0, 1.5 mm and 5mm) at accelerations (6.5 ms-2) and normal stresses (10 MPa) approaching seismic deformation conditions. Initial slip (<2 mm) was concomitant with large frictional weakening (up to 30% of static friction) and CO2emission. Microanalytical observations (FE-SEM, FIB-SEM and TEM) showed that the experimental slipping zones consisted of (1) defects structures, including dislocations, cleavage surfaces and deformation features such as mechanical twins, partially burden beneath (2) a 2-10 micrometer thick layer of nanograins where pervasive nano-fracturing have occurred preserving the grain shape (pulverization) and (3) reaction products attributable to high pressure and high temperature conditions (i.e. calcite decomposition into amorphous carbon rimming the nanograins). All the above features are typical of shock-induced changes in minerals. We interpret the above observations as follows: pre-existing grain boundaries or newly formed defects are the nuclei for the generation of dislocations and for their pile-up; the fast release of those piles-up in avalanches under rapid stress loading (fast moving dislocations) may explain the

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

    Science.gov (United States)

    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

  6. Ionising radiation effect on the luminescence emission of inorganic and biogenic calcium carbonates

    Energy Technology Data Exchange (ETDEWEB)

    Boronat, C. [CIEMAT, Av. Complutense 40, Madrid 28040 (Spain); Correcher, V., E-mail: v.correcher@ciemat.es [CIEMAT, Av. Complutense 40, Madrid 28040 (Spain); Virgos, M.D. [CIEMAT, Av. Complutense 40, Madrid 28040 (Spain); Garcia-Guinea, J. [CSIC, Museo Nacional Ciencias Naturales, José Gutiérrez Abascal 2, Madrid 28006 (Spain)

    2017-06-15

    Highlights: • Aragonite and biogenic Ca-carbonates could be used as a TL dosimeters. • TL can be employed for retrospective dosimetry purposes. • Calcium carbonates show an acceptable ionizing radiation sensitivity. • The stability of the radiation–induced TL remains, at least, till 700 h. - Abstract: As known, the luminescence emission of mineral phases could be potentially employed for dosimetric purposes in the case of radiological terrorism or radiation accident where conventional monitoring is not available. In this sense, this paper reports on the thermo- (TL) and cathodoluminescence (CL) emission of both biogenic (common periwinkle – littorina littorera – shell made of calcite 90% and aragonite 10%) and inorganic (aragonite 100%) Ca-rich carbonates previously characterized by X-ray diffraction and Raman spectroscopy. Whereas the aragonite sample displays the main CL waveband peaked in the red region (linked to point defects), the more intense emission obtained from the common periwinkle shell appears at higher energies (mainly associated with structural defects). The UV-blue TL emission of the samples, regardless of the origin, displays (i) an acceptable ionizing radiation sensitivity, (ii) linear dose response in the range of interest (up to 8 Gy), (iii) reasonable stability of the TL signal after 700 h of storage with an initial decay of ca. 88% for the mineral sample and 60% for the biogenic sample and maintaining the stability from 150 h onwards. (iv) The tests of thermal stability of the TL emission performed in the range of 180–320 °C confirm a continuum in the trap system.

  7. Ionising radiation effect on the luminescence emission of inorganic and biogenic calcium carbonates

    International Nuclear Information System (INIS)

    Boronat, C.; Correcher, V.; Virgos, M.D.; Garcia-Guinea, J.

    2017-01-01

    Highlights: • Aragonite and biogenic Ca-carbonates could be used as a TL dosimeters. • TL can be employed for retrospective dosimetry purposes. • Calcium carbonates show an acceptable ionizing radiation sensitivity. • The stability of the radiation–induced TL remains, at least, till 700 h. - Abstract: As known, the luminescence emission of mineral phases could be potentially employed for dosimetric purposes in the case of radiological terrorism or radiation accident where conventional monitoring is not available. In this sense, this paper reports on the thermo- (TL) and cathodoluminescence (CL) emission of both biogenic (common periwinkle – littorina littorera – shell made of calcite 90% and aragonite 10%) and inorganic (aragonite 100%) Ca-rich carbonates previously characterized by X-ray diffraction and Raman spectroscopy. Whereas the aragonite sample displays the main CL waveband peaked in the red region (linked to point defects), the more intense emission obtained from the common periwinkle shell appears at higher energies (mainly associated with structural defects). The UV-blue TL emission of the samples, regardless of the origin, displays (i) an acceptable ionizing radiation sensitivity, (ii) linear dose response in the range of interest (up to 8 Gy), (iii) reasonable stability of the TL signal after 700 h of storage with an initial decay of ca. 88% for the mineral sample and 60% for the biogenic sample and maintaining the stability from 150 h onwards. (iv) The tests of thermal stability of the TL emission performed in the range of 180–320 °C confirm a continuum in the trap system.

  8. New Environmentalconditions Responsible for the amount of mg Incorporated in Biogenic Carbonates

    Science.gov (United States)

    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

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

    Energy Technology Data Exchange (ETDEWEB)

    Branson, Oscar; Bonnin, Elisa A.; Perea, Daniel E.; Spero, Howard J.; Zhu, Zihua; Winters, Maria; Hönisch, Bärbel; Russell, Ann D.; Fehrenbacher, Jennifer S.; Gagnon, Alexander C.

    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 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 CaCO3 biomineralization.

  10. Copper incorporation in foraminiferal calcite: results from culturing experiments

    NARCIS (Netherlands)

    Nooijer, L.J. de; Reichart, G.-J.; Dueñas Bohórquez, A.D.B.; Wolthers, M.; Ernst, S.R.; Mason, P.R.D.; Zwaan, G.J. van der

    2007-01-01

    A partition coefficient for copper (DCu) in foraminiferal calcite has been determined by culturing individuals of two benthic species under controlled laboratory conditions. The partition coefficient of a trace element (TE) is an emperically determined relation between the TE/Ca ratio in seawater

  11. Molecular ordering of ethanol at the calcite surface

    DEFF Research Database (Denmark)

    Pasarín, I. S.; Yang, M.; Bovet, Nicolas Emile

    2012-01-01

    for constructing accurate predictive models for natural systems. Previous investigations of the activity of coccolith-associated polysaccharides (CAP) on calcite, using atomic force microscopy (AFM) [ Henriksen, K., Young, J. R., Bown, P. R., and Stipp, S. L. S.Palentology 2004, 43 (Part 3), 725...

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

    Science.gov (United States)

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

    2015-12-01

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

  13. Radiation-induced paramagnetic species in natural calcite speleothems

    International Nuclear Information System (INIS)

    Rossi, A.M.; Poupeau, G.

    1989-01-01

    The ESR natural spectrum of humic-free speleothem calcite single crytals in the region of g = 2.0000 is a composite of lines from 4 radiogenic species, in addition to Mn ++ lines. Laboratory irradiation causes appearrance of three more species. Use of isotropic F species (g = 2.0003) for dating is possible if specific cautions are followed. (author) [pt

  14. Removal of trace elements from landfill leachate by calcite precipitation

    Czech Academy of Sciences Publication Activity Database

    Ettler, V.; Zelená, O.; Mihaljevič, M.; Šebek, O.; Strnad, L.; Coufal, P.; Bezdička, Petr

    2006-01-01

    Roč. 88, 1-3 (2006), s. 28-31 ISSN 0375-6742 R&D Projects: GA AV ČR(CZ) KJB3111402 Institutional research plan: CEZ:AV0Z40320502 Keywords : landfill leachate * calcite * scavenging Subject RIV: CA - Inorganic Chemistry Impact factor: 0.922, year: 2006

  15. Biogenic amines in meat and meat products.

    Science.gov (United States)

    Ruiz-Capillas, Claudia; Jiménez-Colmenero, Francisco

    2004-01-01

    It has been recognized for some time that biogenic amines occur in a wide range of foods, among them meat and meat products. Meat is an important component of the diet in developed countries. The presence of these amines in food is of interest for two reasons: firstly, for toxicological reasons, in the sense that high levels of dietary biogenic amines can be toxic for certain consumers, and secondly, for their role as possible quality indicators. Based on these two premises, the present article offers a new analysis on aspects of toxicology and on the use of biogenic amines as a quality control method, as well as on their presence in meat and meat products. The article focuses particularly on factors affecting the production of biogenic amines, with reference to various parameters relating to microorganisms, meat raw materials, and processing conditions. A better understanding of the factors determining their formation (i.e., microorganisms, raw materials used, and technological processes applied) and their effects could lead to ways of controlling their production, limiting their presence in the end product, and hence, rendering them less toxic.

  16. Microbiological, physicochemical properties and biogenic amine ...

    African Journals Online (AJOL)

    Thirty three strained yoghurt samples were collected from local open markets in different provinces of Turkey (Afyon [AF], Aydın [AY], Burdur [B], Isparta [I] and Muğla [M]). Physicochemical and microbiological properties, as well as biogenic amine content, were examined in each of the samples. The dry matter (17.90 to ...

  17. Impacts of seawater saturation state (ΩA = 0.4-4.6) and temperature (10, 25 °C) on the dissolution kinetics of whole-shell biogenic carbonates

    Science.gov (United States)

    Ries, Justin B.; Ghazaleh, Maite N.; Connolly, Brian; Westfield, Isaac; Castillo, Karl D.

    2016-11-01

    Anthropogenic increase of atmospheric pCO2 since the Industrial Revolution has caused seawater pH to decrease and seawater temperatures to increase-trends that are expected to continue into the foreseeable future. Myriad experimental studies have investigated the impacts of ocean acidification and warming on marine calcifiers' ability to build protective shells and skeletons. No studies, however, have investigated the combined impacts of ocean acidification and warming on the whole-shell dissolution kinetics of biogenic carbonates. Here, we present the results of experiments designed to investigate the effects of seawater saturation state (ΩA = 0.4-4.6) and temperature (10, 25 °C) on gross rates of whole-shell dissolution for ten species of benthic marine calcifiers: the oyster Crassostrea virginica, the ivory barnacle Balanus eburneus, the blue mussel Mytilus edulis, the conch Strombus alatus, the tropical coral Siderastrea siderea, the temperate coral Oculina arbuscula, the hard clam Mercenaria mercenaria, the soft clam Mya arenaria, the branching bryozoan Schizoporella errata, and the coralline red alga Neogoniolithon sp. These experiments confirm that dissolution rates of whole-shell biogenic carbonates decrease with calcium carbonate (CaCO3) saturation state, increase with temperature, and vary predictably with respect to the relative solubility of the calcifiers' polymorph mineralogy [high-Mg calcite (mol% Mg > 4) ≥ aragonite > low-Mg calcite (mol% Mg carbonates. Furthermore, the severity of the temperature effects on gross dissolution rates also varied with respect to carbonate polymorph solubility, with warming (10-25 °C) exerting the greatest effect on biogenic high-Mg calcite, an intermediate effect on biogenic aragonite, and the least effect on biogenic low-Mg calcite. These results indicate that both ocean acidification and warming will lead to increased dissolution of biogenic carbonates in future oceans, with shells/skeletons composed of the more

  18. Ion beam modifications of defect sub-structure of calcite cleavages

    Indian Academy of Sciences (India)

    , brought about by He+ ion-bombardment of calcite cleavages (100), have been carried out. Optical and scanning ... stimulation. Planar plastic anisotropy has been studied on irradiated calcite cleavages by measurement of microhardness.

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

    Science.gov (United States)

    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.

  20. Seawater-softening process through formation of calcite ooids

    Directory of Open Access Journals (Sweden)

    A.A. Bakr

    2015-03-01

    Full Text Available Conventional water-softening processes usually involve the exchange of Na+ ions for Ca2+ and Mg2+ using commercial or synthesized ion exchangers. The differences in chemical compositions of the ooids can be attributed to the formation in different environments. In this paper, ooid grains form inside assembled semi-pilot softening unit through a continuous chemical process involving reaction between bicarbonate ions and added lime using natural seawater. Our sample of Mediterranean seawater has low Mg2+/Ca2+ ratio (1.98% within the range chemically favorable for precipitation of low-Mg calcite ooids. Precipitation of calcite occurs around pure quartz sand grains which act as nucleation points (the bed required for sand vessel is 1.65 l. The shape of the sand grains controls the overall external morphology of the resulting ooids; they vary in size from 0.5 to 3.0 mm and have a high degree of polish due to surface abrasion caused by continuous agitation inside the softening system. Calcite ooid grains (1.53 kg formed within the seawater-softening unit every 18 days have many of the ooid features formed in marine environments. Ooids grow to a significant size, at a rate of about 0.17 mm of one layer thickness per day inside the softening unit. The average weight percent of calcite precipitate is 35.48% after 18 days, at 10 °C, 60 l/min and pH 9.0. The pellets comprise mainly CaCO3 and SiO2 and some metal ions which may substitute for calcium ions in calcite are present only in trace amounts of the total composition.

  1. Molecular ordering of ethanol at the calcite surface.

    Science.gov (United States)

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

    2012-02-07

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

  2. Structural incorporation of Neptunyl(V) into Calcite: Interfacial Reactions and Kinetics

    OpenAIRE

    Heberling, Frank

    2010-01-01

    In this experimental work the calcite-water interface is characterized by means of zetapotential and surface diffraction measurements. Based on the experimental results a new Basic Stern Surface Complexation model for calcite is developed. Neptunyl(V) adsorption at the calcite surface and incorporation into the calcite structure is studied by batch type adsorption- and mixed flow reactor experiments. Adsorption and incorporation species of Neptunyl are investigated by EXAFS spectroscopy.

  3. The effect of heat treatment on the thermoluminescence of naturally-occurring calcites and their use as a gamma-ray dosimeter

    International Nuclear Information System (INIS)

    Engin, Birol; Gueven, Olgun

    2000-01-01

    The feasibility of using naturally-occurring calcite for gamma-ray dosimetry was investigated. Anneal treatment above 350 deg. C increased the sensitivity of all radiation-induced TL peaks except the glow peaks above 300 deg. C. On the other hand, annealing in air, at a temperature of 700 deg. C caused a collapse in the TL sensitivity. The increase in TL efficiency was found to depend on the annealing temperature and time. Heating at 600 deg. C for 5 h and quenching in ambient air are the optimum conditions for TL sensitivity enhancement in the calcite materials investigated. These results are explained using the energy scheme of the pre-dose model of and in terms of the impurity rearrangements in the crystal lattice induced by heating. It was found that the values of the kinetic parameters E, s and b for TL glow peaks remained unchanged for annealed samples. The TL dose-response curves for stable dosimetric peaks of annealed and unannealed calcite samples could be fitted to the same linear mathematical function. This implies that the annealing process probably does not change the nature of the trapping centers except the low temperature TL peaks at 125 and 160 deg. C of flowstone. The TL dosimetric parameters of calcite samples annealed, including glow curves, fading characteristics, dose-responses, dose-rate responses and energy responses, have also been studied in detail. The response to gamma-rays of annealed calcite samples was found to be linear from 0.05 to 10 4 Gy. The lower limit of observable doses for each calcite sample was about 0.05 Gy. This offers the possibility of applying the investigated materials for gamma-ray dosimetry within this useful range. These dosimeters can be used in various applications, such as, in industries related to chemical technology (polymerization), food processing and in determining the dose received by the patient during medical examination and treatment

  4. Sorption and catalytic oxidation of Fe(II) at the surface of calcite

    NARCIS (Netherlands)

    Mettler, S.; Wolthers, M.; Charlet, L.; Von Gunten, U.

    The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps:

  5. Kinetics of the direct sulfation of limestone at the initial stage of crystal growth of the solid product

    DEFF Research Database (Denmark)

    Hu, Guilin; Dam-Johansen, Kim; Wedel, Stig

    2011-01-01

    ions toward the gas–solid interface to react, and the gradual shielding of calcite surface area by the product crystal grains. A simple and semi‐empirical mathematical model derived on basis of this theory gives a satisfactory description of the experimental results up to a calcite conversion of about...

  6. From nanometer aggregates to micrometer crystals

    DEFF Research Database (Denmark)

    Schultz, Logan Nicholas; Dideriksen, Knud; Lakshtanov, Leonid

    2014-01-01

    and crystal shapes. Grain coarsening of calcite, CaCO3, is relevant for biomineralization and commercial products and is an important process in diagenesis of sediments to rock during geological time. We investigated coarsening of pure, synthetic calcite powder of sub-micrometer diameter crystals and aged......Grain size increases when crystals respond to dynamic equilibrium in a saturated solution. The pathway to coarsening is generally thought to be driven by Ostwald ripening, that is, simultaneous dissolution and reprecipitation, but models to describe Ostwald ripening neglect solid-solid interactions...... demonstrated steady growth of nanometer crystallites. The results can be described by theory where grains coarsen preferentially by aggregation at early times and high temperatures and by Ostwald ripening at later stages. Crystal form and dimension are influenced by the transition from one growth mechanism...

  7. Formation temperatures of thermogenic and biogenic methane

    Science.gov (United States)

    Stolper, D.A.; Lawson, M.; Davis, C.L.; Ferreira, A.A.; Santos Neto, E. V.; Ellis, G.S.; Lewan, M.D.; Martini, Anna M.; Tang, Y.; Schoell, M.; Sessions, A.L.; Eiler, J.M.

    2014-01-01

    Methane is an important greenhouse gas and energy resource generated dominantly by methanogens at low temperatures and through the breakdown of organic molecules at high temperatures. However, methane-formation temperatures in nature are often poorly constrained. We measured formation temperatures of thermogenic and biogenic methane using a “clumped isotope” technique. Thermogenic gases yield formation temperatures between 157° and 221°C, within the nominal gas window, and biogenic gases yield formation temperatures consistent with their comparatively lower-temperature formational environments (<50°C). In systems where gases have migrated and other proxies for gas-generation temperature yield ambiguous results, methane clumped-isotope temperatures distinguish among and allow for independent tests of possible gas-formation models.

  8. Biogenic Mn-Oxides in Subseafloor Basalts.

    Science.gov (United States)

    Ivarsson, Magnus; Broman, Curt; Gustafsson, Håkan; Holm, Nils G

    2015-01-01

    The deep biosphere of the subseafloor basalts is recognized as a major scientific frontier in disciplines like biology, geology, and oceanography. Recently, the presence of fungi in these environments has involved a change of view regarding diversity and ecology. Here, we describe fossilized fungal communities in vugs in subseafloor basalts from a depth of 936.65 metres below seafloor at the Detroit Seamount, Pacific Ocean. These fungal communities are closely associated with botryoidal Mn oxides composed of todorokite. Analyses of the Mn oxides by Electron Paramagnetic Resonance spectroscopy (EPR) indicate a biogenic signature. We suggest, based on mineralogical, morphological and EPR data, a biological origin of the botryoidal Mn oxides. Our results show that fungi are involved in Mn cycling at great depths in the seafloor and we introduce EPR as a means to easily identify biogenic Mn oxides in these environments.

  9. Manganese-calcium intermixing facilitates heteroepitaxial growth at the 101¯4 calcite-water interface

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Man; Riechers, Shawn L.; Ilton, Eugene S.; Du, Yingge; Kovarik, Libor; Varga, Tamas; Arey, Bruce W.; Qafoku, Odeta; Kerisit, Sebastien

    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 a 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.

  10. Framework for Assessing Biogenic CO2 Emissions from ...

    Science.gov (United States)

    This revision of the 2011 report, Accounting Framework for Biogenic CO2 Emissions from Stationary Sources, evaluates biogenic CO2 emissions from stationary sources, including a detailed study of the scientific and technical issues associated with assessing biogenic carbon dioxide emissions from stationary sources. EPA developed the revised report, Framework for Assessing Biogenic CO2 Emissions from Stationary Sources, to present a methodological framework for assessing the extent to which the production, processing, and use of biogenic material at stationary sources for energy production results in a net atmospheric contribution of biogenic CO2 emissions. Biogenic carbon dioxide emissions are defined as CO2 emissions related to the natural carbon cycle, as well as those resulting from the production, harvest, combustion, digestion, decomposition, and processing of biologically-based materials. The EPA is continuing to refine its technical assessment of biogenic CO2 emissions through another round of targeted peer review of the revised study with the EPA Science Advisory Board (SAB). This study was submitted to the SAB's Biogenic Carbon Emissions Panel in February 2015. http://yosemite.epa.gov/sab/sabproduct.nsf/0/3235dac747c16fe985257da90053f252!OpenDocument&TableRow=2.2#2 The revised report will inform efforts by policymakers, academics, and other stakeholders to evaluate the technical aspects related to assessments of biogenic feedstocks used for energy at s

  11. Copper incorporation in foraminiferal calcite: results from culturing experiments

    Directory of Open Access Journals (Sweden)

    G. J. van der Zwaan

    2007-07-01

    Full Text Available A partition coefficient for copper (DCu in foraminiferal calcite has been determined by culturing individuals of two benthic species under controlled laboratory conditions. The partition coefficient of a trace element (TE is an emperically determined relation between the TE/Ca ratio in seawater and the TE/Ca ratio in foraminiferal calcite and has been established for many divalent cations. Despite its potential to act as a tracer of human-induced, heavy metal pollution, data is not yet available for copper. Since partition coefficients are usually a function of multiple factors (seawater temperature, pH, salinity, metabolic activity of the organism, etc., we chose to analyze calcite from specimens cultured under controlled laboratory conditions. They were subjected to different concentrations of Cu2+ (0.1–20 µmol/l and constant temperature (10 and 20°C, seawater salinity and pH. We monitored the growth of new calcite in specimens of the temperate, shallow-water foraminifer Ammonia tepida and in the tropical, symbiont-bearing Heterostegina depressa. Newly formed chambers were analyzed for Cu/Ca ratios by laser ablation-ICP-MS. The estimated partition coefficient (0.1–0.4 was constant to within experimental error over a large range of (Cu/Caseawater ratios and was remarkably similar for both species. Neither did the presence or absence of symbionts affect the DCu, nor did we find a significant effect of temperature or salinity on Cu-uptake.

  12. Immobilization of nanoparticles by occlusion into microbial calcite

    DEFF Research Database (Denmark)

    Skuce, Rebecca L.; Tobler, Dominique Jeanette; MacLaren, Ian

    2017-01-01

    Binding of nanoparticles (NPs) to mineral surfaces influences their transport through the environment. The potential, however, for growing minerals to immobilize NPs via occlusion (the process of trapping particles inside the growing mineral) has yet to be explored in environmentally relevant...... not influence calcite precipitation at the concentrations used here. Overall, these findings demonstrate that microbially driven mineral precipitation has potential to immobilize nanoparticles in the environment via occlusion....

  13. Origin of calcite in the glacigenic Virttaankangas complex

    OpenAIRE

    Nina M. Kortelainen; Petri J. Korkeakoski; Juha A. Karhu

    2007-01-01

    Groundwaters of the glacigenic Virttaankangas complex in southern Finland are characterized by high pH values ranging up to 9.5. These values are significantly higher than those observed in silicate-rich shallow groundwater formations in crystalline bedrock areas. TheVirttaankangas sediments were discovered to contain small amounts of fine grained, dispersed calcite, which has a high tendency to increase the pH of local groundwaters. The primary goal of this study was to determine the mode of...

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

    Energy Technology Data Exchange (ETDEWEB)

    Nagy, K.L.; Cygan, R.T.; Brinker, C.J.; Ashley, C.S. [Sandia National Labs., Albuquerque, NM (United States); Scotto, C.S. [Naval Research Lab., Washington, DC (United States). Optical Sciences Div.

    1997-02-01

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

  15. Oxygen Isotope Fractionation between Coexisting Calcite and Dolomite.

    Science.gov (United States)

    Weber, J N

    1964-09-18

    The oxygen isotopic composition of calcite from carbonate rocks of the lower unit of the Flagstaff formation (Paleocene) exposed along the western margin of the Wasatch Plateau, Utah, is about 7 per mil lower than that of coexisting dolomite, suggesting that isotopic equilibration of these two minerals can occur at relatively low temperatures. Unlike recent isotopic evidence presented by Degens and Epstein, the data do not preclude a primary chemical origin for the dolomite.

  16. Cytotoxicity and genotoxicity of biogenic silver nanoparticles

    International Nuclear Information System (INIS)

    Lima, R; Feitosa, L O; Ballottin, D; Tasic, L; Durán, N; Marcato, P D

    2013-01-01

    Biogenic silver nanoparticles with 40.3 ± 3.5 nm size and negative surface charge (− 40 mV) were prepared with Fusarium oxysporum. The cytotoxicity of 3T3 cell and human lymphocyte were studied by a TaliTM image-based cytometer and the genotoxicity through Allium cepa and comet assay. The results of BioAg-w (washed) and BioAg-nw (unwashed) biogenic silver nanoparticles showed cytotoxicity exceeding 50 μg/mL with no significant differences of response in 5 and 10 μg/mL regarding viability. Results of genotoxicity at concentrations 5.0 and 10.0 ug/mL show some response, but at concentrations 0.5 and 1.0 μg/mL the washed and unwashed silver nanoparticles did not present any effect. This in an important result since in tests with different bacteria species and strains, including resistant, MIC (minimal inhibitory concentration) had good answers at concentrations less than 1.9 μg/mL. This work concludes that biogenic silver nanoparticles may be a promising option for antimicrobial use in the range where no cyto or genotoxic effect were observed. Furthermore, human cells were found to have a greater resistance to the toxic effects of silver nanoparticles in comparison with other cells.

  17. Rett syndrome - Stimulation of endogenous biogenic amines

    Science.gov (United States)

    Pelligra, R.; Norton, R. D.; Wilkinson, R.; Leon, H. A.; Matson, W. R.

    1992-01-01

    Transient hypercapnic hyperoxemia was induced in two Rett syndrome children by the administration of a gaseous mixture of 80 percent O2 and 20 percent CO2. Time course studies of neurotransmitters and their metabolites showed an immediate and marked increase in central biogenic amine turnover following inhalation of the gas mixture. The increased turnover of biogenic amines was associated with improved clinical changes. This suggests a coupled relationship and provides further support for an etiological role of neurotransmitter dysfunction in Rett syndrome. In a complementary study, elevation of pulmonary CO2 by application of a simple rebreathing device resulted in improvement of abnormal blood gases and elimination of the Cheyne-Stokes-like respiratory pattern of the Rett syndrome. Near normalization of the EEG occurred when a normal respiratory pattern was imposed by means of a respirator. Taken together, these results lead to the preliminary conclusion that cerebral hypoxemia secondary to abnormal respiratory function may contribute to diminished production of biogenic amines in Rett syndrome.

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

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Rodriguez Blanco, Juan Diego; Stipp, Susan Louise Svane

    2016-01-01

    We have used density functional theory with the COSMO-RS implicit solvent model to predict the pKa for the deprotonation of bicarbonate to carbonate, i.e. HCO3− CO32− + H+, when HCO3− is included in, and adsorbed on, a calcite surface. We have used cluster models (80–100 atoms) to represent...... the flat {10.4} surface, acute steps, obtuse steps, two types of kinks on the acute step and two types of kinks on the obtuse steps. Based on the predicted pKa values, which range from −6.0 to 2.4 depending on the surface site, we conclude that bicarbonate deprotonates to carbonate when it is in calcite...... even when pH in solution is very low. This is true for all surface sites, even for solutions where 2.4 bicarbonate is adsorbed on calcite, the predicted pKa for deprotonation is 7.5, which is ∼3 pH units lower than in aqueous solution...

  19. Rate of radiocarbon retention onto calcite by isotope exchange

    Energy Technology Data Exchange (ETDEWEB)

    Lempinen, Janne; Lehto, Jukka [Helsinki Univ. (Finland). Lab. of Radiochemistry

    2016-11-01

    Radiocarbon ({sup 14}C) is a top priority class radionuclide associated with the long-term safety of spent nuclear fuel disposal. Dissolved inorganic radiocarbon can be retained in bedrock via isotope exchange with calcite (CaCO{sub 3}) at solubility equilibrium with groundwater. In the present study, the rate of the isotope exchange process was investigated on synthetic calcite using batch experiments. Experiments were performed in solutions with a calcium concentration of 0.0002-0.1 M, including two synthetic reference groundwaters. The radiocarbon activity in the solutions decreased exponentially as a function of time, thus following first-order kinetics. The rate of isotope exchange was quantified from an exponential fit to the activity data over time. The rate of radiocarbon retention increased as a function of the calcium activity. The isotope exchange half-life was only 4.3 days at calcium ion activities over 0.01. This half-life is very much shorter than the half-life of {sup 14}C or the time scale of groundwater movements; consequently calcite can effectively retain radiocarbon from brackish and saline groundwaters.

  20. Rate of radiocarbon retention onto calcite by isotope exchange

    International Nuclear Information System (INIS)

    Lempinen, Janne; Lehto, Jukka

    2016-01-01

    Radiocarbon ( 14 C) is a top priority class radionuclide associated with the long-term safety of spent nuclear fuel disposal. Dissolved inorganic radiocarbon can be retained in bedrock via isotope exchange with calcite (CaCO 3 ) at solubility equilibrium with groundwater. In the present study, the rate of the isotope exchange process was investigated on synthetic calcite using batch experiments. Experiments were performed in solutions with a calcium concentration of 0.0002-0.1 M, including two synthetic reference groundwaters. The radiocarbon activity in the solutions decreased exponentially as a function of time, thus following first-order kinetics. The rate of isotope exchange was quantified from an exponential fit to the activity data over time. The rate of radiocarbon retention increased as a function of the calcium activity. The isotope exchange half-life was only 4.3 days at calcium ion activities over 0.01. This half-life is very much shorter than the half-life of 14 C or the time scale of groundwater movements; consequently calcite can effectively retain radiocarbon from brackish and saline groundwaters.

  1. Biomimetic mineralization of CaCO3 on a phospholipid monolayer: from an amorphous calcium carbonate precursor to calcite via vaterite.

    Science.gov (United States)

    Xiao, Junwu; Wang, Zhining; Tang, Yecang; Yang, Shihe

    2010-04-06

    A phospholipid monolayer, approximately half the bilayer structure of a biological membrane, can be regarded as an ideal model for investigating biomineralization on biological membranes. In this work on the biomimetic mineralization of CaCO(3) under a phospholipid monolayer, we show the initial heterogeneous nucleation of amorphous calcium carbonate precursor (ACC) nanoparticles at the air-water interface, their subsequent transformation into the metastable vaterite phase instead of the most thermodynamically stable calcite phase, and the ultimate phase transformation to calcite. Furthermore, the spontaneity of the transformation from vaterite to calcite was found to be closely related to the surface tension; high surface pressure could inhibit the process, highlighting the determinant of surface energy. To understand better the mechanisms for ACC formation and the transformation from ACC to vaterite and to calcite, in situ Brewster angle microscopy (BAM), ex situ scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, and X-ray diffraction analysis were employed. This work has clarified the crystallization process of calcium carbonate under phospholipid monolayers and therefore may further our understanding of the biomineralization processes induced by cellular membranes.

  2. PVC mixtures’ mechanical properties with the addition of modified calcite as filler

    Directory of Open Access Journals (Sweden)

    Vučinić Dušica R.

    2012-01-01

    Full Text Available In this study mechanical properties of PVC mixtures (PVC, stabilizer, lubricant, filler such as tensile strength, tensile elongation, breaking strength, and breaking elongation were investigated. Unmodified calcite, as well as calcite modified by stearic acid, were used as fillers in wet and dry processes. The PVC mixtures containing the calcite modified by wet procedure have better mechanical properties compared to those with the calcite modified by the dry process. Tensile and breaking strength of the PVC mixture containing the calcite modified with 1.5% stearic acid using wet process, are higher for 2.8% and 5.2%, respectively, compared to the PVC mixture containing the calcite modified with the same amount of acid used in the dry process. The tensile strength difference between the mixtures increases with the increase of the concentration of used stearic acid up to 3%. The strength of PVC mixture with the calcite modified by wet process is 3.1% higher compared to the mixture containing calcite modified by dry process. The results showed that the bonding strength between calcite and the adsorbed organic component affected tensile strength, tensile elongation and breaking strength of the PVC mixtures. The best filler was obtained by wet modification using 1.5% stearic acid solution that provided the formation of a stearate monolayer chemisorbed on calcite. The PVC mixtures containing the calcite modified by wet process using 1.5% stearic acid solution exhibited the best mechanical properties. This calcite was completely hydrophobic with dominant chemically adsorbed surfactant, which means that stearate chemisorbed on calcite provided stronger interaction in the calcite-stearic acid-PVC system.

  3. Gigantism in unique biogenic magnetite at the Paleocene–Eocene Thermal Maximum

    Science.gov (United States)

    Schumann, Dirk; Raub, Timothy D.; Kopp, Robert E.; Guerquin-Kern, Jean-Luc; Wu, Ting-Di; Rouiller, Isabelle; Smirnov, Aleksey V.; Sears, S. Kelly; Lücken, Uwe; Tikoo, Sonia M.; Hesse, Reinhard; Kirschvink, Joseph L.; Vali, Hojatollah

    2008-01-01

    We report the discovery of exceptionally large biogenic magnetite crystals in clay-rich sediments spanning the Paleocene–Eocene Thermal Maximum (PETM) in a borehole at Ancora, NJ. Aside from previously described abundant bacterial magnetofossils, electron microscopy reveals novel spearhead-like and spindle-like magnetite up to 4 μm long and hexaoctahedral prisms up to 1.4 μm long. Similar to magnetite produced by magnetotactic bacteria, these single-crystal particles exhibit chemical composition, lattice perfection, and oxygen isotopes consistent with an aquatic origin. Electron holography indicates single-domain magnetization despite their large crystal size. We suggest that the development of a thick suboxic zone with high iron bioavailability—a product of dramatic changes in weathering and sedimentation patterns driven by severe global warming—drove diversification of magnetite-forming organisms, likely including eukaryotes. PMID:18936486

  4. Anisotropic Growth of Otavite on Calcite: Implications for Heteroepitaxial Growth Mechanisms

    Energy Technology Data Exchange (ETDEWEB)

    Riechers, Shawn L. [Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Kerisit, Sebastien N. [Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, United States

    2017-12-18

    Elucidating how cation intermixing can affect the mechanisms of heteroepitaxial growth in aqueous media has remained a challenging endeavor. Toward this goal, in situ atomic force microscopy was employed to image the heteroepitaxial growth of otavite (CdCO3) at the (10-14) surface of calcite (CaCO3) single crystals in static aqueous conditions. Heteroepitaxial growth proceeded via spreading of three-dimensional (3D) islands and two-dimensional (2D) atomic layers at low and high initial saturation levels, respectively. Experiments were carried out as a function of applied force and imaging mode thus enabling determination of growth mechanisms unaltered by imaging artifacts. This approach revealed the significant anisotropic nature of heteroepitaxial growth on calcite in both growth modes and its dependence on supersaturation, intermixing, and substrate topography. The 3D islands not only grew preferentially along the [42-1] direction relative to the [010] direction, resulting in rod-like surface precipitates, but also showed clear preference for growth from the island end rich in obtuse/obtuse kink sites. Pinning to step edges was observed to often reverse this tendency. In the 2D growth mode, the relative velocities of acute and obtuse steps were observed to switch between the first and second atomic layers. This phenomenon stemmed from the significant Cd-Ca intermixing in the first layer, despite bulk thermodynamics predicting the formation of almost pure otavite. Composition effects were also responsible for the inability of 3D islands to grow on 2D layers in cases where both modes were observed to occur simultaneously. Overall, the AFM images highlighted the effects of intermixing on heteroepitaxial growth, particularly how it can induce thickness-dependent growth mechanisms at the nanoscale.

  5. Speciation of As in calcite by micro-XAFS: Implications for remediation of As contamination in groundwater

    International Nuclear Information System (INIS)

    Yokoyama, Y; Takahashi, Y; Iwatsuki, T; Terada, Y

    2013-01-01

    To evaluate the role of calcite as a host phase of arsenic (As) in As-contaminated groundwater, distribution behavior of Asbetween natural calcite and groundwater in deep underground was investigated based on As oxidation state. Speciation analyses of As in natural calcite by μ-XRF-XAFS analyses showed (i) preferentialarsenate uptake by calcite, and (ii) promptness of arsenate uptake by minor iron (Fe) carbonate minerals coprecipitated with calcite. These findings suggest that the effect of calcite on As remediation of the As-contamination systems stronglydepends on arsenite to arsenate ratio (i.e., redox condition) in groundwater, and maybe governed bythe amount of Fe coprecipitated with calcite.

  6. To what extent can biogenic SOA be controlled?

    Science.gov (United States)

    Carlton, Annmarie G; Pinder, Robert W; Bhave, Prakash V; Pouliot, George A

    2010-05-01

    The implicit assumption that biogenic secondary organic aerosol (SOA) is natural and can not be controlled hinders effective air quality management. Anthropogenic pollution facilitates transformation of naturally emitted volatile organic compounds (VOCs) to the particle phase, enhancing the ambient concentrations of biogenic secondary organic aerosol (SOA). It is therefore conceivable that some portion of ambient biogenic SOA can be removed by controlling emissions of anthropogenic pollutants. Direct measurement of the controllable fraction of biogenic SOA is not possible, but can be estimated through 3-dimensional photochemical air quality modeling. To examine this in detail, 22 CMAQ model simulations were conducted over the continental U.S. (August 15 to September 4, 2003). The relative contributions of five emitted pollution classes (i.e., NO(x), NH(3), SO(x), reactive non methane carbon (RNMC) and primary carbonaceous particulate matter (PCM)) on biogenic SOA were estimated by removing anthropogenic emissions of these pollutants, one at a time and all together. Model results demonstrate a strong influence of anthropogenic emissions on predicted biogenic SOA concentrations, suggesting more than 50% of biogenic SOA in the eastern U.S. can be controlled. Because biogenic SOA is substantially enhanced by controllable emissions, classification of SOA as biogenic or anthropogenic based solely on VOC origin is not sufficient to describe the controllable fraction.

  7. Incorporation of Mg and Sr in calcite of cultured benthic foraminifera: impact of calcium concentration and associated calcite saturation state

    Directory of Open Access Journals (Sweden)

    M. Raitzsch

    2010-03-01

    Full Text Available We investigated the effect of the calcium concentration in seawater and thereby the calcite saturation state (Ω on the magnesium and strontium incorporation into benthic foraminiferal calcite under laboratory conditions. For this purpose individuals of the shallow-water species Heterostegina depressa (precipitating high-Mg calcite, symbiont-bearing and Ammonia tepida (low-Mg calcite, symbiont-barren were cultured in media under a range of [Ca2+], but similar Mg/Ca ratios. Trace element/Ca ratios of newly formed calcite were analysed with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS and normalized to the seawater elemental composition using the equation DTE=(TE/Cacalcite/(TE/Caseawater. The culturing study shows that DMg of A. tepida significantly decreases with increasing Ω at a gradient of −4.3×10−5 per Ω unit. The DSr value of A. tepida does not change with Ω, suggesting that fossil Sr/Ca in this species may be a potential tool to reconstruct past variations in seawater Sr/Ca. Conversely, DMg of H. depressa shows only a minor decrease with increasing Ω, while DSr increases considerably with Ω at a gradient of 0.009 per Ω unit. The different responses to seawater chemistry of the two species may be explained by a difference in the calcification pathway that is, at the same time, responsible for the variation in the total Mg incorporation between the two species. Since the Mg/Ca ratio in H. depressa is 50–100 times higher than that of A. tepida, it is suggested that the latter exhibits a mechanism that decreases the Mg/Ca ratio of the calcification fluid, while the high-Mg calcite forming species may not have this physiological tool. If the dependency of Mg incorporation on seawater [Ca2+] is also valid for deep

  8. Highly birefringent crystal for Raman transitions with phase modulators

    Science.gov (United States)

    Arias, Nieves; Abediyeh, Vahide; Hamzeloui, Saeed; Jeronimo-Moreno, Yasser; Gomez, Eduardo

    2016-05-01

    We present a system to excite Raman transitions with minimum phase noise. The system uses a phase modulator to generate the phase locked beams required for the transition. We use a long calcite crystal to filter out one of the sidebands, avoiding the cancellation that appears at high detunings for phase modulation. The measured phase noise is limited by the quality of the microwave synthesizer. We use the calcite crystal a second time to produce a co-propagating Raman pair with perpendicular polarizations to drive velocity insensitive Raman transitions. Support from CONACYT and Fundacion Marcos Moshinsky.

  9. Magnetic Dinner Salads: The Role of Biogenic Magnetite in Cryopreservation for Common Food Plants

    Science.gov (United States)

    Chaffee, T. M.; Kirschvink, J. L.; Kobayashi, A. K.

    2015-12-01

    Biogenically-precipitated magnetite has been found in organisms ranging from Bacteria, single-celled protists, and many of the animal phyla, where its major function is navigation and magnetoreception. To date there is but a single report of biogenic magnetite in plants (essentially, magnetoferritin), and that is in common grass (Festuca species, from Gajdardziska-Josifovska et. al. doi:10.1127/0935-1221/2001/0013/0863). Recent developments in cryopreservation suggest that ~ 1 mT, ~ 10 Hz oscillating magnetic fields can drastically reduce ice nucleation during freezing, promote supercooling, and minimize cellular damage in living tissues (e.g., Kaku et al., doi: 10.1016/j.cryobiol.2012.02.001). Kobayashi & Kirschvink (2014, doi:10.1016/j.cryobiol.2013.12.002) suggest that biogenic magnetite crystals could be the nucleating site for damaging ice crystals, and that they would be driven magneto-mechanically to rotate in those oscillating fields which could inhibit the ice crystal nucleation process. This prompted our investigation into the magnetite content of ordinary fruit and vegetable food products, as knowledge of the natural levels of biogenic magnetite in the human food supply could guide the selection of which foods might work for this type of cryopreservation. Our study involved a range of common foods including avocados, bananas, garlic, and apples. Samples were prepared in a clean lab environment kept free of contaminant particles, and subjected to a variety of standard rock-magnetic tests including IRM and ARM acquisition, and the corresponding Af demagnetization, on a standard 2G™ SRM. Results are consistent with moderately interacting single-domain magnetite (see figure), with moderate inter-particle interaction effects. Typical magnetite concentrations in these samples are in the range of .1 to 1 ng/g for room temperature samples, increasing to the range of 1-10 ng/g when measured frozen (to inhibit thermal rotation of small particles and clumps). If

  10. Secondary biogeneous radiation of human organism

    International Nuclear Information System (INIS)

    Kuzin, A.M.; Surkenova, G.N.

    1999-01-01

    When studying samples of three types of tissues of alive healthy human organism (hands, surface of breast, hair) it is shown that hair permanently emit secondary biogeneous radiation (SBR) which may registered with biological detectors. The hypothesis is suggested that natural background radiation permanently exciting biopolymers (proteins, nuclei acids) being present in alive organism in condensed state induces permanently present electromagnetic field of SBR which is vitally important for human organism. The field partly extends beyond the organism, where it is registered with sensitive biological detectors [ru

  11. The sensitized luminescence of manganese-activated calcite

    Science.gov (United States)

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

    1947-01-01

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

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

    Science.gov (United States)

    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

  13. Incorporation of Eu(III) into calcite under recrystallization conditions

    International Nuclear Information System (INIS)

    Hellebrandt, S.E.; Jordan, Norbert; Barkleit, Astrid; Schmidt, Moritz; Hofmann, S.

    2017-01-01

    The interaction of three calcite powders with Eu(III) under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). Batch contact studies with reaction times from 1 week up to 3 years revealed that the speciation differs from that observed previously in co-precipitation experiments and is dominated by a newly identified species ''γ''. The speed of formation of this species was found to depend greatly on the recrystallization rate of the studied minerals.

  14. Incorporation of Eu(III) into calcite under recrystallization conditions

    Energy Technology Data Exchange (ETDEWEB)

    Hellebrandt, S.E. [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. of Resource Ecology; Jordan, Norbert [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Surface Processes; Barkleit, Astrid [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Chemistry of the F-Elements; Schmidt, Moritz [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). HGF Young Investigator Group; Hofmann, S.

    2017-06-01

    The interaction of three calcite powders with Eu(III) under recrystallization conditions was studied on the molecular level using site-selective time-resolved laser fluorescence spectroscopy (TRLFS). Batch contact studies with reaction times from 1 week up to 3 years revealed that the speciation differs from that observed previously in co-precipitation experiments and is dominated by a newly identified species ''γ''. The speed of formation of this species was found to depend greatly on the recrystallization rate of the studied minerals.

  15. Structure, Function, and Evolution of Biogenic Amine-binding Proteins in Soft Ticks

    Energy Technology Data Exchange (ETDEWEB)

    Mans, Ben J.; Ribeiro, Jose M.C.; Andersen, John F. (NIH)

    2008-08-19

    Two highly abundant lipocalins, monomine and monotonin, have been isolated from the salivary gland of the soft tick Argas monolakensis and shown to bind histamine and 5-hydroxytryptamine (5-HT), respectively. The crystal structures of monomine and a paralog of monotonin were determined in the presence of ligands to compare the determinants of ligand binding. Both the structures and binding measurements indicate that the proteins have a single binding site rather than the two sites previously described for the female-specific histamine-binding protein (FS-HBP), the histamine-binding lipocalin of the tick Rhipicephalus appendiculatus. The binding sites of monomine and monotonin are similar to the lower, low affinity site of FS-HBP. The interaction of the protein with the aliphatic amine group of the ligand is very similar for the all of the proteins, whereas specificity is determined by interactions with the aromatic portion of the ligand. Interestingly, protein interaction with the imidazole ring of histamine differs significantly between the low affinity binding site of FS-HBP and monomine, suggesting that histamine binding has evolved independently in the two lineages. From the conserved features of these proteins, a tick lipocalin biogenic amine-binding motif could be derived that was used to predict biogenic amine-binding function in other tick lipocalins. Heterologous expression of genes from salivary gland libraries led to the discovery of biogenic amine-binding proteins in soft (Ornithodoros) and hard (Ixodes) tick genera. The data generated were used to reconstruct the most probable evolutionary pathway for the evolution of biogenic amine-binding in tick lipocalins.

  16. Time-lapse 3D imaging of calcite precipitation in a microporous column

    Science.gov (United States)

    Godinho, Jose R. A.; Withers, Philip J.

    2018-02-01

    Time-lapse X-ray computed tomography is used to image the evolution of calcite precipitation during flow through microporous quartz over the course of 400 h. The growth rate decreases by more than seven times, which is linked to the clogging of flow paths that restricts flow to some regions of the column. Fewer precipitates are observed as a function of column depth, which is found to be related to a differential nucleation density along the sample. A higher nucleation density closer to the inlet implies more crystal volume increase per unit of time without affecting the rate if normalized to the surface area of crystals. Our overall growth rates measured in porous media are orders of magnitude slower than growth rates derived from traditional precipitation experiments on free surfaces. Based on our time-lapse results we hypothesize a scenario where the evolving distribution of precipitates within a pore structure during precipitation progressively modifies the local transport through the pores. Within less permeable regions the saturation index may be lower than along the main flow paths. Therefore, the reactive crystal surfaces within those regions grow at a slower rate than that expected from the bulk fluid composition. Since the amount of reactive surface area within these less permeable regions increases over time, the overall growth rate decreases without a necessary significant change of the bulk fluid composition along more permeable flow paths. In conclusion, the overall growth rates in an evolving porous media expected from bulk fluid compositions alone can be overestimated due to the development of stagnant sub-regions where the reactive surface area is bath by a solution with lower saturation index. In this context we highlight the value of time-lapse 3D studies for understanding the dynamics of mineral precipitation in porous media.

  17. Blood Cockle Shells Waste as Renewable Source for the Production of Biogenic CaCO3 and Its Characterisation

    Science.gov (United States)

    Asmi, D.; Zulfia, A.

    2017-11-01

    The prowess to reuse and recycle of blood cockle shells for raw material in bio-ceramics applications is an attractive component of integrated waste management program. In this paper an attempt is made to introduce a simple process to manufacture biogenic CaCO3 powder from blood cockle shells waste. The biogenic CaCO3 powder was produced from rinsing of blood cockle shells waste using deionised water and oxalic acid for cleaning the dirt and stain on the shells, then drying and grinding followed by heat treatment at 500 and 800 °C for 5 h. The powder obtained was characterised by XRF, DTA/TG, SEM, FTIR, and XRD analysis. The amount of 97.1 % CaO was obtained from XRF result. The thermal decomposition of CaCO3 become CaO due to mass loss was observed in the TG curve. The SEM result shows the needle-like aragonite morphology of blood cockle shells powder transformed to cubic-like calcite after heat treated at 500 °C. These results were consistent with FTIR and XRD results.

  18. Removal of colloidal biogenic selenium from wastewater.

    Science.gov (United States)

    Staicu, Lucian C; van Hullebusch, Eric D; Oturan, Mehmet A; Ackerson, Christopher J; Lens, Piet N L

    2015-04-01

    Biogenic selenium, Se(0), has colloidal properties and thus poses solid-liquid separation problems, such as poor settling and membrane fouling. The separation of Se(0) from the bulk liquid was assessed by centrifugation, filtration, and coagulation-flocculation. Se(0) particles produced by an anaerobic granular sludge are normally distributed, ranging from 50 nm to 250 nm, with an average size of 166±29 nm and a polydispersity index of 0.18. Due to its nanosize range and protein coating-associated negative zeta potential (-15 mV to -23 mV) between pH 2 and 12, biogenic Se(0) exhibits colloidal properties, hampering its removal from suspension. Centrifugation at different centrifugal speeds achieved 22±3% (1500 rpm), 73±2% (3000 rpm) and 91±2% (4500 rpm) removal. Separation by filtration through 0.45 μm filters resulted in 87±1% Se(0) removal. Ferric chloride and aluminum sulfate were used as coagulants in coagulation-flocculation experiments. Aluminum sulfate achieved the highest turbidity removal (92±2%) at a dose of 10(-3) M, whereas ferric chloride achieved a maximum turbidity removal efficiency of only 43±4% at 2.7×10(-4) M. Charge repression plays a minor role in particle neutralization. The sediment volume resulting from Al2(SO3)4 treatment is three times larger than that produced by FeCl3. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. Incidence of biogenic amines in foods implications for the Gambia ...

    African Journals Online (AJOL)

    Amines are found in food. Biogenic amines are a class of amines, which result from decarboxylation. They are food quality indicators. Health-wise biogenic amines play positive roles and have adverse effects as well; they are a public health concern. Certain conditions make it possible for them to be produced. These could ...

  20. Methyl chavicol: characterization of its biogenic emission rate

    NARCIS (Netherlands)

    Bouvier-Brown, N.C.; Goldstein, A.H.; Worton, D.R.; Matross, D.M.; Gilman, J.B.; Kuster, W.C.; Welsh-Bon, D.; Warneke, C.; de Gouw, J.A.; Cahill, M.J.; Holzinger, R.

    2009-01-01

    We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California.

  1. Prediction of calcite Cement Distribution in Shallow Marine Sandstone Reservoirs using Seismic Data

    Energy Technology Data Exchange (ETDEWEB)

    Bakke, N.E.

    1996-12-31

    This doctoral thesis investigates how calcite cemented layers can be detected by reflection seismic data and how seismic data combined with other methods can be used to predict lateral variation in calcite cementation in shallow marine sandstone reservoirs. Focus is on the geophysical aspects. Sequence stratigraphy and stochastic modelling aspects are only covered superficially. Possible sources of calcite in shallow marine sandstone are grouped into internal and external sources depending on their location relative to the presently cemented rock. Well data and seismic data from the Troll Field in the Norwegian North Sea have been analysed. Tuning amplitudes from stacks of thin calcite cemented layers are analysed. Tuning effects are constructive or destructive interference of pulses resulting from two or more closely spaced reflectors. The zero-offset tuning amplitude is shown to depend on calcite content in the stack and vertical stack size. The relationship is found by regression analysis based on extensive seismic modelling. The results are used to predict calcite distribution in a synthetic and a real data example. It is found that describing calcite cemented beds in shallow marine sandstone reservoirs is not a deterministic problem. Hence seismic inversion and sequence stratigraphy interpretation of well data have been combined in a probabilistic approach to produce models of calcite cemented barriers constrained by a maximum amount of information. It is concluded that seismic data can provide valuable information on distribution of calcite cemented beds in reservoirs where the background sandstones are relatively homogeneous. 63 refs., 78 figs., 10 tabs.

  2. Structure and interactions of calcite spherulites with {alpha}-chitin in the brown shrimp (Penaeus aztecus) shell

    Energy Technology Data Exchange (ETDEWEB)

    Heredia, A. [Instituto de Ciencias Nucleares, Departamento de Quimica de Radiaciones y Radioquimica, UNAM, Circuito Exterior C.U. Apdo., Postal 70-543, 04510 Mexico, D.F. (Mexico); Physikalisches Institut and Center for Nanotechnology, Universitaet Muenster, Gievenbecker Weg 11, 48149 Muenster (Germany); Aguilar-Franco, M. [Instituto de Fisica, Depto de Fisicoquimica, UNAM, Circuito Exterior s/n, Ciudad Universitaria Apartado Postal 20-364 01000 Mexico D.F. (Mexico); Magana, C. [Instituto de Fisica, Depto de Estado Solido, UNAM, Circuito Exterior s/n, Ciudad Universitaria Apartado Postal 20-364 01000 Mexico D.F. (Mexico); Flores, C. [Instituto de Investigaciones en Materiales, Depto de Estado Solido, Laboratorio de Biomateriales, UNAM, Circuito Exterior C.U. S/N CP 04510 Mexico, D.F. (Mexico); Pina, C. [Instituto de Investigaciones en Materiales, Depto de Estado Solido, Laboratorio de Biomateriales, UNAM, Circuito Exterior C.U. S/N CP 04510 Mexico, D.F. (Mexico); Velazquez, R. [Centro de Fisica Aplicada Tecnologia Avanzada, UNAM, Km. 15 Carretera Queretaro-San Luis Potosi, C.P. 76230, Queretaro, Qro. (Mexico); Schaeffer, T.E. [Physikalisches Institut and Center for Nanotechnology, Universitaet Muenster, Gievenbecker Weg 11, 48149 Muenster (Germany); Bucio, L. [Instituto de Fisica, Depto de Estado Solido, UNAM, Circuito Exterior s/n, Ciudad Universitaria Apartado Postal 20-364 01000 Mexico D.F. (Mexico); Basiuk, V.A. [Instituto de Ciencias Nucleares, Departamento de Quimica de Radiaciones y Radioquimica, UNAM, Circuito Exterior C.U. Apdo., Postal 70-543, 04510 Mexico, D.F. (Mexico)

    2007-01-15

    White spots form in the brown shrimp (Penaeus aztecus, Decapoda) shell during frozen storage. The mineral formed consists of calcite incorporated into an amorphous {alpha}-chitin matrix. We studied mechanisms of interaction of amorphous {alpha}-chitin macromolecules with hkl crystal planes to form highly ordered structures, as well as the role of specific sites in the biopolymer, which can be related to nucleation and spheroidal crystal growth. We used low vacuum scanning electron microscopy (LVSEM), X-ray powder diffraction (XRD), atomic force microscopy (AFM), Fourier-transform infrared spectroscopy (FT-IR), and molecular mechanics modeling (MM+ method). AFM images showed fingerprint distances in the biopolymer and a highly layered structure in the crystalline material. The presence of {alpha}-chitin, with a specific spatial distribution of radicals, is thought to be responsible for nucleation and to thermodynamically stabilize ions to form the spherulite crystalline phase, which are usually oval to spherical (0.10 to 200 {mu}m in diameter). Our models of crystal-biopolymer interaction found high affinity of CO{sub 3} {sup 2-} anions in the (104) crystalline plane (the main plane in calcite monocrystals) to NH- groups of the biopolymer, as well as of the C=O in the biopolymer to Ca{sup 2+} cations in the crystalline structure. These interactions explain the spherical growth and inhibition in some planes. The specific physicochemical interactions (docking of groups depending on their geometrical distribution) suggest that the biomineral structure is controlled by the biopolymer on a local scale. This information is useful for further design and improvement of (hybrid) materials for versatile application, from nanotechnology to biomedicine and engineering.

  3. Structure and interactions of calcite spherulites with α-chitin in the brown shrimp (Penaeus aztecus) shell

    International Nuclear Information System (INIS)

    Heredia, A.; Aguilar-Franco, M.; Magana, C.; Flores, C.; Pina, C.; Velazquez, R.; Schaeffer, T.E.; Bucio, L.; Basiuk, V.A.

    2007-01-01

    White spots form in the brown shrimp (Penaeus aztecus, Decapoda) shell during frozen storage. The mineral formed consists of calcite incorporated into an amorphous α-chitin matrix. We studied mechanisms of interaction of amorphous α-chitin macromolecules with hkl crystal planes to form highly ordered structures, as well as the role of specific sites in the biopolymer, which can be related to nucleation and spheroidal crystal growth. We used low vacuum scanning electron microscopy (LVSEM), X-ray powder diffraction (XRD), atomic force microscopy (AFM), Fourier-transform infrared spectroscopy (FT-IR), and molecular mechanics modeling (MM+ method). AFM images showed fingerprint distances in the biopolymer and a highly layered structure in the crystalline material. The presence of α-chitin, with a specific spatial distribution of radicals, is thought to be responsible for nucleation and to thermodynamically stabilize ions to form the spherulite crystalline phase, which are usually oval to spherical (0.10 to 200 μm in diameter). Our models of crystal-biopolymer interaction found high affinity of CO 3 2- anions in the (104) crystalline plane (the main plane in calcite monocrystals) to NH- groups of the biopolymer, as well as of the C=O in the biopolymer to Ca 2+ cations in the crystalline structure. These interactions explain the spherical growth and inhibition in some planes. The specific physicochemical interactions (docking of groups depending on their geometrical distribution) suggest that the biomineral structure is controlled by the biopolymer on a local scale. This information is useful for further design and improvement of (hybrid) materials for versatile application, from nanotechnology to biomedicine and engineering

  4. Thermoluminescent of induced calcite by gamma and ultraviolet radiation

    International Nuclear Information System (INIS)

    Lima, J.F. de.

    1987-01-01

    Samples of brazilian calcite, exposed to gamma radiation in laboratory and heated at constant rate of 2.7 0 C/s, showed three glow peaks at 150, 250 and 350 0 C in their thermoluminescent emission curves. The analysis of these peaks, using different models, indicated that they follow a second order kinetics; it has been obtained, for the activation energy, 1.3, 1.5 and 1.7 eV, and, for the pre-exponential factors, 8.1 x 10 14 , 6.8 x10 13 and 2.4 x 10 12 s -1 . Although the total thermoluminescent emission has stayed constant, the relative height of glow peaks has changed with the temperature of annealing in the range of 400 to 700 0 C. Exposed samples were also illuminated with ultraviolet light and the resultant curves showed partial or total bleaching or some glow peaks and the growth of peaks at lower temperatures. Samples of virgin calcite, submited to increasing exposures of gamma rays, showed a corresponding enhancement of the optical absorption bands in the range of 25000 to 47000 cm -1 A subsequent illumination of these samples with ultraviolet light produced a decrease of the optical absorption bands at the same range. (author) [pt

  5. Geochemical and isotope aspects of calcite deposits and calcitic marbles hosts mineralizations, Serra do Carumbe, Vale do Ribeira, Parana state, Brazil

    International Nuclear Information System (INIS)

    Venusso, Gerson Caetano; Andrade e Silva, Antonio C. Gondim de

    2011-01-01

    The calcite deposits and the calcitic marbles hosts occur in Serra do Carumbe, in the Vale do Ribeira region, Parana State, were studied in their geochemical and isotopic aspects viewing the gathering of information about their genesis and economical use. The calcite deposits are constituted by veins and lenses, being three of them concordant and one discordant in relation to the S 0 from the hosting marbles. In these deposits four main types of calcite were recognized: rombohedrical, fibrous, banded and microcrystalline. The calcite reveal themselves having high purity, with CaO concentration above 55.30% and MgO below 0.42%. The lithogeochemical study of the marbles sequence was conducted in various suites revealing an uniformity in their composition, with high values of CaO (above 46.92%) in relation to the MgO values (below 3,37%), what favors their use for cement manufacture, except in sectors that suffered fault influences, where the marbles are impure (siliceous, magnesian, ferruginous and aluminous). Regarding their trace elements content, the hosting calcitic marbles have higher concentrations than the calcite, in the elements Sr, B, Ba and Mg, what makes evident their different formation environments. The δ 13 C values from calcite range from –9,02 to –12,24 ‰ , referring to PDB, while the values δ 18 O range from 24,48 to 25,23 ‰, referring to SMOW; meanwhile, for the calcitic marbles, the δ 13 C values range from –4,03 to 1,42‰ and of δ 18 O range from 20,71 to 23,00 ‰. The high δ 18 O values would indicate enrichment referring to the interaction of the calcite's generator fluid with the carbonatic host rock. The δ 13 C values indicate origin from hydrothermal solution for the calcite, although they would not allow to conclude if their sources would be superficial or profound. As for the hosting calcitic marbles, the isotopic values indicate genesis from pre-cambrian marine limestone. (author)

  6. Selective silicification of Thalassinoides and other biogenic structures in marine platform limestones and hardground (Lower Albian, Sonabia, Cantabria

    Directory of Open Access Journals (Sweden)

    M. A. Bustillo

    2017-06-01

    Full Text Available In this work different types of chert from the Oriñón Limestone Formation (upper Aptian-lower Albian are studied. This formation outcrops in the eastern coast of Cantabria (Liendo-Castro Urdiales area and includes outstanding and abundant cherty nodules, lenticular layers and crusts. The host rock is mainly a biocalcarenite (wackestone/packstone of pellets, echinoids fragments, oysters, foraminifers and calcareous or calcified siliceous sponge spicules. The Oriñón Limestone Formation was deposited in a marine open-shelf environment and preserves a hardground of regional extent with particular chert crusts. The silica source is associated to the dissolution of siliceous sponge spicules or to their calcification. Most of the chert is constituted by mosaics of micro-cryptocrystalline quartz and calcedonite, and it is generated by the selective silicification of biogenic structures, mainly dwelling trace fossils (Thalassinoides isp. because of the higher amount of organic matter and the higher porosity and permeability of the burrow infill. In the hardground, selective silicification affects body fossils such as belemnites, oysters and echinoids, and trace fossils (feeding burrows and borings where in addition cherts is accumulated as an indeterminate crust. The silicification of the biogenic structures firstly occurred in form of opaline phases during the early diagenesis while the oxidation of the organic matter was active. Thus, Thalassinoides trace fossils affected by silicification preserve filaments and cocoids that might have had a microbial origin. Neoformation of dolomite and calcite occur only within the Thalassinoides trace fossils which indicates that diagenetic processes taking place within these burrows differed from those affecting the host rock and other biogenic structures. Dwelling trace fossils would have supposed a close micro-environment where the oxidation conditions changed from high to low rate.

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

    Science.gov (United States)

    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

  8. Nucleation and Epitaxy-Mediated Phase Transformation of a Precursor Cadmium Carbonate Phase at the Calcite/Water Interface

    Energy Technology Data Exchange (ETDEWEB)

    Riechers, Shawn L.; Rosso, Kevin M.; Kerisit, Sebastien N.

    2017-02-24

    Mineral nucleation can be catalyzed by the presence of mineral substrates; however, the mechanisms of heterogeneous nucleation remain poorly understood. A combination of in situ time-sequenced measurements and nano-manipulation experiments were performed using atomic force microscopy (AFM) to probe the mechanisms of heteroepitaxial nucleation of otavite (CdCO3) on calcite (CaCO3) single crystals that exposed the (10-14) surface. Otavite and calcite are isostructural carbonates that display a 4% lattice mismatch, based on their (10-14) surface areas. AFM observations revealed a two-stage process in the nucleation of cadmium carbonate surface precipitates. As evidenced by changes in height, shape, growth behavior, and friction signal of the precipitates, a precursor phase was observed to initially form on the surface and subsequently undergo an epitaxy-mediated phase transformation to otavite, which then grew epitaxially. Nano-manipulation experiments, in which the applied force was increased progressively until precipitates were removed from the surface, showed that adhesion of the precursor phase to the substrate was distinctively weaker than that of the epitaxial phase, consistent with that of an amorphous phase. These findings demonstrate for the first time that heterogeneous mineral nucleation can follow a non-classical pathway like that found in homogenous aqueous conditions.

  9. Bacillus megaterium mediated mineralization of calcium carbonate as biogenic surface treatment of green building materials.

    Science.gov (United States)

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

    2013-12-01

    Microbially induced calcium carbonate precipitation is a biomineralization process that has various applications in remediation and restoration of range of building materials. In the present study, calcifying bacteria, Bacillus megaterium SS3 isolated from calcareous soil was applied as biosealant to enhance the durability of low energy, green building materials (soil-cement blocks). This bacterial isolate produced high amounts of urease, carbonic anhydrase, extra polymeric substances and biofilm. The calcium carbonate polymorphs produced by B. megaterium SS3 were analyzed by scanning electron microscopy, confocal laser scanning microscopy, X-ray diffraction and Fourier transmission infra red spectroscopy. These results suggested that calcite is the most predominant carbonate formed by this bacteria followed by vaterite. Application of B. megaterium SS3 as biogenic surface treatment led to 40 % decrease in water absorption, 31 % decrease in porosity and 18 % increase in compressive strength of low energy building materials. From the present investigation, it is clear that surface treatment of building materials by B. megaterium SS3 is very effective and eco friendly way of biodeposition of coherent carbonates that enhances the durability of building materials.

  10. Biogenic features in calcretes developed on mudstone: Examples from Paleogene sequences of the Himalaya, India

    Science.gov (United States)

    Singh, B. P.; Lee, Yong Il; Pawar, J. S.; Charak, R. S.

    2007-09-01

    Calcrete occurring in the Paleogene sequences of the western Himalayan foreland basin offers very useful information regarding climate and paleogeography of northern part of the Indian subcontinent. These calcretes possess variety of biogenic features (beta fabrics) that include rhizoliths, alveolar septal and vermiform fabric and Microcodium. The Microcodium rosettes show filamentous structures. The rhizoliths and alveolar septal fabric formed by the precipitation of carbonate in soil vadose zone and the vermiform fabric may be a root mat. Perhaps microbes helped in dissolution of carbonate fillings and they were instrumental in precipitation of calcite in the form of rosettes and filaments. Here, the filamentous structure in the Microcodium is significant. We suggest that the Microcodium formed as a result of fungal dissolution and microbial mediation. The lighter values of δ13C and δ18O (calcretes suggest that they developed through meteoric water in the presence of soil organic matter within the dry subtropical climatic zone when the northern part of the Indian subcontinent moved out of wet equatorial climate during its northward flight.

  11. Total balance of biogenic fuels for thermal uses; Ganzheitliche Bilanzierung verschiedener biogener Festbrennstoffe zur thermischen Nutzung

    Energy Technology Data Exchange (ETDEWEB)

    Becher, S.; Kaltschmitt, M. [Stuttgart Univ. (Germany). Inst. fuer Energiewirtschaft und Rationelle Energieanwendung (IER)

    1996-12-31

    In this situation of unfavourable energy price levels, the use of biogenic fuels for power supply can be recommended only if it serves to reduce environmental pollution. Against this background and on the basis of a primary energy balance, the authors attempted a total balance of selected enfironmental effects (global heating and acidification potential) of biomass use as compared to fossil fuel combustion. (orig) [Deutsch] ie Nutzung biogener Festbrennstoffe zur Energienachfragedeckung ist bei dem gegenwaertigen unguenstigen Energiepreisniveau nur dann zu rechtfertigen, wenn es durch die Biomassenutzung zu einer Reduzierung der energiebedingten Umwelteffekte kommt. Vor disem Hintergrund werden ausgehend von der Primaerenergiebilanz ausgewaehlte Umwelteffekte (d.h. das Treibhaus- und das Versauerungspotential) einer Biomassenutzung im Vergleich zu einer Nutzung fossiler Energietraeger ganzheitlich bilanziert. Die wesentlichen Ergebnisse werden zusammengefasst und interpretiert. (orig)

  12. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, Brian P [Colorado School of Mines, Golden, CO (United States)

    2015-09-02

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

  13. EFFECT OF MAGNESIUM AS SUBSTITUTE MATERIAL IN ENZYME MEDIATED CALCITE PRECIPITATION (EMCP FOR SOIL IMPROVEMENT TECHNIQUE

    Directory of Open Access Journals (Sweden)

    Heriansyah ePutra

    2016-05-01

    Full Text Available The optimization of enzyme-mediated calcite precipitation (EMCP was evaluated as a soil improvement technique. In our previous works, purified urease was utilized to bio-catalyze the hydrolysis of urea, which causes the supplied Ca2+ to precipitate with CO32- as calcium carbonate. In the present work, magnesium chloride was newly added to the injecting solutions to delay the reaction rate and to enhance the amount of carbonate precipitation. Soil specimens were prepared in PVC cylinders and treated with concentration-controlled solutions composed of urea, urease, calcium, and magnesium chloride. The mechanical properties of the treated soil specimens were examined through unconfined compressive strength (UCS tests. A precipitation ratio of the carbonate up to 90% of the maximum theoretical precipitation was achieved by adding a small amount of magnesium chloride. Adding magnesium chloride as a delaying agent was indeed found to reduce the reaction rate of the precipitation, which may increase the volume of the treated soil if used in real fields because of the slower precipitation rate and the resulting higher injectivity. A mineralogical analysis revealed that magnesium chloride decreases the crystal size of the precipitated materials and that another carbonate of aragonite is newly formed. Mechanical test results indicated that carbonate precipitates within the soils and brings about a significant improvement in strength. A maximum UCS of 0.6 MPa was obtained from the treated samples.

  14. Controlled cobalt doping in biogenic magnetite nanoparticles

    Science.gov (United States)

    Byrne, J. M.; Coker, V. S.; Moise, S.; Wincott, P. L.; Vaughan, D. J.; Tuna, F.; Arenholz, E.; van der Laan, G.; Pattrick, R. A. D.; Lloyd, J. R.; Telling, N. D.

    2013-01-01

    Cobalt-doped magnetite (CoxFe3 −xO4) nanoparticles have been produced through the microbial reduction of cobalt–iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by superconducting quantum interference device magnetometry, X-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to less than 4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe2+ site with Co2+, with up to 17 per cent Co substituted into tetrahedral sites. PMID:23594814

  15. Controlled cobalt doping in biogenic magnetite nanoparticles.

    Science.gov (United States)

    Byrne, J M; Coker, V S; Moise, S; Wincott, P L; Vaughan, D J; Tuna, F; Arenholz, E; van der Laan, G; Pattrick, R A D; Lloyd, J R; Telling, N D

    2013-06-06

    Cobalt-doped magnetite (CoxFe3 -xO4) nanoparticles have been produced through the microbial reduction of cobalt-iron oxyhydroxide by the bacterium Geobacter sulfurreducens. The materials produced, as measured by superconducting quantum interference device magnetometry, X-ray magnetic circular dichroism, Mössbauer spectroscopy, etc., show dramatic increases in coercivity with increasing cobalt content without a major decrease in overall saturation magnetization. Structural and magnetization analyses reveal a reduction in particle size to less than 4 nm at the highest Co content, combined with an increase in the effective anisotropy of the magnetic nanoparticles. The potential use of these biogenic nanoparticles in aqueous suspensions for magnetic hyperthermia applications is demonstrated. Further analysis of the distribution of cations within the ferrite spinel indicates that the cobalt is predominantly incorporated in octahedral coordination, achieved by the substitution of Fe(2+) site with Co(2+), with up to 17 per cent Co substituted into tetrahedral sites.

  16. Climate/chemistry feedbacks and biogenic emissions.

    Science.gov (United States)

    Pyle, John A; Warwick, Nicola; Yang, Xin; Young, Paul J; Zeng, Guang

    2007-07-15

    The oxidizing capacity of the atmosphere is affected by anthropogenic emissions and is projected to change in the future. Model calculations indicate that the change in surface ozone at some locations could be large and have significant implications for human health. The calculations depend on the precise scenarios used for the anthropogenic emissions and on the details of the feedback processes included in the model. One important factor is how natural biogenic emissions will change in the future. We carry out a sensitivity calculation to address the possible increase in isoprene emissions consequent on increased surface temperature in a future climate. The changes in ozone are significant but depend crucially on the background chemical regime. In these calculations, we find that increased isoprene will increase ozone in the Northern Hemisphere but decrease ozone in the tropics. We also consider the role of bromine compounds in tropospheric chemistry and consider cases where, in a future climate, the impact of bromine could change.

  17. Biogenic amines in Portuguese traditional foods and wines.

    Science.gov (United States)

    Ferreira, Isabel M P L V O; Pinho, Olívia

    2006-09-01

    The presence of biogenic amines in foodstuffs is an important food safety problem because of the implication of these compounds in food intolerance and intoxication. The separation and quantification of biogenic amines in foods is normally performed by chromatographic techniques. This review contains descriptions of the quantification of biogenic amines in Portuguese traditional fermented and/or ripened foods and wines, including Protected Denomination of Origin cheeses, dry-cured sausages, and Portuguese wines (including Port wines), using different analytical methods based on high-pressure liquid chromatography (UV or diode array and/or fluorometric detectors) and gas chromatography (with a mass spectrometry detector). The evolution of biogenic amines during fermentation, ripening, aging, or storage of those products was also evaluated. Biogenic amine concentrations ranged widely within individual food items, and storage, transport, and handling conditions can influence to some extent the biogenic amines present and their concentrations. Traditional foods are an important part of the Portuguese diet, and a high intake of harmful amounts of biogenic amines from traditional Portuguese fermented foods is possible. However, extensive research is needed to extend the current limited database.

  18. Ion beam modifications of defect sub-structure of calcite cleavages

    Indian Academy of Sciences (India)

    WINTEC

    (a) Optical micrograph of calcite cleavage chemically etched with propionic acid with water (1 : 100) (rhombic etch pits; time 30 s). Scanning electron micrographs of calcite cleavages chemically etched after ion bombardment with different ener- gies: (b) 100 KeV, (c) 120 KeV and (d) 140 KeV. connecting Keithley (Model ...

  19. Removal of Pb(II from aqueous solution by natural and synthetic calcites

    Directory of Open Access Journals (Sweden)

    Ayomadewa Mercy Adesola

    2012-08-01

    Full Text Available A comparative evaluation of the adsorption capacity and kinetics of Pb(II uptake by both synthetic and natural calcites has been undertaken using batch equilibration technique. The originality of the calcite materials was confirmed by XRD and elemental composition by XRF. The point of zero charge values of 9.57 and 8.20 were obtained by mass titration method for synthetic and natural calcite, respectively. The maximum adsorption capacities of 200 mg/g and 150 mg/g Pb(II of synthetic calcite and natural calcite were obtained at initial lead loading of 1200 mg/L at 25±2 °C, respectively. The study showed a very slight dependence of sorption capacity on the ionic strength and pH, but a strong dependence on the particle size and contact time. The sorption data results fitted better the Langmuir than the Freundlich isotherms. The kinetic data fitted well to pseudo-first order sorption kinetic model with a regression coefficient value of 0.96 and 0.94 for synthetic and natural calcites, respectively. Desorption of Pb(II from calcite surface was achieved with efficiency of 95% using 4 M HNO3. The extent of reversibility of sorption reaction was a function of the equilibrium pH of calcite-Pb(II solution suspension.DOI: http://dx.doi.org/10.4314/bcse.v26i2.4

  20. A comparative study of modern carbonate mud in reefs and carbonate platforms: Mostly biogenic, some precipitated

    Science.gov (United States)

    Gischler, Eberhard; Dietrich, Sarah; Harris, Daniel; Webster, Jody M.; Ginsburg, Robert N.

    2013-06-01

    Carbonate mud from reefs and carbonate platforms in six locations of the Atlantic, Indian, and Pacific Oceans (Belize, Bahamas, Florida, the Maldives, French Polynesia, Great Barrier Reef) was systematically and quantitatively analyzed with regard to texture, composition, mineralogy, and geochemistry. Mud composition shows considerable variability, however, the data supports the contention that these muds are largely derived from the breakdown of skeletal grains and codiacean algae. Only mud from the Bahamas and northern Belize, areas which are characterized by common whitings, is interpreted to be mainly inorganically precipitated. Three grain-size fractions (63-20 μm, 20-4 μm, aragonite needles, nanograins, and coccoliths. Coccoliths are common in deeper lagoonal settings of the open ocean settings (Maldives, French Polynesia). The geochemistry of the aragonite contents and strontium concentrations, suggesting physico-chemical precipitation. The northern Belize and Great Barrier Reef samples show the highest magnesium calcite values and, accordingly, produced the lowest aragonite and strontium measurements. The high-magnesium calcite portion of the northern Belize mud is either precipitated or due to abundant micritized skeletal grains (e.g., foraminifera): more studies are needed to verify the origin. In the case of the Great Barrier Reef sample, coralline algae appear to be the source of abundant high-magnesium calcite. This study emphasizes that from a global perspective, modern muds in reefs and carbonate platforms exhibit different compositions but are in many cases biologically derived. Even though the composition of modern carbonate muds varies among the six locations investigated, they may serve as analogs for the formation of muds in Cenozoic and Mesozoic reefs and carbonate platforms. Limitations of the interpretation of carbonate-mud origin include the difficulty of identifying, quantifying, and analyzing small grains, the ease with which small

  1. Biogenic amines degradation by microorganisms isolated from cheese

    Directory of Open Access Journals (Sweden)

    Irena Butor

    2017-01-01

    Full Text Available The aim of this study was the isolation and characterization of microorganisms able to degrade biogenic amines and their identification. Individual microorganisms were obtained by isolation from commercially available foodstuffs and food produced in the technological laboratories of Faculty of Technology, Tomas Bata University in Zlín and subsequently identified by MALDI-TOF MS. The results of MALDI-TOF MS identification were verified by 16S rRNA sequenation. In this work was studied the ability of 5 bacterial strains positive to biogenic amines degradation isolated from dairy products to decrease biogenic amines content in vitro and quantified reduction in the concentration of biogenic amines tryptamine, β-phenylethylamine, putrescine, cadaverine, histamine and tyramine. The level of degradation (decrease of biogenic amines was determined on the base of the ability to grow in media with biogenic amines as the sole source carbon and nitrogen. The isolated strains with the ability of degradation of one or more biogenic amines were cultured in medium supplemented with relevant biogenic amines, the media derivatized with dansyl chloride and these amines separated by HPLC at a wavelength of 254 nm. From five tested strains identified as Bacillus subtilis, Bacillus pumilus, Enterobacter cloacae, Rhizobium radiobacter and Acinetobacter pitii, isolated from gouda type cheese, the greatest ability of degradation was observed in Bacillus subtilis, which was capable to degrade almost all amount of histamine, cadaverine and putrescine. Other four strains showed a lower rate of degradation than Bacillus subtilis, but the ability to degrade biogenic amines with these microorganisms was still significant.

  2. Paleohydrogeological implications from fracture calcites and sulfides in a major hydrogeological zone HZ19 at Olkiluoto

    International Nuclear Information System (INIS)

    Sahlstedt, E.; Karhu, J.; Rinne, K.

    2009-08-01

    30 samples of fracture mineral fillings in or near water conducting fractures at Olkiluoto were collected from 10 drill cores for fracture mineral studies. The aim of the study was to obtain information about past hydrogeochemical conditions at Olkiluoto using the calcite morphology, the chemical characteristics and the isotopic composition of carbon and oxygen in calcite. The chemical composition of fracture calcites at Olkiluoto is nearly stoichiometric CaCO 3 . Most variation in the composition of calcite is due to differences in the Mn content, which could indicate variations in groundwater redox conditions. Meaningful REE patterns were obtained for the calcites. REE patterns showed generally negative Eu anomalies, but one fracture calcite specimen had a distinct positive Eu anomaly. This positive anomaly could be related to ancient hydrothermal conditions, although derivation of the anomaly from the host rock cannot be excluded. Preliminary results for calcite U-Th dating of fracture calcites are reported. The isotopic composition of U and Th were analysed by a new multiple collector LA-ICPMS instrument. U and Th concentrations in fracture calcites are generally 18 O values of calcite range from -17 to -7 per mille. Most of the calcites may have been precipitated in the presence of waters with oxygen isotope ratios similar to those in the present-day groundwaters at Olkiluoto. Two samples with an oxygen isotopic composition highly depleted in 18 O were interpreted to have been precipitated at elevated temperatures. The δ 13 C values of calcite showed a wide range of values from -26 to +35 per mille. Multiple sources for carbon are implied. The highest δ 13 C values indicate methanic conditions in the fracture at the time of calcite precipitation. It appears that the methanic environment has earlier extended to shallower depths compared to the location of the methanic environment in the present-day fracture system (> 300 m). Ten pyrite samples were analysed

  3. Effect of dissolution kinetics on flotation response of calcite with oleate

    Directory of Open Access Journals (Sweden)

    D. G. Horta

    Full Text Available Abstract Phosphate flotation performance can be influenced by the dissolution kinetics of the minerals that compose the ore. The purpose of this work was to investigate the effect of dissolution kinetics on flotation response with oleate (collector of calcites from different origins and genesis. The calcite samples were first purified and characterized by x-ray Fluorescence (XRF and the Rietveld method applied to x-ray Diffractometry data (RXD. Experiments of calcite dissolution and microflotationwere performed at pH 8 and pH 10.The pH effect on the calcite dissolution and flotation indicates the possible influence of the carbonate/bicarbonate ions provided by the CO2 present in the air. In addition, the flotation response is greater as the dissolution increases, making more Ca2+ ions available to interact with collector molecules. This result corroborates the surface precipitation mechanism proposed foroleate adsorption on the calcite surface.

  4. Orientation with a Viking sun-compass, a shadow-stick, and two calcite sunstones under various weather conditions.

    Science.gov (United States)

    Bernáth, Balázs; Blahó, Miklós; Egri, Adám; Barta, András; Kriska, György; Horváth, Gábor

    2013-09-01

    It is widely accepted that Vikings used sun-compasses to derive true directions from the cast shadow of a gnomon. It has been hypothesized that when a cast shadow was not formed, Viking navigators relied on crude skylight polarimetry with the aid of dichroic or birefringent crystals, called "sunstones." We demonstrate here that a simple tool, that we call "shadow-stick," could have allowed orientation by a sun-compass with satisfying accuracy when shadows were not formed, but the sun position could have reliably been estimated. In field tests, we performed orientation trials with a set composed of a sun-compass, two calcite sunstones, and a shadow-stick. We show here that such a set could have been an effective orientation tool for Vikings only when clear, blue patches of the sky were visible.

  5. Some Debye temperatures from single-crystal elastic constant data

    Science.gov (United States)

    Robie, R.A.; Edwards, J.L.

    1966-01-01

    The mean velocity of sound has been calculated for 14 crystalline solids by using the best recent values of their single-crystal elastic stiffness constants. These mean sound velocities have been used to obtain the elastic Debye temperatures ??De for these materials. Models of the three wave velocity surfaces for calcite are illustrated. ?? 1966 The American Institute of Physics.

  6. Up-scaling mineral-aqueous interfacial processes that govern isotope and trace element partitioning during calcite growth

    Science.gov (United States)

    Lammers, L. N.

    2014-12-01

    The dependence of the isotopic and trace element composition of calcium carbonate minerals on growth conditions including temperature, pH, and salinity is widely used to infer paleoclimate conditions. These inferences rely heavily on phenomenological observations of biogenic and inorganic precipitation both in and ex situ, where only limited variability in solution conditions can be explored. Ionic fluxes between the mineral surface and aqueous growth solution govern the net uptake of both stoichiometric and trace species during calcification, so developing a mechanistic understanding of the reactions governing these fluxes is critical to refine existing proxies and to develop new ones. The micro-scale mechanisms of calcite precipitation from aqueous solution have been extensively studied, and net ionic uptake post-nucleation is known to occur primarily at monomolecular kink sites along step edges at the mineral surface. In this talk, I will present a theoretical framework that uses the quasi-elementary ion attachment and detachment reactions governing ion uptake at kink sites to simultaneously model bulk mineral growth kinetics and tracer partitioning during calcite precipitation. Several distinct processes occur during ion uptake at kink sites that can influence the distribution of trace species, directly impacting the composition of various carbonate paleoproxies including δ44Ca, δ18O, Sr/Ca and Mg/Ca. The distribution of these trace species will be shown to depend on (1) the relative rates of ion desolvation during attachment to kink sites, (2) the relative rates of bond breaking during detachment from kink sites, and (3) the equilibrium partitioning of trace aqueous species. This model accounts for the impact of solution conditions on net ion fluxes and surface speciation, which in turn controls the population of kink sites available for direct ion exchange with the aqueous phase. The impacts of solution variables including pH, temperature and salinity can

  7. A time-resolved laser fluorescence spectroscopy (TRLFS) study of the interaction of trivalent actinides (curium(III)) with calcite

    International Nuclear Information System (INIS)

    Stumpf, Th.; Fanghaenel, Th.

    2002-01-01

    Cm(III) interaction with calcite was investigated in the trace concentration range. Two different Cm(III)/calcite sorption species were found. The first Cm(III) sorption species consists of a curium ion that is bonded onto the calcite surface. The second Cm(III) sorption species has lost its complete hydration sphere and is incorporated into the calcite bulk structure /1/. (orig.)

  8. Biogenic Sulfur in the Siple Dome Ice Core, Version 1

    Data.gov (United States)

    National Aeronautics and Space Administration — This data set is a continuous, high-resolution record of biogenic sulfur (methanesulfonate, known as MSA and CH3SO3-) in the 1000 m deep Siple Dome A (SDMA) core,...

  9. Biogenic hydrocarbon emission estimates for North Central Texas

    Energy Technology Data Exchange (ETDEWEB)

    Wiedinmyer, C.; Wade Strange, I.; Allen, D.T. [University of Texas at Austin (United States). Dept. of Chemical Engineering; Estes, M. [Texas Natural Resource Conservation Commission, Austin, TX (United States); Yarwood, G. [ENVIRON International Corporation, Novato, CA (United States)

    2000-07-01

    Biogenic hydrocarbon emissions were estimated for a 37 county region in North Central Texas. The estimates were based on several sources of land use/land cover data that were combined using geographical information systems. Field studies were performed to collect species and tree diameter distribution data. These data were used to estimate biomass densities and species distributions for each of the land use and cover classifications. VOC emissions estimates for the domain were produced using the new land use/land cover data and a biogenic emissions model. These emissions were more spatially resolved and a factor of 2 greater in magnitude than those calculated based on the biogenic emissions landuse database (BELD) commonly used in biogenic emissions models. (author)

  10. Biogenic sulfur compounds and the global sulfur cycle

    International Nuclear Information System (INIS)

    Aneja, V.P.; Aneja, A.P.; Adams, D.F.

    1982-01-01

    Field measurements of biogenic sulfur compounds shows a great variation in concentrations and emission rates for H 2 S, DMS, CS 2 and COS. Measurements by the chamber method and estimates from micrometeorological sampling are employed to determine the earth-atmosphere flux of these gases. Much of the variation can be attributed to differences of climate and surface conditions, with marshes being a large source of biogenic sulfur (mean contribution 4 x 10 to the 6th ton/year maximum contribution 142 x 10 to the 6th ton/year). Considering that the estimated biogenic contribution needed to balance the global sulfur cycle ranges from 40- 230 x 10 to the 6th tons/year, the mean values are not sufficient to balance this cycle. Further experimental investigations are suggested in order to characterize the biogenic processes adequately

  11. Quantifying the Global Marine Biogenic Nitrogen Oxides Emissions

    Science.gov (United States)

    Su, H.; Wang, S.; Lin, J.; Hao, N.; Poeschl, U.; Cheng, Y.

    2017-12-01

    Nitrogen oxides (NOx) are among the most important molecules in atmospheric chemistry and nitrogen cycle. The NOx over the ocean areas are traditionally believed to originate from the continental outflows or the inter-continental shipping emissions. By comparing the satellite observations (OMI) and global chemical transport model simulation (GEOS-Chem), we suggest that the underestimated modeled atmospheric NO2 columns over biogenic active ocean areas can be possibly attributed to the biogenic source. Nitrification and denitrification in the ocean water produces nitrites which can be further reduced to NO through microbiological processes. We further report global distributions of marine biogenic NO emissions. The new added emissions improve the agreement between satellite observations and model simulations over large areas. Our model simulations manifest that the marine biogenic NO emissions increase the atmospheric oxidative capacity and aerosol formation rate, providing a closer link between atmospheric chemistry and ocean microbiology.

  12. Calcite veining and feeding conduits in a hydrothermal system: Insights from a natural section across the Pleistocene Gölemezli travertine depositional system (western Anatolia, Turkey)

    Science.gov (United States)

    Capezzuoli, Enrico; Ruggieri, Giovanni; Rimondi, Valentina; Brogi, Andrea; Liotta, Domenico; Alçiçek, Mehmet Cihat; Alçiçek, Hülya; Bülbül, Ali; Gandin, Anna; Meccheri, Marco; Shen, Chuan-Chou; Baykara, Mehmet Oruç

    2018-02-01

    Linking the architecture of structural conduits with the hydrothermal fluids migrating from the reservoir up to the surface is a key-factor in geothermal research. A contribution to this achievement derives from the study of spring-related travertine deposits, but although travertine depositional systems occur widely, their feeding conduits are only rarely exposed. The integrated study carried out in the geothermal Gölemezli area, nearby the well-known Pamukkale area (Denizli Basin, western Anatolia, Turkey), focused on onyx-like calcite veins (banded travertine) and bedded travertine well exposed in a natural cross-section allowing the reconstruction of the shallower part of a geothermal system. The onyx-like veins represent the thickest vein network (> 150 m) so far known. New field mapping and structural/kinematic analyses allowed to document a partially dismantled travertine complex (bedded travertine) formed by proximal fissure ridges and distal terraced/pools depositional systems. The banded calcite veins, WNW-trending and up to 12 m thick, developed within a > 200 m thick damaged rock volume produced by parallel fault zones. Th/U dating indicates a long lasting (middle-late Pleistocene) fluids circulation in a palaeo-geothermal system that, due to its location and chemical characteristics, can be considered the analogue of the nearby, still active, Pamukkale system. The isotopic characteristics of the calcite veins together with data from fluid inclusions analyses, allow the reconstruction of some properties (i.e. temperature, salinity and isotopic composition) and processes (i.e. temperature variation and intensity of degassing) that characterized the parent fluids and the relation between degassing intensity and specific microfabric of calcite crystals (elongated/microsparite-micrite bands), controlled by changes/fluctuations of the physico-chemical fluid characteristics.

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

    Science.gov (United States)

    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.

  14. The coprecipitation of Sr2+ with calcite at 250C and 1 atm

    International Nuclear Information System (INIS)

    Pingitore, N.E. Jr.; Eastman, M.P.

    1986-01-01

    The incorporation of Sr 2+ into calcite at earth surface aqueous conditions is affected by the absolute concentration of Sr 2+ , the presence of Ba 2+ and NaCl in the solution and the rate of precipitation. At solution ratios (molar) of Sr 2+ to Ca 2+ in the low 10 -3 range, which yield calcites with several hundred ppm Sr 2+ , kappasub(calcite) sup(Sr) typically assumes a value between 0.10 and 0.20. Above these concentrations the value of kappasub(calcite) sup(Sr) drops to approximately 0.06. Furthermore, if minor amounts of Ba 2+ or large amounts of Na + (0.48 M) are added to a dilute Sr 2+ solution, a value around 0.06 for kappasub(calcite)sup(Sr) is found. This 'strontium concentration effect' and the associated 'competitive cation effect' suggest that small amounts of Sr 2+ may be incorporated into a limited number of nonlattice sites in calcite. Incorporation of Sr 2+ into these sites, presumably defects, noticeably affects kappasub(calcite)sup(Sr) only at low Sr 2+ concentrations and in the absence of competition from other large cations. An increase in kappasub(calcite)sup(Sr) with rate of precipitation, qualitatively similar to that found in other studies, was observed only when precipitation times were decreased from days to hours. For many geologic settings a partition coefficient for Sr 2+ into calcite of 0.06 appears appropriate, but there are situations - very low Sr 2+ concentrations, the presence of Mg 2+ , and fast precipitation rates - in which a larger value might better approximate natural partitioning. (author)

  15. Biogenic antimicrobial silver nanoparticles produced by fungi.

    Science.gov (United States)

    Rodrigues, Alexandre G; Ping, Liu Yu; Marcato, Priscyla D; Alves, Oswaldo L; Silva, Maria C P; Ruiz, Rita C; Melo, Itamar S; Tasic, Ljubica; De Souza, Ana O

    2013-01-01

    Aspergillus tubingensis and Bionectria ochroleuca showed excellent extracellular ability to synthesize silver nanoparticles (Ag NP), spherical in shape and 35 ± 10 nm in size. Ag NP were characterized by transmission electron microscopy, X-ray diffraction analysis, and photon correlation spectroscopy for particle size and zeta potential. Proteins present in the fungal filtrate and in Ag NP dispersion were analyzed by electrophoresis (sodium dodecyl sulfate polyacrylamide gel electrophoresis). Ag NP showed pronounced antifungal activity against Candida sp, frequently occurring in hospital infections, with minimal inhibitory concentration in the range of 0.11-1.75 μg/mL. Regarding antibacterial activity, nanoparticles produced by A. tubingensis were more effective compared to the other fungus, inhibiting 98.0 % of Pseudomonas. aeruginosa growth at 0.28 μg/mL. A. tubingensis synthesized Ag NP with surprisingly high and positive surface potential, differing greatly from all known fungi. These data open the possibility of obtaining biogenic Ag NP with positive surface potential and new applications.

  16. Biogenic volatile emissions from the soil.

    Science.gov (United States)

    Peñuelas, J; Asensio, D; Tholl, D; Wenke, K; Rosenkranz, M; Piechulla, B; Schnitzler, J P

    2014-08-01

    Volatile compounds are usually associated with an appearance/presence in the atmosphere. Recent advances, however, indicated that the soil is a huge reservoir and source of biogenic volatile organic compounds (bVOCs), which are formed from decomposing litter and dead organic material or are synthesized by underground living organism or organs and tissues of plants. This review summarizes the scarce available data on the exchange of VOCs between soil and atmosphere and the features of the soil and particle structure allowing diffusion of volatiles in the soil, which is the prerequisite for biological VOC-based interactions. In fact, soil may function either as a sink or as a source of bVOCs. Soil VOC emissions to the atmosphere are often 1-2 (0-3) orders of magnitude lower than those from aboveground vegetation. Microorganisms and the plant root system are the major sources for bVOCs. The current methodology to detect belowground volatiles is described as well as the metabolic capabilities resulting in the wealth of microbial and root VOC emissions. Furthermore, VOC profiles are discussed as non-destructive fingerprints for the detection of organisms. In the last chapter, belowground volatile-based bi- and multi-trophic interactions between microorganisms, plants and invertebrates in the soil are discussed. © 2014 John Wiley & Sons Ltd.

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

    Science.gov (United States)

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

    2016-04-01

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

  18. Monitoring of Calcite Precipitation in Hardwater Lakes with Multi-Spectral Remote Sensing Archives

    Directory of Open Access Journals (Sweden)

    Iris Heine

    2017-01-01

    Full Text Available Calcite precipitation is a common phenomenon in calcium-rich hardwater lakes during spring and summer, but the number and spatial distribution of lakes with calcite precipitation is unknown. This paper presents a remote sensing based method to observe calcite precipitation over large areas, which are an important prerequisite for a systematic monitoring and evaluation of restoration measurements. We use globally archived satellite remote sensing data for a retrospective systematic assessment of past multi-temporal calcite precipitation events. The database of this study consists of 205 data sets that comprise freely available Landsat and Sentinel 2 data acquired between 1998 and 2015 covering the Northeast German Plain. Calcite precipitation is automatically identified using the green spectra and the metric BGR area, the triangular area between the blue, green and red reflectance value. The validation is based on field measurements of CaCO3 concentrations at three selected lakes, Feldberger Haussee, Breiter Luzin and Schmaler Luzin. The classification accuracy (0.88 is highest for calcite concentrations ≥0.7 mg/L. False negative results are caused by the choice of a conservative classification threshold. False positive results can be explained by already increased calcite concentrations. We successfully transferred the developed method to 21 other hardwater lakes in Northeast Germany. The average duration of lakes with regular calcite precipitation is 37 days. The frequency of calcite precipitation reaches from single time detections up to detections nearly every year. False negative classification results and gaps in Landsat time series reduce the accuracy of frequency and duration monitoring, but in future the image density will increase by acquisitions of Sentinel-2a (and 2b. Our study tested successfully the transfer of the classification approach to Sentinel-2 images. Our study shows that 15 of the 24 lakes have at least one phase of

  19. Paleohydrogeological implications from fracture calcites in fissures of low transmissivity. A report of investigations in 2011

    International Nuclear Information System (INIS)

    Sahlstedt, E.; Karhu, J.

    2014-07-01

    Samples of fracture fillings were collected from 26 bedrock fractures at Olkiluoto. Special attention was paid to fractures having low transmissivities of <1E-8 m 2 /s. The chemical composition and the C and O isotopic composition of the fracture filling calcite were analysed. In addition, fluid inclusions were studied and microthermometric measurements conducted on fracture filling calcite. The most common minor element in calcite fillings was Mn, having concentrations up to 3.4 wt-%. The δ13C values had a wide range, from -13.0 to 14.5 per mille, and the δ18O values a narrower range, from -13.4 to -7.3 per mille. The δ18O values of late-stage calcite appear to be independent of the transmissivity of the fractures, ranging from -11.2 to -7.3 per mille over a T range from 3E -6 to 1.6E -1 1 m 2 /s. The δ13C values of late-stage calcite appear to have more variation at high transmissivities of >1E-8 m 2 /s. Unusually low and high δ13C values in late-stage calcite fillings occur in the upper ∼ 400 m of the bedrock and are probably related to microbial reduction processes, at near surface (<60 m) conditions to oxidation of organic matter resulting in low δ13C values and at ∼ 55-400 m to methanogenesis, causing high δ 13C values. A relatively low spread in the δ 13C values of late-stage calcite precipitates in low transmissivity (<1E-8 m 2 /s) fractures is most likely caused by stable conditions in the areas of low conductivity in the bedrock, reflecting slow dissolution/reprecipitation of older carbonate fillings. Fluid inclusion data indicate variation in fracture water types from high temperature, ∼ 200 deg C, low salinity fluid with < 4 wt-% of NaCl eq to low temperature, <100 deg C, high salinity fluid with 17-29 wt-% of NaCl eq . The high temperature fluid is associated with Group 5 calcite fillings and the low temperature fluid with Group 3 calcite. The composition of fluids related to Group 4 calcite falls roughly between the compositions

  20. Nitrogen in biogenic and abiogenic minerals from Paleozoic black shales: an NRA study

    International Nuclear Information System (INIS)

    Gallien, J.-P.; Orberger, B.; Daudin, L.; Pinti, D.L.; Pasava, J.

    2004-01-01

    Nuclear reaction analyses were performed on feldspars, quartz, abiogenic and biogenic sulfides and phosphates in organic matter-rich black shales. The goal was to study N-fractionation in black shales during diagenesis and contemporaneous hydrothermalism. Light elements (N, C) together with heavier ones (K, Ca, Ni, Fe, Zn) were analyzed by PIXE. Due to the heterogeneous sample composition, a scanning mode was used. Each phase was identified before extracting the corresponding spectra for quantification. Six phases, carrying nitrogen (and C), have been identified. K-feldspars are the richest in N (1.0-2.4 wt.%), followed by organic carbon (0.67 wt.%). Quartz, biogenic and abiogenic sulfides and phosphates contain N in the range of 0.56-1.08 wt.%. The present N-distribution in the black shales is explained by a two-step nitrogen release: (1) organic matter decay produces N, P, S nutriments for the development of a hydrothermal vent fauna and (2) biomineralization of this vent fauna liberates nitrogen to early diagenetic fluids. The extreme N enrichment of feldspars is related to its crystal structure, favoring the potassium substitution by NH 4 + , and the N-uptake during organic matter replacement

  1. Biogenic and non-biogenic Si pools in terrestrial ecosystems: results from a novel analysis method

    Science.gov (United States)

    Barao, Lucia; Vandevenne, Floor; Clymans, Wim; Meire, Patrick; Frings, Patrick; Conley, Daniel; Struyf, Eric

    2015-04-01

    Silicon (Si) is a chemical element frequently associated with highly abundant silicate minerals in the Earth crust. Over millions of years, the interaction of such minerals with the atmosphere and hydrosphere produces a myriad of processed compounds, and the mineral weathering consumes CO2 during the process. The weathering of minerals also triggers the export of dissolved Si (DSi) to coastal waters and the ocean. Here, DSi is deposited in diatom frustules, in an amorphous biogenic form (BSi). Diatoms account for 50% of the primary production and are crucial for the export of carbon into the deep sea. In recent years, it was acknowledged that terrestrial systems filter the Si transition from the terrestrial mineral to the marine and coastal biological pool, by the incorporation of DSi into plants. In this process, DSi is taken up by roots together with other nutrients and precipitates in plant cells in amorphous structures named phytoliths. After dead, plant tissues become mixed in the top soil, where BSi is available for dissolution and will control the DSi availability in short time scales. Additionally, Si originated from soil forming processes can also significantly interfere with the global cycle. The Si cycle in terrestrial ecosystems is a key factor to coastal ecology, plant ecology, biogeochemistry and agro-sciences, but the high variability of different biogenic and non-biogenic Si pools remains as an obstacle to obtain accurate measurements. The traditional methods, developed to isolate diatoms in ocean sediments, only account for simple mineral corrections. In this dissertation we have adapted a novel continuous analysis method (during alkaline extraction) that uses Si-Al ratios and reactivity to differ biogenic from non-biogenic fractions. The method was originally used in marine sediments, but we have developed it to be applicable in a wide range of terrestrial, aquatic and coastal ecosystems. We first focused on soils under strong human impact in

  2. Sensitivity of modeled ozone concentrations to uncertainties in biogenic emissions

    International Nuclear Information System (INIS)

    Roselle, S.J.

    1992-06-01

    The study examines the sensitivity of regional ozone (O3) modeling to uncertainties in biogenic emissions estimates. The United States Environmental Protection Agency's (EPA) Regional Oxidant Model (ROM) was used to simulate the photochemistry of the northeastern United States for the period July 2-17, 1988. An operational model evaluation showed that ROM had a tendency to underpredict O3 when observed concentrations were above 70-80 ppb and to overpredict O3 when observed values were below this level. On average, the model underpredicted daily maximum O3 by 14 ppb. Spatial patterns of O3, however, were reproduced favorably by the model. Several simulations were performed to analyze the effects of uncertainties in biogenic emissions on predicted O3 and to study the effectiveness of two strategies of controlling anthropogenic emissions for reducing high O3 concentrations. Biogenic hydrocarbon emissions were adjusted by a factor of 3 to account for the existing range of uncertainty in these emissions. The impact of biogenic emission uncertainties on O3 predictions depended upon the availability of NOx. In some extremely NOx-limited areas, increasing the amount of biogenic emissions decreased O3 concentrations. Two control strategies were compared in the simulations: (1) reduced anthropogenic hydrocarbon emissions, and (2) reduced anthropogenic hydrocarbon and NOx emissions. The simulations showed that hydrocarbon emission controls were more beneficial to the New York City area, but that combined NOx and hydrocarbon controls were more beneficial to other areas of the Northeast. Hydrocarbon controls were more effective as biogenic hydrocarbon emissions were reduced, whereas combined NOx and hydrocarbon controls were more effective as biogenic hydrocarbon emissions were increased

  3. Conditions of uranium-bearing calcite formation in ore-enclosing sediments of the Semizbaj deposit (Kazakhstan)

    International Nuclear Information System (INIS)

    Kondrat'eva, I.A.; Maksimova, I.G.; Dojnikova, O.I.

    1995-01-01

    Consideration is given to results of investigation into uranium-bearing calcite, forming the cement of gravelly-sandy rocks of the Semizbaj uranium deposit. Core sampling in prospecting boreholes were used to establish geological conditions, place and time of uranium-bearing calcite formation. Calcite was investigated by optical, electron-microscope and radiographic methods. It is shown that uranium in calcite doesn't form its own mineral phase and exists in scattered state. Uranium in calcite-bearing minerals is present in isomorphic form. Uranium content in calcite was equal to 0.009-0.15 %. It is proposed that mineralization, formed in sedimentary rocks by processes of ground-stratum oxidation, is the source of uranium, enriching calcite. refs., 5 figs., 2 tabs

  4. Hydrothermal Growth of Polyscale Crystals

    Science.gov (United States)

    Byrappa, Kullaiah

    In this chapter, the importance of the hydrothermal technique for growth of polyscale crystals is discussed with reference to its efficiency in synthesizing high-quality crystals of various sizes for modern technological applications. The historical development of the hydrothermal technique is briefly discussed, to show its evolution over time. Also some of the important types of apparatus used in routine hydrothermal research, including the continuous production of nanosize crystals, are discussed. The latest trends in the hydrothermal growth of crystals, such as thermodynamic modeling and understanding of the solution chemistry, are elucidated with appropriate examples. The growth of some selected bulk, fine, and nanosized crystals of current technological significance, such as quartz, aluminum and gallium berlinites, calcite, gemstones, rare-earth vanadates, electroceramic titanates, and carbon polymorphs, is discussed in detail. Future trends in the hydrothermal technique, required to meet the challenges of fast-growing demand for materials in various technological fields, are described. At the end of this chapter, an Appendix 18.A containing a more or less complete list of the characteristic families of crystals synthesized by the hydrothermal technique is given with the solvent and pressure-temperature (PT) conditions used in their synthesis.

  5. Biogenic amines in Italian Pecorino cheese

    Directory of Open Access Journals (Sweden)

    Maria eSchirone

    2012-05-01

    Full Text Available The quality of distinctive artisanal cheeses is closely associated with the territory of production and its traditions. Pedoclimatic characteristics, genetic autochthonous variations and anthropic components create an environment so specific that it would be extremely difficult to reproduce elsewhere. Pecorino cheese is included in this sector of the market and is widely diffused in Italy (approximately 53.727t of production. Pecorino is a common name given to indicate Italian cheeses made exclusively from pure ewes' milk characterized by a high content of fat matter and it is mainly produced in the middle and south of Italy by traditional procedures from raw or thermized milk. The microbiota plays a major role in the development of the organoleptic characteristics of the cheese but it can also be responsible for the accumulation of undesirable substances, such as biogenic amines (BA. Several factors can contribute to the qualitative and quantitative profiles of BA’s in Pecorino cheese such as environmental hygienic conditions, pH, salt concentration, aw, fat content, pasteurization of milk, decarboxylase microorganisms, starter cultures, temperature and time of ripening, storage, part of the cheese (core, edge and the presence of cofactor. Generally, the total content of BA’s can range from about 100-2400 mg/kg, with a prevalence of toxicologically important BA’s, tyramine and histamine. The presence of BA in Pecorino cheeses is becoming increasingly important to consumers and cheese-maker alike, due to the potential threats of toxicity to humans and consequent trade implications.

  6. Seasonal trends of biogenic terpene emissions.

    Science.gov (United States)

    Helmig, Detlev; Daly, Ryan Woodfin; Milford, Jana; Guenther, Alex

    2013-09-01

    Biogenic volatile organic compound (BVOC) emissions from six coniferous tree species, i.e. Pinus ponderosa (Ponderosa Pine), Picea pungens (Blue Spruce), Pseudotsuga menziesii (Rocky Mountain Douglas Fir) and Pinus longaeva (Bristlecone Pine), as well as from two deciduous species, Quercus gambelii (Gamble Oak) and Betula occidentalis (Western River Birch) were studied over a full annual growing cycle. Monoterpene (MT) and sesquiterpene (SQT) emissions rates were quantified in a total of 1236 individual branch enclosure samples. MT dominated coniferous emissions, producing greater than 95% of BVOC emissions. MT and SQT demonstrated short-term emission dependence with temperature. Two oxygenated MT, 1,8-cineol and piperitone, were both light and temperature dependent. Basal emission rates (BER, normalized to 1000μmolm(-2)s(-1) and 30°C) were generally higher in spring and summer than in winter; MT seasonal BER from the coniferous trees maximized between 1.5 and 6.0μgg(-1)h(-1), while seasonal lows were near 0.1μgg(-1)h(-1). The fractional contribution of individual MT to total emissions was found to fluctuate with season. SQT BER measured from the coniferous trees ranged from emissions modeling, was not found to exhibit discernible growth season trends. A seasonal correction factor proposed by others in previous work to account for a sinusoidal shaped emission pattern was applied to the data. Varying levels of agreement were found between the data and model results for the different plant species seasonal data sets using this correction. Consequently, the analyses on this extensive data set suggest that it is not feasible to apply a universal seasonal correction factor across different vegetation species. A modeling exercise comparing two case scenarios, (1) without and (2) with consideration of the seasonal changes in emission factors illustrated large deviations when emission factors are applied for other seasons than those in which they were experimentally

  7. Machine learning approach for predicting the effect of CO2 solubility on dissolution rate of calcite

    Science.gov (United States)

    Nomeli, Mohammad

    2017-11-01

    A machine learning-assisted model is developed to predict the dissolution rate of calcite in saline solutions that are imbibed with dissolved CO2 over a broad range of both subcritical and supercritical conditions. This study focuses on determining the rate of calcite dissolution within a temperature range of 50-100 C and pressures up to 600 bar, relevant for CO2 sequestration in saline aquifers. A general reaction kinetic model is used that is based on the extension of the standard Arrhenius equation with an added, solubility dependent, pH term to account for the saturated concentration of dissolved CO2. The kinetic model helps to obtain a predictive rate equation using machine learning methods to determine the dissolution of calcite as a function of temperature, pressure and salinity. The new rate equation helps us obtain good agreement with experimental data, and it is applied to study the geochemically induced alterations of fracture geometry due to calcite dissolution.

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

    Science.gov (United States)

    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)

  9. Calcite dissolution along a transect in the western tropical Indian Ocean: A multiproxy approach

    Digital Repository Service at National Institute of Oceanography (India)

    Naik, S.S.; Naidu, P.D.

    Three paleocarbonate ion proxies, size index, planktonic foraminifera shell weight, and calcite crystallinity, have been employed here to a set of core top samples from the western tropical Indian Ocean in the water depth ranges from 1086 to 4730 m...

  10. Biogenic Calcium Carbonate with Hierarchical Organic-Inorganic Composite Structure Enhancing the Removal of Pb(II) from Wastewater.

    Science.gov (United States)

    Zhou, Xueli; Liu, Weizhen; Zhang, Jian; Wu, Can; Ou, Xinwen; Tian, Chen; Lin, Zhang; Dang, Zhi

    2017-10-18

    Calcium carbonate from geological sources (geo-CaCO 3 , e.g., calcite, aragonite) is used extensively in removing heavy metals from wastewater through replacement reaction. However, geo-CaCO 3 has an intrinsically compact crystalline structure that results in low efficiency in pollutant removal and thus its use may produce enormous sludge. In this work, biogenic calcium carbonate (bio-CaCO 3 ) derived from oyster shells was used to remove Pb(II) from wastewater and found to significantly outperform geo-CaCO 3 (calcite). The thermodynamics study revealed that the maximum adsorption capacity of bio-CaCO 3 for Pb(II) was three times that of geo-CaCO 3 , reaching up to 1667 mg/g. The kinetics study disclosed that the dissolution kinetics and the rate of intraparticle diffusion of bio-CaCO 3 were faster than those of geo-CaCO 3 . Extensive mechanism research through X-ray powder diffraction (XRD), scanning electron microscopy (SEM), N 2 adsorption/desorption test and mercury intrusion porosimetry showed that the hierarchical porous organic-inorganic hybrid structure of bio-CaCO 3 expedited the dissolution of CaCO 3 to provide abundant CO 3 2- active sites and facilitated the permeation and diffusion of Pb(II) into the bulk solid phases. In addition, Fourier transform infrared spectroscopy (FTIR) study, X-ray photoelectron spectroscopy (XPS) analysis, and the examination of Pb(II) removal ability of bio-CaCO 3 after calcination indicated that the organic functional groups of bio-CaCO 3 also facilitated the immobilization of Pb(II) into CaCO 3 particles, although the major contribution was from the hierarchical porous structure of bio-CaCO 3 .

  11. Precipitation of Calcite during the Deposition of Paleogene Sangkarewang Oil Shale, Ombilin Basin, West Sumatra, Indonesia

    Directory of Open Access Journals (Sweden)

    Agus Haris Widayat

    2015-09-01

    Full Text Available DOI: 10.17014/ijog.2.3.185-197Geochemical and petrographical analyses were carried out to investigate the occurrence of calcite in theformer Ombilin lacustrine lake. The study involves eight samples taken from a 56 m long drill core of Sangkarewangoil shale. Geochemical investigation showed that the samples consist of varied terrigenous input represented by Si, Al, K, and Ti, and autochthonous input represented by S, total organic carbon (TOC, and d13C of bulk organic matter. Along the drill core profile the abundance of autochthonous input decreases upwards, while that of terrigenous input oppositely increases upwards. Petrographical analysis revealed that calcite is a major mineral in the samples. In this study, the abundance of calcite could be represented by the abundance of Ca, as calcite is the only significant Ca containing mineral. Ca is abundant in the samples (8.4% in average and its concentration varies similarly with those of S, TOC, and d13C, suggesting that the element as well as calcite incorporates the autochthonous input. Thevariation of calcite abundance in the drill core profile is considered to be related with primary productivity changes during the development of the former lake. Higher primary productivity represented by more positive of d13C value(-24.8‰ during the deposition of the lower part of the drill core profile promoted the higher amount of deposited organic matter. In such environment, the supersaturation of carbonate ion in lake water was also reached and significant precipitation of authigenic calcite occurred. As the lake developed, the primary productivity decreased as indicated by more negative of d13C value (eventually -26.8‰. This condition led to the decreases of deposited organic matterand calcite in the lake sediments.

  12. Selective Separation of Fluorite, Barite and Calcite with Valonea Extract and Sodium Fluosilicate as Depressants

    OpenAIRE

    Zijie Ren; Futao Yu; Huimin Gao; Zhijie Chen; Yongjun Peng; Lingyun Liu

    2017-01-01

    Fluorite, barite and calcite are important industry minerals. However, they often co-exist, presenting difficulty in selectively separating them due to their similar surface properties. In this study, valonea extract and sodium fluosilicate were used as depressants to selectively separate them by flotation, with sodium oleate as the collector. The single mineral flotation results showed that valonea extract displayed the strongest depression on calcite, while sodium fluosilicate displayed the...

  13. Radiation does response of calcium carbonate crystal in marine shells samples

    Directory of Open Access Journals (Sweden)

    Changkian, S.

    2002-01-01

    Full Text Available A study of the evolution of element, crystal structure and thermoluminescence signal versus gamma irradiation dose were carried out for calcite shells samples. The composition of element was studied by X-ray fluorescence spectrometer. As identified by X-ray diffraction and SEM/EDS analysis, two polymorphs of calcium-carbonate were extracted: calcite and aragonite. The evolution of TL signal versus gamma irradiation dose using the TL reader (Harshaw 2000 was initially dependent on crystal structure and fading effect of the thermoluminescence signal .

  14. Influence of biogenic gas production on coalbed methane recovery index

    Directory of Open Access Journals (Sweden)

    Hongyu Guo

    2017-05-01

    Full Text Available In investigating the effect of biogenic gas production on the recovery of coalbed methane (CBM, coal samples spanning different ranks were applied in the microbial-functioned simulation experiments for biogenic methane production. Based on the biogenic methane yield, testing of pore structures, and the isothermal adsorption data of coals used before and after the simulation experiments, several key parameters related to the recovery of CBM, including recovery rate, gas saturation and ratio of critical desorption pressure to reservoir pressure, etc., were calculated and the corresponding variations were further analyzed. The results show that one of the significant functions of microbial communities on coal is possibly to weaken its affinity for methane gas, especially with the advance of coal ranks; and that by enhancing the pore system of coal, which can be evidenced by the increase of porosity and permeability, the samples collected from Qianqiu (Yima in Henan and Shaqu (Liulin in Shanxi coal mines all see a notable increase in the critical desorption pressure, gas saturation and recovery rate, as compared to the moderate changes of that of Guandi (Xishan in Shanxi coal sample. It is concluded that the significance of enhanced biogenic gas is not only in the increase of CBM resources and the improvement of CBM recoverability, but in serving as an engineering reference for domestic coalbed biogenic gas production.

  15. Accounting for urban biogenic fluxes in regional carbon budgets.

    Science.gov (United States)

    Hardiman, Brady S; Wang, Jonathan A; Hutyra, Lucy R; Gately, Conor K; Getson, Jackie M; Friedl, Mark A

    2017-08-15

    Many ecosystem models incorrectly treat urban areas as devoid of vegetation and biogenic carbon (C) fluxes. We sought to improve estimates of urban biomass and biogenic C fluxes using existing, nationally available data products. We characterized biogenic influence on urban C cycling throughout Massachusetts, USA using an ecosystem model that integrates improved representation of urban vegetation, growing conditions associated with urban heat island (UHI), and altered urban phenology. Boston's biomass density is 1/4 that of rural forests, however 87% of Massachusetts' urban landscape is vegetated. Model results suggest that, kilogram-for-kilogram, urban vegetation cycles C twice as fast as rural forests. Urban vegetation releases (R E ) and absorbs (GEE) the equivalent of 11 and 14%, respectively, of anthropogenic emissions in the most urban portions of the state. While urban vegetation in Massachusetts fully sequesters anthropogenic emissions from smaller cities in the region, Boston's UHI reduces annual C storage by >20% such that vegetation offsets only 2% of anthropogenic emissions. Asynchrony between temporal patterns of biogenic and anthropogenic C fluxes further constrains the emissions mitigation potential of urban vegetation. However, neglecting to account for biogenic C fluxes in cities can impair efforts to accurately monitor, report, verify, and reduce anthropogenic emissions. Copyright © 2017 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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).

  17. Selective adsorption of tannic acid on calcite and implications for separation of fluorite minerals.

    Science.gov (United States)

    Zhang, Chenhu; Wei, Sun; Hu, Yuehua; Tang, Honghu; Gao, Jiande; Yin, Zhigang; Guan, Qingjun

    2018-02-15

    Selective adsorption of tannic acid (TA) on calcite surfaces and the implications of this process for the separation of fluorite ore were studied by microflotation tests, surface adsorption experiments, zeta potential measurements, UV-vis analysis, and X-ray photoelectron spectroscopy (XPS) analysis. The microflotation tests indicated that TA, when added before sodium oleate (NaOl), could selectively depress calcite from fluorite at pH 7. Surface adsorption experiments revealed that TA hinders the interaction of NaOl with calcite. The zeta potential of calcite became more negative with TA than with NaOl. However, the characteristic features of TA adsorption were not observed on fluorite, suggesting that the dominant adsorption sites are dissimilar on the fluorite and calcite surfaces in the pulp. UV-vis spectroscopy, XPS, and solution chemistry analysis were utilized to obtain a better understanding of the mechanism for selective adsorption of TA as well as the key factors determined by the Ca 2+ and Ca(OH) + components on the mineral surfaces. A possible adsorption mechanism along with an adsorption mode is proposed for the surface interaction between TA and calcite. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Sealing of rock joints by induced calcite precipitation. A case study from Bergeforsen hydro power plant

    International Nuclear Information System (INIS)

    Hakami, E.; Qvarfort, U.; Ekstav, A.

    1991-01-01

    The possibilities of sealing rock fractures by injecting water saturated with calcite solution, and hereby inducing a calcite precipitation inside the fracture, is investigated. The way of reaction and the amount of calcite precipitation will depend on the saturation of calcium carbonate in the water, the temperature, the pH and the CO 2 -pressure. There is experience of lime-saturated water injection in the rock foundation below the dam at Bergeforsens power plant (1955-1968). It was observed that the consumption of injected lime water decreased with time. A possible reason to the decrease in lime water consumption is that calcite has precipitated such that the permeability of the rock in general is lowered. Another explanation to this could be that calcite precipitation is concentrated to the fractures surrounding the injection holes, thus preventing the lime water from penetrating further into the rock. It is recommended that further studies of the fracture fillings in drill cores from Bergeforsen is performed. The aim of such study should be to determine the extent of induced calcite precipitation and to investigate its chemical and physical properties. (authors)

  19. Sulfate-dependent Anaerobic Oxidation of Methane as a Generation Mechanism for Calcite Cap Rock in Gulf Coast Salt Domes

    Science.gov (United States)

    Caesar, K. H.; Kyle, R.; Lyons, T. W.; Loyd, S. J.

    2015-12-01

    Gulf Coast salt domes, specifically their calcite cap rocks, have been widely recognized for their association with significant reserves of crude oil and natural gas. However, the specific microbial reactions that facilitate the precipitation of these cap rocks are still largely unknown. Insight into the mineralization mechanism(s) can be obtained from the specific geochemical signatures recorded in these structures. Gulf Coast cap rocks contain carbonate and sulfur minerals that exhibit variable carbon (d13C) and sulfur isotope (δ34S) signatures. Calcite d13C values are isotopically depleted and show a large range of values from -1 to -52‰, reflecting a mixture of various carbon sources including a substantial methane component. These depleted carbon isotope compositions combined with the presence of abundant sulfide minerals in cap rocks have led to interpretations that invoke microbial sulfate reduction as an important carbonate mineral-yielding process in salt dome environments. Sulfur isotope data from carbonate-associated sulfate (CAS: trace sulfate incorporated within the carbonate mineral crystal lattice) provide a more direct proxy for aqueous sulfate in salt dome systems and may provide a means to directly fingerprint ancient sulfate reduction. We find CAS sulfur isotope compositions (δ34SCAS) significantly greater than those of the precursor Jurassic sulfate-salt deposits (which exhibit δ34S values of ~ +15‰). This implies that cap rock carbonate generation occurred via microbial sulfate reduction under closed-system conditions. The co-occurrence of depleted carbonate d13C values (production of alkalinity. Collectively, these data shed new light on a potential hotspot of microbial activity in the deep biosphere.

  20. Mg and Sr in Arctic echinoderm calcite: Nature or nurture?

    Science.gov (United States)

    Iglikowska, A.; Borszcz, T.; Drewnik, A.; Grabowska, M.; Humphreys-Williams, E.; Kędra, M.; Krzemińska, M.; Piwoni-Piórewicz, A.; Kukliński, P.

    2018-04-01

    The Mg/Ca and Sr/Ca ratios in echinoderm skeletal calcite are used as a proxy for Phanerozoic seawater changes, since the skeletal concentrations are, to some extent, controlled by environmental factors. However, it remains unclear how the influence of environmental factors is modified by vital effects, especially in polar waters. Therefore, the goal of this study was to compare the ratios of Mg/Ca and Sr/Ca among the skeletal parts of 10 common Arctic echinoderm species belonging to three classes Echinoidea, Asteroidea and Ophiuroidea that contribute substantially to the carbon cycle in the Arctic benthic system. Significant differences were recorded in echinoid skeletal element concentrations among specific skeletal parts. The lowest Mg/Ca and Sr/Ca ratios were detected in the spines (mean Mg/Ca 37.5 ± 8.8 SD; Sr/Ca 1.8 ± 0.1). The components of the Aristotle's lantern (epiphyses, pyramids and rotulas) were characterised by the highest Mg levels (Mg/Ca 79.9 ± 6.0; 75.2 ± 9.1; 60.1 ± 3.8, respectively). It is likely that mouth parts experience greater mechanical pressure compared to other body parts, and the higher content of Mg in the Aristotle's lantern contributes to its robustness. We did not find any distinctive trends in the distribution of skeletal elements in the asteroid and ophiuroid skeletal parts. The heterogeneous concentrations of Mg and Sr in different skeleton parts of the echinoids suggest possible physiological regulation of the chemical composition rather than the composition only being influenced by the environment. We cannot recommend echinoderm skeletons as reliable indicators in palaeoenvironmental reconstructions due to the possible biological control of skeletal chemistry, which may interfere with the effect of environmental variables.

  1. Developing a single-aliquot protocol for measuring equivalent dose in biogenic carbonates

    International Nuclear Information System (INIS)

    Stirling, R.J.; Duller, G.A.T.; Roberts, H.M.

    2012-01-01

    Exploiting biogenic carbonates as thermoluminescence dosimeters requires an understanding of trap kinetics and an appropriate sequence with which to measure equivalent dose. The trap kinetics of two high temperature peaks (peaks II and III) from calcitic snail opercula have been investigated resulting in the calculation of lifetimes of 7.4 × 10 7 and 1.4 × 10 11 years for the two peaks respectively. Two measurement sequences, based upon changes in the application and measurement of a test dose, have been applied to peaks II and III, and though both methods were equally successful in dose recovery and production of a dose response curve some differences were observed. Primarily, the use of method 1 lead to dose dependant sensitivity change implying competition effects occurring during irradiation; method 2 did not experience this phenomenon. As a consequence method 2 was chosen as the most appropriate protocol for single-aliquot dating of this material. When assessing the TL behaviour of the two peaks, peak II performed poorly in dose recovery experiments recovering a dose 60–100% larger than that applied. Disproportionate growth of peak II in response to a beta dose applied prior to measurement, compared to growth following regeneration doses indicated that peak II was not suitable for use in single-aliquot protocols. However, dose recovery results for peak III were all within errors of unity of the given dose, and peak III was therefore chosen as the most appropriate peak for TL dosimetry in these single-aliquot procedures. The lifetime of charge in peak III is sufficient to date over many millions of years, and furthermore using the chosen method 2 the dose response curve has a D 0 of 3,250 ± 163 Gy allowing dating to over 3 million years.

  2. Technologies for the utilisation of biogenic waste in the bioeconomy.

    Science.gov (United States)

    O'Callaghan, Kenneth

    2016-05-01

    A brief review has been done of technologies involved in the exploitation of biogenic wastes, in order to provide an introduction to the subject from the technological perspective. Biogenic waste materials and biomass have historically been utilised for thousands of years, but a new conversation is emerging on the role of these materials in modern bioeconomies. Due to the nature of the products and commodities now required, a modern bioeconomy is not simply a rerun of former ones. This new dialogue needs to help us understand how technologies for managing and processing biogenic wastes--both established and novel--should be deployed and integrated (or not) to meet the requirements of the sustainability, closed-loop and resource-security agendas that evidently sit behind the bioeconomy aspirations now being voiced in many countries and regions of the world. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

    International Nuclear Information System (INIS)

    Peterman, B.; Moscati, R.

    2000-01-01

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

  4. Non-enzymatic U(VI) interactions with biogenic mackinawite

    Science.gov (United States)

    Veeramani, H.; Qafoku, N. P.; Kukkadapu, R. K.; Murayama, M.; Hochella, M. F.

    2011-12-01

    Reductive immobilization of hexavalent uranium [U(VI)] by stimulation of dissimilatory metal and/or sulfate reducing bacteria (DMRB or DSRB) has been extensively researched as a remediation strategy for subsurface U(VI) contamination. These bacteria derive energy by reducing oxidized metals as terminal electron acceptors, often utilizing organic substrates as electron donors. Thus, when evaluating the potential for in-situ uranium remediation in heterogeneous subsurface media, it is important to understand how the presence of alternative electron acceptors such as Fe(III) and sulfate affect U(VI) remediation and the long term behavior and reactivity of reduced uranium. Iron, an abundant subsurface element, represents a substantial sink for electrons from DMRB, and the reduction of Fe(III) leads to the formation of dissolved Fe(II) or to reactive biogenic Fe(II)- and mixed Fe(II)/Fe(III)- mineral phases. Consequently, abiotic U(VI) reduction by reactive forms of biogenic Fe(II) minerals could be a potentially important process for uranium immobilization. In our study, the DMRB Shewanella putrefaciens CN32 was used to synthesize a biogenic Fe(II)-bearing sulfide mineral: mackinawite, that has been characterized by XRD, SEM, HRTEM and Mössbauer spectroscopy. Batch experiments involving treated biogenic mackinawite and uranium (50:1 molar ratio) were carried out at room temperature under strict anoxic conditions. Following complete removal of uranium from solution, the biogenic mackinawite was analyzed by a suite of analytical techniques including XAS, HRTEM and Mössbauer spectroscopy to determine the speciation of uranium and investigate concomitant Fe(II)-phase transformation. Determining the speciation of uranium is critical to success of a remediation strategy. The present work elucidates non-enzymatic/abiotic molecular scale redox interactions between biogenic mackinawite and uranium.

  5. The occurrence and significance of biogenic opal in the regolith

    Science.gov (United States)

    Clarke, Jonathan

    2003-02-01

    Biogenic opal produced by vascular plants, diatoms, and siliceous sponges have been found in soils and terrestrial sediments of all continents except Antarctica since the middle of the 19th century. The opal particles range in size from fine silt to fine sand. Almost all soils contain detectable opal up to levels of 2-3%, and a significant number contain values in excess of 5%. Even higher values have been found from soils and sediments of all continents in a wide range of soil types. The most important factor is poor soil drainage and seasonal to permanent water logging. This encourages the proliferation of silica producing organisms. Such conditions have been found in the soils and aquatic sediments of the monsoonal tropics, tropical rain forests, temperate forests, tropical savanna, tropical islands, semi-arid grasslands and savanna, and temperate woodland and grassland. The presence of a volcanic substrate also appears favourable in some cases, but is not necessary. Biogenic opal preferentially collects in the A horizon of soils and, to a lesser extent, in the B horizon. This preferential distribution facilitates identification of palaeosols in stacked soil sequences. Biogenic opal is also a component of windblown dust, even in arid environments. Biogenic opal is significant to regolith processes in a number of ways. Firstly, as in the case in marine environments, it is likely to be important in silica cycling and storage because of its greater lability compared to quartz. Secondly, dissolution and reprecipitation of opal A as opal CT or micro-quartz may play a role in cementation and silicification of regolith to form silica hardpans and silcrete. Thirdly, the organisms that form biogenic opal can have considerable palaeoenvironmental significance and be valuable in reconstructing regolith evolution. Finally, some forms of biogenic silica, in particular sponge spicules, can present a health hazard. Their high abundance in some soils and sediments needs to be

  6. Confocal Raman microscopy as a tool to describe different mineral and organic phases at high spatial resolution within marine biogenic carbonates: case study on Nerita undata (Gastropoda, Neritopsina)

    Science.gov (United States)

    Nehrke, G.; Nouet, J.

    2011-06-01

    Marine biogenic carbonates formed by invertebrates (e.g. corals and mollusk shells) represent complex composites of one or more mineral phases and organic molecules. This complexity ranges from the macroscopic structures observed with the naked eye down to sub micrometric structures only revealed by micro analytical techniques. Understanding to what extent and how organisms can control the formation of these structures requires that the mineral and organic phases can be identified and their spatial distribution related. Here we demonstrate the capability of confocal Raman microscopy applied to cross sections of a shell of Nerita undata to describe the distribution of calcite and aragonite including their crystallographic orientation with high lateral resolution (∼300 nm). Moreover, spatial distribution of functional groups of organic compounds can be simultaneously acquired, allowing to specifically relate them to the observed microstructures. The data presented in this case study highlights the possible new contributions of this method to the description of modalities of Nerita undata shell formation, and what could be expected of its application to other marine biogenic carbonates. Localization of areas of interest would also allow further investigations using more localized methods, such as TEM that would provide complementary information on the relation between organic molecules and crystallographic lattice.

  7. Biogenic amines in smear and mould-ripened cheeses

    Directory of Open Access Journals (Sweden)

    Pavel Pleva

    2014-02-01

    Full Text Available The aim of the study was the monitoring of six biogenic amines (histamine, tyramine, phenylethylamine, tryptamine, putrescine, and cadaverine and two polyamines (spermidine and spermine in 30 samples of dairy products purchased in the Czech Republic, namely in 15 samples of mould-ripened cheeses and in 15 samples of smear-ripened cheeses. A further goal was the microbiological analysis of the individual samples of cheeses (total count of microorganisms, number of enterobacteria, enterococci, lactic acid bacteria, yeasts and moulds. The monitored biogenic amines were analyzed by a high performance liquid chromatography equipped with a UV/VIS DAD detector. The amount of enterobacteria in fresh cheese exceeded 105 CFU.g‑1. In smear-ripened cheese flavourless (Romadur type, the amount was >103 CFU.g-1 and 104-105 CFU.g-1 in smear-ripened cheese with flavour. Biogenic amines were observed in two groups of blue cheeses (white veined cheese and blue veined cheese and smear-ripened cheeses. In both groups, there is a possibility of the presence of biogenic amines because the number of microorganisms and concentration of free amino acids increase during ripening. In ten samples of soft smear-ripening acid cheese and in smear-ripened cheese, the total content of biogenic amines were 22-1000 mg.kg-1 and in 5 samples of these cheeses, it was in range 1000-6000 mg.kg-1. The total amount of biogenic amines in the blue cheeses were in range 40-600 mg.kg-1. The presense of the tyramine was observed in the all analysed cheeses. The tyramine producing strains generated more than 900 mg.kg-1 of this biogenic amine. The production of tryptamine in the analysed cheeses was not proved by this study. The results of this study show that biogenic amines and polyamines are common in cheese. However, in some cases, they can pose a significant health danger for consumers. Any legislative control authority does not monitor them, as they are secondary metabolites even

  8. Biogen to produce diagnostic tests, vaccines and ethanol

    Energy Technology Data Exchange (ETDEWEB)

    1982-01-11

    In addition to its work on pharmaceuticals and veterinary products, Europe's largest biotechnology company, Biogen, is reported to be working on the production of ethanol from biomass. The process, based on two strains of clostridia bacteria, can convert both the cellulose and hemicellulose of agricultural wastes to ethanol. Biogen is also studying the production of basic chemicals, such as acetic acid, acetone and butane from cellulosic biomass and is looking at various types of organisms to effect low cost chemical conversions.

  9. Determination of Biogenic Amines in Different Shrimp Species for Export

    International Nuclear Information System (INIS)

    Myat Myat Thaw; Oo Aung; Aung Myint; Bisswanger, Hans

    2004-06-01

    This study is part of the project on the ''Quality Assurance of Different Shrimp Species for Export''. Local shrimp samples were collected from Ministry of Livestock and Fisheries and various private enterprises. Contents of biogenic amines were determined by using benzoyl chloride derivatization method with HPLC (reverse phase high performance liquid chromatography). Based on the biogenic amines, quality index of shrimps were correlated with freshness index so that the grade of shrimp samples can be classified as excellent, good, and acceptable. All sizes of shrimps such as extra large, large, medium were found to excceptable respectively

  10. Fermented functional foods based on probiotics and their biogenic metabolites.

    Science.gov (United States)

    Stanton, Catherine; Ross, R Paul; Fitzgerald, Gerald F; Van Sinderen, Douwe

    2005-04-01

    The claimed health benefits of fermented functional foods are expressed either directly through the interaction of ingested live microorganisms, bacteria or yeast with the host (probiotic effect) or indirectly as a result of ingestion of microbial metabolites produced during the fermentation process (biogenic effect). Although still far from fully understood, several probiotic mechanisms of action have been proposed, including competitive exclusion, competition for nutrients and/or stimulation of an immune response. The biogenic properties of fermented functional foods result from the microbial production of bioactive metabolites such as certain vitamins, bioactive peptides, organic acids or fatty acids during fermentation.

  11. Biomass burning - Combustion emissions, satellite imagery, and biogenic emissions

    Science.gov (United States)

    Levine, Joel S.; Cofer, Wesley R., III; Winstead, Edward L.; Rhinehart, Robert P.; Cahoon, Donald R., Jr.; Sebacher, Daniel I.; Sebacher, Shirley; Stocks, Brian J.

    1991-01-01

    After detailing a technique for the estimation of the instantaneous emission of trace gases produced by biomass burning, using satellite imagery, attention is given to the recent discovery that burning results in significant enhancement of biogenic emissions of N2O, NO, and CH4. Biomass burning accordingly has an immediate and long-term impact on the production of atmospheric trace gases. It is presently demonstrated that satellite imagery of fires may be used to estimate combustion emissions, and could be used to estimate long-term postburn biogenic emission of trace gases to the atmosphere.

  12. Occurrence of gigantic biogenic magnetite during the Paleocene-Eocene Thermal Maximum

    Science.gov (United States)

    Schumann, D.; Raub, T. D.; Kopp, R. E.; Guerquin-Kern, J. L.; Wu, T. D.; Rouiller, I.; Smirnov, A. V.; Sears, S. K.; Lücken, U.; Tikoo, S. M.; Hesse, R.; Kirschvink, J. L.; Vali, H.

    2009-04-01

    The Paleocene-Eocene Thermal Maximum (PETM) is one of the most severe climatic events of the Cenozoic Era. A massive injection of light carbon into the oceans and atmosphere over a few thousand of years triggered drastic perturbation of Earth's climate resulting in abrupt global warming of ~5-9oC [Sluijs et al., 2007] that persisted for ~180,000 years. This episode is marked by the diversification and radiation of terrestrial plants and mammals while in the marine realm numerous deep-sea benthic foraminifera species disappeared and new forms evolved. Sediments deposited during the PETM are clay-rich and contain distinct evidence of these climatic changes. Kopp et al., (2007) and Lippert & Zachos (2007) report an extraordinary magnetofossil ‘Lagerstätte' in lowermost Eocene kaolinite-rich clay sediments deposited at subtropical paleolatitude in the Atlantic Coastal Plain of New Jersey, USA. Magnetofossils are magnetic particles produced most abundantly by magnetotactic bacteria. Kopp et al. (2007) and Lippert & Zachos (2007) used ferromagnetic resonance (FMR) spectroscopy, other rock magnetic methods, and transmission electron microscopy (TEM) of magnetic separates to characterize sediments from boreholes at Ancora (ODP Leg 174AX) and Wilson Lake, NJ, respectively. These sediments contain abundant ~40- to 300-nm cuboidal, elongate-prismatic and bullet-shaped magnetofossils, sometimes arranged in short chains, resembling crystals in living magnetotactic bacteria. Despite the scarcity of intact magnetofossil chains, the asymmetry ratios of the FMR spectra reflects a profusion of elongate single domain (SD) crystals and/or chains. Here we address both conundrums by reporting the discovery from these same sediments of exceptionally large and novel biogenic magnetite crystals unlike any previously reported from living organisms or from sediments. Aside from abundant bacterial magnetofossils, electron microscopy reveals novel spearhead-like and spindle-like magnetite

  13. Crystals in crystals

    DEFF Research Database (Denmark)

    Christensen, Claus H.; Schmidt, I.; Carlsson, A.

    2005-01-01

    A major factor governing the performance of catalytically active particles supported on a zeolite carrier is the degree of dispersion. It is shown that the introduction of noncrystallographic mesopores into zeolite single crystals (silicalite-1, ZSM-5) may increase the degree of particle dispersion...... of the zeolite particles, particularly after thermal treatment. When using mesoporous zeolites, the particles were evenly distributed throughout the mesopore system of the zeolitic support, even after calcination, leading to nanocrystals within mesoporous zeolite single crystals....

  14. Effect of silk sericin on morphology and structure of calcium carbonate crystal

    Science.gov (United States)

    Zhao, Rui-Bo; Han, Hua-Feng; Ding, Shao; Li, Ze-Hao; Kong, Xiang-Dong

    2013-06-01

    In this paper, silk sericin was employed to regulate the mineralization of calcium carbonate (CaCO3). CaCO3 composite particles were prepared by the precipitation reaction of sodium carbonate with calcium chloride solution in the presence of silk sericin. The as-prepared samples were collected at different reaction time to study the crystallization process of CaCO3 by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray diffraction (XRD). The results showed that silk sericin significantly affected the morphology and crystallographic polymorph of CaCO3. With increasing the reaction time, the crystal phase of CaCO3 transferred from calcite dominated to vaterite dominated mixtures, while the morphology of CaCO3 changed from disk-like calcite crystal to spherical vaterite crystal. These studies showed the potential of silk sericin used as a template molecule to control the growth of inorganic crystal.

  15. Thermal and Evolved Gas Behavior of Calcite Under Mars Phoenix TEGA Operating Conditions

    Science.gov (United States)

    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 calcite literature thermal data was obtained at 1000 mbar or higher pressures.

  16. Neutralization of sulfuric acid solutions by calcite dissolution and the application to anoxic limestone drain design

    International Nuclear Information System (INIS)

    Huminicki, Danielle M.C.; Rimstidt, J. Donald

    2008-01-01

    Batch reactor (BR) experiments were conducted to measure the effect of hydrodynamics and gypsum coatings on calcite neutralization rates. A factorial array of BR experiments measured the H + concentration change by calcite dissolution over a pH range of 1.5-3.5 and Na 2 SO 4 concentrations of 0-1 M. The rate of H + concentration change with time was determined by numerical differentiation of H + concentration versus time. Regression modeling showed that for uncoated calcite, rates are only significantly affected by pH, r=-10 -2.32 a H + 0.76 . Whereas, for calcite coated with gypsum only time had a significant effect on calcite dissolution rates, r = -10 -1.96 t -0.53 . Because transport-limited dissolution rates for uncoated calcite are a function of the pH and Reynolds number, a model was developed to express the effects of these two variables on the rate of H + consumption for a solution with a Darcy velocity, q, through a porous medium with a particle radius, r p , such that r ' =1.08x10 -3 q 0.31 r p -0.69 m H + 0.87 . This equation was integrated via a numerical model to simulate the performance of an idealized anoxic limestone drain (ALD). This model predicts the pH and alkalinity change along the length of an ALD. The model shows that the efficiency of an ALD is greater when the Darcy velocity is low and the particle radius is small. In addition, the growth of gypsum coatings causes the rate of H + neutralization to decline as the square root of time as they form and block the H + transport to the calcite surface. Supersaturation with respect to gypsum, leading to coating formation, can be avoided by diluting the ALD feed solution or by replacing limestone with dolomite

  17. FORMATION OF CALCITE AND SILICA FROM PERCOLATION IN A HYDROLOGICALLY UNSATURATED SETTING, YUCCA MOUNTAIN, NEVADA

    International Nuclear Information System (INIS)

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

    2000-01-01

    Geological, mineralogical, chemical, and isotopic evidence from coatings of calcite and silica on open fractures and lithophysal cavities within welded tuffs at Yucca Mountain indicate an origin from meteoric water percolating through a thick (500 to 700 m) unsaturated zone (UZ) rather than from pulses of ascending ground water. Geologic evidence for a UZ setting includes the presence of coatings in only a small percentage of cavities, the restriction of coatings to fracture footwalls and cavity floors, and an absence of mineral high-water marks indicative of water ponding. Systematic mineral sequences (early calcite, followed by chalcedony with minor quartz and fluorite, and finally calcite with intercalated opal forming the bulk of the coatings) indicate progressive changes in UZ conditions through time, rather than repeated saturation by flooding. Percolation under the influence of gravity also results in mineral textures that vary between steeply dipping sites (thinner coatings of blocky calcite) and shallowly dipping sites (thicker coatings of coarse, commonly bladed calcite, with globules and sheets of opal). Micrometer-scale growth banding in both calcite and opal reflects slow average growth rates (scale of mm/m.y.) over millions of years rather than only a few rapidly deposited growth episodes. Isotopic compositions of C, O, Sr, and U from calcite and opal indicate a percolation-modified meteoric water source, and collectively refute a deeper ground-water source. Chemical and isotopic variations in coatings also indicate long-term evolution of water compositions. Although some compositional changes are related to shifts in climate, growth rates in the deeper UZ are buffered from large changes in meteoric input. Coatings most likely formed from films of water flowing down connected fracture pathways. Mineral precipitation is consistent with water vapor and carbon dioxide loss from films at very slow rates. Data collectively indicate that mineral coatings

  18. Distribution of planktonic biogenic carbonate organisms in the Southern Ocean south of Australia: a baseline for ocean acidification impact assessment

    Directory of Open Access Journals (Sweden)

    T. W. Trull

    2018-01-01

    Full Text Available The Southern Ocean provides a vital service by absorbing about one-sixth of humankind's annual emissions of CO2. This comes with a cost – an increase in ocean acidity that is expected to have negative impacts on ocean ecosystems. The reduced ability of phytoplankton and zooplankton to precipitate carbonate shells is a clearly identified risk. The impact depends on the significance of these organisms in Southern Ocean ecosystems, but there is very little information on their abundance or distribution. To quantify their presence, we used coulometric measurement of particulate inorganic carbonate (PIC on particles filtered from surface seawater into two size fractions: 50–1000 µm to capture foraminifera (the most important biogenic carbonate-forming zooplankton and 1–50 µm to capture coccolithophores (the most important biogenic carbonate-forming phytoplankton. Ancillary measurements of biogenic silica (BSi and particulate organic carbon (POC provided context, as estimates of the biomass of diatoms (the highest biomass phytoplankton in polar waters and total microbial biomass, respectively. Results for nine transects from Australia to Antarctica in 2008–2015 showed low levels of PIC compared to Northern Hemisphere polar waters. Coccolithophores slightly exceeded the biomass of diatoms in subantarctic waters, but their abundance decreased more than 30-fold poleward, while diatom abundances increased, so that on a molar basis PIC was only 1 % of BSi in Antarctic waters. This limited importance of coccolithophores in the Southern Ocean is further emphasized in terms of their associated POC, representing less than 1 % of total POC in Antarctic waters and less than 10 % in subantarctic waters. NASA satellite ocean-colour-based PIC estimates were in reasonable agreement with the shipboard results in subantarctic waters but greatly overestimated PIC in Antarctic waters. Contrastingly, the NASA Ocean Biogeochemical Model (NOBM shows

  19. Distribution of planktonic biogenic carbonate organisms in the Southern Ocean south of Australia: a baseline for ocean acidification impact assessment

    Science.gov (United States)

    Trull, Thomas W.; Passmore, Abraham; Davies, Diana M.; Smit, Tim; Berry, Kate; Tilbrook, Bronte

    2018-01-01

    The Southern Ocean provides a vital service by absorbing about one-sixth of humankind's annual emissions of CO2. This comes with a cost - an increase in ocean acidity that is expected to have negative impacts on ocean ecosystems. The reduced ability of phytoplankton and zooplankton to precipitate carbonate shells is a clearly identified risk. The impact depends on the significance of these organisms in Southern Ocean ecosystems, but there is very little information on their abundance or distribution. To quantify their presence, we used coulometric measurement of particulate inorganic carbonate (PIC) on particles filtered from surface seawater into two size fractions: 50-1000 µm to capture foraminifera (the most important biogenic carbonate-forming zooplankton) and 1-50 µm to capture coccolithophores (the most important biogenic carbonate-forming phytoplankton). Ancillary measurements of biogenic silica (BSi) and particulate organic carbon (POC) provided context, as estimates of the biomass of diatoms (the highest biomass phytoplankton in polar waters) and total microbial biomass, respectively. Results for nine transects from Australia to Antarctica in 2008-2015 showed low levels of PIC compared to Northern Hemisphere polar waters. Coccolithophores slightly exceeded the biomass of diatoms in subantarctic waters, but their abundance decreased more than 30-fold poleward, while diatom abundances increased, so that on a molar basis PIC was only 1 % of BSi in Antarctic waters. This limited importance of coccolithophores in the Southern Ocean is further emphasized in terms of their associated POC, representing less than 1 % of total POC in Antarctic waters and less than 10 % in subantarctic waters. NASA satellite ocean-colour-based PIC estimates were in reasonable agreement with the shipboard results in subantarctic waters but greatly overestimated PIC in Antarctic waters. Contrastingly, the NASA Ocean Biogeochemical Model (NOBM) shows coccolithophores as overly

  20. 76 FR 80368 - Notification of Teleconferences of the Science Advisory Board Biogenic Carbon Emissions Panel

    Science.gov (United States)

    2011-12-23

    ... Advisory Board Biogenic Carbon Emissions Panel AGENCY: Environmental Protection Agency (EPA). ACTION... Office announces two teleconferences of the SAB Biogenic Carbon Emissions Panel to review EPA's draft Accounting Framework for Biogenic CO2 Emissions from Stationary Sources (September 2011). DATES: The...

  1. Biogenic volatile organic compounds - small is beautiful

    Science.gov (United States)

    Owen, S. M.; Asensio, D.; Li, Q.; Penuelas, J.

    2012-12-01

    While canopy and regional scale flux measurements of biogenic volatile organic compounds (bVOCs) are essential to obtain an integrated picture of total compound reaching the atmosphere, many fascinating and important emission details are waiting to be discovered at smaller scales, in different ecological and functional compartments. We concentrate on bVOCs below ground to soil surfaces are small, bVOCs are exuded by roots of some plant species, and can be extracted from decaying litter. Naturally occurring monoterpenes in the rhizosphere provide a specialised carbon source for micro-organisms, helping to define the micro-organism community structure, and impacting on nutrient cycles which are partly controlled by microorganisms. Naturally occurring monoterpenes in the soil system could also affect the aboveground structure of ecosystems because of their role in plant defence strategies and as mediating chemicals in allelopathy. A gradient of monoterpene concentration was found in soil around Pinus sylvestris and Pinus halepensis, decreasing with distance from the tree. Some compounds (α-pinene, sabinene, humulene and caryophyllene) in mineral soil were linearly correlated with the total amount of each compound in the overlying litter, indicating that litter might be the dominant source of these compounds. However, α-pinene did not fall within the correlation, indicating a source other than litter, probably root exudates. We also show that rhizosphere bVOCs can be a carbon source for soil microbes. In a horizontal gradient from Populus tremula trees, microbes closest to the tree trunk were better enzymatically equipped to metabolise labeled monoterpene substrate. Monoterpenes can also increase the degradation rate in soil of the persistant organic pollutants, likely acting as analogues for the cometabo-lism of polychlorinated biphenyls (PCBs) Flowers of a ginger species (Alpinia kwangsiensis) and a fig species (Ficus hispida) showed different bVOC signals pre- and

  2. Biogenic gases in tropical floodplain river

    Directory of Open Access Journals (Sweden)

    Maria Victória Ramos Ballester

    2001-06-01

    Full Text Available Analysis of the distribution of biogenic gases in the floodplain of the Mogi-Guaçu River (São Paulo, Brazil enabled the establishment of a "redox hierarchy", in which the main channel was the most oxidizing environment, followed by Diogo Lake, with Infernão Lake having the most reducing conditions of the subsystems evaluated. Diogo Lake exported about 853.4 g C.m-2.year-1, of which, 14.6% was generated from methanogenesis and 36.7% by aerobic respiration. For Infernão Lake, these values were 2016 g C.m-2.year-1, 1.8 % and 41.5 %, respectively. Carbon export by these systems was predominantly in the form of CO2, which was responsible for the release of 728.78 g C.m-2.year-1 at Diogo Lake and 1979.72 g C.m-2. year-1 at Infernão Lake. Such patterns may result from the nature of the hydrological conditions, the action of the hydroperiod, and morphological characteristics of the environment.A análise da distribuição de gases biogênicos na planície de inundação do Rio Mogi Guaçu (São Paulo, Brasil possibilitou o estabelecimento de um gradiente redox para os sistemas aquáticos avaliados, em que o canal principal do rio apresentou-se como o ambiente mais oxidado, seguido da Lagoa do Diogo, e a Lagoa do Infernão apresentando as condições mais redutoras entre os ambientes em questão. A Lagoa do Diogo exporta um total de 853,4 g C.m-2.ano-1, do qual 14,6% é produzido pela metanogênese e 36,7% pela respiração aeróbia. Para a Lagoa do Infernão estes valores foram respectivamente de 2.016 g C.m-2.ano-1, 1,8% e de 41,5%. A exportação de carbono por estes sistemas é realizada, predominantemente na forma de CO2, nos valores de 728,78 g C.m-2.ano-1 para a Lagoa do Diogo e 1.979,72 g C.m-2.ano-1 para a Lagoa do Infernão. Estes padrões parecem estar relacionados com a natureza das condições hidrológicas, com a ação do hidroperíodo e com as características morfológicas do ambiente.

  3. The role of pH and Mg on the stability and crystallization of amorphous calcium carbonate

    International Nuclear Information System (INIS)

    Rodriguez-Blanco, J.D.; Shaw, S.; Bots, P.; Roncal-Herrero, T.; Benning, L.G.

    2012-01-01

    Highlights: ► We studied the effect of pH and Mg in the crystallization of amorphous CaCO 3 (ACC). ► The study combined synchrotron-based scattering with electron microscopy. ► The pH-dependent C speciation and hydration strength of Mg 2+ control ACC structure. ► This ACC structure governs the ACC dissolution rate and crystallization pathway. - Abstract: The effects of pH and Mg on the crystallization of amorphous calcium carbonate (ACC) to vaterite and/or calcite were studied using a combination of in situ time resolved synchrotron-based techniques and electron microscopy. The experiments showed that Mg increased the stability of ACC and favoured the formation of calcite over vaterite. A neutral (∼7) starting pH during mixing promoted the transformation of ACC into calcite via a dissolution/reprecipitation mechanism. Conversely, when ACC formed in a solution that started with a high initial pH (∼11.5), the transformation to calcite occurred via metastable vaterite, which formed via a spherulitic growth mechanism. In a second stage this vaterite transformed to calcite via a surface-controlled dissolution and recrystallization mechanism. These crystallization pathways can be explained as a consequence of the pH-dependent composition, local structure, stability and dissolution rates of ACC.

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

    Science.gov (United States)

    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.

  5. Sequestration of Antimony on Calcite Observed by Time-Resolved Nanoscale Imaging.

    Science.gov (United States)

    Renard, François; Putnis, Christine V; Montes-Hernandez, German; King, Helen E; Breedveld, Gijs D; Okkenhaug, Gudny

    2018-01-02

    Antimony, which has damaging effects on the human body and the ecosystem, can be released into soils, ground-, and surface waters either from ore minerals that weather in near surface environments, or due to anthropogenic releases from waste rich in antimony, a component used in batteries, electronics, ammunitions, plastics, and many other industrial applications. Here, we show that dissolved Sb can interact with calcite, a widespread carbonate mineral, through a coupled dissolution-precipitation mechanism. The process is imaged in situ, at room temperature, at the nanometer scale by using an atomic force microscope equipped with a flow-through cell. Time-resolved imaging allowed following the coupled process of calcite dissolution, nucleation of precipitates at the calcite surface and growth of these precipitates. Sb(V) forms a precipitate, whereas Sb(III) needs to be oxidized to Sb(V) before being incorporated in the new phase. Scanning-electron microscopy and Raman spectroscopy allowed identification of the precipitates as two different calcium-antimony phases (Ca 2 Sb 2 O 7 ). This coupled dissolution-precipitation process that occurs in a boundary layer at the calcite surface can sequester Sb as a solid phase on calcite, which has environmental implications as it may reduce the mobility of this hazardous compound in soils and groundwaters.

  6. Selective Separation of Fluorite, Barite and Calcite with Valonea Extract and Sodium Fluosilicate as Depressants

    Directory of Open Access Journals (Sweden)

    Zijie Ren

    2017-02-01

    Full Text Available Fluorite, barite and calcite are important industry minerals. However, they often co-exist, presenting difficulty in selectively separating them due to their similar surface properties. In this study, valonea extract and sodium fluosilicate were used as depressants to selectively separate them by flotation, with sodium oleate as the collector. The single mineral flotation results showed that valonea extract displayed the strongest depression on calcite, while sodium fluosilicate displayed the strongest depression on barite. These two depressants allowed selective separation of the three minerals through sequential flotation. The flotation of mixed minerals showed that 94% of the calcite was successfully depressed by the valonea extract, and 95% recovery of the fluorite was achieved in the subsequent flotation with sodium fluosilicate depressing barite. The different depressant–mineral interactions were investigated via electro-kinetic studies and molecular dynamics (MD simulations using the Materials Studio 6.0 program. The valonea extract exhibited the strongest adsorption on the calcite surface, and sodium fluosilicate exhibited the strongest adsorption on the barite surface, which prevented oleate species from reacting with Ca2+ or Ba2+ surface sites. This study provides useful guidance for how to process fluorite, barite and calcite resources.

  7. Use of biogenic sulfide for ZnS precipitation

    NARCIS (Netherlands)

    Esposito, G.; Veeken, A.; Weijma, J.; Lens, P.N.L.

    2006-01-01

    A 600 ml continuously stirred tank reactor was used to assess the performance of a zinc sulfide precipitation process using a biogenic sulfide solution (the effluent of a sulfate-reducing bioreactor) as sulfide source. In all experiments, a proportional-integral (PI) control algorithm was used to

  8. Azo dye decolorization assisted by chemical and biogenic sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Prato-Garcia, Dorian [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico); Cervantes, Francisco J. [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica, Camino a la Presa de San José 2055, San Luis Potosí 78216 (Mexico); Buitrón, Germán, E-mail: gbuitronm@ii.unam.mx [Laboratory for Research on Advanced Processes for Water Treatment, Unidad Académica Juriquilla, Instituto de Ingeniería, Universidad Nacional Autónoma de México, Blvd. Juriquilla 3001, Querétaro 76230 (Mexico)

    2013-04-15

    Highlights: ► Azo dyes were reduced efficiently by chemical and biogenic sulfide. ► Biogenic sulfide was more efficient than chemical sulfide. ► There was no competition between dyes and sulfate for reducing equivalents. ► Aromatic amines barely affected the sulfate-reducing process. -- Abstract: The effectiveness of chemical and biogenic sulfide in decolorizing three sulfonated azo dyes and the robustness of a sulfate-reducing process for simultaneous decolorization and sulfate removal were evaluated. The results demonstrated that decolorization of azo dyes assisted by chemical sulfide and anthraquinone-2,6-disulfonate (AQDS) was effective. In the absence of AQDS, biogenic sulfide was more efficient than chemical sulfide for decolorizing the azo dyes. The performance of sulfate-reducing bacteria in attached-growth sequencing batch reactors suggested the absence of competition between the studied azo dyes and the sulfate-reducing process for the reducing equivalents. Additionally, the presence of chemical reduction by-products had an almost negligible effect on the sulfate removal rate, which was nearly constant (94%) after azo dye injection.

  9. Biogenic ZnO nanoparticles synthesized using L. aculeata leaf

    Indian Academy of Sciences (India)

    ... Refresher Courses · Symposia · Live Streaming. Home; Journals; Bulletin of Materials Science; Volume 39; Issue 1. Biogenic ZnO nanoparticles synthesized using L. aculeata leaf extract and their antifungal activity against plant fungal pathogens. S Narendhran Rajeshwari Sivaraj. Volume 39 Issue 1 February 2016 pp 1- ...

  10. Conditions allowing the formation of biogenic amines in cheese

    NARCIS (Netherlands)

    Joosten, H.M.L.J.

    1988-01-01

    A study was undertaken to reveal the conditions that allow the formation of biogenic amines in cheese.

    The starters most commonly used in the Dutch cheese industry do not have decarboxylative properties. Only if the milk or curd is contaminated with non-starter bacteria, amine

  11. incidence of biogenic amines in foods implications for the gambia

    African Journals Online (AJOL)

    Temechegn

    Health-wise biogenic amines play positive roles and ... BAs include, fish, fish products, meat products, eggs, cheeses, fermented vegetables, soybean ... The amount of. BAs present in foods, fruits and vegetables provides an index for measuring food quality [3]. In the tropics fish are caught in temperatures more than 200C.

  12. Biogenic volatile compounds of activated sludge and their ...

    African Journals Online (AJOL)

    Heavy metals pollution is nowadays one of the most important environmental concerns. This paper illustrates the employment of the biogenic volatile compounds generated during the aerobic growth of activated sludge on raw domestic wastewater for heavy metals removal. Most of the tested metals even as individual or ...

  13. Biogenic volatile organic compound (VOC) emissions from forests in Finland

    International Nuclear Information System (INIS)

    Lindfors, V.; Laurila, T.

    2000-01-01

    We present model estimates of biogenic volatile organic compound (VOC) emissions from the forests in Finland. The emissions were calculated for the years 1995-1997 using the measured isoprene and monoterpene emission factors of boreal tree species together with detailed satellite land cover information and meteorological data. The three-year average emission is 319 kilotonnes per annum, which is significantly higher than the estimated annual anthropogenic VOC emissions of 193 kilotonnes. The biogenic emissions of the Finnish forests are dominated by monoterpenes, which contribute approximately 45% of the annual total. The main isoprene emitter is the Norway spruce (Picea abies) due to its high foliar biomass density. Compared to the monoterpenes, however, the total isoprene emissions are very low, contributing only about 7% of the annual forest VOC emissions. The isoprene emissions are more sensitive to the meteorological conditions than the monoterpene emissions, but the progress of the thermal growing season is clearly reflected in all biogenic emission fluxes. The biogenic emission densities in northern Finland are approximately half of the emissions in the southern parts of the country. (orig.)

  14. The secondary biogenic radiation of gamma-irradiated human blood

    International Nuclear Information System (INIS)

    Kuzin, A.M.; Surkenova, G.N.; Budagovskij, A.V.; Gudi, G.A.

    1997-01-01

    The sample of blood freshly taken from healthy men were gamma-irradiated with a dose of 10 Gy. It was shown that after the treatment the blood gained the capacity to emit secondary biogenic radiation. Emission lasted for some hours, passed through quartz-glass curette and was revealed by stimulating influence on biological detector (sprouting seeds)

  15. Mineralogical and Biogenic Composition of the Zanzibar Channel Sediments, Tanzania

    Science.gov (United States)

    Shaghude, Y. W.; Wannäs, K. O.

    2000-10-01

    Sediments from the Zanzibar Channel have been analysed for mineralogical and biogenic composition. The main objective of the study was to describe the depositional environment of the sediments based on these parameters. The study was also conducted to give an insight into sediment provenance of the sediments. Quartz, feldspar (both microcline and plagioclase) and hornblende are the main mineralogical components, while zircon, muscovite, biotite and augite occur as accessory minerals. The quartz grains are generally angular to sub-angular and highly strained, indicative of immature sediments, probably derived from highly metamorphosed rocks. The presence of hornblende also supports the conclusion that the sediments are immature. A possible source is the metamorphic rocks of the Mozambique belt, located about 25-50 km from the coastline. Benthic foraminifera are the dominant biogenic constituents. Other common biogenic constituents are molluscs (pelecypods and gastropods) and corals. Bryozoans and ostracods are relatively less common, while sea urchins are accessory biogenic components. The composition and abundance of these biogenic components and morphological, sedimentological and mineralogical data permit construction of a simple model which distinguishes between three bio-physiographic settings in the Zanzibar Channel using depth contours: (1) the coastal zone (0-10 m depth); (2) the reef platform/patch reefs zone (10-20 m depth) and (3) the central channel zone (>20 cm depth). In the coastal zone, the sediments are dominated by fine sand, sized with a very prominent fine sand mode. The proportion of benthic foraminifera is lower than in the other two zones (25%). Two lithogenic mineral components (quartz and feldspar) occur in significant proportions. In the reef platform/patch reefs zone, the sediments are coarse to medium sand sized with no distinct mode. the proportion of benthic foraminifera is highest (80-85%) there, and so is the biogenic:quartz ratio

  16. Biogenic Calcium Phosphate Transformation in Soils over Millennium Time Scales

    Energy Technology Data Exchange (ETDEWEB)

    Sato, S.; Neves, E; Solomon, D; Liang, B; Lehmann, J

    2009-01-01

    Changes in bioavailability of phosphorus (P) during pedogenesis and ecosystem development have been shown for geogenic calcium phosphate (Ca-P). However, very little is known about long-term changes of biogenic Ca-P in soil. Long-term transformation characteristics of biogenic Ca-P were examined using anthropogenic soils along a chronosequence from centennial to millennial time scales. Phosphorus fractionation of Anthrosols resulted in overall consistency with the Walker and Syers model of geogenic Ca-P transformation during pedogenesis. The biogenic Ca-P (e.g., animal and fish bones) disappeared to 3% of total P within the first ca. 2,000 years of soil development. This change concurred with increases in P adsorbed on metal-oxides surfaces, organic P, and occluded P at different pedogenic time. Phosphorus K-edge X-ray absorption near-edge structure (XANES) spectroscopy revealed that the crystalline and therefore thermodynamically most stable biogenic Ca-P was transformed into more soluble forms of Ca-P over time. While crystalline hydroxyapatite (34% of total P) dominated Ca-P species after about 600-1,000 years, {Beta}-tricalcium phosphate increased to 16% of total P after 900-1,100 years, after which both Ca-P species disappeared. Iron-associated P was observable concurrently with Ca-P disappearance. Soluble P and organic P determined by XANES maintained relatively constant (58-65%) across the time scale studied. Conclusions - Disappearance of crystalline biogenic Ca-P on a time scale of a few thousand years appears to be ten times faster than that of geogenic Ca-P.

  17. Formation of Nano-crystalline Todorokite from Biogenic Mn Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Feng, X.; Zhu, M; Ginder-Vogel, M; Ni, C; Parikh, S; Sparks, D

    2010-01-01

    Todorokite, as one of three main Mn oxide phases present in oceanic Mn nodules and an active MnO{sub 6} octahedral molecular sieve (OMS), has garnered much interest; however, its formation pathway in natural systems is not fully understood. Todorokite is widely considered to form from layer structured Mn oxides with hexagonal symmetry, such as vernadite ({delta}-MnO{sub 2}), which are generally of biogenic origin. However, this geochemical process has not been documented in the environment or demonstrated in the laboratory, except for precursor phases with triclinic symmetry. Here we report on the formation of a nanoscale, todorokite-like phase from biogenic Mn oxides produced by the freshwater bacterium Pseudomonas putida strain GB-1. At long- and short-range structural scales biogenic Mn oxides were transformed to a todorokite-like phase at atmospheric pressure through refluxing. Topotactic transformation was observed during the transformation. Furthermore, the todorokite-like phases formed via refluxing had thin layers along the c* axis and a lack of c* periodicity, making the basal plane undetectable with X-ray diffraction reflection. The proposed pathway of the todorokite-like phase formation is proposed as: hexagonal biogenic Mn oxide {yields} 10-{angstrom} triclinic phyllomanganate {yields} todorokite. These observations provide evidence supporting the possible bio-related origin of natural todorokites and provide important clues for understanding the transformation of biogenic Mn oxides to other Mn oxides in the environment. Additionally this method may be a viable biosynthesis route for porous, nano-crystalline OMS materials for use in practical applications.

  18. The relationship between Al and Si in biogenic silica as determined by PIXE and XAS

    International Nuclear Information System (INIS)

    Beck, L.; Gehlen, M.; Flank, A.-M.; Bennekom, A.J. van; Beusekom, J.E.E. van

    2002-01-01

    Biogenic silica, one of the major constituents of marine sediments, is a potentially powerful paleoceanographic tool, revealing information on past productivity. Interpreting the sedimentary records of the biogenic silica requires, however, an understanding of its preservation. Dissolution of biogenic silica is controlled by the presence of trace elements such as Al. The work in this paper focuses on the association of Al and Si in biogenic silica. The composition and the atomic structure of cultured and natural diatoms were determined by using PIXE and XAS techniques. This study provides the first evidence for a structural association of Al and Si in biogenic silica

  19. Strontium, nickel, cadmium, and lead substitution into calcite, studied by density functional theory

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Sakuma, Hiroshi; Stipp, Susan Louise Svane

    2014-01-01

    We have used density functional theory to predict the ion exchange energies for divalent cations Ni(2+), Sr(2+), Cd(2+), and Pb(2+) into a calcite {10.4} surface in equilibrium with water. Exchange energies were calculated for substitution into the topmost surface layer, at the mineral-fluid inte......We have used density functional theory to predict the ion exchange energies for divalent cations Ni(2+), Sr(2+), Cd(2+), and Pb(2+) into a calcite {10.4} surface in equilibrium with water. Exchange energies were calculated for substitution into the topmost surface layer, at the mineral...... is favored at the mineral-fluid interface compared with bulk substitution, which also agrees with experimental data. Our results predict that Ni(2+), Cd(2+), and Pb(2+) form a stable solid solution with calcite. Successful prediction of the experimental results gives us confidence in our ability to predict...

  20. Index of refraction enhancement of calcite particles coated with zinc carbonate

    Science.gov (United States)

    Lattaud, Kathleen; Vilminot, Serge; Hirlimann, Charles; Parant, Hubert; Schoelkopf, Joachim; Gane, Patrick

    2006-10-01

    ZnCO 3 coating on calcite particles has been developed in order to enhance the index of refraction of this mineral that is used as a charge in paper, paint and polymer industries. Chemical reaction between calcite particles in an aqueous suspension with zinc chloride promotes the formation of a ZnCO 3 coating consisting of two layers with different interactions with the calcite particle. The refraction index of the resulting composite particles increases with the Zn/Ca ratio. A model allows to evaluate the coating thickness. The value of the scattering S and diffusion K coefficients of sheets coated with the ZnCO 3 coated particles reveal a dependence on the preparation conditions with a 15% increase for the best samples.

  1. Strontium isotope evolution of pore water and calcite in the Topopah Spring Tuff, Yucca Mountain, Nevada

    International Nuclear Information System (INIS)

    Marshall, Brian D.; Futa, Kiyoto

    2001-01-01

    Pore water in the Topopah Spring Tuff has a narrow range of (delta) 87 Sr values that can be calculated from the (delta) 87 Sr values of the rock considering advection through and reaction with the overlying nonwelded tuffs of the PTn. This model can be extended to estimate the variation of (delta) 87 Sr in the pore water through time; this approximates the variation of (delta) 87 Sr measured in calcite fracture coatings. In samples of calcite where no silica can be dated by other methods, strontium isotope data may be the only method to determine ages. In addition, other Sr-bearing minerals in the calcite and opal coatings, such as fluorite, may be dated using the same model

  2. Thermoluminescence and cathodoluminescence studies of calcite and MgO: surface defects and heat treatment

    International Nuclear Information System (INIS)

    Goeksu, H.Y.; Brown, L.M.

    1988-01-01

    Some of the problems which preclude accurate thermoluminescence (TL) dating of geologically formed calcite stem from different sample pre-treatment procedures, such as grinding, drilling or pre-heating. It has long been known that grinding can introduce spurious TL in calcite, but there have been wide differences of opinion as to the magnitude of the influence and its importance. Therefore, various grinding and acid-washing procedures have been suggested to avoid spurious thermoluminescence. Various models have been developed to explain the mechanism. We have studied the changes in thermoluminescence (TL) and cathodoluminescence (CL) properties as well as in the spectral composition of the glow from calcite and MgO due to surface defects and heat treatment. It is found that both laboratory heat treatment and surface indents give rise to changes in TL efficiency. (author)

  3. Neutron-activation determination of the rare earths in natural calcites using a semiconductor detector

    International Nuclear Information System (INIS)

    Vaganov, N.A.; Bulnaev, A.I.; Mejer, V.A.; Ponomarev, V.S.

    1976-01-01

    The application of germanium semiconducting detector is described. The detector has an energy resolution about 1 KeV and makes it possible to determine the content of Ce, Nd, Eu, Gd, Tb, and Yb in natural calcites with high sensitivity. The region of soft γ-radiation of activated calcites is more favourable for measurements to be performed than the region of hard γ-rays. Semiconducting detectors of radiation type are relatively cheap; they can be stored at room temperature. The limit of determining rare earth elements in calcites is (g): Eu-1.5.10 -9 ; Tb-4.0.10 -9 ; Yb-7.0.10 -9 ; Ce-1.0.10 -7 ; Nd-5.0.10 -7 ; Gd-1.0.10 -6 . A relative error of concentration determination is 10-20%

  4. Alkaliphilic Bacillus species show potential application in concrete crack repair by virtue of rapid spore production and germination then extracellular calcite formation.

    Science.gov (United States)

    Sharma, T K; Alazhari, M; Heath, A; Paine, K; Cooper, R M

    2017-05-01

    Characterization of alkaliphilic Bacillus species for spore production and germination and calcite formation as a prelude to investigate their potential in microcrack remediation in concrete. Conditions, extent and timing of endospore production was determined by dark-field light microscopy; germination induction and kinetics were assessed by combining reduction in optical density with formation of refractile bodies by phase-contrast microscopy. Bacillus pseudofirmus was selected from several species as the most suitable isolate. Levels and timing of calcium carbonate precipitated in vitro by B. pseudofirmus were evaluated by atomic absorption spectroscopy and structural identity confirmed as calcite and aragonite by Raman spectroscopy and FTIR. The isolate produced copious spores that germinated rapidly in the presence of germinants l-alanine, inosine and NaCl. Bacterial cells produced CaCO 3 crystals in microcracks and the resulting occlusion markedly restricted water ingress. By virtue of rapid spore production and germination, calcium carbonate formation in vitro and in situ, leading to sealing of microcracks, B. pseudofirmus shows clear potential for remediation of concrete on a commercial scale. Microbial sealing of microcracks should become a practicable and sustainable means of increasing concrete durability. © 2017 The Authors. Journal of Applied Microbiology published by John Wiley & Sons Ltd on behalf of The Society for Applied Microbiology.

  5. Dissolution Processes at Step Edges of Calcite in Water Investigated by High-Speed Frequency Modulation Atomic Force Microscopy and Simulation.

    Science.gov (United States)

    Miyata, Kazuki; Tracey, John; Miyazawa, Keisuke; Haapasilta, Ville; Spijker, Peter; Kawagoe, Yuta; Foster, Adam S; Tsukamoto, Katsuo; Fukuma, Takeshi

    2017-07-12

    The microscopic understanding of the crystal growth and dissolution processes have been greatly advanced by the direct imaging of nanoscale step flows by atomic force microscopy (AFM), optical interferometry, and X-ray microscopy. However, one of the most fundamental events that govern their kinetics, namely, atomistic events at the step edges, have not been well understood. In this study, we have developed high-speed frequency modulation AFM (FM-AFM) and enabled true atomic-resolution imaging in liquid at ∼1 s/frame, which is ∼50 times faster than the conventional FM-AFM. With the developed AFM, we have directly imaged subnanometer-scale surface structures around the moving step edges of calcite during its dissolution in water. The obtained images reveal that the transition region with typical width of a few nanometers is formed along the step edges. Building upon insight in previous studies, our simulations suggest that the transition region is most likely to be a Ca(OH) 2 monolayer formed as an intermediate state in the dissolution process. On the basis of this finding, we improve our understanding of the atomistic dissolution model of calcite in water. These results open up a wide range of future applications of the high-speed FM-AFM to the studies on various dynamic processes at solid-liquid interfaces with true atomic resolution.

  6. Genesis of amethyst geodes in basaltic rocks of the Serra Geral Formation (Ametista do Sul, Rio Grande do Sul, Brazil): a fluid inclusion, REE, oxygen, carbon, and Sr isotope study on basalt, quartz, and calcite

    Science.gov (United States)

    Gilg, H. Albert; Morteani, Giulio; Kostitsyn, Yuri; Preinfalk, Christine; Gatter, Istvan; Strieder, Adelir J.

    2003-12-01

    In the Ametista do Sul area, Rio Grande do Sul, Brazil, amethyst-bearing geodes are hosted by a ~40- to 50-m-thick subhorizontal high-Ti basaltic lava flow of the Lower Cretaceous Paraná Continental Flood Basalt Province. The typically spherical cap-shaped, sometimes vertically elongated geodes display an outer rim of celadonite followed inwards by agate and colorless and finally amethystine quartz. Calcite formed throughout the whole crystallization sequence, but most commonly as very late euhedral crystals, sometimes with gypsum, in the central cavity. Fluid inclusions in colorless quartz and amethyst are predominantly monophase and contain an aqueous liquid. Two-phase liquid-vapor inclusions are rare. Some with a consistent degree of fill homogenize into the liquid between 95 and 98 °C. Ice-melting temperatures in the absence of a vapor phase between -4 and +4 °C indicate low salinities. Chondrite-normalized REE patterns of calcites are highly variable and show generally no systematic correlation with the paragenetic sequence. The oxygen isotope composition of calcites is very homogeneous (δ18OVSMOW=24.9±1.1‰, n=34) indicating crystallization temperatures of less than 100 °C. Carbon isotope values of calcites show a considerable variation ranging from -18.7 to -2.9‰ (VPDB). The 87Sr/86Sr ratio of calcites varies between 0.706 and 0.708 and is more radiogenic than that of the host basalt (~0.705). The most likely source of silica, calcium, carbon, and minor elements in the infill of the geodes is the highly reactive interstitial glass of the host basalts leached by gas-poor aqueous solutions of meteoric origin ascending from the locally artesian Botucatú aquifer system in the footwall of the volcanic sequence. The genesis of amethyst geodes in basalts at Ametista do Sul, Brazil, is thus considered as a two-stage process with an early magmatic protogeode formation and a late, low temperature infill of the cavity.

  7. Controls on trace-element partitioning in cave-analogue calcite

    Science.gov (United States)

    Day, Christopher C.; Henderson, Gideon M.

    2013-11-01

    We report trace-element data from a series of carbonate growth experiments in cave-analogue conditions in the laboratory with the goal of better understanding environmental controls on trace-element incorporation in stalagmites. The experimental setup closely mimics natural processes (e.g. precipitation driven by CO2-degassing, low ionic strength solution, thin solution-film) but with a tight control on growth conditions (temperature, pCO2, drip rate, calcite saturation index and the composition of the initial solution). Calcite is dissolved in deionized water in a 20,000 ppmV pCO2 environment, with trace-elements (Li, Na, Mg, Co, Sr, Cd, Ba, U) at appropriate concentrations to mimic natural cave drip-waters. This solution is dripped onto glass plates (coated with seed-calcite) in a lower pCO2 environment at 7, 15, 25 and 35 °C and drip rates of 2, 6 and 10 drips per minute. D(Sr) was shown to be statistically invariant over the full range of temperature and growth rate studied. No relationship between Sr/Ca and growth rate is therefore expected in stalagmite samples over comparable growth rates. D(Mg) has a relationship with temperature defined by D(Mg) = 0.01e0.02[±0.006]T, but temperature is not expected to be the dominant control on Mg/Ca in cave calcite due to the larger impact of calcite precipitation on Mg/Ca. Over short timescales, in conditions where temperature is well buffered, the fraction of calcium remaining in solution (f) is likely to be the dominant control on Mg/Ca and other trace-element ratios. But differences in the response of trace-elements to f and T may allow their combined use to assess past cave conditions. High Cd/Castalagmite is particularly indicative of low amounts of prior calcite precipitation and Cd/Ca would be a useful addition to trace-element studies of natural stalagmites. Significant scatter is observed in trace-element ratios during the laboratory experiments, which cannot be explained by simple Rayleigh distillation. This

  8. Organic geochemistry and stable isotope composition of New Zealand carbonate concretions and calcite fracture fills

    International Nuclear Information System (INIS)

    Pearson, M.J.; Nelson, C.S.

    2005-01-01

    Carbonate concretion bodies, representing a number of morphological types, and associated calcite fracture fills, mainly from New Zealand, have been studied both organically and inorganically. Extracted organic material is dominated by a complex polymeric dark brown highly polar fraction with a subordinate less polar and lighter coloured lipid fraction. The relative proportion of the two fractions is the principal control on the colour of fracture fill calcites. Concretions are classified mainly by reference to their carbonate stable carbon and oxygen isotope and cation composition. Typical subspherical calcitic septarian concretions, such as those in the Paleocene Moeraki and the Eocene Rotowaro Siltstones, contain carbon derived mainly by bacterial sulfate reduction in marine strata during early diagenesis. Other concretions, including a septarian calcitic type from the Northland Allochthon, have a later diagenetic origin. Siderite concretions, abundant in the nonmarine Waikato Coal Measures, are typically dominated by methanogenic carbon, whereas paramoudra-like structures from the Taranaki Miocene have the most extreme carbon isotope compositions, probably resulting from methane formation or oxidation in fluid escape conduits. Lipids from concretion bodies and most fracture fill calcites contain significant concentrations of fatty acids. Concretion bodies dominated by bimodally distributed n-fatty acids with strong even-over-odd preference, in which long chain n-acids are of terrestrial origin, have very low hydrocarbon biomarker maturities. Concretion bodies that lack long chain n-acids often have higher apparent biomarker maturity and prominent alpha-omega diacids. Such diacids are abundant in fracture fill calcites at Rotowaro, especially where calcite infills the septaria of a siderite concretion in the non-marine Waikato Coal Measures, and support the view that fluid transport resulted in carbonate entrapment of the fracture-hosted acids. Diacids also

  9. Characteristics of a calcite "limestone"-marble from Macedonia, used as flux material

    Directory of Open Access Journals (Sweden)

    Hristova E.

    2003-01-01

    Full Text Available The phase characteristics of calcite "limestone"-marble from Banjany area village (near Skopje, Macedonia were examined by means of XRD, SEM microscope in polarizing and reflected lights, chemical, DT/TG-analyses. It was concluded as follows: - calcite (CaCO3 is a major mineral component (cca 80-90 % prevailing in the marble over the other minerals - dolomite is generally of minor importance (cca 10-20 % in the rock - quartz, micas graphite, pyrite represent typical accessories. As result of the mentioned phase characteristics, this raw materials was for a long time (more than 30 years used as flux in the iron and steel metallurgy in Macedonia.

  10. Sturgeon and paddlefish (Acipenseridae) sagittal otoliths are composed of the calcium carbonate polymorphs vaterite and calcite.

    Science.gov (United States)

    Pracheil, B M; Chakoumakos, B C; Feygenson, M; Whitledge, G W; Koenigs, R P; Bruch, R M

    2017-02-01

    This study sought to resolve whether sturgeon (Acipenseridae) sagittae (otoliths) contain a non-vaterite fraction and to quantify how large a non-vaterite fraction is using neutron diffraction analysis. This study found that all otoliths examined had a calcite fraction that ranged from 18 ± 6 to 36 ± 3% by mass. This calcite fraction is most probably due to biological variation during otolith formation rather than an artefact of polymorph transformation during preparation. © 2016 The Fisheries Society of the British Isles.

  11. Thickness and structure of the water film deposited from vapour on calcite surfaces

    DEFF Research Database (Denmark)

    Bohr, Jakob; Wogelius, Roy A.; Morris, Peter M.

    2010-01-01

    Synchrotron X-ray reflectivity (SXR) was used to measure the thickness of the water film that adsorbs on a {10¯14} cleavage surface of calcite (CaCO3) in a sample chamber where relative humidity could be controlled within the range from......Synchrotron X-ray reflectivity (SXR) was used to measure the thickness of the water film that adsorbs on a {10¯14} cleavage surface of calcite (CaCO3) in a sample chamber where relative humidity could be controlled within the range from...

  12. Interaction of ethanol and water with the {1014} surface of calcite

    DEFF Research Database (Denmark)

    Cooke, David; Gray, R J; Sand, K K

    2010-01-01

    Molecular dynamics simulations have been used to model the interaction between ethanol, water, and the {1014} surface of calcite. Our results demonstrate that a single ethanol molecule is able to form two interactions with the mineral surface (both Ca-O and O-H), resulting in a highly ordered...... the starting configuration consists of a complete monolayer of water at the surface. The computational results are in good agreement with the results from atomic force microscopy experiments where it is observed that a layer of ethanol remains attached to the calcite surface, decreasing its ability to interact...

  13. Mineralization Process of Biocemented Sand and Impact of Bacteria and Calcium Ions Concentrations on Crystal Morphology

    OpenAIRE

    Xu, Guobin; Tang, Yang; Lian, Jijian; Yan, Yue; Fu, Dengfeng

    2017-01-01

    Microbial-induced calcite precipitation (MICP) is a sustainable technique used to improve sandy soil. Analysis of the mineralization process, as well as different bacterial suspensions and calcium concentrations on the crystal morphology, revealed that the mineralization process included four stages: self-organised hydrolysis of microorganisms, molecular recognition and interface interaction, growth modulation, and epitaxial growth. By increasing bacterial suspensions and calcium concentratio...

  14. Extracellular matrix protein in calcified endoskeleton: a potential additive for crystal growth and design

    Science.gov (United States)

    Azizur Rahman, M.; Fujimura, Hiroyuki; Shinjo, Ryuichi; Oomori, Tamotsu

    2011-06-01

    In this study, we demonstrate a key function of extracellular matrix proteins (ECMPs) on seed crystals, which are isolated from calcified endoskeletons of soft coral and contain only CaCO 3 without any living cells. This is the first report that an ECMP protein extracted from a marine organism could potentially influence in modifying the surface of a substrate for designing materials via crystallization. We previously studied with the ECMPs from a different type of soft coral ( Sinularia polydactyla) without introducing any seed crystals in the process , which showed different results. Thus, crystallization on the seed in the presence of ECMPs of present species is an important first step toward linking function to individual proteins from soft coral. For understanding this interesting phenomenon, in vitro crystallization was initiated in a supersaturated solution on seed particles of calcite (1 0 4) with and without ECMPs. No change in the crystal growth shape occurred without ECMPs present during the crystallization process. However, with ECMPs, the morphology and phase of the crystals in the crystallization process changed dramatically. Upon completion of crystallization with ECMPs, an attractive crystal morphology was found. Scanning electron microscopy (SEM) was utilized to observe the crystal morphologies on the seeds surface. The mineral phases of crystals nucleated by ECMPs on the seeds surface were examined by Raman spectroscopy. Although 50 mM Mg 2+ is influential in making aragonite in the crystallization process, the ECMPs significantly made calcite crystals even when 50 mM Mg 2+ was present in the process. Crystallization with the ECMP additive seems to be a technically attractive strategy to generate assembled micro crystals that could be used in crystals growth and design in the Pharmaceutical and biotechnology industries.

  15. Adsorption of arsenic and phosphate onto the surface of calcite as revealed by batch experiments and surface complexation modelling

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt

    in sorption edges, pKa’s and geometry of the two anions. The adsorption of arsenate and phosphate in the single sorbate systems was modelled successfully using either the constant capacitance model (CCM) for calcite or the CD-MUSIC model for calcite. Generally the models capture the variation in arsenate...

  16. Time scales for dissolution of calcite fracture fillings and implications for saturated zone radionuclide transport at Yucca Mountain, Nevada

    International Nuclear Information System (INIS)

    Winterle, J.R.; Murphy, W.M.

    1999-01-01

    An analysis was performed to estimate time scales for dissolution of calcite fracture fillings in the fractured tuff aquifer that underlies Yucca Mountain (YM), Nevada, where groundwater is chemically undersaturated with respect to calcite. The impetus for this analysis originates from speculation that undissolved calcite in the saturated zone is evidence for limited diffusive exchange between fracture and matrix waters. Assuming that matrix diffusion is the rate-limiting process, the time scale for dissolution of calcite fracture fillings depends on the amount of calcite initially deposited, the distance between flowing fractures, the degree of chemical disequilibrium, and the rate of diffusion. Assuming geochemistry of J-13 well water in free-flowing fractures, estimated time scales for complete dissolution of matrix-entrapped calcite range from about 10 4 yr for a 2 mm-thick deposit located 1 m from a flowing fracture, to over 10 7 yr for a 2 cm-thick deposit located 100 m from a flowing fracture. The authors conclude that, given the geochemical and hydrologic characteristics observed at YM, the persistence of calcite minerals over geologic time scales in aquifers where flowing water is under-saturated with calcite does not necessarily preclude matrix diffusion as a dilution mechanism. However, the model suggests that the effective spacing between flowing fractures may be large enough to diminish the overall benefit of matrix diffusion to proposed high-level waste repository performance

  17. Green technological approach to synthesis hydrophobic stable crystalline calcite particles with one-pot synthesis for oil-water separation during oil spill cleanup.

    Science.gov (United States)

    Wu, Min-Nan; Maity, Jyoti Prakash; Bundschuh, Jochen; Li, Che-Feng; Lee, Chin-Rong; Hsu, Chun-Mei; Lee, Wen-Chien; Huang, Chung-Ho; Chen, Chien-Yen

    2017-10-15

    The process of separating oil and water from oil/water mixtures is an attractive strategy to answer the menace caused by industrial oil spills and oily wastewater. In addition, water coproduced during hydrocarbon exploitation, which can be an economic burden and risk for freshwater resources, can become an important freshwater source after suitable water-oil separation. For oil-water separation purposes, considerable attention has been paid to the preparation of hydrophobic-oleophilic materials with modified surface roughness. However, due to issues of thermodynamic instability, costly and complex methods as well as lack of ecofriendly compounds, most of hydrophobic surface modified particles are of limited practical application. The study presents a facile procedure, to synthesize crystalline particles of calcite, which is the most stable polymorph of CaCO 3 from industrial CaCO 3 using oleic acid as an additive in a one-pot synthesis method. The XRD results show that the synthesized particles were a well-crystallized form of calcite. The FTIR results reflect the appearance of the alkyl groups from the oleic acid in synthesized particles which promotes the production of calcite with 'rice shape' (1.64 μm) (aggregated by spherical nanoparticle of 19.56 nm) morphology with concomitant changes in its surface wettability from hydrophilic to hydrophobic. The synthesized particles exhibited near to super hydrophobicity with ∼99% active ratio and a contact angle of 143.8°. The synthesized hydrophobic calcite particles had an oleophilic nature where waste diesel oil adsorption capacity of synthesized calcium carbonate (HCF) showed a very high (>99%) and fast (7 s) oil removal from oil-water mixture. The functional group of long alkyl chain including of CO bounds may play critical roles for adsorption of diesel oils. Moreover, the thermodynamically stable crystalline polymorph calcite (compared to vaterite) exhibited excellent recyclability. The isothermal study

  18. Modeling Global Biogenic Emission of Isoprene: Exploration of Model Drivers

    Science.gov (United States)

    Alexander, Susan E.; Potter, Christopher S.; Coughlan, Joseph C.; Klooster, Steven A.; Lerdau, Manuel T.; Chatfield, Robert B.; Peterson, David L. (Technical Monitor)

    1996-01-01

    Vegetation provides the major source of isoprene emission to the atmosphere. We present a modeling approach to estimate global biogenic isoprene emission. The isoprene flux model is linked to a process-based computer simulation model of biogenic trace-gas fluxes that operates on scales that link regional and global data sets and ecosystem nutrient transformations Isoprene emission estimates are determined from estimates of ecosystem specific biomass, emission factors, and algorithms based on light and temperature. Our approach differs from an existing modeling framework by including the process-based global model for terrestrial ecosystem production, satellite derived ecosystem classification, and isoprene emission measurements from a tropical deciduous forest. We explore the sensitivity of model estimates to input parameters. The resulting emission products from the global 1 degree x 1 degree coverage provided by the satellite datasets and the process model allow flux estimations across large spatial scales and enable direct linkage to atmospheric models of trace-gas transport and transformation.

  19. Biomass burning: Combustion emissions, satellite imagery, and biogenic emissions

    International Nuclear Information System (INIS)

    Levine, J.S.; Cofer, W.R III; Rhinehart, R.P.; Cahoon, D.R. J.; Winstead, E.L.; Sebacher, S.; Sebacher, D.I.; Stocks, B.J.

    1991-01-01

    This chapter deals with two different, but related, aspects of biomass burning. The first part of the chapter deals with a technique to estimate the instantaneous emissions of trace gases produced by biomass burning using satellite imagery. The second part of the chapter concerns the recent discovery that burning results in significantly enhanced biogenic emissions of N 2 O, NO, and CH 4 . Hence, biomass burning has both an immediate and long-term impact on the production of trace gases to the atmosphere. The objective of this research is to better assess and quantify the role of this research is to better assess and quantify the role and impact of biomass as a driver for global change. It will be demonstrated that satellite imagery of fires may be used to estimate combustion emissions and may in the future be used to estimate the long-term postburn biogenic emissions of trace gases to the atmosphere

  20. Evidence of a Biological Control over Origin, Growth and End of the Calcite Prisms in the Shells of Pinctada margaritifera (Pelecypod, Pterioidea

    Directory of Open Access Journals (Sweden)

    Jean-Pierre Cuif

    2014-12-01

    Full Text Available Consistently classified among the references for calcite simple prisms, the microstructural units that form the outer layer of the Pinctada margaritifera have been investigated through a series of morphological, crystallographical and biochemical characterizations. It is often said that the polygonal transverse shape of the prisms result from the competition for space between adjacent crystals. In contrast to this classical scheme the Pinctada prisms appear to be composed of four successive developmental stages from the concentrically growing disks on the internal side of the periostracum to the morphological, structural and compositional changes in both envelopes and mineral components at the end of the prisms. These latest structural and compositional changes predate nacre deposition, so that the end of prism growth is not caused by occurrence of nacre, but by metabolic changes in the secretory epithelium. This sequence makes obvious the permanent biological control exerted by the outer cell layer of the mantle in both organic envelopes and mineralizing organic phases.

  1. Mechanics, microstructure and AMS evolution of a synthetic porphyritic calcite aggregate deformed in torsion

    Czech Academy of Sciences Publication Activity Database

    Marques, F. O.; Machek, Matěj; Roxerová, Zuzana; Burg, J.-P.; Almqvist, B. S. G.

    2015-01-01

    Roč. 655, August (2015), s. 41-57 ISSN 0040-1951 Institutional support: RVO:67985530 Keywords : experimental rock deformation * porphyritic calcite aggregate * EBSD and plastic deformation Subject RIV: DB - Geology ; Mineralogy Impact factor: 2.650, year: 2015

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

    NARCIS (Netherlands)

    Neuweiler, F.; D'Orazio, M.; Immenhauser, A.M.; Geipel, G.; Heise, K.H.; Cocozza, C.; Miano, T.M.

    2003-01-01

    Intracrystalline organic compounds, enclosed within in situprecipitated 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)

  3. Inferences of paleoenvironment from petrographic, chemical and stable-isotope studies of calcretes and fracture calcites

    International Nuclear Information System (INIS)

    Vaniman, D.T.; Whelan, J.F.

    1994-01-01

    Past research has indicated a genetic connection between calcite formed in calcretes at the surface of Yucca Mountain, Nevada, and calcites deposited in underlying fractures of the unsaturated zone. This common genesis suggests that paleoenvironmental information, as well as the timing and pathways of past recharge episodes, might be obtained from studies of the deposits in both the calcretes and the unsaturated fractures. Chemical and isotopic modification of calcite-precipitating fluids appears to begin at the surface, largely under the influence of plant roots and their decay products. Chemical characteristics of the deeper calcites are either initiated or largely defined within the first few meters of fluid migration into the unsaturated tuffs beneath the calcretes. However, petrographic and isotopic data indicate a very unique low-δ 13 C microenvironment that is localized at the upper surfaces of the calcretes. These surfaces form an interface in the soil horizon where infiltration may pond above the underlying carbonate open-quotes plugclose quotes. In order to decipher the chemistry and petrology of past recharge events, it is important to first understand microenvironments such as this that contribute to mineral precipitation/dissolution events in the pedogenic environment

  4. Inferences of paleoenvironment from petrographic, chemical and stable-isotope studies of calcretes and fracture calcites

    International Nuclear Information System (INIS)

    Vaniman, D.T.; Whelan, J.F.

    1994-01-01

    Past research has indicated a genetic connection between calcite formed in calcretes at the surface of Yucca Mountain, Nevada, and calcites deposited in underlying fractures of the unsaturated zone. This common genesis suggests that paleoenvironmental information, as well as the timing and pathways of past recharge episodes, might be obtained from studies of the deposits in both the calcretes and the unsaturated fractures. Chemical and isotopic modification of calcite-precipitating fluids appears to begin at the surface, largely under the influence of plant roots and their decay products. Chemical characteristics of the deeper calcites are either initiated or largely defined within the first few meters of fluid migration into the unsaturated tuffs beneath the calcretes. However, petrographic and isotopic data indicate a very unique low-δ 13 C microenvironment that is localized at the upper surfaces of the calcretes. These surfaces form an interface in the soil horizon where infiltration may pond above the underlying carbonate ''plug.'' In order to decipher the chemistry and petrology of past recharge events, it is important to first understand microenvironments such as this that contribute to mineral precipitation/dissolution events in the pedogenic environment

  5. Rapid stepwise onset of Antarctic glaciation and deeper calcite compensation in the Pacific Ocean.

    Science.gov (United States)

    Coxall, Helen K; Wilson, Paul A; Pälike, Heiko; Lear, Caroline H; Backman, Jan

    2005-01-06

    The ocean depth at which the rate of calcium carbonate input from surface waters equals the rate of dissolution is termed the calcite compensation depth. At present, this depth is approximately 4,500 m, with some variation between and within ocean basins. The calcite compensation depth is linked to ocean acidity, which is in turn linked to atmospheric carbon dioxide concentrations and hence global climate. Geological records of changes in the calcite compensation depth show a prominent deepening of more than 1 km near the Eocene/Oligocene boundary (approximately 34 million years ago) when significant permanent ice sheets first appeared on Antarctica, but the relationship between these two events is poorly understood. Here we present ocean sediment records of calcium carbonate content as well as carbon and oxygen isotopic compositions from the tropical Pacific Ocean that cover the Eocene/Oligocene boundary. We find that the deepening of the calcite compensation depth was more rapid than previously documented and occurred in two jumps of about 40,000 years each, synchronous with the stepwise onset of Antarctic ice-sheet growth. The glaciation was initiated, after climatic preconditioning, by an interval when the Earth's orbit of the Sun favoured cool summers. The changes in oxygen-isotope composition across the Eocene/Oligocene boundary are too large to be explained by Antarctic ice-sheet growth alone and must therefore also indicate contemporaneous global cooling and/or Northern Hemisphere glaciation.

  6. Cryogenic cave calcite from several Central European caves: age, carbon and a genetic model

    Czech Academy of Sciences Publication Activity Database

    Žák, K.; Urban, J.; Cílek, Václav; Hercman, H.

    2004-01-01

    Roč. 206, 1/2 (2004), s. 119-136 ISSN 0009-2541 R&D Projects: GA ČR(CZ) GA205/02/0449 Keywords : cryogenic calcite * periglacial zone Subject RIV: DB - Geology ; Mineralogy Impact factor: 3.174, year: 2004

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

    Science.gov (United States)

    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...

  8. Inferences of paleoenvironment from petrographic, chemical and stable-isotope studies of calcretes and fracture calcites

    Energy Technology Data Exchange (ETDEWEB)

    Vaniman, D.T. [Los Alamos National Lab., NM (United States); Whelan, J.F. [Geological Survey, Denver, CO (United States)

    1994-03-01

    Past research has indicated a genetic connection between calcite formed in calcretes at the surface of Yucca Mountain, Nevada, and calcites deposited in underlying fractures of the unsaturated zone. This common genesis suggests that paleoenvironmental information, as well as the timing and pathways of past recharge episodes, might be obtained from studies of the deposits in both the calcretes and the unsaturated fractures. Chemical and isotopic modification of calcite-precipitating fluids appears to begin at the surface, largely under the influence of plant roots and their decay products. Chemical characteristics of the deeper calcites are either initiated or largely defined within the first few meters of fluid migration into the unsaturated tuffs beneath the calcretes. However, petrographic and isotopic data indicate a very unique low-{delta}{sup 13}C microenvironment that is localized at the upper surfaces of the calcretes. These surfaces form an interface in the soil horizon where infiltration may pond above the underlying carbonate ``plug.`` In order to decipher the chemistry and petrology of past recharge events, it is important to first understand microenvironments such as this that contribute to mineral precipitation/dissolution events in the pedogenic environment.

  9. A generalised chemical precipitation modelling approach in wastewater treatment applied to calcite

    DEFF Research Database (Denmark)

    Mbamba, Christian Kazadi; Batstone, Damien J.; Flores Alsina, Xavier

    2015-01-01

    , the present study aims to identify a broadly applicable precipitation modelling approach. The study uses two experimental platforms applied to calcite precipitating from synthetic aqueous solutions to identify and validate the model approach. Firstly, dynamic pH titration tests are performed to define...

  10. Ethanol adsorption on the {10(1)over-bar4} calcite surface

    DEFF Research Database (Denmark)

    Sand, Karina Krarup; Stipp, Susan Louise Svane; Hassenkam, Tue

    2008-01-01

    Preliminary atomic force microscopy investigations of the {10 (1) over bar4} calcite Surface cleaved in ethanol indicate a different surface behaviour than that of the {10 (1) over bar4} surface cleaved in air. The results are consistent with recent theoretical studies and suggest strong ordering...

  11. Interactions of Ni and Ca at the calcite-solution interface

    International Nuclear Information System (INIS)

    Carlsson, T.; Aalto, H.

    1996-10-01

    The performance assessment of repositories for spent nuclear fuel need, among other things, data describing the solubilities of radionuclides in the near field and far field. The solubility limits are often used in order to estimate the maximum concentrations of radionuclides during their possible transport to the biosphere. The solubilities used are mostly the individual solubilities for pure solids of the actual radionuclides. This way of using solubility limits represents a conservative performance assessment where the estimated nuclide concentrations are unrealistically high. This is acceptable from a performance assessment point of view but very unsatisfactory for an optimal design of the repository. In order to make the assessment more realistic, coprecipitation and solid solution formation should be taken into account. Only solids which are, in geological terms, formed in fast reactions need to be considered, which in practice restricts the number of radionuclide scavengers to calcite and iron(III)oxihydroxide. This work focuses on the Ni coprecipitation with calcite. The systems were studied under anoxic conditions and consisted of calcite-saturated 0.05 M NaCl solutions in equilibrium with synthetic calcite. The solutions were initially spiked with 63 Ni and 45 Ca and the concentrations of these elements were determined using liquid scintillation counting. (18 refs.)

  12. Growth kinetics of racemic heptahelicene-2-carboxylic acid nanowires on calcite (104)

    Czech Academy of Sciences Publication Activity Database

    Einax, M.; Richter, T.; Nimmrich, M.; Rahe, P.; Stará, Irena G.; Starý, Ivo; Kühnle, A.; Maass, P.

    2016-01-01

    Roč. 145, č. 13 (2016), č. článku 134702. ISSN 0021-9606 Institutional support: RVO:61388963 Keywords : heptahelicene-2-carboxylic acid nanowires * nc-AFM * calcite * growth kinetics Subject RIV: CC - Organic Chemistry Impact factor: 2.965, year: 2016

  13. BAECC Biogenic Aerosols - Effects on Clouds and Climate

    Energy Technology Data Exchange (ETDEWEB)

    Petäjä, Tuukka [Univ. of Helsinki (Finland); Moisseev, Dmitri [Univ. of Helsinki (Finland); Sinclair, Victoria [Univ. of Helsinki (Finland); O' Connor, Ewan J. [Finnish Meteorological Institute, Helsinki (Finland); Manninen, Antti J. [Univ. of Helsinki (Finland); Levula, Janne [Univ. of Helsinki (Finland); Väänänen, Riikka [Univ. of Helsinki (Finland); Heikkinen, Liine [Univ. of Helsinki (Finland); Äijälä, Mikko [Univ. of Helsinki (Finland); Aalto, Juho [Univ. of Helsinki (Finland); Bäck, Jaana [University of Helsinki, Finland

    2015-11-01

    Biogenic Aerosols - Effects on Clouds and Climate (BAECC)”, featured the U.S. Department of Energy’s Atmospheric Radiation Measurement (ARM) Program’s 2nd Mobile Facility (AMF2) in Hyytiälä, Finland. It operated for an 8-month intensive measurement campaign from February to September 2014. The main research goal was to understand the role of biogenic aerosols in cloud formation. One of the reasons to perform BAECC study in Hyytiälä was the fact that it hosts SMEAR-II (Station for Measuring Forest Ecosystem-Atmosphere Relations), which is one of the world’s most comprehensive surface in-situ observation sites in a boreal forest environment. The station has been measuring atmospheric aerosols, biogenic emissions and an extensive suite of parameters relevant to atmosphere-biosphere interactions continuously since 1996. The BAECC enables combining vertical profiles from AMF2 with surface-based in-situ SMEAR-II observations and allows the processes at the surface to be directly related to processes occurring throughout the entire tropospheric column. With the inclusion of extensive surface precipitation measurements, and intensive observation periods involving aircraft flights and novel radiosonde launches, the complementary observations of AMF2 and SMEAR-II provide a unique opportunity for investigating aerosol-cloud interactions, and cloud-to-precipitation processes. The BAECC dataset will initiate new opportunities for evaluating and improving models of aerosol sources and transport, cloud microphysical processes, and boundary-layer structures.

  14. Influence of Calcite and Dissolved Calcium on Uranium(VI) Sorption to a Hanford Subsurface Sediment

    International Nuclear Information System (INIS)

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

    2005-01-01

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

  15. Molecular dynamics simulation of the rotational order-disorder phase transition in calcite

    International Nuclear Information System (INIS)

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

    2009-01-01

    Molecular dynamics (MD) simulation of calcite was carried out with the interatomic potential model based on ab initio calculations to elucidate the phase relations for calcite polymorphs and the mechanism of the rotational order-disorder transition of calcite at high temperature at the atomic scale. From runs of MD calculations with increasing temperature within a pressure range of 1 atm and 2 GPa, the transition of calcite with R3-barc symmetry into a high-temperature phase with R3-barm symmetry was reproduced. In the high-temperature R3-barm phase, CO 3 groups vibrate with large amplitudes either around the original positions in the R3-barc structure or around other positions rotated ± 60 deg., and their positions change continuously with time. Moreover, contrary to the suggestion of previous investigators, the motion of CO 3 groups is not two-dimensional. At 1 atm, the transition between R3-barc and R3-barm is first order in character. Upon increasing temperature at high pressure, however, first a first-order isosymmetric phase transition between the R3-barc phases occurs, which corresponds to the start of ± 120 deg. flipping of CO 3 groups. Then, at higher temperatures, the transition of R3-barc to R3-barm phases happens, which can be considered second order. This set of two types of transitions at elevated pressure can be characterized by the appearance of an 'intermediate' R3-barc phase between the stable region of calcite and the high-temperature R3-barm phase, which may correspond to the CaCO 3 -IV phase.

  16. Arsenic Removal By Gypsum and Calcite: The Continuum Between Soption and Solid Solution Precipitation Phenomenon

    Science.gov (United States)

    Ross, G. Roman; Charlet, L.; Cuello, G.

    The sorption of As onto mineral surface, via the precipitation of Ca3(AsO4)2, controls the As solubility in industrial and mining sites. In spite of the progress in environmental chemistry, there is little data on As sorption reactions in calcite and gypsum and on the precipitation/dissolution of Ca3(AsO4)2. Recent studies have reported that As (III) can be adsorbed by the calcite and As(V) by the gypsum. In order to determine the kinetic reactions developed during the As (III, V) uptake by calcite and gypsum from aqueous solutions, we have performed adsorption isotherm and neutron diffraction experiments. The influence of pH and CO2(g) concentration was also tested. Our results show a continuum between adsorption and the formation of solid solutions Ca(SO4,HAsO4) and Ca(CO3, HAsO3 ). Higher As adsorption was registered for both, calcite and gypsum at increasing CO2(g) levels in aqueous solutions and pH conditions between 7 and 10. The study of the interaction of different arsenic compounds with geological materials is of regional relevance concerning both environmental and health aspects. Immobilisation of arsenic in presence of gypsum (CaSO4 .2H2O) and calcite (CaCO3) should be undertaken to remove arsenic in calcium rich sites if their long-term stability is assessed. Understanding the behavior of the different compounds of As is necessary to estimate and predict possible consequences to forecasted or accidental events and to propose remediation actions at the concerned sites.

  17. Experimental studies of the deformation of carbonated rocks by dissolution crystallization under stress

    International Nuclear Information System (INIS)

    Zubtsov, Sergey

    2003-01-01

    The first part of this research thesis reports the experimental investigation and the modelling of the deformation of poly-mineral rocks under the influence of mechanism of dissolution-crystallization under stress. This mechanism has a significant role in the compaction of sedimentary rocks, in the folding process of the earth's crust. The author notably reports the results of the experimental deformation of calcite in presence of water (calcite is present in marls in which the deposit of nuclear wastes in planned in France). The second part deals with the fact that healing is possible between two grains of similar mineralogy, and slows down or even stops deformation

  18. Time Resolved Measurements of Primary Biogenic Aerosol Particles in Amazonia

    Science.gov (United States)

    Wollny, A. G.; Garland, R.; Pöschl, U.

    2009-04-01

    Biogenic aerosols are ubiquitous in the Earth's atmosphere and they influence atmospheric chemistry and physics, the biosphere, climate, and public health. They play an important role in the spread of biological organisms and reproductive materials, and they can cause or enhance human, animal, and plant diseases. Moreover, they influence the Earth's energy budget by scattering and absorbing radiation, and they can initiate the formation of clouds and precipitation as cloud condensation and ice nuclei. The composition, abundance, and origin of biogenic aerosol particles and components are, however, still not well understood and poorly quantified. Prominent examples of primary biogenic aerosol particles, which are directly emitted from the biosphere to the atmosphere, are pollen, bacteria, fungal spores, viruses, and fragments of animals and plants. During the Amazonian Aerosol Characterization Experiment (AMAZE-08) a large number of aerosol and gas-phase measurements were taken on a remote site close to Manaus, Brazil, during a period of five weeks in February and March 2008. This presented study is focused on data from an ultraviolet aerodynamic particle sizer (UVAPS, TSI inc.) that has been deployed for the first time in Amazonia. In this instrument, particle counting and aerodynamic sizing over the range of 0.5-20 µm are complemented by the measurement of UV fluorescence at 355 nm (excitation) and 420-575 nm (emission), respectively. Fluorescence at these wavelengths is characteristic for reduced pyridine nucleotides (e.g., NAD(P)H) and for riboflavin, which are specific for living cells. Thus particles exhibiting fluorescence signals can be regarded as "viable aerosols" or "fluorescent bioparticles" (FBAP), and their concentration can be considered as lower limit for the actual abundance of primary biogenic aerosol particles. Data from the UVAPS were averaged over 5 minute time intervals. The presence of bioparticles in the observed size range has been

  19. Crystal Systems.

    Science.gov (United States)

    Schomaker, Verner; Lingafelter, E. C.

    1985-01-01

    Discusses characteristics of crystal systems, comparing (in table format) crystal systems with lattice types, number of restrictions, nature of the restrictions, and other lattices that can accidently show the same metrical symmetry. (JN)

  20. Virtual Crystallizer

    Energy Technology Data Exchange (ETDEWEB)

    Land, T A; Dylla-Spears, R; Thorsness, C B

    2006-08-29

    Large dihydrogen phosphate (KDP) crystals are grown in large crystallizers to provide raw material for the manufacture of optical components for large laser systems. It is a challenge to grow crystal with sufficient mass and geometric properties to allow large optical plates to be cut from them. In addition, KDP has long been the canonical solution crystal for study of growth processes. To assist in the production of the crystals and the understanding of crystal growth phenomena, analysis of growth habits of large KDP crystals has been studied, small scale kinetic experiments have been performed, mass transfer rates in model systems have been measured, and computational-fluid-mechanics tools have been used to develop an engineering model of the crystal growth process. The model has been tested by looking at its ability to simulate the growth of nine KDP boules that all weighed more than 200 kg.

  1. Crystal Engineering

    Indian Academy of Sciences (India)

    Nangia (2002). “Today, research areas under the wide umbrella of crystal engineering include: supramolecular synthesis; nanotechnology; separation science and catalysis; supramolecular materials and devices; polymorphism; cocrystals, crystal structure prediction; drug design and ligand–protein binding.”

  2. 40K in the Black Sea: a proxy to estimate biogenic sedimentation

    International Nuclear Information System (INIS)

    Gulin, S.B.; Gulina, L.V.; Sidorov, I.G.; Proskurnin, V.Yu.; Duka, M.S.; Moseichenko, I.N.; Rodina, E.A.

    2014-01-01

    An approach to estimate the rate of biogenic sedimentation in the Black Sea using the naturally occurring radionuclide 40 K has been considered. It allows assessment of the contribution of suspended matter of biological origin to the overall sediment accumulation in the Black Sea coastal, shelf and deep-water areas. Based upon this method, a relationship between the biogenic fraction of the seabed sediments and the water depth has been established with a view to differentiating the contributions of allochthonous and autochthonous suspended matter to the sedimentation rate. Overall, 40 K can be considered as an easily applicable proxy to assess sedimentation rate of biogenic fraction of particulate matter in marine environments. - Highlights: • 40 K-based approach was developed to assess biogenic sedimentation in the Black Sea. • 40 K-derived relationship between biogenic sedimentation and water depth was traced. • 40 K is an easily applicable proxy to estimate rate of biogenic sedimentation in sea

  3. First-principles calculations of structural, electronic, optical and elastic properties of magnesite MgCO3 and calcite CaCO3

    International Nuclear Information System (INIS)

    Brik, M.G.

    2011-01-01

    Detailed ab initio calculations of the structural, electronic, optical and elastic properties of two crystals - magnesite (MgCO 3 ) and calcite (CaCO 3 ) - are reported in the present paper. Both compounds are important natural minerals, playing an important role in the carbon dioxide cycling. The optimized crystal structures, band gaps, density of states diagrams, elastic constants, optical absorption spectra and refractive indexes dependence on the wavelength all have been calculated and compared, when available, with literature data. Both crystals are indirect band compounds, with calculated band gaps of 5.08 eV for MgCO 3 and 5.023 eV for CaCO 3 . Both values are underestimated by approximately 1.0 eV with respect to the experimental data. Although both crystals have the same structure, substitution of Mg by Ca ions leads to certain differences, which manifest themselves in noticeable change in the electronic bands profiles and widths, shape of the calculated absorption spectra, and values of the elastic constants. Response of both crystals to the applied hydrostatic pressure was analyzed in the pressure range of phase stability, variations of the lattice parameters and characteristic interionic distances were considered. The obtained dependencies of lattice constants and calculated band gap on pressure can be used for prediction of properties of these two hosts at elevated pressures that occur in the Earth's mantle. -- Research highlights: → Ab initio calculations of physical properties of MgCO 3 and CaCO 3 were performed. → Changes of the calculated properties with replacement of Mg by Ca were followed. → Pressure dependence of the structural and electronic properties was analyzed. → Good agreement with experimental data was demonstrated.

  4. Calcite dissolution by Brevibacterium sp. SOTI06: A futuristic approach for the reclamation of calcareous sodic soils

    Directory of Open Access Journals (Sweden)

    Tamilselvi S.M

    2016-12-01

    Full Text Available Assessing the ability of soil microorganisms to dissolute poorly soluble native calcite to supply Ca2+ is a new area to be explored in reclaiming sodic soils by supplying adequate Ca2+ and reducing the recurrent sodicity. Hence, the present study aimed to isolate a calcite dissolving bacteria (CDB from calcareous sodic soils and to understand the mechanism of calcite dissolution. Of the thirty three CDB isolates recovered from the calcareous sodic soils of Tamil Nadu (Coimbatore, Ramnad and Trichy, eleven isolates were screened for calcite dissolution based on titratable acidity. 16S rRNA gene sequence analysis of the three best isolates viz., SORI09, SOTI05 and SOTI06 revealed 99 % similarity to Bacillus aryabhattai, 100 % to B. megaterium and 93 % to Brevibacterium sp., respectively. Among them, Brevibacterium sp. SOTI06 released more Ca2+ (3.6 g.l-1 by dissolving 18.6 % of the native calcite. The spectral data of FTIR also showed reduction in the intensity of calcite (55.36 to 41.27 by the isolate at a wave number of 1636 cm-1 which confirmed the dissolution. Besides producing organic acids (gluconic acid and acetic acid, Brevibacterium sp. SOTI06 also produced siderophore (91.6 % and extracellular polysaccharides (EPS, 13.3 µg. ml-1 which might have enhanced the calcite dissolution.

  5. Targeting polyamines and biogenic amines by green tea epigallocatechin-3-gallate.

    Science.gov (United States)

    Melgarejo, Esther; Urdiales, José Luis; Sánchez-Jiménez, Francisca; Medina, Miguel Angel

    2010-02-01

    Biogenic amines and polyamines are organic polycations derived from aromatic or cationic amino acids. They exert pleiotropic effects, more related to intercellular communication in the case of biogenic amines, and to intracellular signaling in the case of polyamines. The bioactive compound epigallocatechin-3-gallate (EGCG), a major component of green tea, has been shown to target key enzyme of biogenic amine and polyamine metabolic pathways. Herein, we review the specific effects of EGCG on concrete molecular targets of both biogenic amine and polyamine metabolic pathways, and discuss the relevance of these data to support the potential therapeutic interest of this compound.

  6. Control of Biogenic Amines in Fermented Sausages: Role of Starter Cultures

    Science.gov (United States)

    Latorre-Moratalla, M.L.; Bover-Cid, Sara; Veciana-Nogués, M.T.; Vidal-Carou, M.C.

    2012-01-01

    Biogenic amines show biological activity and exert undesirable physiological effects when absorbed at high concentrations. Biogenic amines are mainly formed by microbial decarboxylation of amino acids and thus are usually present in a wide range of foods, fermented sausages being one of the major biogenic amine sources. The use of selected starter cultures is one of the best technological measures to control aminogenesis during meat fermentation. Although with variable effectiveness, several works show the ability of some starters to render biogenic amine-free sausages. In this paper, the effect of different starter culture is reviewed and the factors determining their performance discussed. PMID:22586423

  7. Control of biogenic amines in fermented sausages: role of starter cultures

    Directory of Open Access Journals (Sweden)

    Mariluz eLatorre-Moratalla

    2012-05-01

    Full Text Available Biogenic amines show biological activity and exert undesirable physiological effects when absorbed at high concentrations. Biogenic amines are mainly formed by microbial decarboxylation of amino acids and thus are usually present in a wide range of foods, fermented sausages being one of the major biogenic amine sources. The use of selected starter cultures is one of the best technological measures to control aminogenesis during meat fermentation. Although with variable effectiveness, several works show the ability of some starters to render biogenic amine-free sausages. In this paper, the effect of different starter culture is reviewed and the factors determining their performance discussed.

  8. Determination of biogenic component in waste and liquid fuels by the 14C method

    OpenAIRE

    Krajcar Bronić, Ines; Barešić, Jadranka; Horvatinčić, Nada

    2015-01-01

    Intensive use of fossil fuels for energy production and transport during 20th century caused an increase of CO2 concentration in the atmosphere. The increase of CO2 concentration can be slowed down by the use of biogenic materials for energy production and/or transport. One of the method for determination of the fraction of the biogenic component in any type of fuel or waste is the 14C method, which is based on different content of 14C in biogenic and in fossil component: while the biogenic c...

  9. LBA-ECO TG-02 Biogenic VOC Emissions from Brazilian Amazon Forest and Pasture Sites

    Data.gov (United States)

    National Aeronautics and Space Administration — ABSTRACT: This data set reports concentrations of biogenic volatile organic compounds (BVOCs) collected from tethered balloon-sampling platforms above selected...

  10. LBA-ECO TG-02 Biogenic VOC Emissions from Brazilian Amazon Forest and Pasture Sites

    Data.gov (United States)

    National Aeronautics and Space Administration — This data set reports concentrations of biogenic volatile organic compounds (BVOCs) collected from tethered balloon-sampling platforms above selected forest and...

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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

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

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Hem, Caroline Piper; Schultz, Logan Nicholas

    2014-01-01

    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...... 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...

  14. Inhibition of calcium carbonate crystal growth by organic additives using the constant composition method in conditions of recirculating cooling circuits

    Science.gov (United States)

    Chhim, Norinda; Kharbachi, Chams; Neveux, Thibaut; Bouteleux, Céline; Teychené, Sébastien; Biscans, Béatrice

    2017-08-01

    The cooling circuits used in power plants are subject to mineral crystallization which can cause scaling on the surfaces of equipment and construction materials reducing their heat exchange efficiency. Precipitated calcium carbonate is the predominant mineral scale commonly observed in cooling systems. Supersaturation is the key parameter controlling the nucleation and growth of calcite in these systems. The present work focuses on the precipitation of calcite using the constant composition method at constant supersaturation, through controlled addition of reactants to a semi-batch crystallizer, in order to maintain constant solution pH. The determination of the thermodynamic driving force (supersaturation) was based on the relevant chemical equilibria, total alkalinity and calculation of the activity coefficients. Calcite crystallization rates were derived from the experiments performed at supersaturation levels similar to those found in industrial station cooling circuits. Several types of seeds particles were added into the aqueous solution to mimic natural river water conditions in terms of suspended particulate matters content, typically: calcite, silica or illite particles. The effect of citric and copolycarboxylic additive inhibitors added to the aqueous solution was studied. The calcium carbonate growth rate was reduced by 38.6% in the presence of the citric additive and a reduction of 92.7% was observed when the copolycarboxylic additive was used under identical experimental conditions. These results are explained by the location of the adsorbed inhibitor at the crystal surface and by the degree of chemical bonding to the surface.

  15. Temperature effects in EPR spectra of radical centers in dripstone calcite samples used for ESR dating

    International Nuclear Information System (INIS)

    Wencka, M.; Hoffmann, S.K.; Krzyminiewski, R.; Mielcarek, S.

    2005-01-01

    Natural calcite samples were collected from the dripstone layers of the Black Cave of the Tatra mountains. ESR spectra, thermal analysis, and thermoluminescence data were analysed to obtain a consistent picture of the calcite properties. The ESR spectra were analysed using computer enhanced resolution spectra and an influence of the thermal annealing on intensity of individual ESR lines was measured. These results together with the effects of γ-irradiation in ESR spectra allowed one to discriminate between ESR lines from various paramagnetic centers. A general conclusion of the paper is that in the ESR dating the outer ESR lines of CO 3 - (g = 2.0125) and CO 2 - (g = 1.9980) radicals should be used instead of the commonly used multicomponent central line. (author)

  16. A calcite permeable reactive barrier for the remediation of Fluoride from spent potliner (SPL) contaminated groundwater

    DEFF Research Database (Denmark)

    Turner, B.D.; Binning, Philip John; Sloan, S.W.

    2008-01-01

    The use of calcite (CaCO3) as a substrate for a permeable reactive barrier (PRB) for removing fluoride from contaminated groundwater is proposed and is illustrated by application to groundwater contaminated by spent potliner leachate (SPL), a waste derived from the aluminium smelting process....... The paper focuses on two issues in the implementation of calcite permeable reactive barriers for remediating fluoride contaminated water: the impact of the groundwater chemical matrix and CO2 addition on fluoride removal. Column tests comparing pure NaF solutions, synthetic SPL solutions, and actual SPL...... leachate indicate that the complex chemical matrix of the SPL leachate can impact fluoride removal significantly. For SPL contaminant mixtures, fluoride removal is initially less than expected from idealized, pure, solutions. However, with time, the effect of other contaminants on fluoride removal...

  17. Substrate templating guides the photoinduced reaction of C60 on calcite.

    Science.gov (United States)

    Lindner, Robert; Rahe, Philipp; Kittelmann, Markus; Gourdon, André; Bechstein, Ralf; Kühnle, Angelika

    2014-07-21

    A substrate-guided photochemical reaction of C60 fullerenes on calcite, a bulk insulator, investigated by non-contact atomic force microscopy is presented. The success of the covalent linkage is evident from a shortening of the intermolecular distances, which is clearly expressed by the disappearance of the moiré pattern. Furthermore, UV/Vis spectroscopy and mass spectrometry measurements carried out on thick films demonstrate the ability of our setup for initiating the photoinduced reaction. The irradiation of C60 results in well-oriented covalently linked domains. The orientation of these domains is dictated by the lattice dimensions of the underlying calcite substrate. Using the lattice mismatch to deliberately steer the direction of the chemical reaction is expected to constitute a general design principle for on-surface synthesis. This work thus provides a strategy for controlled fabrication of oriented, covalent networks on bulk insulators. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Potentially biogenic carbon preserved in a 4.1 billion-year-old zircon.

    Science.gov (United States)

    Bell, Elizabeth A; Boehnke, Patrick; Harrison, T Mark; Mao, Wendy L

    2015-11-24

    Evidence of life on Earth is manifestly preserved in the rock record. However, the microfossil record only extends to ∼ 3.5 billion years (Ga), the chemofossil record arguably to ∼ 3.8 Ga, and the rock record to 4.0 Ga. Detrital zircons from Jack Hills, Western Australia range in age up to nearly 4.4 Ga. From a population of over 10,000 Jack Hills zircons, we identified one >3.8-Ga zircon that contains primary graphite inclusions. Here, we report carbon isotopic measurements on these inclusions in a concordant, 4.10 ± 0.01-Ga zircon. We interpret these inclusions as primary due to their enclosure in a crack-free host as shown by transmission X-ray microscopy and their crystal habit. Their δ(13)CPDB of -24 ± 5‰ is consistent with a biogenic origin and may be evidence that a terrestrial biosphere had emerged by 4.1 Ga, or ∼ 300 My earlier than has been previously proposed.

  19. Cation Effects on the Layer Structure of Biogenic Mn-Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, M.; Ginder-Vogel, M; Parikh, S; Feng, X; Sparks, D

    2010-01-01

    Biologically catalyzed Mn(II) oxidation produces biogenic Mn-oxides (BioMnO{sub x}) and may serve as one of the major formation pathways for layered Mn-oxides in soils and sediments. The structure of Mn octahedral layers in layered Mn-oxides controls its metal sequestration properties, photochemistry, oxidizing ability, and topotactic transformation to tunneled structures. This study investigates the impacts of cations (H{sup +}, Ni(II), Na{sup +}, and Ca{sup 2+}) during biotic Mn(II) oxidation on the structure of Mn octahedral layers of BioMnO{sub x} using solution chemistry and synchrotron X-ray techniques. Results demonstrate that Mn octahedral layer symmetry and composition are sensitive to previous cations during BioMnO{sub x} formation. Specifically, H{sup +} and Ni(II) enhance vacant site formation, whereas Na{sup +} and Ca{sup 2+} favor formation of Mn(III) and its ordered distribution in Mn octahedral layers. This study emphasizes the importance of the abiotic reaction between Mn(II) and BioMnO{sub x} and dependence of the crystal structure of BioMnO{sub x} on solution chemistry.

  20. Extracellular Proteins Limit the Dispersal of BiogenicNanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Moreau, John W.; Weber, Peter K.; Martin, Michael C.; Gilbert,Benjamin; Hutcheon, Ian D.; Banfield, Jillian F.

    2007-04-27

    High spatial-resolution secondaryion microprobespectrometry, synchrotron radiation Fourier-transform infraredspectroscopy and polyacrylamide gel analysis demonstrate the intimateassociation of proteins with spheroidal aggregates of biogenic zincsulfide nanocrystals, an example of extracellular biomineralization.Experiments involving synthetic ZnS nanoparticles and representativeamino acids indicate a driving role for cysteine in rapid nanoparticleaggregation. These findings suggest that microbially-derivedextracellular proteins can limit dispersal of nanoparticulatemetal-bearing phases, such as the mineral products of bioremediation,that may otherwise be transported away from their source by subsurfacefluid flow.

  1. EFFICIENCY OF REMOVING BIOGENIC COMPOUNDS IN WATER TREATMENT

    Directory of Open Access Journals (Sweden)

    Artur Jachimowski

    2017-08-01

    Full Text Available The aim of the study was to determine the effectiveness of removal of biogenic compounds from water during the treatment process in water treatment plants of Municipal Water Supply and Sewerage Company in Cracow. The selected water quality indicators were analyzed before and after the treatment process in 2007 - 2014. The research was carried out in waters taken from plants that differed in treatment and production. In the analyzed technological systems it was stated that the biggest objections raised the concentration of nitrates, the average content of which is higher in treated water in three plants: Rudawa, Dłubnia and Bielany.

  2. Carbon nanomaterial based electrochemical sensors for biogenic amines

    International Nuclear Information System (INIS)

    Yang, Xiao; He, Xiulan; Li, Fangping; Fei, Junjie; Feng, Bo; Ding, Yonglan

    2013-01-01

    This review describes recent advances in the use of carbon nanomaterials for electroanalytical detection of biogenic amines (BAs). It starts with a short introduction into carbon nanomaterials such as carbon nanotubes, graphene, nanodiamonds, carbon nanofibers, fullerenes, and their composites. Next, electrochemical sensing schemes are discussed for various BAs including dopamine, serotonin, epinephrine, norepinephrine, tyramine, histamine and putrescine. Examples are then given for methods for simultaneous detection of various BAs. Finally, we discuss the current and future challenges of carbon nanomaterial-based electrochemical sensors for BAs. The review contains 175 references. (author)

  3. Pulmonary extraction of biogenic amines during septic shock

    International Nuclear Information System (INIS)

    Kerstein, M.D.; Kohler, J.; Gould, S.; Moseley, P.

    1982-01-01

    The effect of live Escherichia coli on the pulmonary extraction of the biogenic amines 14 C 5-hydroxytryptamine, (5-HT) and 3 H-epinephrine was investigated. The labeled isotopes were injected into a central venous catheter and collected from an aortic catheter. One hundred per cent of the labeled epinephrine was recovered in the control and septic state. Only 32.8 +/- 3.6% SEM of the 5-hydroxytryptamine was recovered before sepsis and 42.5 +/- 4.9% SEM after sepsis. During sepsis, mean arterial pressure fell to 58 mm Hg from 121 mm Hg. Pulmonary shunt increased from .7 +/- .05 SEM to .33 +/- .09 SEM

  4. The surface interactions of a near-neutral carbon nanoparticle tracer with calcite

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yan Vivian, E-mail: yan.li@colostate.edu [Colorado State University, Department of Design and Merchandising (United States); Cathles, Lawrence M., E-mail: lmc19@cornell.edu [Cornell University, Earth and Atmospheric Sciences (United States)

    2016-03-15

    A new class of nearly charge-neutral carbon-cored nanoparticle tracers are remarkably non-interactive with solid surfaces and could provide a valuable baseline for diverse hydrological and environmental studies of subsurface flow and particle transport. We investigate the causes of inertness by studying the interactions with calcite of a nanoparticle of this class synthesized from malic acid and ethanolamine (M-dots) dispersed in brine (NaCl, CaCl{sub 2}, and MgCl{sub 2}) solutions. None of the M-dots are retained in calcite sand-packed columns when dispersed in DI water. Dispersed in the NaCl and mixed brine solutions, 5.6 % of and 7.3 % of the M-dots are initially retained, but 65 and 13 % of these retained particles are subsequently released when the column is flushed with DI water. When dispersed in the CaCl{sub 2} and MgCl{sub 2} solutions, 65 and 54 % of the M-dots are initially retained, and 28 and 26 % subsequently released in the DI water flush. The M-dots have a small negative zeta potential in all solutions, but the calcite zeta potential changes from strongly negative to strongly positive across the solution series, and the particle retention tracks this change. Derjaguin–Landau–Verwey–Overbeek (DLVO) modeling of the force between a calcite probe and an M-dot coated surface shows that hydration forces repel the particles in the DI water, NaCl, and mixed solutions, but not in the CaCl{sub 2} and MgCl{sub 2} solutions. These results show that near-zero charge and strongly hydrophilic decoration are the causes of the remarkable inertness of carbon-cored nanoparticles, and also suggest that nanoparticles could be useful in solute-surface interaction studies.Graphical Abstract.

  5. The surface interactions of a near-neutral carbon nanoparticle tracer with calcite

    International Nuclear Information System (INIS)

    Li, Yan Vivian; Cathles, Lawrence M.

    2016-01-01

    A new class of nearly charge-neutral carbon-cored nanoparticle tracers are remarkably non-interactive with solid surfaces and could provide a valuable baseline for diverse hydrological and environmental studies of subsurface flow and particle transport. We investigate the causes of inertness by studying the interactions with calcite of a nanoparticle of this class synthesized from malic acid and ethanolamine (M-dots) dispersed in brine (NaCl, CaCl 2 , and MgCl 2 ) solutions. None of the M-dots are retained in calcite sand-packed columns when dispersed in DI water. Dispersed in the NaCl and mixed brine solutions, 5.6 % of and 7.3 % of the M-dots are initially retained, but 65 and 13 % of these retained particles are subsequently released when the column is flushed with DI water. When dispersed in the CaCl 2 and MgCl 2 solutions, 65 and 54 % of the M-dots are initially retained, and 28 and 26 % subsequently released in the DI water flush. The M-dots have a small negative zeta potential in all solutions, but the calcite zeta potential changes from strongly negative to strongly positive across the solution series, and the particle retention tracks this change. Derjaguin–Landau–Verwey–Overbeek (DLVO) modeling of the force between a calcite probe and an M-dot coated surface shows that hydration forces repel the particles in the DI water, NaCl, and mixed solutions, but not in the CaCl 2 and MgCl 2 solutions. These results show that near-zero charge and strongly hydrophilic decoration are the causes of the remarkable inertness of carbon-cored nanoparticles, and also suggest that nanoparticles could be useful in solute-surface interaction studies.Graphical Abstract

  6. EFFECT OF MAGNESIUM AS SUBSTITUTE MATERIAL IN ENZYME MEDIATED CALCITE PRECIPITATION (EMCP) FOR SOIL IMPROVEMENT TECHNIQUE

    OpenAIRE

    Heriansyah ePutra; Heriansyah ePutra; Hideaki eYasuhara; Naoki eKinoshita; Debendra eNeupane

    2016-01-01

    The optimization of enzyme-mediated calcite precipitation (EMCP) was evaluated as a soil improvement technique. In our previous works, purified urease was utilized to bio-catalyze the hydrolysis of urea, which causes the supplied Ca2+ to precipitate with CO32- as calcium carbonate. In the present work, magnesium chloride was newly added to the injecting solutions to delay the reaction rate and to enhance the amount of carbonate precipitation. Soil specimens were prepared in PVC cylinders and ...

  7. Study on effect of Microbial Induced Calcite Precipitates on strength of fine grained soils

    OpenAIRE

    Sharma, Animesh; R., Ramkrishnan

    2016-01-01

    For construction purposes, it is very essential to provide a strong foundation for the structure. If required, the suitability of soil has to be improved; this process of improving properties of soil is called Soil Stabilisation. This study intends to experimentally analyse the effectiveness of use of an unorthodox liquid soil stabiliser, Microbial Induced Calcite Precipitates (MICP) for improving the shear strength parameters of two different types of fine grained soils. For this process, a ...

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

    Science.gov (United States)

    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.

  9. The surface interactions of a near-neutral carbon nanoparticle tracer with calcite

    KAUST Repository

    Li, Yan Vivian

    2016-03-02

    A new class of nearly charge-neutral carbon-cored nanoparticle tracers are remarkably non-interactive with solid surfaces and could provide a valuable baseline for diverse hydrological and environmental studies of subsurface flow and particle transport. We investigate the causes of inertness by studying the interactions with calcite of a nanoparticle of this class synthesized from malic acid and ethanolamine (M-dots) dispersed in brine (NaCl, CaCl2, and MgCl2) solutions. None of the M-dots are retained in calcite sand-packed columns when dispersed in DI water. Dispersed in the NaCl and mixed brine solutions, 5.6 % of and 7.3 % of the M-dots are initially retained, but 65 and 13 % of these retained particles are subsequently released when the column is flushed with DI water. When dispersed in the CaCl2 and MgCl2 solutions, 65 and 54 % of the M-dots are initially retained, and 28 and 26 % subsequently released in the DI water flush. The M-dots have a small negative zeta potential in all solutions, but the calcite zeta potential changes from strongly negative to strongly positive across the solution series, and the particle retention tracks this change. Derjaguin–Landau–Verwey–Overbeek (DLVO) modeling of the force between a calcite probe and an M-dot coated surface shows that hydration forces repel the particles in the DI water, NaCl, and mixed solutions, but not in the CaCl2 and MgCl2 solutions. These results show that near-zero charge and strongly hydrophilic decoration are the causes of the remarkable inertness of carbon-cored nanoparticles, and also suggest that nanoparticles could be useful in solute-surface interaction studies.

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

    Science.gov (United States)

    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.

  11. Structure in continuously cored, deep drill holes at Yucca Mountain, Nevada, with notes on calcite occurrence

    International Nuclear Information System (INIS)

    Carr, W.J.

    1992-12-01

    A study of more than 22,000 feet of core from five deep drill holes at Yucca Mountain, Nevada, provided data on the attitude and vertical distribution of faults and fractures, the sense of fault displacement, and the occurrence of calcite. The study was done mainly to look for evidence of fault flattening at depth, but no consistent downward decrease in dip of faults was found, and no increase in strata rotation was evident with increasing depth. In the two drill holes located near prominent faults that dip toward the holes (USW G-3 and G-2), an apparent increase in the frequency of faults occurs below the tuffs and lavas of Calico Hills. Some of this increase occurs in brittle lavas and flow breccias in the lower part of the volcanic section. In the two holes presumed to be relatively removed from the influence of important faults at depth, the vertical distribution of faults is relatively uniform. Calcite occurs mainly in two general zones, voids in welded portions of the Paintbrush Tuff, and in a deeper zone, mostly below 3,500 feet. Calcite is least abundant in USW G-4, which may reflect the fewer faults and fractures encountered in that drill hole

  12. Intermediate-scale tests of sodium interactions with calcite and dolomite aggregate concretes

    International Nuclear Information System (INIS)

    Randich, E.; Acton, R.U.

    1983-09-01

    Two intermediate-scale tests were performed to compare the behavior of calcite and dolomite aggregate concretes when attacked by molten sodium. The tests were performed as part of an interlaboratory comparison between Sandia National Laboratories and Hanford Engineering Development Laboratories. Results of the tests at Sandia National Laboratories are reported here. The results show that both concretes exhibit similar exothermic reactions with molten sodium. The large difference in reaction vigor suggested by thermodynamic considerations of CO 2 release from calcite and dolomite was not realized. Penetration rates of 1.4 to 1.7 mm/min were observed for short periods of time with reaction zone temperatures in excess of 800 0 C during the energetic attack. The penetration was not uniform over the entire sodium-concrete contact area. Rapid attack may be localized due to inhomogeneities in the concrete. The chemical reaction zone is less then one cm thick for the calcite concrete but is about seven cm thick for the dolomite concrete

  13. Intermediate-scale tests of sodium interactions with calcite and dolomite aggregate concretes. [LMFBR

    Energy Technology Data Exchange (ETDEWEB)

    Randich, E.; Acton, R.U.

    1983-09-01

    Two intermediate-scale tests were performed to compare the behavior of calcite and dolomite aggregate concretes when attacked by molten sodium. The tests were performed as part of an interlaboratory comparison between Sandia National Laboratories and Hanford Engineering Development Laboratories. Results of the tests at Sandia National Laboratories are reported here. The results show that both concretes exhibit similar exothermic reactions with molten sodium. The large difference in reaction vigor suggested by thermodynamic considerations of CO/sub 2/ release from calcite and dolomite was not realized. Penetration rates of 1.4 to 1.7 mm/min were observed for short periods of time with reaction zone temperatures in excess of 800/sup 0/C during the energetic attack. The penetration was not uniform over the entire sodium-concrete contact area. Rapid attack may be localized due to inhomogeneities in the concrete. The chemical reaction zone is less then one cm thick for the calcite concrete but is about seven cm thick for the dolomite concrete.

  14. Calcite production by Coccolithophores in the South East Pacific Ocean: from desert to jungle

    Science.gov (United States)

    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.

  15. RNA Crystallization

    Science.gov (United States)

    Golden, Barbara L.; Kundrot, Craig E.

    2003-01-01

    RNA molecules may be crystallized using variations of the methods developed for protein crystallography. As the technology has become available to syntheisize and purify RNA molecules in the quantities and with the quality that is required for crystallography, the field of RNA structure has exploded. The first consideration when crystallizing an RNA is the sequence, which may be varied in a rational way to enhance crystallizability or prevent formation of alternate structures. Once a sequence has been designed, the RNA may be synthesized chemically by solid-state synthesis, or it may be produced enzymatically using RNA polymerase and an appropriate DNA template. Purification of milligram quantities of RNA can be accomplished by HPLC or gel electrophoresis. As with proteins, crystallization of RNA is usually accomplished by vapor diffusion techniques. There are several considerations that are either unique to RNA crystallization or more important for RNA crystallization. Techniques for design, synthesis, purification, and crystallization of RNAs will be reviewed here.

  16. Growing spherulitic calcite grains in saline, hyperalkaline lakes: Experimental evaluation of the effects of Mg-clays and organic acids

    NARCIS (Netherlands)

    Mercedes-Martín, R.; Rogerson, M.R.; Brasier, A.T.; Vonhof, H.B.; Prior, T.; Fellows, S.M.; Reijmer, J.J.G.; Billing, I.; Pedley, H.M.

    2016-01-01

    The origin of spherical-radial calcite bodies - spherulites - in sublacustrine, hyperalkaline and saline systems is unclear, and therefore their palaeoenvironmental significance as allochems is disputed. Here, we experimentally investigate two hypotheses concerning the origin of spherulites. The

  17. Biogenic emissions of isoprenoids and NO in China and comparison to anthropogenic emissions

    International Nuclear Information System (INIS)

    Tie Xuexi; Li Guohui; Ying, Zhuming; Guenther, Alex; Madronich, Sasha

    2006-01-01

    In this study, a regional dynamical model (WRF) is used to drive biogenic emission models to calculate high resolution (10 x 10 km) biogenic emissions of isoprene (C 5 H 8 ), monoterpenes (C 1 H 16 ), and nitric oxide (NO) in China. This high resolution biogenic inventory will be available for the community to study the effect of biogenic emissions on photochemical oxidants in China. The biogenic emissions are compared to anthropogenic emissions to gain insight on the potential impact of the biogenic emissions on tropospheric chemistry, especially ozone production in this region. The results show that the biogenic emissions in China exhibit strongly diurnal, seasonal, and spatial variations. The isoprenoid (including both isoprene and monoterpenes) emissions are closely correlated to tree density and strongly vary with season and local time. During winter (January), the biogenic isoprenoid emissions are the lowest, resulting from lower temperature and solar radiation, and highest in summer (July) due to higher temperature and solar radiation. The biogenic NO emissions are also higher during summer and lower during winter, but the magnitude of the seasonal variation is smaller than the emissions of isoprene and monoterpenes. The biogenic emissions of NO are widely spread out in the northern, eastern, and southern China regions, where high-density agricultural soil lands are located. Both biogenic NO and isoprenoid emissions are very small in western China. The calculated total biogenic emission budget is smaller than the total anthropogenic VOC emission budget in China. The biogenic isoprenoid and anthropogenic VOC emissions are 10.9 and 15.1 Tg year -1 , respectively. The total biogenic and anthropogenic emissions of NO are 5.9 and 11.5 Tg(NO) year -1 , respectively. The study shows that in central eastern China, the estimated biogenic emissions of isoprenoids are very small, and the anthropogenic emissions of VOCs are dominant in this region. However, in

  18. Biogenic emissions of isoprenoids and NO in China and comparison to anthropogenic emissions.

    Science.gov (United States)

    Tie, Xuexi; Li, Guohui; Ying, Zhuming; Guenther, Alex; Madronich, Sasha

    2006-12-01

    In this study, a regional dynamical model (WRF) is used to drive biogenic emission models to calculate high resolution (10x10 km) biogenic emissions of isoprene (C(5)H(8)), monoterpenes (C(10)H(16)), and nitric oxide (NO) in China. This high resolution biogenic inventory will be available for the community to study the effect of biogenic emissions on photochemical oxidants in China. The biogenic emissions are compared to anthropogenic emissions to gain insight on the potential impact of the biogenic emissions on tropospheric chemistry, especially ozone production in this region. The results show that the biogenic emissions in China exhibit strongly diurnal, seasonal, and spatial variations. The isoprenoid (including both isoprene and monoterpenes) emissions are closely correlated to tree density and strongly vary with season and local time. During winter (January), the biogenic isoprenoid emissions are the lowest, resulting from lower temperature and solar radiation, and highest in summer (July) due to higher temperature and solar radiation. The biogenic NO emissions are also higher during summer and lower during winter, but the magnitude of the seasonal variation is smaller than the emissions of isoprene and monoterpenes. The biogenic emissions of NO are widely spread out in the northern, eastern, and southern China regions, where high-density agricultural soil lands are located. Both biogenic NO and isoprenoid emissions are very small in western China. The calculated total biogenic emission budget is smaller than the total anthropogenic VOC emission budget in China. The biogenic isoprenoid and anthropogenic VOC emissions are 10.9 and 15.1 Tg year(-1), respectively. The total biogenic and anthropogenic emissions of NO are 5.9 and 11.5 Tg(NO) year(-1), respectively. The study shows that in central eastern China, the estimated biogenic emissions of isoprenoids are very small, and the anthropogenic emissions of VOCs are dominant in this region. However, in

  19. An isotopic and fluid inclusion study of fracture calcite from borehole OL-KR1 at the Olkiluoto site, Finland

    International Nuclear Information System (INIS)

    Blyth, A.; Frape, S.; Blomqvist, R.; Nissinen, P.; McNutt, R.

    1998-04-01

    A study of the geochemistry of fracture filling calcite in borehole OL-KR1 at the radioactive waste disposal investigation site Olkiluoto (in Finland) was undertaken in 1998. The purpose of the present study is to characterize the fracture calcite using mineralogy, oxygen, carbon and strontium isotopes, and fluid inclusions in order to determine past and present chemical and isotopic condition at the site

  20. Comparative study of biogenic and abiotic iron-containing materials

    Energy Technology Data Exchange (ETDEWEB)

    Cherkezova-Zheleva, Z., E-mail: zzhel@ic.bas.bg; Shopska, M., E-mail: shopska@ic.bas.bg; Paneva, D. [Bulgarian Academy of Sciences, Institute of Catalysis (Bulgaria); Kovacheva, D. [Bulgarian Academy of Sciences, Institute of General and Inorganic Chemistry (Bulgaria); Kadinov, G.; Mitov, I. [Bulgarian Academy of Sciences, Institute of Catalysis (Bulgaria)

    2016-12-15

    Series of iron-based biogenic materials prepared by cultivation of Leptothrix group of bacteria in different feeding media (Sphaerotilus-Leptothrix group of bacteria isolation medium, Adler, Lieske and silicon-iron-glucose-peptone) were studied. Control samples were obtained in the same conditions and procedures but the nutrition media were not infected with bacteria, i.e. they were sterile. Room and low temperature Mössbauer spectroscopy, powder X-ray diffraction (XRD), and infrared spectroscopy (IRS) were used to reveal the composition and physicochemical properties of biomass and respective control samples. Comparative analysis showed differences in their composition and dispersity of present phases. Sample composition included different ratio of nanodimensional iron oxyhydroxide and oxide phases. Relaxation phenomena such as superparamagnetism or collective magnetic excitation behaviour were registered for some of them. The experimental data showed that the biogenic materials were enriched in oxyhydroxides of high dispersion. Catalytic behaviour of a selected biomass and abiotic material were studied in the reaction of CO oxidation. In situ diffuse-reflectance (DR) IRS was used to monitor the phase transformations in the biomass and CO conversion.

  1. Technological factors affecting biogenic amine content in foods: a review

    Directory of Open Access Journals (Sweden)

    Fausto Gardini

    2016-08-01

    Full Text Available Biogenic amines (BAs are molecules which can be present in foods and, due to their toxicity, can cause adverse effects on the consumers. BAs are generally produced by microbial decarboxylation of amino acids in food products. The most significant BAs occurring in foods are histamine, tyramine, putrescine, cadaverine, tryptamine, 2-phenylethylamine, spermine, spermidine and agmatine. The importance of preventing the excessive accumulation of BAs in food is related to their impact on human health and food quality. Quality criteria in connection with the presence of BAs in food and food products are necessary from a toxicological point of view. This is particularly important in fermented foods in which the massive microbial proliferation required for obtaining specific products is often relater with BA accumulation. In this review, up-to-date information and recent discoveries about technological factors affecting biogenic amine content in foods are reviewed. Specifically, BA forming-microorganism and decarboxylation activity, genetic and metabolic organization of decarboxylases, risk associated to BAs (histamine, tyramine toxicity and other BAs, environmental factors influencing BA formation (temperature, salt concentration, pH. In addition, the technological factors for controlling BA production (use of starter culture, technological additives, effects of packaging, other non-thermal treatments, metabolising BA by microorganisms, effects of pressure treatments on BA formation and antimicrobial substances are addressed.

  2. Estimating the Biogenic Non-Methane Hydrocarbon Emissions over Greece

    Directory of Open Access Journals (Sweden)

    Ermioni Dimitropoulou

    2018-01-01

    Full Text Available Biogenic emissions affect the urban air quality as they are ozone and secondary organic aerosol (SOA precursors and should be taken into account when applying photochemical pollution models. The present study presents an estimation of the magnitude of non-methane volatile organic compounds (BNMVOCs emitted by vegetation over Greece. The methodology is based on computation developed with the aid of a Geographic Information System (GIS and theoretical equations in order to produce an emission inventory on a 6 × 6 km2 spatial resolution, in a temporal resolution of 1 h covering one year (2016. For this purpose, a variety of input data was used: updated satellite land-use data, land-use specific emission potentials, foliar biomass densities, temperature, and solar radiation data. Hourly, daily, and annual isoprene, monoterpenes, and other volatile organic compounds (OVOCs were estimated. In the area under study, the annual biogenic emissions were estimated up to 472 kt, consisting of 46.6% isoprene, 28% monoterpenes, and 25.4% OVOCs. Results delineate an annual cycle with increasing values from March to April, while maximum emissions were observed from May to September, followed by a decrease from October to January.

  3. Antimicrobial textiles: Biogenic silver nanoparticles against Candida and Xanthomonas.

    Science.gov (United States)

    Ballottin, Daniela; Fulaz, Stephanie; Cabrini, Flávia; Tsukamoto, Junko; Durán, Nelson; Alves, Oswaldo L; Tasic, Ljubica

    2017-06-01

    This paper introduces cotton fibers impregnated with biogenic silver nanoparticles (AgNPs), synthesized from a Fusarium oxysporum fungal filtrate (FF) solution, and open up the possibility for their use in medical environment and agriculture clothing as means to avoid microbial spreading. After thorough AgNPs characterization, regarding their physical, chemical and biochemical properties, Minimum Inhibitory Concentrations (MIC) against some human and orange tree pathogens were determined. We report the strong AgNPs activity against Candida parapsilosis and Xanthomonas axonopodis pv. citri (Xac) that was morphologically characterized, pointing to strong AgNPs effects on microorganisms' membranes. Cotton fibers were then impregnated with AgNPs suspension and these maintained strong antimicrobial activity even after repeated mechanical washing cycles (up to 10). Reported data might point to an application for biogenic AgNPs as potent agrochemicals, as well as, to their application in textiles for antiseptic clothing for medical and agronomic applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Selection of Nutrient Used in Biogenic Healing Agent for Cementitious Materials

    NARCIS (Netherlands)

    Tziviloglou, E.; Wiktor, V.A.C.; Jonkers, H.M.; Schlangen, H.E.J.G.

    2017-01-01

    Biogenic self-healing cementitious materials target on the closure of micro-cracks with precipitated inorganic minerals originating from bacterial metabolic activity. Dormant bacterial spores and organic mineral compounds often constitute a biogenic healing agent. The current paper focuses on the

  5. Measurement of carbon storage in landfills from the biogenic carbon content of excavated waste samples.

    Science.gov (United States)

    De la Cruz, Florentino B; Chanton, Jeffrey P; Barlaz, Morton A

    2013-10-01

    Landfills are an anaerobic ecosystem and represent the major disposal alternative for municipal solid waste (MSW) in the U.S. While some fraction of the biogenic carbon, primarily cellulose (Cel) and hemicellulose (H), is converted to carbon dioxide and methane, lignin (L) is essentially recalcitrant. The biogenic carbon that is not mineralized is stored within the landfill. This carbon storage represents a significant component of a landfill carbon balance. The fraction of biogenic carbon that is not reactive in the landfill environment and therefore stored was derived for samples of excavated waste by measurement of the total organic carbon, its biogenic fraction, and the remaining methane potential. The average biogenic carbon content of the excavated samples was 64.6±18.0% (average±standard deviation), while the average carbon storage factor was 0.09±0.06g biogenic-C stored per g dry sample or 0.66±0.16g biogenic-C stored per g biogenic C. Published by Elsevier Ltd.

  6. Biogenic Carbon Fraction of Biogas and Natural Gas Fuel Mixtures Determined with 14C

    NARCIS (Netherlands)

    Palstra, Sanne W. L.; Meijer, Harro A. J.

    2014-01-01

    This study investigates the accuracy of the radiocarbon-based calculation of the biogenic carbon fraction for different biogas and biofossil gas mixtures. The focus is on the uncertainty in the C-14 reference values for 100% biogenic carbon and on the C-13-based isotope fractionation correction of

  7. 77 FR 21772 - Notification of Two Public Teleconferences of the Science Advisory Board Biogenic Carbon...

    Science.gov (United States)

    2012-04-11

    ... of Air and Radiation requested SAB review of EPA's draft accounting framework. As noticed in 76 FR... review and discuss its advice on EPA's draft Accounting Framework for Biogenic CO2 Emissions from... Accounting Framework for Biogenic CO2 Emissions from Stationary Sources (September 2011). DATES: The public...

  8. DEVELOPMENT OF SEASONAL AND ANNUAL BIOGENIC EMISSIONS INVENTORIES FOR THE U.S. AND CANADA

    Science.gov (United States)

    The report describes the development of a biogenic emissions inventory for the U.S. and Canada, to assess the role of biogenic emissions in ozone formation. Emission inventories were developed at hourly and grid (1/4 x 116 degree) level from input data at the same scales. Emissio...

  9. Estimation of biogenic volatile organic compounds emissions in subtropical island--Taiwan.

    Science.gov (United States)

    Chang, Ken-Hui; Chen, Tu-Fu; Huang, Ho-Chun

    2005-06-15

    Elevated tropospheric ozone is harmful to human health and plants. It is formed through the photochemical reactions involving volatile organic compounds (VOCs) and nitrogen oxides (NO(x)). The elevated ozone episodes occur mainly in summer months in the United States, while the high-ozone episodes frequently occur during the fall in Taiwan. The unique landscape of Taiwan produces tremendous amounts of biogenic VOCs in the mountain regions that are adjacent to concentrated urban areas. The urban areas, in turn, generate prodigious amounts of anthropogenic emissions. Biogenic VOC emissions have direct influence on tropospheric ozone formation. To explore the air quality problems in Taiwan, this study attempts to develop a biogenic VOC emission model suitable for air quality applications in Taiwan. The emission model is based on the Biogenic Emissions Inventory System Version 2 and coupled with a detailed Taiwan land use database. The 1999 total Taiwan biogenic VOC emissions were estimated at 214,000 metric tons. The emissions of isoprene, monoterpenes, and other VOCs were about 37.2%, 30.4%, and 32.4% of total biogenic VOC emissions, respectively. The annual total biogenic VOC emission per unit area was more than two times the value of that in any European country, implying that detailed emissions estimates in any size of region will benefit the global biogenic emission inventories.

  10. Biogenic silica in space and time in sediments of Central Indian Ocean

    Digital Repository Service at National Institute of Oceanography (India)

    Pattan, J.N.; Gupta, S.M.; Mudholkar, A.V.; Parthiban, G.

    rate averages 2.25 x 10/5 g.cm/2.y/1 and it is contributed from 33 to 50% of the total silica. Higher biogenic silica content of the surface sediment is well correlated with Mn, Cu and Ni concentration of the overlying manganese nodules. Higher biogenic...

  11. Constraining biogenic silica dissolution in marine sediments: a comparison between diagenetic models and experimental dissolution rates

    NARCIS (Netherlands)

    Khalil, K.; Rabouille, C.; Gallinari, M.; Soetaert, K.E.R.; DeMaster, D.J.; Ragueneau, O.

    2007-01-01

    The processes controlling preservation and recycling of particulate biogenic silica in sediments must be understood in order to calculate oceanic silica mass balances. The new contribution of this work is the coupled use of advanced models including reprecipitation and different phases of biogenic

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

    Science.gov (United States)

    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

  13. Simulated oxygen isotopes in cave drip water and speleothem calcite in European caves

    Directory of Open Access Journals (Sweden)

    A. Wackerbarth

    2012-11-01

    Full Text Available Interpreting stable oxygen isotope (δ18O records from stalagmites is still one of the complex tasks in speleothem research. Here, we present a novel model-based approach, where we force a model describing the processes and modifications of δ18O from rain water to speleothem calcite (Oxygen isotope Drip water and Stalagmite Model – ODSM with the results of a state-of-the-art atmospheric general circulation model enhanced by explicit isotope diagnostics (ECHAM5-wiso. The approach is neither climate nor cave-specific and allows an integrated assessment of the influence of different varying climate variables, e.g. temperature and precipitation amount, on the isotopic composition of drip water and speleothem calcite.

    First, we apply and evaluate this new approach under present-day climate conditions using observational data from seven caves from different geographical regions in Europe. Each of these caves provides measured δ18O values of drip water and speleothem calcite to which we compare our simulated isotope values. For six of the seven caves modeled δ18O values of drip water and speleothem calcite are in good agreement with observed values. The mismatch of the remaining caves might be caused by the complexity of the cave system, beyond the parameterizations included in our cave model.

    We then examine the response of the cave system to mid-Holocene (6000 yr before present, 6 ka climate conditions by forcing the ODSM with ECHAM5-wiso results from 6 ka simulations. For a set of twelve European caves, we compare the modeled mid-Holocene-to-modern difference in speleothem calcite δ18O to available measurements. We show that the general European changes are simulated well. However, local discrepancies are found, and might be explained either by a too low model resolution, complex local soil-atmosphere interactions affecting evapotranspiration or by cave specific factors

  14. Bulk and Surface Aqueous Speciation of Calcite: Implications for Low-Salinity Waterflooding of Carbonate Reservoirs

    KAUST Repository

    Yutkin, Maxim P.

    2017-08-25

    Low-salinity waterflooding (LSW) is ineffective when reservoir rock is strongly water-wet or when crude oil is not asphaltenic. Success of LSW relies heavily on the ability of injected brine to alter surface chemistry of reservoir crude-oil brine/rock (COBR) interfaces. Implementation of LSW in carbonate reservoirs is especially challenging because of high reservoir-brine salinity and, more importantly, because of high reactivity of the rock minerals. Both features complicate understanding of the COBR surface chemistries pertinent to successful LSW. Here, we tackle the complex physicochemical processes in chemically active carbonates flooded with diluted brine that is saturated with atmospheric carbon dioxide (CO2) and possibly supplemented with additional ionic species, such as sulfates or phosphates. When waterflooding carbonate reservoirs, rock equilibrates with the injected brine over short distances. Injected-brine ion speciation is shifted substantially in the presence of reactive carbonate rock. Our new calculations demonstrate that rock-equilibrated aqueous pH is slightly alkaline quite independent of injected-brine pH. We establish, for the first time, that CO2 content of a carbonate reservoir, originating from CO2-rich crude oil and gas, plays a dominant role in setting aqueous pH and rock-surface speciation. A simple ion-complexing model predicts the calcite-surface charge as a function of composition of reservoir brine. The surface charge of calcite may be positive or negative, depending on speciation of reservoir brine in contact with the calcite. There is no single point of zero charge; all dissolved aqueous species are charge determining. Rock-equilibrated aqueous composition controls the calcite-surface ion-exchange behavior, not the injected-brine composition. At high ionic strength, the electrical double layer collapses and is no longer diffuse. All surface charges are located directly in the inner and outer Helmholtz planes. Our evaluation of

  15. A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

    Science.gov (United States)

    Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

    2018-04-01

    Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

  16. Isostructural exclusion of elements between aragonite and calcite layers in the shell of the Pacific oyster Crassostrea gigas

    International Nuclear Information System (INIS)

    Markwitz, A.; Gauldie, R.W.; Trompetter, W.J.; Pithie, J.; Jamieson, D.N.; Sharma, S.K.

    1999-01-01

    Sections of the shell of the farmed Pacific oyster 'Crassostrea gigas' that are available commercially in Wellington, New Zealand, showed a distinct alternating pattern in the shell mineral when observed by reflected light. The layers were identified by Raman scattering as alternating bands of the calcite and aragonite mineral forms of calcium carbonate using the micro-Raman facility at the Hawaii Institute of Geophysics and Planetology. The differences in the unit cell structure of calcite and aragonite favour different trace elements in the two minerals. Aragonite is isostructural with Strontianite SrCO 3 , and calcite is isostructural with Smithsonite ZnCO 3 . As a result, Sr deposition should be favoured in the aragonite layer and is excluded from the calcite layer; and, conversely, Zn deposition should be favoured in the calcite layer and is excluded from the aragonite layer. However, up to today, significant differences in the pattern of Sr and Zn in microprobe scans are not discovered. By ion microprobe analysis, it was shown that differences in the unit cell structure of calcite and aragonite favor different trace elements in the two minerals

  17. Fabrication of calcite blocks from gypsum blocks by compositional transformation based on dissolution-precipitation reactions in sodium carbonate solution.

    Science.gov (United States)

    Ishikawa, Kunio; Kawachi, Giichiro; Tsuru, Kanji; Yoshimoto, Ayami

    2017-03-01

    Calcium carbonate (CaCO 3 ) has been used as a bone substitute, and is a precursor for carbonate apatite, which is also a promising bone substitute. However, limited studies have been reported on the fabrication of artificial calcite blocks. In the present study, cylindrical calcite blocks (ϕ6×3mm) were fabricated by compositional transformation based on dissolution-precipitation reactions using different calcium sulfate blocks as a precursor. In the dissolution-precipitation reactions, both CaSO 4 ·2H 2 O and CaSO 4 transformed into calcite, a polymorph of CaCO 3 , while maintaining their macroscopic structure when immersed in 1mol/L Na 2 CO 3 solution at 80°C for 1week. The diametral tensile strengths of the calcite blocks formed using CaSO 4 ·2H 2 O and CaSO 4 were 1.0±0.3 and 2.3±0.7MPa, respectively. The fabrication of calcite blocks using CaSO 4 ·2H 2 O and CaSO 4 proposed in this investigation may be a useful method to produce calcite blocks because of the self-setting ability and high temperature stability of gypsum precursors. Copyright © 2016 Elsevier B.V. All rights reserved.

  18. Calcite as a bone substitute. Comparison with hydroxyapatite and tricalcium phosphate with regard to the osteoblastic activity

    Energy Technology Data Exchange (ETDEWEB)

    Monchau, F., E-mail: Francine.monchau@univ-artois.fr [Laboratoire Genie Civil et geo-Environnement (EA 4515, Universite Lille Nord de France), Equipe Biomateriaux Artois (Universite d' Artois), IUT/GMP, 1230, rue de l' Universite, BP 819, 62408 Bethune cedex (France); Hivart, Ph.; Genestie, B. [Laboratoire Genie Civil et geo-Environnement (EA 4515, Universite Lille Nord de France), Equipe Biomateriaux Artois (Universite d' Artois), IUT/GMP, 1230, rue de l' Universite, BP 819, 62408 Bethune cedex (France); Chai, F. [Laboratoire Medicaments et Biomateriaux a Liberation Controlee (INSERM U 1008, Universite Lille Nord de France), Groupe de Recherche sur les Biomateriaux (Universite Lille-2), Faculte de Medecine, 1, place de Verdun, 59045 Lille cedex (France); and others

    2013-01-01

    Close to the bone mineral phase, the calcic bioceramics, such as hydroxyapatite (HA) and {beta}-tricalcium phosphate ({beta}-TCP), are commonly used as substitutes or filling materials in bone surgery. Besides, calcium carbonate (CaCO{sub 3}) is also used for their excellent biocompatibility and bioactivity. However, the problem with the animal-origin aragonite demands the new technique to synthesize pure calcite capable of forming 3D bone implant. This study aims to manufacture and evaluate a highly-pure synthetic crystalline calcite with good cytocompatibility regarding to the osteoblasts, comparing to that of HA and {beta}-TCP. After the manufacture of macroporous bioceramic scaffolds with the identical internal architecture, their cytocompatibility is studied through MC3T3-E1 osteoblasts with the tests of cell viability, proliferation, vitality, etc. The results confirmed that the studied process is able to form a macroporous material with a controlled internal architecture, and this synthesized calcite is non-cytotoxic and facilitate the cell proliferation. Indeed requiring further improvement, the studied calcite is definitely an interesting alternative not only to coralline aragonite but also to calcium phosphate ceramics, particularly in bone sites with the large bone remodelling. Highlights: Black-Right-Pointing-Pointer Macroporous calcite manufacturing with controlled architecture as bone substitute Black-Right-Pointing-Pointer Cytotoxicity: adaptation of the colony-forming method with the target cells: MC3T3-E1 osteoblasts Black-Right-Pointing-Pointer Study of osteoblast proliferation and activity on calcite, HA and TCP.

  19. Picoplankton contribution to biogenic silica stocks and production rates in the Sargasso Sea

    Science.gov (United States)

    Krause, J. W.; Brzezinski, M. A.; Baines, S. B.; Collier, J.; Ohnemus, D.; Twining, B. S.

    2016-02-01

    The picoplankton size class (total biogenic silica (>0.4 µm) standing stock and to its rate of production in the Sargasso Sea. These trends were robust after correcting biogenic silica, and the calculated rates which use these data, for interference by lithogenic silica. The 100-m total integrated biogenic silica concentration was low and ranged from 0.7 - 5.0 mmol Si m-2, with the highest value within a mesoscale eddy. Material within the picoplankton size fraction was present at every low-biomass station and provided a relatively consistent contribution to total biogenic silica (10 - 24%, average 14%). The integrated rates of total biogenic silica production were reflective of the low biomass: 0.2 - 1.8 mmol Si m-2 d-1 in non-eddy stations and 6.0 mmol Si m-2 d-1 within the eddy. The average proportion of biogenic silica production in the picoplankton was 16% (range 3 - 38%), with a lower value within the eddy. Outside the eddy, the biomass-normalized rates of silica production were similar for each size class, 0.6 d-1. Using Synechococcus abundance data in the upper 30 m and assuming this group was the only contributor to the picoplankton biogenic silica, we calculate an average Si quota of 229 amol Si cell-1; this is two-fold higher than reported previously by direct measurement on cells using x-ray fluorescence. In the eddy, the estimated Synechococcus Si-quotas were up to 50-fold higher than estimated at other stations, suggesting that most of the pico-sized biogenic silica in this feature may have been diatom fragments. This interpretation is also supported by the eddy having the lowest biomass-normalized production rates for the picoplankton. Our results suggest picoplankton may have a small, but relatively stable, contribution to biogenic silica in this region, which underlies a more dynamic microplankton biogenic silica pool driven by diatoms.

  20. Crystal Data

    Science.gov (United States)

    SRD 3 NIST Crystal Data (PC database for purchase)   NIST Crystal Data contains chemical, physical, and crystallographic information useful to characterize more than 237,671 inorganic and organic crystalline materials. The data include the standard cell parameters, cell volume, space group number and symbol, calculated density, chemical formula, chemical name, and classification by chemical type.

  1. 76 FR 61100 - Notification of a Public Meeting of the Science Advisory Board Biogenic Carbon Emissions Panel

    Science.gov (United States)

    2011-10-03

    ... Advisory Board Biogenic Carbon Emissions Panel AGENCY: Environmental Protection Agency (EPA). ACTION... Office announces a public face-to-face meeting of the SAB Biogenic Carbon Emissions Panel to review EPA's draft Accounting Framework for Biogenic CO 2 Emissions from Stationary Sources (September 2011). DATES...

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

    Science.gov (United States)

    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

  3. Competitive adsorption of arsenate and phosphate onto calcite; experimental results and modeling with CCM and CD-MUSIC

    Science.gov (United States)

    Sø, Helle Ugilt; Postma, Dieke; Jakobsen, Rasmus; Larsen, Flemming

    2012-09-01

    The competitive adsorption of arsenate and phosphate onto calcite was studied in batch experiments using calcite-equilibrated solutions. The solutions had circum-neutral pH (7-8.3) and covered a wide span in the activity of Ca2+ and CO32-. The results show that the adsorption of arsenate onto calcite is strongly reduced by the presence of phosphate, whereas phosphate adsorption is only slightly reduced by arsenate addition. Simultaneous and sequential addition (3 h apart) yields the same reduction in adsorption, underlining the high reversibility of the system. The reduction in adsorption of both arsenate and phosphate is most likely due to competition for the same sorption sites at the calcite surface, considering the similarity in sorption edges, pKa's and geometry of the two anions. The strong reduction in arsenate adsorption by competition with phosphate suggests that adsorption of arsenate onto calcite is of minor importance in most groundwater aquifers, as phosphate is often present at concentration levels sufficient to significantly reduce arsenate adsorption. The CD-MUSIC model for calcite was used successfully to model adsorption of arsenate and phosphate separately. By combining the models for single sorbate systems the competitive adsorption of phosphate and arsenate onto calcite in the binary system could be predicted. This is in contrast to the constant capacitance model (CCM) which under-predicted the competition when combining the models for single sorbate systems. This study clearly shows the importance of performing competitive adsorption studies for validation of multi-component models and for estimating the mobility of an ion in the environment.

  4. Texture evolution in calcite gouge formed at sub-seismic slip

    Science.gov (United States)

    Delle Piane, Claudio; Luzin, Vladimir; Timms, Nick E.; Ben Clennell, M.; Giwelli, Ausama

    2016-04-01

    Carbonate rocks are abundant in the upper crust and are notoriously seismogenic with Mw>6 earthquakes nucleating in fault zones in carbonate dominated units around the world. Field observations describe fault zones as characterised by a narrow principal slip zone at their core, containing fine, granular wear material referred to as fault gouge, produced during cumulative slip. The current literature on the link between texture and frictional properties of calcite gouges is very limited and somewhat contradictory: based on the study of a natural calcite gouge a link has been proposed between the presence of a crystallographic preferred orientation (CPO) and past seismic activity on the gouge hosting fault zone. However, similar features in terms of CPO were also identified on gouges experimentally generated at slip velocities well below the seismic ones, therefore questioning their interpretation as diagnostic of past seismic events. We studied the evolution of friction coefficient and texture on calcite gouges experimentally produced by means of high pressure direct shear experiments on large, water saturated, intact blocks of travertine (calcite 99 % wt.). Several blocks were deformed at room temperature up to different amounts of maximum displacements (20 mm, 70 mm and 120 mm) under an imposed sub-seismic slip rate of approximately 0.1 microns/s. Microstructural characterization of the deformed blocks was subsequently carried out on samples representing the highest strained portion s of each blocks (i.e. gouge zones). Local and bulk texture of the original and deformed materials was studied by means of electron backscattered diffraction (EBSD) and neutron diffraction, respectively. Direct shear experiments consistently indicate an evolution of the friction coefficient stabilizing at around values of 0.6 after 15 mm of slip. Macroscopic observations on the deformed blocks indicate that deformation is localised in a narrow band of extreme grain size reduction

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

    Science.gov (United States)

    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

  6. A quantitative analysis of microbially-induced calcite precipitation employing artificial and naturally-occurring sediments

    Science.gov (United States)

    Lokier, Stephen; Krieg Dosier, Ginger

    2013-04-01

    Microbially-induced calcite precipitation is a strong candidate for the production of sustainable construction materials. The process employs the microbe Sporosarcina pasteurii as an agent to microbially mediate the precipitation of calcium carbonate to bind unconsolidated sediment. As this process can be achieved under ambient temperature conditions and can utilise a wide variety of easily-available sediments, potentially including waste materials, it is envisioned that this procedure could significantly reduce carbon-dioxide emissions in the construction industry. This study describes and quantifies the precipitation of calcite cement in a range of naturally-occurring sediments compared with a control matrix. The study establishes the optimum treatment time for effective cement precipitation in order to produce a material that meets the standards required for construction whilst keeping economic and environmental outlays at a minimum. The 'control sediment' employed industrial-grade glass beads with a grain size range of 595-1180 microns (16-30 US mesh). Sporosarcina pasteurii were mixed in a solution of urea and calcium chloride and then inoculated into the control sediment. The microbes attach to the surface of the sediment grains and employ urea as a source of energy to produce ammonia and carbon dioxide. By so doing, they increase the pH of the solution allowing calcium carbonate to precipitate at the cell walls to act as nucleation points facilitating the precipitation of cements as a grain-coating and biocementing the unconsolidated sediment. The solution treatment was repeated at eight hour intervals with samples removed for detailed analysis after each every five consecutive treatments (i.e. 40 hours). The process was repeated to produce 20 samples with treatment times between 40 and 800 hours. Cemented samples were impregnated with blue epoxy and examined petrographically to monitor cement development. Modal analysis was undertaken on each cemented

  7. Emission of Biogenic Volatile Organic Compounds in the Arctic

    DEFF Research Database (Denmark)

    Lindwall, Frida

    , emitted in order to communicate within and between trophic levels and as protection against biotic and abiotic stresses, or as byproducts. Some BVOCs are very reactive, and when entering the atmosphere they rapidly react with for example hydroxyl radicals and ozone, affecting the oxidative capacity......Emissions of biogenic volatile organic compounds (BVOCs) from arctic ecosystems are scarcely studied and the effect of climate change on BVOC emissions even less so. BVOCs are emitted from all living organisms and play a role for atmospheric chemistry. The major part of BVOCs derives from plants...... dependent and the emissions will increase in a future warmer climate. The aims of this dissertation were to study BVOC emission rates and blends from arctic ecosystems and to reveal the effect of climate change on BVOC emissions from the Arctic. BVOC emissions were measured in ambient and modified...

  8. Monitoring biogenic volatile compounds emitted by Eucalyptus citriodora using SPME.

    Science.gov (United States)

    Zini, C A; Augusto, F; Christensen, T E; Smith, B P; Caramão, E B; Pawliszy, J

    2001-10-01

    A procedure to monitor BVOC emitted by living plants using SPME technique is presented. For this purpose, a glass sampling chamber was designed. This device was employed for the characterization of biogenic volatile compounds emitted by leaves of Eucalyptus citriodora. After extraction with SPME fibers coated with PDMS/ DVB, it was possible to identify or detect 33 compounds emitted by this plant. A semiquantitative approach was applied to monitor the behavior of the emitted BVOC during 9 days. Circadian profiles of the variation in the concentration of isoprene were plotted. Using diffusion-based SPME quantitation, a recently introduced analytical approach, with extraction times as short as 15 s, it was possible to quantify subparts-per-billion amounts of isoprene emitted by this plant.

  9. Pharmacological potential of biogenic amine-polyamine interactions beyond neurotransmission.

    Science.gov (United States)

    Sánchez-Jiménez, F; Ruiz-Pérez, M V; Urdiales, J L; Medina, M A

    2013-09-01

    Histamine, serotonin and dopamine are biogenic amines involved in intercellular communication with multiple effects on human pathophysiology. They are products of two highly homologous enzymes, histidine decarboxylase and l-aromatic amino acid decarboxylase, and transmit their signals through different receptors and signal transduction mechanisms. Polyamines derived from ornithine (putrescine, spermidine and spermine) are mainly involved in intracellular effects related to cell proliferation and death mechanisms. This review summarizes structural and functional evidence for interactions between components of all these amine metabolic and signalling networks (decarboxylases, transporters, oxidases, receptors etc.) at cellular and tissue levels, distinct from nervous and neuroendocrine systems, where the crosstalk among these amine-related components can also have important pathophysiological consequences. The discussion highlights aspects that could help to predict and discuss the effects of intervention strategies. © 2013 The Authors. British Journal of Pharmacology © 2013 The British Pharmacological Society.

  10. Impact of biogenic emissions on feedbacks in the climate system

    Science.gov (United States)

    Krüger, Olaf

    2017-04-01

    Impact of biogenic emissions on feedbacks in the climate system Bio-geophysical feedback between marine or continental ecosystems and the atmosphere potentially can alter climate change. A prominent feedback loop which is under discussion since 1983 bases on the emission of biologically produced gases - molecular oxygen, sulphur containing compounds and possibly isoprene, supersaturated in oceanic waters - into the marine troposphere. These by-products of phytoplankton metabolism lead to aerosol production and procure sustained influence on climate via modulation of cloud optical properties. In this contribution some findings related to the above mentioned climate processes are presented with special emphasis on marine ecosystems. A comparison of marine and continental ecosystems is made and different processes with major impact on feedbacks in the climate system are discussed.

  11. Emissions of biogenic sulfur gases from northern bogs and fens

    Science.gov (United States)

    Demello, William Zamboni; Hines, Mark E.; Bayley, Suzanne E.

    1992-01-01

    Sulfur gases are important components of the global cycle of S. They contribute to the acidity of precipitation and they influence global radiation balance and climate. The role of terrestrial sources of biogenic S and their effect on atmospheric chemistry remain as major unanswered questions in our understanding of the natural S cycle. The role of northern wetlands as sources and sinks of gaseous S by measuring rates of S gas exchange as a function of season, hydrologic conditions, and gradients in tropic status was investigated. Experiments were conducted in wetlands in New Hampshire, particularly a poor fen, and in Mire 239, a poor fen at the Experimental Lakes Area (ELA) in Ontario. Emissions were determined using Teflon enclosures, gas cryotrapping methods and gas chromatography (GC) with flame photometric detection. Dynamic (sweep flow) and static enclosures were employed which yielded similar results. Dissolved S gases and methane were determined by gas stripping followed by GC.

  12. Sustainable use of biogenic fuels resources through industrial synergies

    International Nuclear Information System (INIS)

    Schuech, Andrea; Nelles, Michael; Nassour, Abdallah

    2017-01-01

    The term industrial symbiosis is used when traditionally separate companies and industries work together in a collective approach to physically exchange materials, energy, water and by-products with a mutual competitive advantage. Aim of the European project ''UBIS - Urban Baltic Industrial Symbiosis'' (INTERREG South-Baltic Programme) is to use biogenic resources as well as waste and residues sustainable in industrial symbiosis and to reduce emissions at the same time. Even if a lot has already been achieved in this area, there are still many unused material flows and there are possibilities to use them even more efficiently. In the project existing collaborations will be investigated as well as new ones identified and evaluated. This article introduces the UBIS project and provides an insight into the subject of industrial symbiosis as well examples described.

  13. Ion-induced nucleation of pure biogenic particles

    CERN Document Server

    Kirkby, Jasper; Sengupta, Kamalika; Frege, Carla; Gordon, Hamish; Williamson, Christina; Heinritzi, Martin; Simon, Mario; Yan, Chao; Almeida, João; Tröstl, Jasmin; Nieminen, Tuomo; Ortega, Ismael K; Wagner, Robert; Adamov, Alexey; Amorim, Antonio; Bernhammer, Anne-Kathrin; Bianchi, Federico; Breitenlechner, Martin; Brilke, Sophia; Chen, Xuemeng; Craven, Jill; Dias, antonio; Ehrhart, Sebastian; Flagan, Richard C; Franchin, Alessandro; Fuchs, Claudia; Guida, Roberto; Hakala, Jani; Hoyle, Christopher R; Jokinen, Tuija; Junninen, Heikki; Kangasluoma, Juha; Kim, Jaeseok; Krapf, Manuel; Kürten, andreas; Laaksonen, Ari; Lehtipalo, Katrianne; Makhmutov, Vladimir; Mathot, Serge; Molteni, Ugo; Onnela, antti; Peräkylä, Otso; Piel, Felix; Petäjä, Tuukka; Praplan, Arnaud P; Pringle, Kirsty; Rap, Alexandru; Richards, Nigel A D; Riipinen, Ilona; Rissanen, Matti P; Rondo, Linda; Sarnela, Nina; Schobesberger, Siegfried; Scott, Catherine E; Seinfeld, John H; Sipilä, Mikko; Steiner, Gerhard; Stozhkov, Yuri; Stratmann, Frank; Tomé, Antonio; Virtanen, Annele; Vogel, Alexander L; Wagner, Andrea C; Wagner, Paul E; Weingartner, Ernest; Wimmer, Daniela; Winkler, Paul M; Ye, Penglin; Zhang, Xuan; Hansel, Armin; Dommen, Josef; Donahue, Neil M; Worsnop, Douglas R; Baltensperger, Urs; Kulmala, Markku; Carslaw, Kenneth S; Curtius, Joachim

    2016-01-01

    Atmospheric aerosols and their effect on clouds are thought to be important for anthropogenic radiative forcing of the climate, yet remain poorly understood. Globally, around half of cloud condensation nuclei originate from nucleation of atmospheric vapours. It is thought that sulfuric acid is essential to initiate most particle formation in the atmosphere and that ions have a relatively minor role. Some laboratory studies, however, have reported organic particle formation without the intentional addition of sulfuric acid, although contamination could not be excluded. Here we present evidence for the formation of aerosol particles from highly oxidized biogenic vapours in the absence of sulfuric acid in a large chamber under atmospheric conditions. The highly oxygenated molecules (HOMs) are produced by ozonolysis of $\\alpha$-pinene. We find that ions from Galactic cosmic rays increase the nucleation rate by one to two orders of magnitude compared with neutral nucleation. Our experimental findings are supported...

  14. Liquid crystal tunable photonic crystal dye laser

    DEFF Research Database (Denmark)

    Buss, Thomas; Christiansen, Mads Brøkner; Smith, Cameron

    2010-01-01

    We present a dye-doped liquid crystal laser using a photonic crystal cavity. An applied electric field to the liquid crystal provides wavelength tunability. The photonic crystal enhances resonant interaction with the gain medium.......We present a dye-doped liquid crystal laser using a photonic crystal cavity. An applied electric field to the liquid crystal provides wavelength tunability. The photonic crystal enhances resonant interaction with the gain medium....

  15. The MUMBA campaign: measurements of urban, marine and biogenic air

    Directory of Open Access Journals (Sweden)

    C. Paton-Walsh

    2017-06-01

    Full Text Available The Measurements of Urban, Marine and Biogenic Air (MUMBA campaign took place in Wollongong, New South Wales (a small coastal city approximately 80 km south of Sydney, Australia from 21 December 2012 to 15 February 2013. Like many Australian cities, Wollongong is surrounded by dense eucalyptus forest, so the urban airshed is heavily influenced by biogenic emissions. Instruments were deployed during MUMBA to measure the gaseous and aerosol composition of the atmosphere with the aim of providing a detailed characterisation of the complex environment of the ocean–forest–urban interface that could be used to test the skill of atmospheric models. The gases measured included ozone, oxides of nitrogen, carbon monoxide, carbon dioxide, methane and many of the most abundant volatile organic compounds. The aerosol characterisation included total particle counts above 3 nm, total cloud condensation nuclei counts, mass concentration, number concentration size distribution, aerosol chemical analyses and elemental analysis.The campaign captured varied meteorological conditions, including two extreme heat events, providing a potentially valuable test for models of future air quality in a warmer climate. There was also an episode when the site sampled clean marine air for many hours, providing a useful additional measure of the background concentrations of these trace gases within this poorly sampled region of the globe. In this paper we describe the campaign, the meteorology and the resulting observations of atmospheric composition in general terms in order to equip the reader with a sufficient understanding of the Wollongong regional influences to use the MUMBA datasets as a case study for testing a chemical transport model. The data are available from PANGAEA (http://doi.pangaea.de/10.1594/PANGAEA.871982.

  16. Emission of the main biogenic volatile organic compounds in France

    International Nuclear Information System (INIS)

    Luchetta, L.; Simon, V.; Torres, L.

    2000-01-01

    An estimation of biogenic emissions of the main non-methanic Volatile Organic Compounds (VOCs) due to the forest cover in France has been realized. 32 species representing 98% of French forest have been considered for the estimation. The latter dealt on a net made of 93 irregular spatial grids (Departments) with an average size of 75 km x 75 km. We assigned emission rates and foliar biomass densities specific to each of the 32 species. The environmental variables (temperature, light intensity) have been collected for the whole of French Departments. A special effort was extended so as to use ''Guenther's'' calculation algorithms, and specific emitting factors to species growing in France or in bordering countries. Along the way of the five years (1994-1998) of the study we have calculated the yearly mean of isoprene, mono-terpenes and Other Volatile Organic Compounds (OVOCs) emissions on the scale of the French Departments. At the national level isoprene emission is reckoned at 457 kt yr -1 and represents nearly 49% of the total emission, whereas mono-terpenes with 350 kt yr -1 and OVOCs with 129 kt yr -1 represent respectively 37% and 14% of the total. The yearly biogenic emission of VOCs in France represents virtually half the anthropic source. However in some regions (Mediterranean area) natural emissions can widely exceed anthropic emissions during certain periods. Let's note the whole of our results remains tinged with a great uncertainty because the estimations carried out are presented with correction factors that can reach values comprised between 4 and 7. (author)

  17. The MUMBA campaign: measurements of urban, marine and biogenic air

    Science.gov (United States)

    Paton-Walsh, Clare; Guérette, Élise-Andrée; Kubistin, Dagmar; Humphries, Ruhi; Wilson, Stephen R.; Dominick, Doreena; Galbally, Ian; Buchholz, Rebecca; Bhujel, Mahendra; Chambers, Scott; Cheng, Min; Cope, Martin; Davy, Perry; Emmerson, Kathryn; Griffith, David W. T.; Griffiths, Alan; Keywood, Melita; Lawson, Sarah; Molloy, Suzie; Rea, Géraldine; Selleck, Paul; Shi, Xue; Simmons, Jack; Velazco, Voltaire

    2017-06-01

    The Measurements of Urban, Marine and Biogenic Air (MUMBA) campaign took place in Wollongong, New South Wales (a small coastal city approximately 80 km south of Sydney, Australia) from 21 December 2012 to 15 February 2013. Like many Australian cities, Wollongong is surrounded by dense eucalyptus forest, so the urban airshed is heavily influenced by biogenic emissions. Instruments were deployed during MUMBA to measure the gaseous and aerosol composition of the atmosphere with the aim of providing a detailed characterisation of the complex environment of the ocean-forest-urban interface that could be used to test the skill of atmospheric models. The gases measured included ozone, oxides of nitrogen, carbon monoxide, carbon dioxide, methane and many of the most abundant volatile organic compounds. The aerosol characterisation included total particle counts above 3 nm, total cloud condensation nuclei counts, mass concentration, number concentration size distribution, aerosol chemical analyses and elemental analysis.The campaign captured varied meteorological conditions, including two extreme heat events, providing a potentially valuable test for models of future air quality in a warmer climate. There was also an episode when the site sampled clean marine air for many hours, providing a useful additional measure of the background concentrations of these trace gases within this poorly sampled region of the globe. In this paper we describe the campaign, the meteorology and the resulting observations of atmospheric composition in general terms in order to equip the reader with a sufficient understanding of the Wollongong regional influences to use the MUMBA datasets as a case study for testing a chemical transport model. The data are available from PANGAEA (http://doi.pangaea.de/10.1594/PANGAEA.871982).

  18. Calcite Twin Analysis in the Central Andes of Northern Argentina and Southern Bolivia

    Science.gov (United States)

    Hardesty, E.; Hindle, D.

    2005-12-01

    The use of calcite twinning to infer compression directions and strain axes patterns has been applied widely in both fold and thrust belts, and continental interiors. Calcite twinning is noted to be one of the most precise methods for determining the internal strain of deformed rocks. Until now, such data from the deformed plate boundary of the Central Andes were lacking. This study has examined twinning orientations along the deformed Andean foreland (southern Bolivia and northern Argentina) from -25 to -20 latitude. In the Central Andes, we find an abundance of calcite twins in intervals of the Cretaceous age Yacorite limestone. Twin samples were collected, measured for orientation and type (I and II can be best used for strain analysis), and processed using the Groshong method, to give resultant strain tensors. The orientations of the twin short axes trend mostly NE-SW, which is close to the plate convergence direction. However, in a limited number of samples from the north, adjacent to the southern culmination of the active Subandean fold thrust belt, they trend NW-SE. This difference may be related to the more active, or more recent, shortening of the southern portion of the Eastern Cordillera, south of the culmination of the Subandean belt. This implies that twin short axes vary consistently with respect to geographic location and local tectonic regime. NW-SE trends in the northern region match well with fault kinematic studies in rocks pre-dating the San Juan del Oro unconformity (9-10 Ma). NE-SW trends in the south could correspond to much younger (~1-3 Ma) fault kinematic trends. In the Eastern Cordillera, where there is present day tectonic activity, the plunges of the twin short axes are found to be almost horizontal. This suggests that the twins were formed after folding occurred.

  19. Subglacial Calcites from Northern Victoria Land: archive of Antarctic volcanism in the Last Glacial Maximum

    Science.gov (United States)

    Frisia, Silvia; Weirich, Laura; Hellstrom, John; Borsato, Andrea; Golledge, Nicholas R.; Anesio, Alexandre M.; Bajo, Petra; Drysdale, Russell N.; Augustinus, Paul C.; Barbante, Carlo; Cooper, Alan

    2017-04-01

    Subglacial carbonates bear similarities to stalagmites in their fabrics and the potential to obtain precise chronologies using U-series methods. Their chemical properties also reflect those of their parent waters, which, in contrast to stalagmites, are those of subglacial meltwaters. In analogy to speleothems, stable Carbon isotope ratios and trace elements such as Uranium, Iron and Manganese provide the opportunity to investigate ancient extreme environments without the need to drill through thousands of metres of ice. Sedimentological, geochemical and microbial evidence preserved in LGM subglacial calcites from Northern Victoria Land, close to the East Antarctic Ice Sheet margin, allow us to infer that subglacial volcanism was active in the Trans Antarctic Mountain region and induced basal ice melting. We hypothesize that a meltwater reservoir was drained and injected into interconnected basal pore systems where microbial processes enhanced bedrock weathering and, thus, released micronutrients. Volcanic influence is supported by the presence of fluorine (F) and sulphur in sediment-laden calcite layers containing termophilic species. Notably, calcite δ13C points to dissolved inorganic carbon evolved from subglacial metabolic processes. Once transported to the sea, soluble iron likely contributed to fertilizing the Southern Ocean and CO2 drawdown. This is the first well-dated evidence for LGM volcanism in Antarctica, which complements the record of volcanic eruptions retrieved from Talos Dome ice core, and supports the hypothesis of large-scale volcanism as an important driver of climate change. We conclude that subglacial carbonates are equivalent to speleothems in their palaeoclimate potential and may become a most useful source of information of ecosystems and processes at peak glacials in high altitude/high latitude settings.

  20. Calcite/opal deposits at Yucca Mountain, Nevada: Pedogenic or hypogene?

    International Nuclear Information System (INIS)

    Hill, C.A.; Schluter, C.M.; Harmon, R.S.

    1994-01-01

    This study is part of the research program of the Yucca Mountain Project intended to provide the State of Nevada with a detailed assessment of the geology and geochemistry of Yucca Mountain and adjacent regions. The purpose of this paper is to consider all of the geological and geochemical data available for the calcite/opal deposits at Yucca Mountain and to ascertain whether this data favors a pedogenic or hyogene origin for these deposits. Far from being of esoteric concern, this subject is of paramount importance to the debate which rages around the suitability of Yucca Mountain as a high-level radioactive waste repository site. It is also the purpose of this paper to serve as a foundation for a lengthy feature article to be submitted for publication in 1994. In addition, a stand has been taken by the National Research Council of the National Academy of Sciences against the upwelling-water model (a vote of 17 to 0 against), and this same panel report has concluded that open-quotes there is no compelling evidence for the repetitive flooding of the environment by expulsion of groundwaterclose quotes and that open-quotes instead, the evidence strongly supports the idea that the near-surface mineral deposits resulted from percolating rainwater, which carried soil minerals down into rock fracturesclose quotes. Based on such information the Department of Energy has stated that it open-quotes finds no basis to continue to study the origin of these specific depositsclose quotes. This study, based upon many different independent lines of evidence, reaches the opposite conclusion and instead favors a hypogene spring-travertine origin for the controversial calcite/opal deposits at Yucca Mountain. This study recognizes a pedogenic carbonate component at Yucca Mountain, but argues that this component is distinct from, and sometimes intermixed with, the calcite/opal deposits

  1. The evolution of Carbon isotopes in calcite in the presence of cyanobacteria

    Science.gov (United States)

    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

  2. Sorption of phosphate onto calcite; results from batch experiments and surface complexation modeling

    DEFF Research Database (Denmark)

    Sø, Helle Ugilt; Postma, Dieke; Jakobsen, Rasmus

    2011-01-01

    of a high degree of super-saturation with respect to hydroxyapatite (SIHAP⩽7.83). The amount of phosphate adsorbed varied with the solution composition, in particular, adsorption increases as the CO32- activity decreases (at constant pH) and as pH increases (at constant CO32- activity). The primary effect....... Generally the model captures the variation in phosphate adsorption onto calcite as a function of solution composition, though it was necessary to include two types of sorption sites (strong and weak) in the model to reproduce the convex shape of the sorption isotherms....

  3. Rapid high temperature field test method for evaluation of geothermal calcite scale inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Asperger, R.G.

    1982-08-01

    A test method is described which allows the rapid field testing of calcite scale inhibitors in high- temperature geothermal brines. Five commercial formulations, chosen on the basis of laboratory screening tests, were tested in brines with low total dissolved solids at ca 500 F. Four were found to be effective; of these, 2 were found to be capable of removing recently deposited scale. One chemical was tested in the full-flow brine line for 6 wks. It was shown to stop a severe surface scaling problem at the well's control valve, thus proving the viability of the rapid test method. (12 refs.)

  4. Structure and dynamics of microbe-exuded polymers and their interactions with calcite surfaces.

    Energy Technology Data Exchange (ETDEWEB)

    Cygan, Randall Timothy; Mitchell, Ralph (Harvard University, Cambridge, MA); Perry, Thomas D. (Harvard University, Cambridge, MA)

    2005-12-01

    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 organo-cation interactions are well suited to predictive molecular modeling studies for investigating the roles of conformation and configuration of polysaccharides on cation binding. In this study, alginic acid was chosen as a model polymer and representative disaccharide and polysaccharide subunits were modeled. The ability of disaccharide subunits to bind calcium and to associate with the surface of calcite was investigated. The findings were extended to modeling polymer interactions with calcium ions.

  5. Impacts of biogenic emissions of VOC and NOx on tropospheric ozone during summertime in eastern China.

    Science.gov (United States)

    Wang, Qin'geng; Han, Zhiwei; Wang, Tijian; Zhang, Renjian

    2008-05-20

    This study is intended to understand and quantify the impacts of biogenic emissions of volatile organic compounds (VOC) and nitrogen oxides (NO(x)) on the formation of tropospheric ozone during summertime in eastern China. The model system consists of the non-hydrostatic mesoscale meteorological model (MM5) and a tropospheric chemical and transport model (TCTM) with the updated carbon-bond chemical reaction mechanism (CBM-IV). The spatial resolution of the system domain is 30 km x 30 km. The impacts of biogenic emissions are investigated by performing simulations (36 h) with and without biogenic emissions, while anthropogenic emissions are constant. The results indicate that biogenic emissions have remarkable impacts on surface ozone in eastern China. In big cities and their surrounding areas, surface ozone formation tends to be VOC-limited. The increase in ozone concentration by biogenic VOC is generally 5 ppbv or less, but could be more than 10 ppbv or even 30 ppbv in some local places. The impacts of biogenic NO(x) are different or even contrary in different regions, depending on the relative availability of NO(x) and VOC. The surface ozone concentrations reduced or increased by the biogenic NO(x) could be as much as 10 ppbv or 20 ppbv, respectively. The impacts of biogenic emissions on ozone aloft are generally restricted to the boundary layer and generally more obvious during the daytime than during the nighttime. This study is useful for understanding the role of biogenic emissions and for planning strategies for surface ozone abatement in eastern China. Due to limitations of the emission inventories used and the highly non-linear nature of zone formation, however, some uncertainties remain in the results.

  6. Sifat fisik hidroksiapatit sintesis kalsit sebagai bahan pengisi pada sealer saluran akar resin epoxy (Physical properties of calcite synthesized hydroxyapatite as the filler of epoxy-resin-based root canal sealer

    Directory of Open Access Journals (Sweden)

    Ema Mulyawati

    2013-12-01

    Full Text Available Background: The filler addition to resin based sealers will enhance the physical properties of the polymer. Because of its biological properties, the synthetic hydroxyapatite (HA has been proposed as filler for dental material such as composite resin. The calcite synthesized HA is the HA produced of calcite minerals that came from many Indonesian mining. Purpose: The aim of study was to determine the effect of different concentration of calcite synthesized HA as the filler of the epoxy-resin-based root canal sealer on the physical properties such as its contact angle, the film thickness and the microhardness. Methods: The crystal of the calcite synthesized hydroxyapatite with the size between 77.721-88.710 nm and the ratio of Ca/P 1.6886 were synthesized at Ceramic Laboratory, Mechanical Engineering, using wet method of hydrothermal microwave. The powders of the epoxy- resin were prepared by added the synthesized hydroxyapatite crystal in 5 different weight ratios (e.g.: HA-10%, HA-20%, HA-30%, HA-40% and HA-50%. Each of these was mixed with the paste of 3:1 ratio using spatula on a glass plate until homogen and then measuring the contact angle and the film thickness. Microhardness test was conducted after the mixture of experimental sealer was stored for 24 hrs at 37 oC to reach perfect polymerization. Results: All of contact angles were <90o and were not significantly different to each other (p= 0.510. All groups had a film thickness in accordance with ISO 6876 (<50 um and with no statistical difference (p= 0.858. In the HA of 10%, 20%, 30% seen that the microhardness were increased, while in the HA-50% was decreased and in the HA-40% has the same microhardness to the control groups (HA-0%. Conclusion: Calcite synthesized HA as the filler did not affect contact angle and film thickness of the sealer. Microhardness of the epoxy-resin based sealer could be increased using maximum 30% of the calcite synthesized HA as the filler.Latar belakang

  7. Operation of Marine Diesel Engines on Biogenic Fuels: Modification of Emissions and Resulting Climate Effects

    OpenAIRE

    Petzold, A.; Lauer, P.; Fritsche, U.; Hasselbach, J.; Lichtenstern, M.; Schlager, H.; Fleischer, F.

    2011-01-01

    The modification of emissions of climate-sensitive exhaust compounds such as CO2, NOx, hydrocarbons, and particulate matter from medium-speed marine diesel engines was studied for a set of fossil and biogenic fuels. Applied fossil fuels were the reference heavy fuel oil (HFO) and the low-sulfur marine gas oil (MGO); biogenic fuels were palm oil, soybean oil, sunflower oil, and animal fat. Greenhouse gas (GHG) emissions related to the production of biogenic fuels were treated by means of a fue...

  8. Sustainable use of biogenic fuels resources through industrial synergies; Nachhaltige energetische Nutzung biogener Ressourcen durch industrielle Synergien

    Energy Technology Data Exchange (ETDEWEB)

    Schuech, Andrea [Rostock Univ. (Germany). Professur Abfall- und Stoffstromwirtschaft; Nelles, Michael [Rostock Univ. (Germany). Agrar- und Umweltwissenschaftliche Fakultaet; Nassour, Abdallah

    2017-08-01

    The term industrial symbiosis is used when traditionally separate companies and industries work together in a collective approach to physically exchange materials, energy, water and by-products with a mutual competitive advantage. Aim of the European project ''UBIS - Urban Baltic Industrial Symbiosis'' (INTERREG South-Baltic Programme) is to use biogenic resources as well as waste and residues sustainable in industrial symbiosis and to reduce emissions at the same time. Even if a lot has already been achieved in this area, there are still many unused material flows and there are possibilities to use them even more efficiently. In the project existing collaborations will be investigated as well as new ones identified and evaluated. This article introduces the UBIS project and provides an insight into the subject of industrial symbiosis as well examples described.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

    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. (paper)

  10. Study on effect of Microbial Induced Calcite Precipitates on strength of fine grained soils

    Directory of Open Access Journals (Sweden)

    Animesh Sharma

    2016-09-01

    Full Text Available For construction purposes, it is very essential to provide a strong foundation for the structure. If required, the suitability of soil has to be improved; this process of improving properties of soil is called Soil Stabilisation. This study intends to experimentally analyse the effectiveness of use of an unorthodox liquid soil stabiliser, Microbial Induced Calcite Precipitates (MICP for improving the shear strength parameters of two different types of fine grained soils. For this process, a species of Bacillus group, B. pastuerii was used to activate and catalyse the calcite precipitation caused by reaction between urea and calcium chloride. Two types of soils, i.e. intermediate compressible clay and highly compressible clay were used for the study. Parameters included concentration of B. pasteurii, concentration of the cementation reagent and duration of treatment. These parameters were applied on both the soils in a specified range in order to optimise their usage. The results proved that with the use of MICP, there was a noticeable improvement (1.5–2.9 times in the unconfined compressive strength of both type of soils. It was also found that the strength increased with an increase in duration of treatment. Based on this study, optimum quantity and concentration of liquid additive to be added for different soil types for better strength increments were established.

  11. Environmentally acceptable effect of hydrogen peroxide on cave 'lamp-flora', calcite speleothems and limestones

    International Nuclear Information System (INIS)

    Faimon, Jiri; Stelcl, Jindrich; Kubesova, Svatava; Zimak, Jiri

    2003-01-01

    Hydrogen peroxide plus limestone fragments allows removal of organisms without corrosion of limestone and speleothem. - Mosses, algae, and cyanobacteria (lamp-flora) colonize illuminated areas in show caves. This biota is commonly removed by a sodium hypochlorite solution. Because chlorine and other deleterious compounds are released into a cave environment during lamp-flora cleansing, hydrogen peroxide was tested as an alternative agent. In a multidisciplinary study conducted in the Katerinska Cave (Moravian Karst, Czech Republic), 12 algae- and cyanobacteria taxons and 19 moss taxons were detected. The threshold hydrogen peroxide concentration for the destruction of this lamp-flora was found to be 15 vol.%. Based on laboratory experiments in stirred batch reactors, the dissolution rates of limestones and calcite speleothems in water were determined as 3.77x10 -3 and 1.81x10 -3 mol m -2 h -1 , respectively. In the 15% peroxide solution, the limestone and speleothem dissolution rates were one order of magnitude higher, 2.00x10 -2 and 2.21x10 -2 mol m -2 h -1 , respectively. So, the peroxide solution was recognised to attack carbonates somewhat more aggressively than karst water. In order to prevent the potential corrosion of limestone and speleothems, the reaching of preliminary peroxide saturation with respect to calcite is recommended, for example, by adding of few limestone fragments into the solution at least 10 h prior to its application

  12. Continuous 500,000-year climate record from vein calcite in devils hole, nevada.

    Science.gov (United States)

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

    1992-10-09

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

  13. Environmentally acceptable effect of hydrogen peroxide on cave "lamp-flora", calcite speleothems and limestones.

    Science.gov (United States)

    Faimon, Jirí; Stelcl, Jindrich; Kubesová, Svatava; Zimák, Jirí

    2003-01-01

    Mosses, algae, and cyanobacteria (lamp-flora) colonize illuminated areas in show caves. This biota is commonly removed by a sodium hypochlorite solution. Because chlorine and other deleterious compounds are released into a cave environment during lamp-flora cleansing, hydrogen peroxide was tested as an alternative agent. In a multidisciplinary study conducted in the Kateinská Cave (Moravian Karst, Czech Republic), 12 algae- and cyanobacteria taxons and 19 moss taxons were detected. The threshold hydrogen peroxide concentration for the destruction of this lamp-flora was found to be 15 vol.%. Based on laboratory experiments in stirred batch reactors, the dissolution rates of limestones and calcite speleothems in water were determined as 3.77 x 10-3 and 1.81 x 10-3 mol m-2 h-1, respectively. In the 15% peroxide solution, the limestone and speleothem dissolution rates were one order of magnitude higher, 2.00 x 10-2 and 2.21 x 10-2 mol m-2 h-1, respectively. So, the peroxide solution was recognised to attack carbonates somewhat more aggressively than karst water. In order to prevent the potential corrosion of limestone and speleothems, the reaching of preliminary peroxide saturation with respect to calcite is recommended, for example, by adding of few limestone fragments into the solution at least 10 h prior to its application.

  14. Remineralization of permeate water by calcite bed in the Daoura's plant (south of Morocco)

    Science.gov (United States)

    Biyoune, M. G.; Atbir, A.; Bari, H.; Hassnaoui, L.; Mongach, E.; Khadir, A.; Boukbir, L.; Bellajrou, R.; Elhadek, M.

    2017-04-01

    To face water shortage and to fight drought, the National office of Water and Electricity (ONEE) carried out a program aiming at constructing several desalination stations of seawater in the South of Morocco. However, the final product water after desalination (osmosis water) has turned out to be unbalanced and has an aggressive character. Therefore, a post-treatment of remineralization is necessary to recover the calco-carbonic equilibrium of water and to protect the distribution network from corrosion degradation. Thereby, our work aims to examine the performance of the remineralization used in Daoura plant by the calcite bed in the absence of carbon dioxide CO2 (without acidification), we have followed many parameters indicating the performance of this technique adopted such as pH, TAC (hydroxide, carbonate and bicarbonate content), Ca content, Langelier saturation index (LSI), Larson index (LR). The results obtained show that this technique adopted in Daoura plant brings to water back its entire calco-carbonic balance to measure up to the Moroccan standards of drinking water. Generally, the exploitation of the calcite bed technique for remineralization is simple, easy and it does not require any major efforts or precautions.

  15. Assessing the effect of dissolved organic ligands on mineral dissolution rates: An example from calcite dissolution

    International Nuclear Information System (INIS)

    DeMaio, T.; Grandstaff, D.E.

    1997-01-01

    Experiments suggest that dissolved organic ligands may primarily modify mineral dissolution rates by three mechanisms: (1) metal-ligand (M-L) complex formation in solution, which increases the degree of undersaturation, (2) formation of surface M-L complexes that attack the surface, and (3) formation of surface complexes which passivate or protect the surface. Mechanisms (1) and (2) increase the dissolution rate and the third decreases it compared with organic-free solutions. The types and importance of these mechanisms may be assessed from plots of dissolution rate versus degree of undersaturation. To illustrate this technique, calcite, a common repository cementing and vein-filling mineral, was dissolved at pH 7.8 and 22 C in Na-Ca-HCO 3 -Cl solutions with low concentrations of three organic ligands. Low citrate concentrations (50 microM) increased the dissolution rate consistent with mechanism (1). Oxalate decreased the rate, consistent with mechanism (3). Low phthalate concentration (<50 microM) decreased calcite dissolution rates; however, higher concentrations increased the dissolution rates, which became faster than in inorganic solutions. Thus, phthalate exhibits both mechanisms (2) and (3) at different concentrations. In such cases linear extrapolations of dissolution rates from high organic ligand concentrations may not be valid

  16. Effects of Citrate and Arginine on Sorption of Nickel to Yazd Sepiolite and Calcite

    Directory of Open Access Journals (Sweden)

    Ahmadreza Sheikhhosseini

    2017-03-01

    Full Text Available Introduction: Pollution of soil and water environment by release of heavy metals is of great concerns of the last decades. Sorption of heavy metals by low cost materials is considered as an inexpensive and efficient method used for removal of heavy metals from soil-water systems. The presence of different ligands with various complexing abilities can change the sorption properties of heavy metals and their fate in the environment as well. In order to assess the effect of citrate and arginine as natural organic ligands in soil environment, in a batch study we investigated the effects of these ligands on equilibrium sorption of nickel to sepiolite and calcite minerals and also kinetics of Ni sorption by these minerals. Materials and Methods: Minerals used in this study included sepiolite from Yazd (Iran and pure calcite (Analytical grade, Merck, Germany. Sepiolite was purified, saturated with Ca using 0.5 M CaCl2, powdered in a mortar and sieved by non-metal 230 mesh standard wire sieve. For equilibrium sorption study, in a 50-mL polyethylene centrifuge tube,0.3 g sample of each mineral was suspended in 30 mL of a 0.01 M CaCl2 solution containing 0, 5, 10, 20, 40, 60, 80 and 100 mg L-1 Ni (NiCl2 and containing zero (as control or 0.1mmol L-1 citrate or arginine ligands. The applied concentrationsfor each ligand can naturally occur in soils. Preparedtubes were shaken (180±2 rpm, 25±1oC for 24 h using an orbital shaker and centrifuged (4000×g for 10 min and the supernatants were analyzed for Ni concentration using an atomic absorption spectrophotometer (AAnalyst 200 Perkin-Elmer at a wavelength of 232 nm and a detection limit of 0.05 mg L-1. The quantity of Ni retained by each mineral at equilibrium was calculated using equation qe = (Ci - CeV/W where qe was the amount of nickel retained by mineral surface at equilibrium. Ci and Ce were the initial and the equilibrium concentrations (mg L-1 of Ni, respectively, V was the volume (L of the solution

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

    Science.gov (United States)

    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.

  18. Characterization of Shock Effects in Calcite by Raman Spectroscopy: Results of Experiments

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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.

  20. Induction of calcite precipitation through heightened production of extracellular carbonic anhydrase by CO2 sequestering bacteria.

    Science.gov (United States)

    Sundaram, Smita; Thakur, Indu Shekhar

    2018-04-01

    The thermo-alkalotolerant bacterium exhibiting heightened extracellular carbonic anhydrase (CA) activity, survived at 100 mM sodium bicarbonateand 5% gaseous CO 2 was identified as Bacillus sp. by 16S rRNA sequencing. Extracellular carbonic anhydrase was purified by ammonium sulfate precipitation, gel filtration chromatography and affinity chromatography with a yield of 46.61% and specific activity of 481.66 U/mg. The size of purified carbonic anhydrase was approximately 28 kDa in SDS-PAGE gel filtration and further their role in calcium carbonate production was correlated. The purified enzyme was stable with half-life of 25.36 min at 90 °C and pH 8. K M and Vmax values of the enzyme were 1.77 mg/mL and 385.69 U/mg respectively. The production of calcite was confirmed by Scanning Electron Microscopy (SEM) analysis, FTIR, and Energy-Dispersive X-ray (EDX) analysis. Carbonic anhydrase and calcite deposition coupled with CO 2 fixingbacteria is a significant approach for CO 2 sequestration. Copyright © 2018 Elsevier Ltd. All rights reserved.

  1. The effect of water on strain localization in calcite fault gouge sheared at seismic slip rates

    Science.gov (United States)

    Rempe, Marieke; Smith, Steven; Mitchell, Thomas; Hirose, Takehiro; Di Toro, Giulio

    2017-04-01

    Strain localization during coseismic slip in fault gouges is a critical mechanical process that has implications for understanding frictional heating, the earthquake energy budget and the evolution of fault rock microstructure. To assess the nature of strain localization during shearing of calcite fault gouges, high-velocity (vmax = 1m /s) rotary-shear experiments at normal stresses of 3-20 MPa were conducted under room-dry and wet conditions on synthetic calcite gouges containing dolomite gouge strain markers. When sheared at 1 m/s, the room-dry gouges showed a prolonged strengthening phase prior to dynamic weakening, whereas the wet gouges weakened nearly instantaneously. Microstructural analysis revealed that a thin (PSS) developed after several centimeters of slip in both dry and wet gouges, and that strain localization at 1 m/s occurred progressively and rapidly. The strain accommodated in the bulk gouge layer did not change significantly with increasing displacement indicating that, once formed, the high-strain layer and PSS accommodated most of the displacement. Thus, a substantial strain gradient is present in the gouge layer. In water-dampened gouges, localization likely occurs during and after dynamic weakening. Our results suggest that natural fault zones in limestone are more prone to rapid dynamic weakening if water is present in the granular slipping zones.

  2. Fluoride removal by calcite: evidence for fluorite precipitation and surface adsorption.

    Science.gov (United States)

    Turner, Brett D; Binning, Philip; Stipp, S L S

    2005-12-15

    Fluoride contamination of groundwater, both anthropogenic and natural, is a major problem worldwide. In this study, fluoride removal by crushed limestone (99% pure calcite) was investigated by batch studies and surface-sensitive techniques from solutions with fluoride concentrations from 150 micromol/L (3 mg/L) to 110 mM (approximately 2100 mg/L). Surface-sensitive techniques, including atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) as well as zeta potential measurements, confirm that, in addition to precipitation reactions, adsorption of fluoride also occurs. Results indicate that fluoride adsorption occurs immediately over the entire calcite surface with fluorite precipitating at step edges and kinks, where dissolved Ca2+ concentration is highest. The PHREEQ geochemical model was applied to the observed data and indicates that existing models, especially at low fluoride concentrations and high pH (>7.5) are not equipped to describe this complex system, largely because the PHREEQ model includes only precipitation reactions, whereas a combination of adsorption and precipitation parameters are required.

  3. Constraints on the vital effect in coccolithophore and dinoflagellate calcite by oxygen isotopic modification of seawater

    Science.gov (United States)

    Hermoso, Michaël; Horner, Tristan J.; Minoletti, Fabrice; Rickaby, Rosalind E. M.

    2014-09-01

    In this study, we show that there are independent controls of 18O/16O and 13C/12C fractionation in coccolithophore and dinoflagellate calcite due to the contrasting kinetics of each isotope system. We demonstrate that the direction and magnitude of the oxygen isotope fractionation with respect to equilibrium is related to the balance between calcification rate and the replenishment of the internal pool of dissolved inorganic carbon (DIC). As such, in fast growing cells, such as those of Emiliania huxleyi and Gephyrocapsa oceanica (forming the so-called ;heavy group;), calcification of the internal carbon pool occurs faster than complete isotopic re-adjustment of the internal DIC pool with H2O molecules. Hence, coccoliths reflect the heavy oxygen isotope signature of the CO2 overprinting the whole DIC pool. Conversely, in large and slow growing cells, such as Coccolithus pelagicus ssp. braarudii, complete re-equilibration is achieved due to limited influx of CO2 leading to coccoliths that are precipitated in conditions close to isotopic equilibrium (;equilibrium group;). Species exhibiting the most negative oxygen isotope composition, such as Calcidiscus leptoporus (;light group;), precipitate coccolith under increased pH in the coccolith vesicle, as previously documented by the ;carbonate ion effect;. We suggest that, for the carbon isotope system, any observed deviation from isotopic equilibrium is only ;apparent;, as the carbon isotopic composition in coccolith calcite is controlled by a Rayleigh fractionation originating from preferential incorporation of 12C into organic matter. Therefore, species with low PIC/POC ratios as E. huxleyi and G. oceanica are shifted towards positive carbon isotope values as a result of predominant carbon fixation into the organic matter. By contrast, cells with higher PIC/POC as C. braarudii and C. leptoporus maintain, to some extent, the original negative isotopic composition of the CO2. The calcareous dinoflagellate

  4. Calcite Precipitation at an Arctic Geothermal Spring Leads to Endolith Colonization and Ecological Succession

    Science.gov (United States)

    Starke, V.; Fogel, M. L.; Steele, A.

    2012-12-01

    A critical question in microbial ecology concerns how environmental conditions affect community makeup. Troll Springs, a geothermal spring at 79°23'N, 13°26'E on Svalbard in the high Arctic, provides an opportunity to study microbial communities and succession along steep environmental gradients that impose strong selective pressures. At Troll, warm water is released into cold, dry climate conditions. Precipitation of calcite from the spring's waters has built terraces that host a range of microbial communities. Microorganisms exist in warm water as periphyton, in moist granular materials, and in cold, dry rock as endoliths. Troll therefore has two distinct ecosystems, aquatic and terrestrial, in close proximity, with different underlying environmental factors shaping their microbial communities. We use microscopic and phylogeny-based molecular methods to study microbial community makeup at Troll Springs. Periphyton are entrapped by precipitation of calcite, becoming precursors for endolithic communities. Much of the pore space originally occupied by periphyton becomes inhabited either by organisms that were already present in minor quantities in the periphyton, or by new organisms that colonized an environment for which they were well suited. This process differs from most endolith colonization, where rock predates the communities that colonize it. In the aquatic environments, the strongest dependence of community makeup is on pH and temperature, with gradual changes in community makeup along a pH/temperature gradient among the pools. Illumination (as limited by calcite precipitation) and thermal stability also appear to exert influence. In contrast, in the granular and endolithic terrestrial environments, where water is scarce and therefore exerts selective pressure, there is a strong relationship between community makeup and water content. The richness, evenness, and diversity of microbial taxa are all strongly correlated at Troll Springs. These parameters all

  5. The Uptake of Eu(III) and Th(IV) by Calcite under Hyperalkaline Conditions

    International Nuclear Information System (INIS)

    Tits, J.; Wieland, E.; Bradbury, M.H.; Eckert, P.; Schaible, A.

    2002-10-01

    Calcite is an important component of Valanginian marl, a potential host rock for a low and intermediate level radioactive waste (L/ILW) repository in Switzerland. This mineral also forms an important component of the disturbed zone around a repository, as it remains largely unaffected by the hyperalkaline waters migrating out of the cementitious repository . The sorption behaviour of Eu(III) and Th(IV) on Merck calcite in an artificial cement pore water (ACW) at pH 13.3 has been studied in batch-type sorption experiments. In addition, the effect of α-isosaccharinic acid (ISA) and gluconic acid (GLU) on the sorption of these two cations has been investigated. In the absence of ISA and GLU, a strong interaction of Eu(III) and Th(IV) with Merck calcite was observed. Eu(III) and Th(IV) sorption kinetics were fast and the isotherms indicated a linear adsorption behaviour over the experimentally accessible concentration range. In the case of Eu(III), a decrease of the R d value with increasing solid to liquid (S:L) ratio was observed indicating that, along with adsorption, other processes might influence the immobilisation of this cation by Merck calcite under ACW conditions. In the case of Th(IV), however, changes in the S:L ratio had no effect on the sorption behaviour . High ISA and GLU concentrations in solution significantly affected the sorption of both Eu(III) and Th(IV): R d values for Eu(III) decreased significantly at ISA concentrations higher than 10 -5 M and at GLU concentrations higher than 10 -7 M. The sorption of Th(IV) was reduced at ISA concentrations above 2.10 -5 M and at GLU concentrations above 10 -6 M. The effects of ISA and GLU on the immobilisation of Eu(III) and Th(IV) were interpreted in terms of complex formation in solution. In the case of Eu(III) the metal ligand complexes were found to have a 1 : 1 stoichiometry. Complexation constants derived for the aqueous Eu(III)-ISA. and Eu(III)GLU complexes were determined to be logβ 0 EulSA = -31.1

  6. A comparison between acoustic properties and heat effects in biogenic (magnetosomes) and abiotic magnetite nanoparticle suspensions

    Energy Technology Data Exchange (ETDEWEB)

    Józefczak, A., E-mail: aras@amu.edu.pl [Institute of Acoustics, Faculty of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Leszczyński, B. [Institute of Acoustics, Faculty of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); NanoBioMedical Centre, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland); Skumiel, A.; Hornowski, T. [Institute of Acoustics, Faculty of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań (Poland)

    2016-06-01

    Magnetic nanoparticles show unique properties and find many applications because of the possibility to control their properties using magnetic field. Magnetic nanoparticles are usually synthesized chemically and modification of the particle surface is necessary. Another source of magnetic nanoparticles are various magnetotactic bacteria. These biogenic nanoparticles (magnetosomes) represent an attractive alternative to chemically synthesized iron oxide particles because of their unique characteristics and a high potential for biotechnological and biomedical applications. This work presents a comparison between acoustic properties of biogenic and abiotic magnetite nanoparticle suspensions. Experimental studies have shown the influence of a biological membrane on the ultrasound properties of magnetosomes suspension. Finally the heat effect in synthetic and biogenic magnetite nanoparticles is also discussed. The experimental study shows that magnetosomes present good heating efficiency. - Highlights: • A biogenic and abiotic magnetite nanoparticle suspensions are investigated. • A comparison between ultrasonic properties and heat effects is presented. • Magnetosomes and abiotic magnetite nanoparticles exhibit good heating efficiency.

  7. Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions

    DEFF Research Database (Denmark)

    Donahue, Neil M.; Henry, Kaytlin M.; Mentel, Thomas F.

    2012-01-01

    The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging signi