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Sample records for calcitic hydrated lime

  1. Effects of direct land application of calcitic lime and lime- and cement kiln dust-sanitized biosolids on the chemical and spectroscopic characteristics of soil lipids

    SciTech Connect

    Dinel, H.; Schnitzer, M.; Pare, T.; Topp, E. ); Lemee, L.; Ambles, A. . Lab. de Chimie); Pelzer, N. )

    1999-05-01

    To determine the extent to which applications of calcitic lime and sanitized biosolids affect the quality of soil organic matter (SOM), lipids extracted from an unamended soil (CON) and from soils amended with calcitic lime (CAL), and lime (LSB)- and cement kiln dust (CDB)-sanitized biosolids were characterized by chemical analysis and Pyrolysis-Gas chromatography (Py-GC). From diethyl ether (DEE) and CHCl[sub 3] soluble lipids, and from weight ratios of the extracts, the organic matter in the soil amended with CDB-treated biosolids seemed to be more biodegraded and biochemically inert than the organic matter in soils that received LSB-treated biosolids and calcitic lime and that in the control soil.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  3. Hydrated lime for metals immobilization and explosives transformation: Treatability study.

    PubMed

    Martin, W Andy; Larson, S L; Nestler, C C; Fabian, G; O'Connor, G; Felt, D R

    2012-05-15

    Fragmentation grenades contain Composition B (RDX and TNT) within a steel shell casing. There is the potential for off-site migration of high explosives and metals from hand grenade training ranges by transport in surface water and subsurface transport in leachate. This treatability study used bench-scale columns and mesocosm-scale laboratory lysimeters to investigate the potential of hydrated lime as a soil amendment for in situ remediation of explosives and metals stabilization in hand grenade range soils. Compared to the unamended soil there was a 26-92% reduction of RDX in the leachate and runoff water from the lime treated soils and a 66-83% reduction of zinc in the leachate and runoff water samples; where the hand grenade range metals of concern were zinc, iron, and manganese. The amended soil was maintained at the target pH of greater than 10.5 for optimum explosives decomposition. The treatability study indicated a high potential of success for scale-up to an in situ field study. PMID:22445717

  4. Internal friction of hydrated soda-lime-silicate glasses

    NASA Astrophysics Data System (ADS)

    Reinsch, S.; Mller, R.; Deubener, J.; Behrens, H.

    2013-11-01

    The internal friction of hydrated soda-lime-silica glasses with total water content (CW) up to 1.9 wt. % was studied by dynamic mechanical analysis (DMA) using temperature-frequency sweeps from 723 K to 273 K and from 1 s-1 to 50 s-1. Total water content and concentrations of H2O molecules (C_{H_2 O}) and OH groups (COH) in the DMA specimens were determined by infrared spectroscopy. For low water contents (CW ? COH < 0.25 wt. %) two discrete internal friction peaks below the glass transition (? relaxation) were assigned to the low-temperature motion of alkali ions (? relaxation) and cooperative movements of dissimilar mobile species under participation of OH at higher temperature (?OH relaxation). For large water contents (CW > 1 wt. %), where significant amounts of molecular water are evident (C_{H_2 O} > 0.15 wt. %), however, internal friction spectra change unexpectedly: the ?OH peak heights saturate and a low temperature shoulder appears on the ?-relaxation peak. This emerging relaxation mode (? _{H_2 O} relaxation) was assigned to the motions of H2O molecules. ? _{H_2 O} relaxation was found to be faster than ?OH but slower than ? relaxation. Activation energy of the different relaxation modes increased in the order ? < ? _{H_2 O} < ?OH < ?.

  5. Properties of waste soilhydrated lime composite

    NASA Astrophysics Data System (ADS)

    Lpez-Lara, T.; Horta-Rangel, J.; Hernndez-Zaragoza, J. B.; Castao, V. M.

    2006-06-01

    There are vast zones of clay soils which are generally extracted up to 3m deep (active layer). Owing to humidity variations throughout the year, this type of soil causes much damage to structures due to continuous changes in volume. Very often the clay is discarded and substituted by inert materials at the construction stage. The use of hydrated lime with this type of soil is a treatment that aims to inhibit the already volumetric instability by using the resulting mixture as inert material (Nelson, J.D., Miller, D.J.: Expansive Soils, Problems and Practice in Foundation and Pavement Engineering. John Wiley & Sons, Inc., USA, (1992)). Additionally, it is known that such a mixture also improves the strength properties, and it is possible to use it as a resistant inert composite, at low cost, for construction material. Nevertheless, due to the lack of tracking of this composite over time, safety issues related to the durability of such properties are uncertain. Because of the above, in this work, the composite was subjected to a constant exposure to temperature to simulate the evolution process of the composition on a laboratory scale, assuming that the acquired properties originate from the mineralogical composition created at the time of the sample. The permanence of such composition is associated to the properties acquired since the beginning.

  6. Disposal, recycle, and utilization of modified fly ash from hydrated lime injection into coal-fired utility boilers

    SciTech Connect

    Dahlin, R.S.; Lishawa, C.L.; Clark, C.C. ); Nolan, P.S. )

    1987-01-01

    This paper presents an assessment of the disposal, utilization, and recycle of a modified fly ash from the injection of hydrated lime into a coal-fired utility boiler. The hydrated lime injection process is being developed by the US Environmental Protection Agency (EPA) as a low-cost alternative for achieving moderate degrees of SO/sub 2/ control at coal-fired power plants. In this process, hydrated lime is injected into the upper furnace where the flue gas temperature is about 2200{sup 0}F (1200{sup 0}C). The hydrated lime decomposes, and the resulting quicklime, CaO, captures SO/sub 2/ according to a formula given.

  7. Advanced treatment of swine wastewater using an agent synthesized from amorphous silica and hydrated lime.

    PubMed

    Tanaka, Yasuo; Hasegawa, Teruaki; Sugimoto, Kiyomi; Miura, Keiichi; Aketo, Tsuyoshi; Minowa, Nobutaka; Toda, Masaya; Kinoshita, Katsumi; Yamashita, Takahiro; Ogino, Akifumi

    2014-01-01

    Advanced treatment using an agent synthesized from amorphous silica and hydrated lime (M-CSH-lime) was developed and applied to swine wastewater treatment. Biologically treated wastewater and M-CSH-lime (approximately 6 w/v% slurry) were fed continuously into a column-shaped reactor from its bottom. Accumulated M-CSH-lime gradually formed a bed layer. The influent permeated this layer and contacted the M-CSH-lime, and the treatment reaction progressed. Treated liquid overflowing from the top of the reactor was neutralized with CO?gas bubbling. The colour removal rate approximately exceeded 50% with M-CSH-lime addition rates of > 0.15 w/v%. The removal rate of PO(3?)(4) exceeded 80% with the addition of>0.03 w/v% of M-CSH-lime. The removal rates of coliform bacteria and Escherichia coli exceeded 99.9% with > 0.1 w/v%. Accumulated M-CSH-lime in the reactor was periodically withdrawn from the upper part of the bed layer. The content of citric-acid-soluble P?O? in the recovered matter was>15% when the weight ratio of influent PO(3?)(4) -P to added M-CSH-lime was > 0.15. This content was comparable with commercial phosphorus fertilizer. The inhibitory effect of recovered M-CSH-lime on germination and growth of leafy vegetable komatsuna (Brassica rapa var. perviridis) was evaluated by an experiment using the Neubauer's pot. The recovered M-CSH-lime had no negative effect on germination and growth. These results suggest that advanced water treatment with M-CSH-lime was effective for simultaneous removal of colour, [Formula: see text] and coliform bacteria at an addition rate of 0.03-0.15 w/v%, and that the recovered M-CSH-lime would be suitable as phosphorus fertilizer. PMID:25189846

  8. Low temperature steam curing hydration of lime-fly-ash compacts

    SciTech Connect

    Marcialis, A.; Massidda, L.; Sanna, U.

    1983-11-01

    Low pressure steam-curing hydration of mixtures with different fly ash-to-lime ratios compacted at 50 and 150 MPa was studied. The pastes were cured for between 8 and 72 h at 60, 75 and 90 degrees C. For comparative purposes duplicate samples were treated for 28 days at 25 degrees C. Compressive strength tests were performed on the hydrated samples and the results obtained compared with those pertaining to combined lime and porosity. Higher lime contents of the anhydrous mixtures correspond to greater amounts of reacted product and enhanced strengths. Higher temperature accelerates the reaction rate and produces a moderate increment in strength in passing from 75 to 90 degrees. This can be attributed to the corresponding increase in porosity of the specimens which contrasts with the positive effect produced by the progression of the pozzolanic reaction. 9 references.

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

    NASA Astrophysics Data System (ADS)

    Hein, James R.; Normark, William R.; McIntyre, Brandie R.; Lorenson, Thomas D.; Powell, Charles L., II

    2006-02-01

    Methane and hydrogen sulfide vent from a cold seep above a shallowly buried methane hydrate in a mud volcano located 24 km offshore southern California in 800 m of water. Bivalves, authigenic calcite, and methane hydrate were recovered in a 2.1 m piston core. Aragonite shells of two bivalve species are unusually depleted in 13C (to -19 ?13C), the most 13C-depleted shells of marine macrofauna yet discovered. Carbon isotopes for both living and dead specimens indicate that they used, in part, carbon derived from anaerobically oxidized methane to construct their shells. The ?13C values are highly variable, but most are within the range -12 to -19. This variability may be diagnostic for identifying cold-seep hydrate systems in the geologic record. Authigenic calcite is abundant in the cores down to 1.5 m subbottom, the top of the methane hydrate. The calcite is depleted in 13C (?13C = -46 to -58), indicating that carbon produced by anaerobically oxidized methane is the main source of the calcite. Methane sources include a geologic hydrocarbon reservoir from Miocene source rocks, and biogenic and thermogenic degradation of organic matter in basin sediments. Oxygen isotopes indicate that most calcite formed out of isotopic equilibrium with ambient bottom water, under the influence of gas hydrate dissociation and strong methane flux. High metal content in the mud volcano sediment indicates leaching of basement rocks by fluid circulating along an underlying fault, which also allows for a high flux of fossil methane.

  10. CONTROL OF SOX EMISSIONS BY IN-FURNACE SORBENT INJECTION: CARBONATES VS HYDRATES

    EPA Science Inventory

    The paper provides high-temperature isothermal data on SO2 capture by calcium-based sorbents, obtained in a dispersed-phase reactor for limestones, dolomites, hydrated calcitic limes, and hydrated dolomitic limes as a function of Ca/S molar ratio, temperature, and SO2 partial pre...

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

    USGS Publications Warehouse

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

    2006-01-01

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

  12. Evaluating slurried-hydrated lime pond-shoreline treatments for reducing populations of rams-horn snails

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Trematodes can cause massive infections in fish, and the most promising approach for the control of these infections is the reduction or elimination of snails that vector the trematodes. A recent approach, the application of high concentrations of slurried-hydrated lime (SHL) or copper sulfate pent...

  13. DISPOSAL, RECYCLE, AND UTILIZATION OF MODIFIED FLY ASH FROM HYDRATED LIME INJECTION INTO COAL-FIRED UTILITY BOILERS

    EPA Science Inventory

    The paper gives results of an assessment of the disposal, utilization, and recycle os a modified fly ash from the injection of hydrated lime into a coal-fired utility boiler. The process, developed as a low-cost alternative for achieving moderate degrees of SO2 control at coal-fi...

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

    NASA Astrophysics Data System (ADS)

    Marutschke, Christoph; Walters, Deron; Cleveland, Jason; Hermes, Ilka; Bechstein, Ralf; Khnle, Angelika

    2014-08-01

    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 basicyet decisivequestion 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.

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

    PubMed

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

    2014-08-22

    Calcite, the most stable modification of calcium carbonate, is a major mineral in nature. It is, therefore, highly relevant in a broad range of fields such as biomineralization, sea water desalination and oil production. Knowledge of the surface structure and reactivity of the most stable cleavage plane, calcite (10.4), is pivotal for understanding the role of calcite in these diverse areas. Given the fact that most biological processes and technical applications take place in an aqueous environment, perhaps the most basic - yet decisive - question addresses the interaction of water molecules with the calcite (10.4) surface. In this work, amplitude modulation atomic force microscopy is used for three-dimensional (3D) mapping of the surface structure and the hydration layers above the surface. An easy-to-use scanning protocol is implemented for collecting reliable 3D data. We carefully discuss a comprehensible criterion for identifying the solid-liquid interface within our data. In our data three hydration layers form a characteristic pattern that is commensurate with the underlying calcite surface. PMID:25074402

  16. Modeling dry-scrubbing of gaseous HCl with hydrated lime in cyclones with and without recirculation.

    PubMed

    Chibante, Vania G; Fonseca, Ana M; Salcedo, Romualdo R

    2010-06-15

    A mathematical model describing the dry-scrubbing of gaseous hydrogen chloride (HCl) with solid hydrated lime particles (Ca(OH)(2)) was developed and experimentally verified. The model applies to cyclone systems with and without recirculation, where reaction and particle collection occurs in the same processing unit. The Modified Grain Model was selected to describe the behavior of the reaction process and it was assumed that the gas and the solid particles flow in the reactor with a plug flow. In this work, this behavior is approximated by a cascade of N CSTRs in series. Some of the model parameters were estimated by optimization taking into account the experimental results obtained. A good agreement was observed between the experimental results and those predicted by the model, where the main control resistance is the diffusion of the gaseous reactant in the layer of solid product formed. PMID:20185231

  17. Simultaneous NO sub x /SO sub 2 removal by the dry injection of lime-urea hydrate

    SciTech Connect

    Muzio, L.J.; Himes, R.M.; Thompson, R.E.

    1990-03-01

    The attractiveness of dry SO{sub 2} removal processes may be enhanced if NO{sub x} could be removed along with SO{sub 2} using a single dry sorbent. A modified hydrate was developed that simultaneously removes SO{sub 2} and NO{sub x}. The hydrate is prepared by hydrating quicklime, CaO, with a urea water solution. Pilot-scale results of injecting this single dry lime-urea hydrate powder into a furnace are presented. An economic assessment was also conducted in order to ascertain the cost benefit derived from the simultaneous removal of SO{sub 2} and NO{sub x} with a single sorbent. The economics focused on the process as a retrofit technique on existing units. In order to provide a comparative basis with alternative technologies, the sensitivity of the levelized costs for the lime-urea hydrate were examined as a function of unite size; coal sulfur; capacity factor; and plant remaining life. These costs were normalized on a dollar per ton pollutant removed to facilitate a comparative assessment with alternative SO{sub 2} and NO{sub x} reduction technologies. Alternative technologies examined were comprised of combinations of wet flue gas desulfurization (FGD) and furnace sorbent injection (FSI) for SO{sub 2} reduction; and selective catalytic reduction (SCR), low-NO{sub x} burners (LNB), and Thermal DeNO{sub x} for NO{sub x} reductions. 38 refs., 50 figs., 32 tabs.

  18. Investigation of fatigue properties of granite asphalt mixtures containing hydrated lime

    NASA Astrophysics Data System (ADS)

    Wu, Shaopeng; Huang, Xu

    2009-12-01

    This paper presents the results of a laboratory study of evaluating the fatigue characteristics of granite asphalt mixtures (GAM) using different testing methods. In the study, the fatigue performances of GAM were evaluated with Superpave indirect tensile test (IDT) and four-point beam fatigue test. Specimens were conditioned by four different methods: (1) one cycle of freeze-thaw (F-T), (2) two cycles of F-T, (3) immersion in 60C water bath for 30min (4) immersion in 60C water bath for 48h, and contrastive analysis was made with unconditioned specimens. Investigation of moisture damage influence on the fatigue properties of GAM with and without Hydrated Lime (HL) was done. The results from this study indicated that both Superpave IDT and four-point beam fatigue test agreed with each other in ranking the fatigue property of GAM. Increasing F-T cycles or immersion time would decrease fatigue life in GAM, and the addition of HL was effective to prolong the fatigue life in GAM.

  19. Investigation of fatigue properties of granite asphalt mixtures containing hydrated lime

    NASA Astrophysics Data System (ADS)

    Wu, Shaopeng; Huang, Xu

    2010-03-01

    This paper presents the results of a laboratory study of evaluating the fatigue characteristics of granite asphalt mixtures (GAM) using different testing methods. In the study, the fatigue performances of GAM were evaluated with Superpave indirect tensile test (IDT) and four-point beam fatigue test. Specimens were conditioned by four different methods: (1) one cycle of freeze-thaw (F-T), (2) two cycles of F-T, (3) immersion in 60C water bath for 30min (4) immersion in 60C water bath for 48h, and contrastive analysis was made with unconditioned specimens. Investigation of moisture damage influence on the fatigue properties of GAM with and without Hydrated Lime (HL) was done. The results from this study indicated that both Superpave IDT and four-point beam fatigue test agreed with each other in ranking the fatigue property of GAM. Increasing F-T cycles or immersion time would decrease fatigue life in GAM, and the addition of HL was effective to prolong the fatigue life in GAM.

  20. Long-term effects of hydrated lime and quicklime on the decay of human remains using pig cadavers as human body analogues: Field experiments.

    PubMed

    Schotsmans, Eline M J; Fletcher, Jonathan N; Denton, John; Janaway, Robert C; Wilson, Andrew S

    2014-05-01

    An increased number of police enquiries involving human remains buried with lime have demonstrated the need for more research into the effect of different types of lime on cadaver decomposition and its micro-environment. This study follows previous studies by the authors who have investigated the effects of lime on the decay of human remains in laboratory conditions and 6 months of field experiments. Six pig carcasses (Sus scrofa), used as human body analogues, were buried without lime with hydrated lime (Ca(OH)2) and quicklime (CaO) in shallow graves in sandy-loam soil in Belgium and recovered after 17 and 42 months of burial. Analysis of the soil, lime and carcasses included entomology, pH, moisture content, microbial activity, histology and lime carbonation. The results of this study demonstrate that despite conflicting evidence in the literature, the extent of decomposition is slowed down by burial with both hydrated lime and quicklime. The more advanced the decay process, the more similar the degree of liquefaction between the limed and unlimed remains. The end result for each mode of burial will ultimately result in skeletonisation. This study has implications for the investigation of clandestine burials, for a better understanding of archaeological plaster burials and potentially for the interpretation of mass graves and management of mass disasters by humanitarian organisation and DVI teams. PMID:24513400

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

    SciTech Connect

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

    2014-11-15

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

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

    PubMed

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

    2011-11-01

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

  3. Effect of Planting Site Preparation, Hydrated Lime, and DBCP (1, 2-dibromo-3-chloropropane) on Populations of Macroposthonia xenoplax and Peach Tree Short Life in Georgia

    PubMed Central

    Wehunt, E. J.; Weaver, D. J.

    1982-01-01

    Annual postplanting applications of 40.7 kg/ha DBCP (1,2-dibromo-3-chloropropane) controlled Macroposthonia xenoplax (Raski, 1952) deGrisse and Loof, 1965 in peach tree short life sites, reduced bacterial canker incidence from 74% to 6%, and inreased the average life of the trees from 3.9 to 6.8 yr for a 7-yr test period. Hydrated lime at 5.5 kg per planting site reduced bacterial canker incidence from 81% 57 % and increased the tree longevity from 2.6 to 6.0 yr. Populations M. xenoplax were inversely correlated with tree longevity. PMID:19295753

  4. Trichloroethylene decomposition and in-situ dry sorption of Cl-products by calcium oxides prepared from hydrated limes.

    PubMed

    Gotoh, Yoshimi; Iwata, Goichi; Choh, Kyaw; Kubota, Mitsuhiro; Matsuda, Hitoki

    2011-10-01

    A comparison of CaOs produced by calcining two types of hydrated lime and calcium carbonate was made for decomposition of trichloroethylene and in-situ dry sorption of the decomposed Cl-products using a lab-scale gas flow type tubular packed bed reactor. About 20 mg of CaO sample was mixed with about 2 g of Al2O3 particles and packed in the reactor and allowed to react with a flowing standard gas containing 500 ppm of C2HCl3 (N2 balance) at 673 and 873 K, under the condition that the reaction of CaO with C2HCl3 might be completed within a few hours. It was found that no thermal decomposition of C2HCl3 at or below 673 K was observed in a reactor packed only with Al2O3 particles. However, a considerable amount of decomposition of C2HCl3 was obtained in a reactor packed with CaO and Al2O3, even at 673 K. For 1 mol of CaO prepared by calcining highly reactive Ca(OH)2 at 673 K, decomposition of 0.42 mol of C2HCl3 and in-situ absorption product of 0.53 mol of CaCl2 were obtained. At 873 K, about 46% of C2HCl3 was thermally decomposed. The total amount of C2HCl3 decomposed in CaO-Al2O3 particle bed at 873 K became nearly twice larger than that at 673 K. For 1 mol of CaO prepared by calcining highly reactive Ca(OH)2 at 873 K, decomposition of 0.59 mol of C2HCl3 and in-situ absorption product of 0.67 mol of CaCl2 were obtained. Small amounts of C2Cl2, C2Cl4, CCl4, etc. were detected during decomposition of C2HCl3 at 673 and 873 K. It was recognized that the data on decomposition of C2HCl3 as well as in-situ dry sorption of Cl-products in CaO particle bed were correlated with specific surface area of the CaO employed. PMID:21821273

  5. Genesis and geometry of the Meiklejohn Peak lime mud-mound, Bare Mountain Quadrangle, Nevada, USA: Ordovician limestone with submarine frost heave structures—a possible response to gas clathrate hydrate evolution

    NASA Astrophysics Data System (ADS)

    Krause, Federico F.

    2001-12-01

    During the Early Middle Ordovician (Early Whiterockian) the Meiklejohn Peak lime mud-mound, a large whaleback or dolphin back dome, grew on a carbonate ramp tens to hundreds of kilometres offshore. This ramp extended from the northwest margin of Laurentia into the open waters of the ancestral Pacific Ocean to the north. The mound developed in an outer ramp environment, in relatively deep and cold water. A steep northern margin with a slope that exceeds 55° characterizes the mound. This margin is split by a 14-m long vertical fracture that separates a zone of slumped, drag-folded and brecciated rocks from the main mass of the mound. Failure along this fracture occurred subcutaneously, as highlighted by covering beds that are folded next to the mound. Brecciated blocks and clasts contain zebra and stromatactis structures indicating that these rocks and structures were lithified early in the history of the mound. The southern end of the mound is less steep and is characterized by large, echinodermal grainstone cross-beds. These deposits are part of a large, subaqueous dune that grew northwards and preceded the main development of the mound. Southward dipping and downlapping layers of mud-mound mudstone and wackestone overlie the dune. These muddy limestone layers are cut in several places by injection dykes and are pierced, near the contact with the underlying dune, by a 25-m long pipe filled with rotated nodular and brecciated mud-mound clasts. This long pipe extends to the edge of the mound and appears to have been a conduit where fluidized materials that came from the mound's interior were vented. The interior of the mound is typified by light grey limestone with zebra bands and stromatactis structures. Both structures represent former cavity systems that are filled with fibrous and bladed calcite and pelleted and laminated geopetal mudstone. Spar bands of zebra limestone often extend for several metres and appear to have been unsupported over these distances. Zebra banded rocks are also accompanied by snout and socket structures and, in some instances, are folded and sheared by curving kink bands. Zebra and stromatactis limestone structures found throughout the mud-mound resemble frost heave and cryoturbation structures identified in both Holocene and Pleistocene cryosols, and in laboratory experiments with advancing freezing fronts in clay-size sediment. Significantly, modern occurrences of methane clathrate hydrate (methane-charged ice) display parallel and digitate layering similar in depositional appearance to that of zebra and stromatactis limestone from Meiklejohn Peak. Early carbonate cements are also commonly associated with these modern clathrate hydrate deposits. Consequently, gas clathrate hydrates may have been the propping agent for zebra and stromatactis structures observed in the mud-mound. In this scenario, carbonate cements would have precipitated and stabilized these structures, both with the consolidation and dissociation of gas clathrate hydrates, and with the oxidation and reduction of associated gases. Stable δ13C and δ18O isotope ratios collected from mudstone and spar of zebra and stromatactis structures indicate that they were lithified in equilibrium with Ordovician seawater. The δ13C isotope ratios recorded at Meiklejohn Peak are similar to δ13C isotopic ratios obtained from ∑CO 2 evolving from modern seafloor. These isotopic ratios may indicate that frost heave structures in the Meiklejohn Peak mud-mound are the result of consolidation and dissociation of carbon dioxide clathrate hydrates. Even though the bulk of gas clathrate hydrates identified to date in modern ocean floors are composed of methane, carbon dioxide clathrate hydrates are known from the modern seafloor of the Okinawa Trough. They may also be common in areas of abundant carbonate sediment accumulation, as suggested by recent observations from the Great Australian Bight.

  6. Kinetics of the reaction of hydrated lime with SO{sub 2} at low temperatures: effects of the presence of CO{sub 2}, O{sub 2}, and NOx

    SciTech Connect

    Liu, C.F.; Shih, S.M.

    2008-12-15

    The effects of the presence Of CO{sub 2}, O{sub 2}, and NOx in the flue gas on the kinetics of the sulfation of hydrated lime at low temperatures were studied using a differential fixed-bed reactor. When O{sub 2} and NOx were not present together the reaction kinetics was about the same as that under gas mixtures containing SO{sub 2}, H{sub 2}O, and N2 only. When both O{sub 2} and NOx were present, sulfation of hydrated lime was greatly enhanced, forming a large amount of calcium sulfate in addition to calcium sulfite. Sulfation of hydrated lime was well described by the surface coverage model, despite the gas-phase conditions being different. Relative humidity is the major factor affecting the reaction, and its effect was more marked when both O{sub 2} and NOx were present. The kinetic model equations obtained in this work can be used to describe the sulfation of hydrated lime in the low-temperature dry and semidry flue gas desulfurization processes with or without an upstream NOx removal unit.

  7. Evaluation of Ohio fly ash/hydrated lime slurries and Type 1 cement sorbent slurries in the U.C. Pilot spray dryer facility. Final report, September 1, 1993--August 31, 1994

    SciTech Connect

    Keener, T.C.; Khang, S.J.; Meyers, G.R.

    1995-02-01

    The objectives of this year`s work included an evaluation of the performance of fly ash/hydrated lime as well as hydrated cement sorbents for spray drying adsorption (SDA) of SO{sub 2} from a simulated high-sulfur flue gas. These sorbents were evaluated for several different hydration methods, and under different SDA operating conditions. In addition, the physical properties of surface area and porosity of the sorbents was determined. The most reactive fly ash/hydrated lime sorbent studied was prepared at room temperature with milled fly ash. Milling fly ash prior to hydration with lime did have a beneficial effect on calcium utilization. No benefit in utilization was experienced either by hydrating the slurries at a temperature of 90{degrees}C as compared to hydration at room temperature, or by increasing hydration time. While the surface areas varied greatly from sorbent to sorbent, the pore size distributions indicated ``ink bottle`` pores with surface porosity on the order of 0.5 microns. No correlation could be drawn between the surface area of the sorbents and calcium utilization. These results suggest that the composition of the resulting sorbent might be more important than its surface area. The most effective sorbent studied this year was produced by hydrating cement for 3 days at room temperature. This sorbent provided a removal efficiency and a calcium utilization over 25 percent higher than baseline results at an approach to saturation temperature of 30{degrees}F and a stoichiometric ratio of 0.9. A maximum SO{sub 2} removal efficiency of about 90 percent was experienced with this sorbent at an approach to saturation temperature of 20{degrees}F.

  8. Liming acid ponds in New York

    SciTech Connect

    Blake, L.M.

    1981-01-01

    Cost-benefit ratios are considered. Application of hydrated lime in New York State is limited to open-water periods for economic reasons. Hydrated lime is superior to the less potent agricultural lime, calcium carbonate, although the latter permits a longer time between treatments. No matter which type of lime is used, the lime is dumped from bags from a slowly moving boat. More lime is spread in shallow water areas than over deep water areas so that the lime is placed where the fish live and it is exposed more effectively to wave action and currents. The use of lime in remote areas is more difficult due to the high cost of transport. Possible increases in mercury content of fish after lime treatment were studied. Mercury levels were determined in brook trout from selected lakes, limed and unlimed. No increase in mercury levels was apparent in either limed or unlimed control waters. Costs for liming remote ponds range as high as $297 per acre. Experience with the dry dispersal method has shown that lime can be moved at a rate of 5 tons per hour. The average cost of this method should be about $100 per acre. It was concluded that for both accessible and remote ponds, liming is an effective and economically feasible tool which can be used to counteract the adverse impact of acid precipitation and maintain selected fisheries. 8 references, 1 figure, 2 tables.

  9. A Reacidification Model for Acidified Lakes Neutralized With Calcite

    NASA Astrophysics Data System (ADS)

    Sverdrup, Harald; Warfvinge, Per

    1985-09-01

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

  10. Nickel and manganese interaction with calcite

    SciTech Connect

    Doner, H; Zavarin, M

    1999-08-09

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

  11. [Study on Archaeological Lime Powders from Taosi and Yinxu Sites by FTIR].

    PubMed

    Wei, Guo-feng; Zhang, Chen; Chen, Guo-liang; He, Yu-ling; Gao, Jiang-tao; Zhang, Bing-jian

    2015-03-01

    Archaeological lime powders samples from Taosi and Yinxu sites, natural limestone and experimentally prepared lime mortar were investigated by means of Fourier transform infrared spectrometry (FTIR) to identify the raw material of lime powders from Taosi and Yinxu sites. Results show that ?2/?4 ratio of calcite resulted from carbonation reaction of man-made lime is around 6.31, which is higher than that of calcite in natural limestone and reflects the difference in the disorder of calcite crystal structure among the natural limestone and prepared lime mortar. With additional grinding, the values of v2 and ?4 in natural limestone and prepared lime mortar decrease. Meanwhile, the trend lines of ?2 versus ?4 for calcite in experimentally prepared lime mortar have a steeper slope when compared to calcite in natural limestone. These imply that ?2/?4 ratio and the slope of the trend lines of ?2 versus ?4 can be used to determine the archaeological man-made lime. Based on the experiment results, it is possible that the archaeological lime powder from Taosi and Yinxu sites was prepared using man-made lime and the ancient Chinese have mastered the calcining technology of man-made lime in the late Neolithic period about 4 300 years ago. PMID:26117865

  12. Microstructure and rheology of lime putty.

    PubMed

    Ruiz-Agudo, E; Rodriguez-Navarro, C

    2010-03-16

    The rheology of lime binders, which is critical in the final performance of lime mortars and plasters, is poorly understood, particularly in its relationship with the microstructure and colloidal characteristics of slaked lime (Ca(OH)(2)) suspensions (i.e., lime putties). Here, the contrasting flow behavior of lime putties obtained upon slaking (hydration) of soft and hard burnt quicklimes (CaO) is compared and discussed in terms of the differences found in particle size, morphology, degree of aggregation, and fractal nature of aggregates as well as their evolution with aging time. We show that lime putties behave as non-Newtonian fluids, with thixotropic and rheopectic behavior observed for hard and soft burnt limes, respectively. Aggregation of portlandite nanoparticles in the aqueous suspension controls the time evolution of the rheological properties of lime putty, which is also influenced by the dominant slaking mechanism, that is, liquid versus vapor slaking in hard and soft burnt quicklimes, respectively. These results may be of relevance in the selection of optimal procedures and conditions for the preparation of lime mortars used in the conservation of historical buildings. PMID:19916534

  13. An integrated study of limestone behavior during calcination and hydration processes

    NASA Astrophysics Data System (ADS)

    Leontakianakos, George; Baziotis, Ioannis; Kiousis, George; Giavis, Dimitrios; Tsimas, Stamatios

    2010-05-01

    One of the most important processes in industrial scale, represents the dissociation of carbonates to lime and CO2. This process, called calcination, occur at relative high temperatures (>9000C). Lime rapidly reacts with the water, liberating high amounts of heat producing Ca(OH)2. For the purpose of the present study five samples of different limestones from different quarries from Greece were collected. The aim of the study was to analyze the behavior of the limestones during calcination and test the hydraulic properties of the quick lime. Limestone particles (1.6-2 cm) were reacted in a pre-heated oven at three different temperatures (900, 1050 and 1200oC) for 30 min in order to produce quick lime. Petrographic features of studied limestones were done using secondary electron microscopy (SEM). X-ray diffractometry and Raman micro-spectroscopy were applied in order to identify the carbonate phases (calcite and dolomite) in the studied limestones. Chemical composition of limestones and limes were determined by Atomic absorption spectroscopy (AAS) method. 25 gr of the produced lime were hydrated by adding 100 ml distilled water having a room temperature (~250C) to produce Ca(OH)2 through the exothermic reaction CaO(s) + H2O(l)-Ca(OH)2(aq). We measured the temperature difference in the water until a maximum value is reached; this value represents the reactivity of the produced slaked lime. Chemical composition and reactivity estimation were done following European Standards EN-459-2. The reactivity of quick lime depends on various factors with the most important being the internal structure of the limestone, calcination temperature/duration applied to the limestone, the admixtures such as the MgO content, hard-burned phenomena etc. The treatment of the experimental results suggests the following: i) The (CaO+MgO)Lime value have similar variation for both samples calcined at temperatures of 1050oC (58-90 wt%) and 1200oC (57-94 wt%); whereas the samples calcined at 900oC share a small (CaO+MgO)Lime value (5-17wt%). ii) The limestones calcined at 9000C have the lowest reactivity values in oppose to the samples calcined at 10500C which show the highest reactivity. The temperature rise of the limestone samples calcined at 12000C was lower than that of the 10500C. iii) At constant reactivity rate the water required to complete hydration is lower; for example, the quick lime calcined at temperature of 10500C needs much less water for hydration relative to the equivalent samples at 12000C. A thorough interpretation of our results suggest that the low reactivity values for the samples calcined at 9000C could be due to the low calcination temperature or the calcination time of 30 min was too short to produce enough lime. The differences in hydraulic behavior of the samples calcined at higher temperatures of 12000C probably indicates that the structure of quick lime becomes more dense and compact and the grains recrystallized tending to become larger, leading to reduction of the existing pore space. Consequently, the hydration process cannot entirely proceed into the interior mass of the quick lime requiring more time to be accomplished.

  14. Pressure effect on magnesian calcite coating calcite and synthetic magnesian calcite seeds added to seawater in a closed system

    NASA Astrophysics Data System (ADS)

    Koch, B.; Disteche, A.

    1984-03-01

    When pure crystalline calcite seeds are added to supersaturated seawater, precipitation results in a coating which with time equilibrates at atmospheric pressure with seawater and corresponds to a calcite containing probably only 2 or 3% of MgCO 3 (mole fraction). If synthetic crystalline magnesian calcite is added, the surface layer equilibrates not only with respect to seawater but also in relation with the crystalline sites initiating precipitation. Adding Mg 0.03Ca 0.97CO 3 results in a coating with a solubility close to that of calcite. This confirms that the surface coating on pure calcite seeds contains about 2 or 3% MgCO 3 ( K' sp = 10-6.30). The surface layer precipitated on a synthetic Mg 0.08Ca 0.92CO 3 equilibrates finally with a carbonate more soluble than calcite ( K' sp = 10-5.94) corresponding to the seeds composition. Experiments at 1000 kg cm t-2 imply that when magnesian calcites are precipitated at the surface of calcite or magnesian calcite seeds, the precipitate must be hydrated, otherwise pressure accelerated recrystallization or rearrangement with loss of Mg would thermodynamically be impossible. By changing the pressure of a seawater sample originally saturated with a solid carbonate phase, changes in pH result from the effect of pressure on the dissociation constants of carbonic acid and boric acid causing either undersaturation or supersaturation with respect to the solid. By changing pressure we can show whether precipitation, dissolution and recrystallization are reversible processes if pH is taken as criteria of reversibility.

  15. Kinetics of the reaction of iron blast furnace slag/hydrated lime sorbents with SO{sub 2} at low temperatures: effects of the presence of CO{sub 2}, O{sub 2}, and NOx

    SciTech Connect

    Liu, C.F.; Shih, S.M.

    2009-09-15

    The effects of the presence of CO{sub 2}, O{sub 2}, and NOx in the flue gas on the kinetics of the sulfation of blast furnace slag/hydrated lime sorbents at low temperatures were studied using a differential fixed-bed reactor. When O{sub 2} and NOx were not present simultaneously, the reaction kinetics was about the same as that under the gas mixtures containing SO{sub 2}, H{sub 2}O, and N{sub 2} only, being affected mainly by the relative humidity. The sulfation of sorbents can be described by the surface coverage model and the model equations derived for the latter case. When both O{sub 2} and NOx, were present, the sulfation of sorbents was greatly enhanced, forming a great amount of sulfate in addition to sulfite. The surface coverage model is still valid in this case, but the model equations obtained show a more marked effect of relative humidity and negligible effects of SO{sub 2} concentration and temperature on the reaction. The effect of sorbent composition on the reaction kinetics was entirely represented by the effects of the initial specific surface area (S{sub g0}) and the Ca molar content (M{sup -1}) of sorbent. The initial conversion rate of sorbent increased linearly with increasing S{sub g0}, and the ultimate conversion increased linearly with increasing S{sub g0}M{sup -1}. The model equations obtained in this work are applicable to describe the kinetics of the sulfation of the sorbents in the low-temperature dry and semidry fine gas desulfurization processes either with an upstream NOx, removal unit or without.111

  16. High surface area calcite

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

  17. The mechanism of vapor phase hydration of calcium oxide: implications for CO2 capture.

    PubMed

    Kudłacz, Krzysztof; Rodriguez-Navarro, Carlos

    2014-10-21

    Lime-based sorbents are used for fuel- and flue-gas capture, thereby representing an economic and effective way to reduce CO2 emissions. Their use involves cyclic carbonation/calcination which results in a significant conversion reduction with increasing number of cycles. To reactivate spent CaO, vapor phase hydration is typically performed. However, little is known about the ultimate mechanism of such a hydration process. Here, we show that the vapor phase hydration of CaO formed after calcination of calcite (CaCO3) single crystals is a pseudomorphic, topotactic process, which progresses via an intermediate disordered phase prior to the final formation of oriented Ca(OH)2 nanocrystals. The strong structural control during this solid-state phase transition implies that the microstructural features of the CaO parent phase predetermine the final structural and physicochemical (reactivity and attrition) features of the product hydroxide. The higher molar volume of the product can create an impervious shell around unreacted CaO, thereby limiting the efficiency of the reactivation process. However, in the case of compact, sintered CaO structures, volume expansion cannot be accommodated in the reduced pore volume, and stress generation leads to pervasive cracking. This favors complete hydration but also detrimental attrition. Implications of these results in carbon capture and storage (CCS) are discussed. PMID:25233236

  18. Flash calcining system converts waste lime to usable products while running on gas, oil or coal

    SciTech Connect

    Not Available

    1982-07-01

    This article focuses on the energy efficiency of a flash calcining system which converts waste lime to usable products while running on gas, oil, or coal. The flash calciner can turn significant amounts of undercalcined and normally wasted lime into useful products such as hydrated lime, soil stabilizers and neutralizers. The system has demonstrated that waste fines and dust can be processed into a product having less than two percent loss-on-ignition.

  19. Calcite (1 0 1 4) surface in humid environments

    NASA Astrophysics Data System (ADS)

    Baltrusaitis, Jonas; Grassian, Vicki H.

    2009-09-01

    In this study, alternating current (AC) mode Atomic Force Microscopy (AFM) height images combined with force measurements and phase imaging were used to investigate the surface reconstruction and chemistry of the lowest energy surface, (1 0 1 4) plane, of calcite, a stable form of calcium carbonate (CaCO 3), in the presence of relative humidity at different temperatures. At 296 K and 70% RH, calcite (1 0 1 4) undergoes rapid restructuring during hydration forming regions on the surface that are most likely characterized as an amorphous hydrate layer similar to what forms in solution under high [Ca 2+] supersaturation conditions. This hydrate layer in turn serves as a substrate for the crystallization of another layer that possesses structural properties which differ from hydrate layer. Phase imaging reveals that these different layer structures formed in the process of water adsorption and surface reconstruction have very different energy dissipation modes. The origin of the different dissipation modes are likely due to differences in water content and hydrophobicity of these regions. The newly formed layer on top of the hydration layer is proposed to be vaterite, another polymorph of calcium carbonate. At 278 K the formation mechanism of the vaterite layer changes due to nucleation of a more crystalline hydrate layer, similar to calcium carbonate hexahydrate, instead of the amorphous hydrate layer that forms at 296 K. Force measurements corroborate the assignment of the speciation of different regions on the surface. Importantly, the AFM data show that the surface of calcite is highly inhomogeneous with regions that vary in water content. This suggests that the reactivity of calcite in humid environments will be highly spatially dependent.

  20. LIMESTONE AND LIME NEUTRALIZATION OF FERROUS IRON ACID MINE DRAINAGE

    EPA Science Inventory

    The U.S. Environmental Protection Agency conducted a 2-yr study on hydrated lime and rock-dust limestone neutralization of acid mine drainage containing ferrous iron at the EPA Crown Mine Drainage Control Field Site near Rivesville, West Virginia. The study investigated optimizat...

  1. Elastic constants of calcite

    USGS Publications Warehouse

    Peselnick, L.; Robie, R.A.

    1962-01-01

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

  2. Uranyl incorporation in natural calcite.

    SciTech Connect

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

    2003-01-01

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

  3. Hydrate detection

    SciTech Connect

    Dillon, W.P.; Ahlbrandt, T.S.

    1992-06-01

    Project objectives were: (1) to create methods of analyzing gas hydrates in natural sea-floor sediments, using available data, (2) to make estimates of the amount of gas hydrates in marine sediments, (3) to map the distribution of hydrates, (4) to relate concentrations of gas hydrates to natural processes and infer the factors that control hydrate concentration or that result in loss of hydrate from the sea floor. (VC)

  4. Hydrate detection

    SciTech Connect

    Dillon, W.P.; Ahlbrandt, T.S.

    1992-01-01

    Project objectives were: (1) to create methods of analyzing gas hydrates in natural sea-floor sediments, using available data, (2) to make estimates of the amount of gas hydrates in marine sediments, (3) to map the distribution of hydrates, (4) to relate concentrations of gas hydrates to natural processes and infer the factors that control hydrate concentration or that result in loss of hydrate from the sea floor. (VC)

  5. LIME 0.5

    Energy Science and Technology Software Center (ESTSC)

    2011-01-14

    LIME 0.5 is an initial version of a Lightweight Integrating Multi-physics Environment for coupling codes. LIME by itself is not a code for doing multiphysics simulations. Instead, LIME provides the key high-level software, a flexible but defined approach, and interface requirements for a collection of (potentially disparate) physics codes to be combined with strong coupling (when needed) though non-linear solution methods (e.g. JFNK, fixed point), thus creating a new multi-physics simulation capability customized for amore » particular need. ! ! The approach taken is designed to! •! preserve and leverage any important specialized algorithms and/or functionality an existing application may provide,! •! minimize the requirements barrier for an application to participate,! •! work within advanced solver frameworks (e.g. as extensions to the Trilinos/NOX nonlinear solver libraries, PETSc, . . .),! Of note is that components/physics codes that can be coupled within LIME are NOT limited to:! •! components written in one particular language,! •! a particular numerical discretization approach ( e.g. Finite Element), or! •! physical models expressed as PDEʼs.!« less

  6. LIME 0.5

    SciTech Connect

    2011-01-14

    LIME 0.5 is an initial version of a Lightweight Integrating Multi-physics Environment for coupling codes. LIME by itself is not a code for doing multiphysics simulations. Instead, LIME provides the key high-level software, a flexible but defined approach, and interface requirements for a collection of (potentially disparate) physics codes to be combined with strong coupling (when needed) though non-linear solution methods (e.g. JFNK, fixed point), thus creating a new multi-physics simulation capability customized for a particular need. ! ! The approach taken is designed to! ?! preserve and leverage any important specialized algorithms and/or functionality an existing application may provide,! ?! minimize the requirements barrier for an application to participate,! ?! work within advanced solver frameworks (e.g. as extensions to the Trilinos/NOX nonlinear solver libraries, PETSc, . . .),! Of note is that components/physics codes that can be coupled within LIME are NOT limited to:! ?! components written in one particular language,! ?! a particular numerical discretization approach ( e.g. Finite Element), or! ?! physical models expressed as PDE?s.!

  7. Fluidized bed combustion residue as an alternative liming material and Ca source. [Prunus persica

    SciTech Connect

    Edwards, J.H.; Horton, B.D.; White, A.W. Jr.; Bennett, O.L.

    1985-01-01

    Fluidized bed combustion residue (FBCR), a by-product of fossil fuel fired boilers, was evaluated as a liming material and a source of calcium for peaches (Prunus persica (L.) Batsch). Incubation studies involving a medium textured soil indicated that FBCR (calcite (FBCRC) or dolomitic (FBCRD) sources) was as effective a liming amendment as the respective agricultural limestone. Maximum soil pH occurred after 26 days incubation with FBCRC, but soil pH increased continuously throughout 137 days incubation with dolomitic limestone. Ammonium acetate extractable Ca was not affected by calcitic source, but Mg concentration increased with rates with the two dolomitic sources, and was highest in the FBCRD source after 137 days incubation. In greenhouse studies with Elberta peach seedlings, FBCRC was more effective in neutralizing soil acidity and increasing extractable soil Ca than calcitic limestone.

  8. Water transfer properties and shrinkage in lime-based rendering mortars

    NASA Astrophysics Data System (ADS)

    Arizzi, A.; Cultrone, G.

    2012-04-01

    Rendering is the practice of covering a wall or a building faade with one or more layers of mortar, with the main aim to protect the masonry structure against weathering. The render applied must show high flexibility, good adhesion and compatibility with the support (i.e. stone, brick) and, overall, it should be characterised by low water absorption and high water vapour permeability. Water (in the solid, liquid and vapour state) is one of the main factors that drive construction materials to deterioration. Therefore, to evaluate the quality and durability of a rendering mortar, thus ensuring its protective function in the masonry structure, it is fundamental to assess the behaviour of this mortar towards water. Mortars were elaborated with a calcitic dry hydrated lime, a calcareous aggregate, a pozzolan, a lightweight aggregate, a water-retaining agent and a plasticiser. Four types of lime mortars were prepared, in which the binder-to-aggregate ratios were 1:3, 1:4, 1:6 and 1:9 by weight, whilst the pozzolan was kept at 10% of the lime (by mass) and the total admixtures proportion was less than 2% of the total mass. The influence of the characteristics of mortars pore system on the amount of water absorbed and the kinetics of absorption was investigated by means of: free water absorption and drying; capillary uptake; water permeability; water vapour permeability. Interesting deductions can be made from the values of water and water vapour permeability found for mortars: the former increases exponentially with the sand volume of the mortar, whilst the latter increases almost exponentially with the initial water content added to the mortar mixes during their elaboration. However, the relationship obtained between porosity of mortars and permeability values is not really clear. This finding suggests that the permeability of a material cannot be estimated on the basis of its porosity as it can be made for the capillary uptake and free water absorption. Another aspect to be considered in the evaluation of the decay caused by water is the high shrinkage suffered by renders when they are applied on an extended surface (i.e. a wall), especially when they are aerial lime-based mortars. The shrinkage causes the formation of fissures that become an easy way for water to entry and diffuse through the mortar pore system. This factor is rarely taken into consideration during the hydric assays performed in the laboratory, since mortar samples of 4x4x16 or 4x4x4 cm in size do not undergo to such degree of shrinkage. For this reason, we have also studied the shrinkage of these mortars and considered it in the final assessment of mortars hydric properties. The shrinkage was evaluated according to a non-standardized method, by means of a shrinkage-measuring device that measures the mortar dimensional variations over time. This measurement has shown that the highest the lime content the biggest the mortar shrinkage and, consequently, the strongest the decay due to water.

  9. Tracing formation and durability of calcite in a Punic-Roman cistern mortar (Pantelleria Island, Italy).

    PubMed

    Dietzel, Martin; Schön, Frerich; Heinrichs, Jens; Deditius, Artur P; Leis, Albrecht

    2016-01-01

    Ancient hydraulic lime mortar preserves chemical and isotopic signatures that provide important information about historical processing and its durability. The distribution and isotopic composition of calcite in a mortar of a well-preserved Punic-Roman cistern at Pantelleria Island (Italy) was used to trace the formation conditions, durability, and individual processing periods of the cistern mortar. The analyses of stable carbon and oxygen isotopes of calcite revealed four individual horizons, D, E, B-1 and B-2, of mortar from the top to the bottom of the cistern floor. Volcanic and ceramic aggregates were used for the production of the mortar of horizons E/D and B-1/B-2, respectively. All horizons comprise hydraulic lime mortar characterized by a mean cementation index of 1.5 ± 1, and a constant binder to aggregate ratio of 0.31 ± 0.01. This suggests standardized and highly effective processing of the cistern. The high durability of calcite formed during carbonation of slaked lime within the matrix of the ancient mortar, and thus the excellent resistance of the hydraulic lime mortar against water, was documented by (i) a distinct positive correlation of δ(18)Ocalcite and δ(13)Ccalcite; typical for carbonation through a mortar horizon, (ii) a characteristic evolution of δ(18)Ocalcite and δ(13)Ccalcite through each of the four mortar horizons; lighter follow heavier isotopic values from upper to lower part of the cistern floor, and (iii) δ(18)Ocalcite varying from -10 to -5 ‰ Vienna Pee Dee belemnite (VPDB). The range of δ(18)Ocalcite values rule out recrystallization and/or neoformation of calcite through chemical attack of water stored in cistern. The combined studies of the chemical composition of the binder and the isotopic composition of the calcite in an ancient mortar provide powerful tools for elucidating the ancient techniques and processing periods. This approach helps to evaluate the durability of primary calcite and demonstrates the importance of calcite as a proxy for chemical attack and quality of the ancient inorganic binder. PMID:25760891

  10. COMBINATION LIMESTONE-LIME NEUTRALIZATION OF FERROUS IRON ACID MINE DRAINAGE

    EPA Science Inventory

    Studies were conducted on ferrous-iron acid mine drainage (AMD) treatment by a two-step neutralization process in which rock-dust limestone was mixed with the influent AMD and then hydrated lime was added in a polishing reactor. This combination treatment process resulted in reag...

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  12. Depositional environments and original mineralogy of the lower Smackover lime mudstones, Mississippi salt basin

    SciTech Connect

    Heydari, E.; Wade, W.J. . Basin Research Inst. and Dept. of Geology)

    1992-01-01

    Three lithofacies are recognized in the lower member of the Smackover Formation. In ascending order these are: (1) laminated mudstone, consisting of alternating dark and light colored laminae, (2) thin-bedded mudstone, containing alternating beds of dark, laminated mudstone and light, bioturbated mudstone, and (3) burrowed mudstone, consisting of massive, wispy laminated mudstone. Basinward mudstones are composed of small calcite crystals (2-15 [mu]m), with Sr and [delta] O-18 compositions of 300 ppm and [minus]4.0 % PDB, respectively. The more landward mudstones are composed of larger calcite crystals (10-80 [mu]m), with Sr and [delta] O-18 contents of 1300 ppm and [minus]2.0% PDB, respectively. Absence of current-induced structures and nektoplanktonic fossils, perfect preservation of laminae, and abundant early anhydrite indicate that the laminated mudstone lithofacies was deposited below fair weather wave base in anoxic and hypersaline bottom water, possibly as annual varves. The alternating dark, laminated and light, bioturbated beds within the thin-bedded lithofacies may represent redox cycles caused by productivity fluctuations in the basin. Ubiquitous bioturbation in the burrowed mudstone lithofacies indicates that a transition from anoxic to oxic or suboxic conditions had occurred. Landward increase in crystal size and Sr composition resulted from differences in original mineralogy of the lime mud precursor, with originally aragonite lime mud precipitating landward, and originally calcite lime mud basinward. Landward increase in [delta]O-18 composition of the mudstone reflects shoreward increase in seawater salinity. This salinity gradient may have been partially responsible for the change in mineralogy of the lime mud. Lack of fossils, the anoxic nature of bottom water in the basin, and the systematic shift in mineralogy and geochemical signatures suggest that lime mud was precipitated inorganically.

  13. Fullerenol entrapment in calcite microspheres.

    PubMed

    Calvaresi, Matteo; Falini, Giuseppe; Bonacchi, Sara; Genovese, Damiano; Fermani, Simona; Montalti, Marco; Prodi, Luca; Zerbetto, Francesco

    2011-10-14

    Hybrid microspheres of calcium carbonate/fullerenol were synthesized and characterized. Their morphology depends on the concentration of the fullerenol solutions. XRD and FT-IR measurements proved that the mineral phase is consistently calcite, while fluorescence confocal microscopy indicated that fullerenol is homogenously included in the crystalline matrix. PMID:21881667

  14. A study on engineering characteristics of asphalt concrete using filler with recycled waste lime.

    PubMed

    Sung Do, Hwang; Hee Mun, Park; Suk keun, Rhee

    2008-01-01

    This study focuses on determining the engineering characteristics of asphalt concrete using mineral fillers with recycled waste lime, which is a by-product of the production of soda ash (Na(2)CO(3)). The materials tested in this study were made using a 25%, 50%, 75%, and 100% mixing ratio based on the conventional mineral filler ratio to analyze the possibility of using recycled waste lime. The asphalt concretes, made of recycled waste lime, hydrated lime, and conventional asphalt concrete, were evaluated through their fundamental engineering properties such as Marshall stability, indirect tensile strength, resilient modulus, permanent deformation characteristics, moisture susceptibility, and fatigue resistance. The results indicate that the application of recycled waste lime as mineral filler improves the permanent deformation characteristics, stiffness and fatigue endurance of asphalt concrete at the wide range of temperatures. It was also determined that the mixtures with recycled waste lime showed higher resistance against stripping than conventional asphalt concrete. It was concluded from various test results that a waste lime can be used as mineral filler and, especially, can greatly improve the resistance of asphalt concrete to permanent deformation at high temperatures. PMID:17408942

  15. Gas hydrates

    SciTech Connect

    Not Available

    1985-04-01

    There is a definite need for the US government to provide leadership for research in gas hydrates and to coordinate its activities with academia, industry, private groups, federal agencies, and their foreign counterparts. In response to this need, the DOE Morgantown Energy Technology Center implemented a gas hydrates R and D program. Understanding the resource will be achieved through: assessment of current technology; characterization of gas hydrate geology and reservoir engineering; and development of diagnostic tools and methods. Research to date has focused on geology. As work progressed, areas where gas hydrates are likely to occur were identified, and specific high potential areas were targeted for future detailed investigation. Initial research activities involved the development of the Geologic Analysis System (GAS); which will provide, through approximately 30 software packages, the capability to manipulate and correlate several types of geologic and petroleum data into maps, graphics, and reports. Preliminary mapping of hydrate prospects for the Alaskan North Slope is underway. Geological research includes physical system characterization which focuses on creating synthetic methane hydrates and developing synthetic hydrate cores using tetrahydrofuran, consolidated rock cores, frost base mixtures, water/ice base mixtures, and water base mixtures. Laboratory work produced measurements of the sonic velocity and electrical resistivity of these synthetic hydrates. During 1983, a sample from a natural hydrate core recovered from the Pacific coast of Guatemala was tested for these properties by METC. More recently, a natural hydrate sample from the Gulf of Mexico was also acquired and testing of this sample is currently underway. In addition to the development of GAS, modeling and systems analysis work focused on the development of conceptual gas hydrate production models. 16 figs., 6 tabs.

  16. Structure and phase investigations on crystallization of 11 A tobermorite in lime sand pellets

    SciTech Connect

    Hartmann, A. . E-mail: a.hartmann@tudelft.nl; Buhl, J.-Ch.; Breugel, K. van

    2007-01-15

    The present work examines the crystallization behaviour of 11 A tobermorite and its dependence on the reactivity of different silica sources (quartz sand, grain-size {<=} 0.30 mm; quartz powder, grain-size {<=} 0.08 mm; inflated clay sand, grain-size {<=} 0.50 mm and raw perlite, grain-size {<=} 1 mm). The influence of different C/S ratios (calcium/silica ratio: 0.53, 0.83) was also investigated. For simulation of the industrial production process of lime sand products, a synthesis of lime sand pellets was carried out with a hydrothermal treatment (T = 200 deg. C, t = 40.5 h). The C-S-H phases were characterized by ESEM, EDX and X-ray powder diffraction. The investigations revealed that the grain-size, C/S ratio and porosity of the silica sources influence the formation of 11 A tobermorite. A formation of 11 A tobermorite using inflated clay sand with a grain-size {<=} 0.50 mm and a high porosity was only found with a C/S ratio of 0.53. This indicates a negative influence of an increase of lime content inside the synthesis mixture for tobermorite crystallization. Besides, a formation of xonotlite inside big pores of the lime sand pellet with inflated clay sand could be observed. The formation of portlandite and calcite was detected in all samples. The amount of calcite increased with the grain-size and with a higher C/S ratio.

  17. Lime pretreatment of lignocellulosic biomass

    NASA Astrophysics Data System (ADS)

    Chang, Shushien

    Lignocellulose is a valuable alternative energy source. The susceptibility of lignocellulosic biomass to enzymatic hydrolysis is constrained due to its structural features, so pretreatment is essential to enhance enzymatic digestibility. Of the chemicals used as pretreatment agents, it has been reported that alkalis improve biomass digestibility significantly. In comparison with other alkalis such as NaOH and ammonia, lime (calcium hydroxide) has many advantages; it is very inexpensive, is safe, and can be recovered by carbonating wash water. The effects of lime pretreatment were explored on switchgrass and poplar wood, representing herbaceous and woody biomass, respectively. The effects of pretreatment conditions (time, temperature, lime loading, water loading, particle size, and oxygen pressure) have been systematically studies. Lime alone enhances the digestibility of switchgrass significantly; under the recommended conditions, the 3-d total sugar (glucose + xylose) yields of lime-treated switchgrass were 7 times that of untreated sample. When treating poplar wood, lime must be combined with oxygen to achieve high digestibility; oxidative lime pretreatment increased the 3-d total sugar yield of poplar wood to 12 times that of untreated sample. In a fundamental study, to determine why lime pretreatment is effective, the effects of three structural features on enzymatic digestibility were studied: lignin content, acetyl content, and crystallinity index (CrI). Poplar wood was treated with peracetic acid, potassium hydroxide, and ball milling to produce model lignocelluloses with a broad spectrum of lignin contents, acetyl contents, and CrI, respectively. Enzymatic hydrolysis was performed on the model lignocelluloses to determine the digestibility. Correlations between lignin/carbohydrate ratio, acetyl/carbohydrate ratio, CrI and digestibility were developed. The 95% prediction intervals show that the correlations predict the 1-h and 3-d total sugar conversions of a biomass sample within a precision of 5% and 20%, respectively. The digestibility of a variety of lime-treated biomass and ball-milled alpha-cellulose was compared to the correlations determined from the model compounds. The agreement between the measured and predicted values shows that the correlations are satisfactory and the three structural features---lignin content, acetyl content, and CrI---are the major factors that determine enzymatic digestibility.

  18. Gas hydrates

    SciTech Connect

    Berecz, E.; Balla-Achs, M.

    1983-01-01

    In the presence of water, particularly at low temperatures, many industrial gas systems under pressure tend to form solid crystalline compounds. These compounds are referred to as gas hydrates, and result from the association of the gas molecules with water. This book draws attention to the theoretical, practical and technological aspects of this interesting and important class of compounds. The topics covered include the structures, properties and thermodynamic characteristics of the gas hydrates, the changes induced in the equilibrium conditions by additives, and the methods and studies relating to the prevention and elimination of hydrate plugs in technological operations with industrial gases. In the discussion of the technological aspects, special emphasis is given to the production and transportation of natural gas and to the application of freon coolants. Such questions as the possibility of the desalination of seawater and the formation of gas hydrates in interplanetary space are also dealt with.

  19. Structure of the (1014) Surfaces of Calcite, Dolomite, and Magnesite under Wet and Dry Conditions

    SciTech Connect

    WRIGHT,KATE; CYGAN,RANDALL T.; SLATER,BEN

    2000-06-12

    Atomistic computer simulation methods have been employed to model the structure of the (10{bar 1}4) surfaces of calcite, dolomite and magnesite. The authors calculations show that under vacuum conditions, calcite undergoes the greatest degree of surface relaxation with rotation and distortion of the carbonate group accompanied by movement of the calcium ion. The magnesite surface is the least distorted of the three carbonates, with dolomite being intermediate to the two end members. When water molecules are placed on the surface to produce complete monolayer coverage, the calcite surface is stabilized and the amount of relaxation is substantially reduced. In contrast, the dolomite and magnesite surfaces are destabilized by hydration as indicated by a significant increase in the surface energies relative to the dry surface.

  20. Shock-induced devolatilization of calcite

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Astrophysics Data System (ADS)

    Mkhonto, D.; Sahai, N.

    2008-12-01

    Organic molecules of a wide range of molecular weights from small organic acids, amino-acids, acidic peptides and acidic proteins to humic and fulvic acids play a key role in modulating nucleation, crystal growth and dissolution of calcium carbonate polymorphs. In general, these acidic molecules inhibit calcite growth and, promote dissolution preferentially along specific crystallographic directions, in the process, regulating crystal shape and size, and even whether a metastable polymorph (e.g., vaterite or aragonite) is nucleated first. For example, chiral faces of calcite are selected by chiral amino-acids and the unusual {hk0} faces are expressed in the presence of amino-acids [Orme et al., 2001], and unusual heptagonal dissolution etch-pit are seen in the presence of succinate compared to the normal rhombohedral pits in water alone [Teng et al., 2006]. Thus, the presence of unusual crystal morphologies may indicate organic-mediated growth, thus serving as a biosignature. We have conducted the Molecular Dynamics (MD) simulations using the Consistent Valence Force Field (CVFF) as implemented in the FORCITE module of the Materials Studio software package (Accelrys, Inc. TM) to model the adsorption of succinate, a dicarboxylic acid, and charge- balancing Na+ ions on dry and hydrated steps in different directions on the {104} cleavage face of calcite [Mkhonto and Sahai, in prep.]. At the site of succinate adsorption, we find elongation of the interatomic distances (Ca-OCO3,i) between surface Ca2+ cation and the oxygen of the underlying inorganic CO32- anion the first surface layer of calcite, compared to the corresponding distances in the presence of water alone, suggesting greater ease of surface Ca2+ detachment. This result is consistent with the empirically observed increase in overall dissolution rate with succinate [Teng et al., 2006]. Furthermore, succinate adsorption lowers the step energies, which explains the appearance of steps in the unsusual [42-1] and [010] directions in the presence of succinate as observed by Atomic Force Microscopy [Teng et al., 2006]. Finally, the calculated succinate adsorption energies at hydrated steps decreases in the sequence [-441] > [42-1] > [010], which also corresponds to the sequence of steps opening at dissolution etch-pits in the presence of succinate [Teng et al., 2006]. Our study provides a strong example of the utility of MD simulations in exploring organic-mediated mineral crystal dissolution (and growth) mechanisms, resulting in unusual morphologies, that may serve as biosignatures on Earth, and potentially on Mars and other worlds.

  2. Stabilities of calcite and aragonite

    USGS Publications Warehouse

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

    1974-01-01

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

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

    USGS Publications Warehouse

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

    1987-01-01

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

  4. Effect of calcite on lead-rich cementitious solid waste forms

    SciTech Connect

    Lee, Dongjin; Swarbrick, Gareth; Waite, T. David . E-mail: D.waite@unsw.edu.au

    2005-06-01

    The effect of calcite on lead-rich solidified waste forms generated using Portland cement has been investigated. Samples of cementitious wastes in the absence and presence of Pb and in the absence and presence of calcite were examined separately at 2, 7, 14 and 28 days of hydration by X-ray diffraction and SEM/EDS and for compressive strength. The presence of lead was observed to produce lead carbonate sulfate hydroxide (Pb{sub 4}SO{sub 4}(CO{sub 3}){sub 2}(OH){sub 2}), lead carbonate hydroxide hydrate (3PbCO{sub 3}.2Pb(OH){sub 2}.H{sub 2}O) and two other unidentified lead salts in cavity areas, and was observed to significantly retard the hydration of cement. Calcite addition to the Pb wastes was found to induce the rapid crystallization of calcium hydroxide coincident with the onset of C-S-H gel germination. The rapid dissolution of lead precipitates was observed with the subsequent development of very insoluble gel products of the form C-Pb-S-H. These products are formed by chemical incorporation of re-dissolved Pb species into silicate structures.

  5. Metallurgical properties of iron-bearing lime

    SciTech Connect

    Sokolova, T.G.; Khaidukov, V.P.; Markov, B.L.; Trubnikov, A.A.; Dereza, V.P.

    1988-05-01

    The Novolipetsk Metallurgical Combine developed a technology for producing iron-bearing lime by the combined calcining of limestone and converter slag in kilns. The resulting flux was a lumpy two-layer product with a core consisting of high reactivity lime and a surrounding shell of calcium ferrites. Compared to conventional lime, iron-bearing lime has smaller losses during calcining and contains less sulfur and more iron oxides. The cooling effect was 8.2% less than for normal lime. Replacing conventional lime with iron-bearing lime also makes it possible to reduce the amount of sulfur contributed to the bath by the fluxing materials and to increase the output of usable metal.

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

    NASA Astrophysics Data System (ADS)

    Kowal-Linka, Monika

    2010-03-01

    Although bedding-parallel cone-in-cone structure calcite veins are present in the Middle Triassic Gogolin Formation in Opole Silesia, their occurrence is limited to the Emilwka Cellular Limestone Member. Marly limestones (dedolomites) consisting of calcite pseudospar are the host rocks. The veins, which are up to 3 mm high and 30 cm long, are built of densely packed cone columns, with individual cones up to 0.7 mm high and 0.6 mm wide at their bases, and with vertex angle values ranging from 30 to 50. The cones are microfractured, and the adjacent cones are vertically shifted in oblique planes. The exceptionally small veins consist of calcite fibres up to 0.15 mm high. The veins are built of low-magnesium and non-ferroan calcite, characterized by low ? 18O values ranging from - 6.8 to - 7.4, and low ? 13C values ranging from - 2.9 to - 4.5 vs. PDB. These isotopic values are similar to those obtained from the host rocks (? 18O from - 6.8 to - 7.4, and ? 13C from - 3.2 to - 3.6 vs. PDB) and they are strongly depleted in comparison with the isotopic values of other carbonate particles from the Gogolin Formation. The veins only formed in one lithostratigraphic member, suggesting that their origin is related to processes which acted only locally. There are two unique processes that the Emilwka Cellular Limestone Member alone in the Gogolin Formation underwent: early diagenetic evaporitic dolomitization of lime mud in the sabkha environment, and subsequent calcitization of dolomite. Dolomitization led to sediment cohesion loss, porosity increase and initial horizontal laminae separation as a result of the transformation of calcium carbonate to dolomite within anisotropic deposits. Similar values of geochemical parameters obtained from the vein calcite and the host rock calcite are evidence that vein-filling precipitation was contemporary with dedolomitization. Geochemical data combined with sedimentological research and burial history show meteoric-derived waters saturated with respect to calcite as a source of the vein calcite. Dedolomitization and vein precipitation may have taken place from the Norian/Early Jurassic to the Late Jurassic when the study area became eroded land, and the Emilwka Cellular Limestone Member may have acted as a local paleoaquifer conducting the meteoric-derived waters. Solid inclusions in the veins, detached from the host rock and the calcitized nodules, show that the force of calcite crystallization was the main factor responsible for vein widening. Vertical shifts of adjacent cones, remnants of primary fibrous calcite crystals, as well as the burial history justify the application of Tarr's theory in interpreting the origin of the secondary cone-in-cone structure within the fibrous structure veins. The timing and the particular conditions required for the cones to develop are uncertain.

  7. Chloral hydrate

    Integrated Risk Information System (IRIS)

    Chloral hydrate ; CASRN 302 - 17 - 0 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic E

  8. Chloral hydrate

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 00 / 006 TOXICOLOGICAL REVIEW OF CHLORAL HYDRATE ( CAS No . 302 - 17 - 0 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) August 2000 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This document has been reviewed in accordance w

  9. Lime application for the efficient production of nutraceutical glucooligosaccharides from Leuconostoc mesenteroides NRRL B-742 (ATCC13146).

    PubMed

    Moon, Young Hwan; Madsen, Lee; Chung, Chang-Ho; Kim, Doman; Day, Donal F

    2015-02-01

    We have previously demonstrated the production of glucooligosaccharides via a fermentation of sucrose with Leuconostoc mesenteroides NRRL B-742 using sodium hydroxide (NaOH) to control the pH. Because NaOH is expensive, we sought to minimize the cost of our process by substituting hydrated lime and saccharate of lime (lime sucrate) in its place. The yield of glucooligosaccharides using either 5 % lime (41.4 0.5 g/100 g) or 5 % lime sucrate (40.0 1.4 g/100 g) were both similar to the NaOH control (42.4 1.5 g/100 g). Based on this, it appears that the cost associated with pH control in our process can be reduced by a factor of approximately 2.4 using lime instead of NaOH. Because our chromatographic stage is based on a Ca(2+)-form resin to separate glucooligosaccharides, the use of lime not only negates the need for costly de-salting via ion-exchange (elimination of two ion-exchange sections) prior to separation, but also greatly reduces the resin regeneration cost. PMID:25533635

  10. Crystal lattice tilting in prismatic calcite.

    PubMed

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

    2013-08-01

    We analyzed the calcitic prismatic layers in Atrina rigida (Ar), Haliotis iris (Hi), Haliotis laevigata (HL), Haliotis rufescens (Hrf), Mytilus californianus (Mc), Pinctada fucata (Pf), Pinctada margaritifera (Pm) shells, and the aragonitic prismatic layer in the Nautilus pompilius (Np) shell. Dramatic structural differences were observed across species, with 100-?m wide single-crystalline prisms in Hi, HL and Hrf, 1-?m wide needle-shaped calcite prisms in Mc, 1-?m wide spherulitic aragonite prisms in Np, 20-?m wide single-crystalline calcite prisms in Ar, and 20-?m wide polycrystalline calcite prisms in Pf and Pm. The calcite prisms in Pf and Pm are subdivided into sub-prismatic domains of orientations, and within each of these domains the calcite crystal lattice tilts gradually over long distances, on the order of 100 ?m, with an angle spread of crystal orientation of 10-20. Furthermore, prisms in Pf and Pm are harder than in any other calcite prisms analyzed, their nanoparticles are smaller, and the angle spread is strongly correlated with hardness in all shells that form calcitic prismatic layers. One can hypothesize a causal relationship of these correlated parameters: greater angle spread may confer greater hardness and resistance to wear, thus providing Pf and Pm with a structural advantage in their environment. This is the first structure-property relationship thus far hypothesized in mollusk shell prisms. PMID:23806677

  11. Olefin hydration

    SciTech Connect

    Butt, M.H.D.; Waller, F.J.

    1993-08-03

    An improved process for the hydration of olefins to alcohols is described wherein the improvement comprises contacting said olefins with the catalytic composition comprising a perfluorinated ion-exchange polymer containing sulfonic acid groups supported on an inert carrier wherein said carrier comprises calcined shot coke with a mean pore diameter of about 1,000 Angstroms in the presence of water at a temperature of from about 180 C to about 250 C.

  12. Lime for environmental uses. STP 931

    SciTech Connect

    Gutschick, K.A.

    1987-01-01

    This book STP 931 discusses the use of lime and industrial limestone for the control of factors that influence the environment - including the treatment of gaseous, liquid, and solid wastes. Current research shows that lime is one of the key chemicals that can help solve the problem of air, water, and land pollution. Topics covered are: the many environmental uses of lime including water treatment, sewage and industrial waste treatment, and the scrubbing of sulfur dioxide from power plant gases; various lime types and the engineering considerations in the design of lime handling systems; a hazardous waste incident where the waste was solidified with quicklime and lime kiln dust for burial; the growing use of lime and fly-ash for stabilizing scrubber sludges produced in wet scrubbing installations at more than 20 power plants in the United States; use of lime for stabilizing sewage sludge for land fill disposal; neutralization of calcium and magnesium calcium hydroxides through the use of carbon dioxide; and lime stabilization of expansive clays and silty clays for use in earth dams, irrigation canals, and levees.

  13. Evidence for carbon sequestration by agricultural liming

    NASA Astrophysics Data System (ADS)

    Hamilton, Stephen K.; Kurzman, Amanda L.; Arango, Clay; Jin, Lixin; Robertson, G. Philip

    2007-06-01

    Agricultural lime can be a source or a sink for CO2, depending on whether reaction occurs with strong acids or carbonic acid. Here we examine the impact of liming on global warming potential by comparing the sum of Ca2+ and Mg2+ to carbonate alkalinity in soil solutions beneath unmanaged vegetation versus limed row crops, and of streams and rivers in agricultural versus forested watersheds, mainly in southern Michigan. Soil solutions sampled by tension indicated that lime can act as either a source or a sink for CO2. However, infiltrating waters tended to indicate net CO2 uptake, as did tile drainage waters and streams draining agricultural watersheds. As nitrate concentrations increased in infiltrating waters, lime switched from a net CO2 sink to a source, implying nitrification as a major acidifying process. Dissolution of lime may sequester CO2 equal to roughly 25-50% of its C content, in contrast to the prevailing assumption that all of the carbon in lime becomes CO2. The ˜30 Tg/yr of agricultural lime applied in the United States could thus sequester up to 1.9 Tg C/yr, about 15% of the annual change in the U.S. CO2 emissions (12 Tg C/yr for 2002-2003). The implications of liming for atmospheric CO2 stabilization should be considered in strategies to mitigate global climate change.

  14. Fly ash chemical classification based on lime

    SciTech Connect

    Fox, J.

    2007-07-01

    Typically, total lime content (CaO) of fly ash is shown in fly ash reports, but its significance is not addressed in US specifications. For certain applications a low lime ash is preferred. When a class C fly ash must be cementitious, lime content above 20% is required. A ternary S-A-C phase diagram pilot is given showing the location of fly ash compositions by coal rank and source in North America. Fly ashes from subbituminous coal from the Powder River Basin usually contain sufficient lime to be cementitious but blending with other coals may result in calcium being present in phases other than tricalcium aluminate. 9 refs., 1 fig.

  15. Why calcite can be stronger than quartz

    NASA Astrophysics Data System (ADS)

    Mancktelow, N. S.; Pennacchioni, G.

    2009-04-01

    Calcite and quartz are two of the most common minerals in the continental crust and it is therefore not surprising that these minerals have been extensively studied since the very beginning of laboratory rock mechanics experiments. Extending such laboratory data to geological deformation rates around 10-14 s-1 requires an extrapolation of more than 7 orders of magnitude, with correspondingly large uncertainties. Extrapolation is based on the assumption that flow parameters are constant with changing conditions and that parameters not included in the flow law have a negligible influence on the creep properties. The validity of this extrapolation can only be tested, at least semi-quantitatively, by comparison with naturally deformed rocks. Observations generally indicate that quartz is significantly stronger than calcite in natural rocks, with quartz forming porphyroclasts in calcite marble mylonites, or with quartzite layers being folded or boudinaged within a weaker calcite marble matrix. However, in the Neves area (Tauern Window, Eastern Alps), shearing of Alpine coarse grained quartz-calcite veins under hydrous amphibolite facies conditions (ca. 550? C) produced quartz mylonites containing asymmetric cm-scale single crystal calcite porphyroclasts. Under these conditions, coarse calcite is clearly stronger than the surrounding polycrystalline, dynamically recrystallized, quartz matrix. The important parameter controlling this difference in observed natural behaviour is the grain size of the calcite. Although there is considerable variation, uncertainty and even contradiction in the published experimental results, we show that extrapolation of laboratory creep data on calcite single crystals and coarse marbles, together with the corresponding data for wet quartzites, is indeed consistent with these natural observations. Extrapolation indicates an inversion in the relative strength of coarse calcite and quartz at a strain rate around 10-11 s-1, corresponding to a differential flow stress of ca. 50 MPa. At lower strain rates and stresses, wet quartz should be weaker than coarse calcite crystals. Field evidence (flow of quartz-rich layers even for orientations with very low resolved shear stress) and the preserved microstructure (lack of recrystallized or bulged twins in the calcite porphyroclasts) in the Neves area are also consistent with flow stresses of less than ca. 50 MPa. These low values during deformation under water-rich amphibolite facies conditions are in marked contrast to the much higher differential stresses reported for the flow (and fracture) of quartz-rich rocks under dry conditions in the middle to lower crust.

  16. Alginic Acid Accelerates Calcite Dissolution

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

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

  17. Do organic ligands affect calcite dissolution rates?

    NASA Astrophysics Data System (ADS)

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

    2011-04-01

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

  18. Hydrate habitat

    NASA Astrophysics Data System (ADS)

    Showstack, Randy

    Whoever said there is nothing new under the sun did not delve deeply enough to the bottom of the ocean. There in the Gulf of Mexico, about 150 miles south of New Orleans, scientists have just discovered what could be a new species of centipede—like worms living on or within gas hydrates— mounds of methane ice— rising from the ocean floor.Scientists have previously recognized an association between some bacteria and these hydrates. However, this is the first discovery of a higher life form there.

  19. Effect of calcite on Pb-doped solidified waste forms in leaching.

    PubMed

    Lee, Dong-Jin

    2006-06-01

    The alkalinity of cementitious materials rectifies a low pH of leachant to be over 12 in leaching. The rapid change of leachant pH produces the remarked variation of solubility of heavy metals in the toxicity characteristic leaching procedure. The release of lead on cementitious solid waste forms in leaching was observed in the pH range of particularly 12. The release of lead is significant dependant on the changed values of leachant pH. The pH static leaching procedure (PSLP) was implemented for assessing a quantitative measurement of total potential leachability with the continuing addition of acidic leachant up to the point of no change of leachant pH. The release of lead on Pb-doped solidified waste forms (SWF), in the PSLP, was 27.0% of initial concentration at the maximum meq CH3COOH (about 24.0) added to g dry solidified wastes. In this study, the immobilization effect of calcite on SWF was investigated in the acidic condition by the PSLP. Calcite additions to SWF make a good fixation efficiency of about 92%. Calcite addition abundantly provides the acid neutralization capacity to protect SWF from the attack of acid, with the marked development of hydrated minerals (mainly portlandite and C-S-H) in accordance with the accelerating effect of cement hydration. PMID:16376409

  20. Diffusion of Ca and Mg in Calcite

    SciTech Connect

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

    1999-02-10

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

  1. Nickel adsorption on chalk and calcite

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  2. Simple Analysis of Historical Lime Mortars

    ERIC Educational Resources Information Center

    Pires, Joa~o

    2015-01-01

    A laboratory experiment is described in which a simple characterization of a historical lime mortar is made by the determination of its approximate composition by a gravimetric method. Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) are also used for the qualitative characterization of the lime mortar components. These…

  3. Simple Analysis of Historical Lime Mortars

    ERIC Educational Resources Information Center

    Pires, Joa~o

    2015-01-01

    A laboratory experiment is described in which a simple characterization of a historical lime mortar is made by the determination of its approximate composition by a gravimetric method. Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) are also used for the qualitative characterization of the lime mortar components. These

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

    NASA Astrophysics Data System (ADS)

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

    2008-12-01

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

  5. Calcite dissolution in two deep eutrophic lakes

    SciTech Connect

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

    1999-10-01

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

  6. Lactic Acid Fermentation, Urea and Lime Addition: Promising Faecal Sludge Sanitizing Methods for Emergency Sanitation

    PubMed Central

    Anderson, Catherine; Malambo, Dennis Hanjalika; Gonzalez Perez, Maria Eliette; Nobela, Happiness Ngwanamoseka; de Pooter, Lobke; Spit, Jan; Hooijmans, Christine Maria; van de Vossenberg, Jack; Greya, Wilson; Thole, Bernard; van Lier, Jules B.; Brdjanovic, Damir

    2015-01-01

    In this research, three faecal sludge sanitizing methods—lactic acid fermentation, urea treatment and lime treatment—were studied for application in emergency situations. These methods were investigated by undertaking small scale field trials with pit latrine sludge in Blantyre, Malawi. Hydrated lime was able to reduce the E. coli count in the sludge to below the detectable limit within 1 h applying a pH > 11 (using a dosage from 7% to 17% w/w, depending faecal sludge alkalinity), urea treatment required about 4 days using 2.5% wet weight urea addition, and lactic acid fermentation needed approximately 1 week after being dosed with 10% wet weight molasses (2 g (glucose/fructose)/kg) and 10% wet weight pre-culture (99.8% pasteurised whole milk and 0.02% fermented milk drink containing Lactobacillus casei Shirota). Based on Malawian prices, the cost of sanitizing 1 m3 of faecal sludge was estimated to be €32 for lactic acid fermentation, €20 for urea treatment and €12 for hydrated lime treatment. PMID:26528995

  7. Lactic Acid Fermentation, Urea and Lime Addition: Promising Faecal Sludge Sanitizing Methods for Emergency Sanitation.

    PubMed

    Anderson, Catherine; Malambo, Dennis Hanjalika; Perez, Maria Eliette Gonzalez; Nobela, Happiness Ngwanamoseka; de Pooter, Lobke; Spit, Jan; Hooijmans, Christine Maria; de Vossenberg, Jack van; Greya, Wilson; Thole, Bernard; van Lier, Jules B; Brdjanovic, Damir

    2015-11-01

    In this research, three faecal sludge sanitizing methods-lactic acid fermentation, urea treatment and lime treatment-were studied for application in emergency situations. These methods were investigated by undertaking small scale field trials with pit latrine sludge in Blantyre, Malawi. Hydrated lime was able to reduce the E. coli count in the sludge to below the detectable limit within 1 h applying a pH > 11 (using a dosage from 7% to 17% w/w, depending faecal sludge alkalinity), urea treatment required about 4 days using 2.5% wet weight urea addition, and lactic acid fermentation needed approximately 1 week after being dosed with 10% wet weight molasses (2 g (glucose/fructose)/kg) and 10% wet weight pre-culture (99.8% pasteurised whole milk and 0.02% fermented milk drink containing Lactobacillus casei Shirota). Based on Malawian prices, the cost of sanitizing 1 m³ of faecal sludge was estimated to be €32 for lactic acid fermentation, €20 for urea treatment and €12 for hydrated lime treatment. PMID:26528995

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    PubMed Central

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

    2008-01-01

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

  10. Effects of carbonation on the pore structure of non-hydraulic lime mortars

    SciTech Connect

    Lawrence, Robert M. . E-mail: mike@cc-w.co.uk; Mays, Timothy J.; Rigby, Sean P.; Walker, Peter; D'Ayala, Dina

    2007-07-15

    The pore structures of carbonated non-hydraulic lime mortars made with a range of different aggregates and concentrations of lime have been determined using mercury intrusion porosimetry (MIP). MIP data have been correlated with scanning electron microscopy images and other porosity data. During carbonation there is an increase in pore volume in the {approx} 0.1 {mu}m pore diameter range across all mortar types which is attributed to the transformation of portlandite to calcite. Also there is a monotonic increase in the volumes of pores with diameters below 0.03 {mu}m. A model is proposed for the changes in pore structure caused by carbonation. This attributes the increase in the volume of sub 0.03 {mu}m pores to the attachment of calcite crystals to the surface of aggregate particles, and in some cases to the surface of portlandite crystals. This phenomenon may explain the continuing presence of portlandite in mortars that, apparently, have fully carbonated.

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

    PubMed

    Choquette, P W

    1968-09-13

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

  12. Arsenic removal in conjunction with lime softening

    DOEpatents

    Khandaker, Nadim R.; Brady, Patrick V.; Teter, David M.; Krumhansl, James L.

    2004-10-12

    A method for removing dissolved arsenic from an aqueous medium comprising adding lime to the aqueous medium, and adding one or more sources of divalent metal ions other than calcium and magnesium to the aqueous medium, whereby dissolved arsenic in the aqueous medium is reduced to a lower level than possible if only the step of adding lime were performed. Also a composition of matter for removing dissolved arsenic from an aqueous medium comprising lime and one or more sources of divalent copper and/or zinc metal ions.

  13. pH-dependence of calcite growth kinetics at constant solution calcium to carbonate activity ratio and supersaturation: an in situ Atomic Force Microscopy study

    NASA Astrophysics Data System (ADS)

    Ruiz-Agudo, Encarnacin; Putnis, Christine V.; Rodriguez-Navarro, Carlos Manuel; Putnis, Andrew

    2010-05-01

    Calcite-solution reactions (growth, dissolution and replacement) are critical in a range of both engineering and natural processes. Classical crystal growth theory relates calcite growth rates to the degree of supersaturation. The solution composition may also affect the growth rate of carbonate minerals, via the Ca2+ to CO32- concentration ratio (Nehrke et al., 2007; Perdikouri et al., 2009), ionic strength (Zuddas and Mucci, 1998) or the presence of organic matter (Hoch et al., 2000). Most calcite growth studies so far have been performed at a constant pH of ca. 8 or 10, or changing the pH together with the degree of supersaturation with respect to calcite and/or the aCa2+ to aCO32- ratio in solution, which hinders an evaluation of the pH effect on calcite growth kinetics. In this work, in situ Atomic Force Microscopy (AFM) was employed to study the growth of calcite at a constant supersaturation (? = 6.46) and solution stoichiometry (Ca2+-CO32- = 1) in the pH range 7.5 to 12. How pH may influence calcite growth is relevant to improve our understanding of the effects on carbonate-solution reactions when variations in atmospheric CO2result in changes in the pH of the oceans and surface waters. We observed that the calcite growth rate decreases with increasing pH in the studied range. The results can be successfully explained by the mechanistic model for calcite growth based on surface complexation proposed by Nilsson and Sternbeck (1999) and by solute hydration. At pH below 8.5, growth occurs mainly by CaCO30 incorporation at >CaHCO30 surface sites. CaCO30 should be more easily incorporated than free Ca2+ ions, as water exchange usually is faster if water molecules in the ion hydration shells are substituted for by other ligands, as in CaCO30. However, at pH above 9, Ca2+ incorporation at >CaHCO30 sites also contributes to calcite growth as a result of increased frequency of water exchange in calcium hydration shells due to the presence of strongly hydrated OH-. The decrease in calcite growth rate is a consequence of decreasing surface concentration of growth active sites (i.e. >CaHCO30) with increasing pH in our experimental conditions. Changes in 2D island morphology were observed at high pH (12), possibly due to the stabilization of polar scalenohedral faces by the presence of OH- ions. References Hoch, A.R.; Reddy, M.M.; Aiken, G.R. Calcite crystal growth inhibition by humic substances with emphasis on hydrophobic acids from the Florida Everglades. Geochim. Cosmochim. Acta 2000, 64, 61-72. Nehrke, G.; Reichart, G. J.; Van Cappellen, P.; Meile, C.; Bijma, J. Dependence of calcite growth rate and Sr partitioning on solution stoichiometry: Non-Kossel crystal growth. Geochim. Cosmochim. Acta 2007, 71, 2240-2249 Nilsson O.; Sternbeck J. A mechanistic model for calcite crystal growth using surface speciation. Geochim. Cosmochim.Acta 1999, 63, 217-225. Perdikouri, C.; Putnis, C.V.; Kasioptas, A.; Putnis, A. An Atomic Force Microscopy Study of the Growth of a Calcite Surface as a Function of Calcium/Total Carbonate Concentration Ratio in Solution at Constant Supersaturation. Cryst. Growth Des. 2009, 9, 4344-4350. Zuddas, P.; Mucci, A. Kinetics of Calcite Precipitation from Seawater: II. The Influence of the Ionic Strength. Geochim. Cosmochim. Acta 1998, 62, 757-766.

  14. Lime or lime:fly ash pretreated pavement construction material and method

    SciTech Connect

    Gnaedinger, J.P.

    1985-01-29

    A composition for use as a base course in a pavement construction is prepared by prereacting uncompacted incinerator ash with 2-10% by weight lime or 2-10% by weight of a 2:3 lime:fly ash mixture for several days and then adding 2-10% by weight lime and 20-25% by weight water to the composition before compaction.

  15. New Origins of the Vital Effect in Calcites: Mg-Enhancing Influence of Biomolecules

    NASA Astrophysics Data System (ADS)

    Stephenson, A. E.; Wu, L.; Wu, K. J.; Deyoreo, J. J.; Dove, P. M.

    2007-12-01

    Owing to the intense interest in the compositional signatures of biominerals, the mechanistic basis for vital effects and their roles in modifying or masking impurity contents are receiving increasing scrutiny. To date, much of the effort has been focused on the influence of physical environment and inorganic chemical factors. In a recent study that investigated the effects of acidic proteins on calcite growth, our research group found that nanomolar concentratios of acidic amino acids, peptides, and full proteins accelerate the rate of mineral formation by a relationship that correlates with the acidity (hydrophilicity) of the biomolecule (Elhadj et al., 2006, PNAS). Experimental and theoretical evidence suggest that the measured rate-enhancing effect (up to 25X) arises from weak interactions of the biomolecule with the calcite surface to alter the local solvation environment. This relation suggests that the acidic macromolecules that have been isolated from diverse calcifying taxa may have yet unrecognized effects on mineralization. Because Mg has a strong hydration shell relative to Ca, we hypothesized that the presence of these rate-modifying peptides in growth solutions would also lower the barrier to incorporating Mg, and thereby increase the MgCO3 content of calcite overgrowths. To test this idea, measurements of calcite growth rate were made using Atomic Force Microscopy, and in the presence or absence of acidic, hydrophilic 27-mer peptides. The peptide increased the growth rate of obtuse flanks (42% faster, on average, and up to 92% faster) and acute flanks (17% faster on average; up to 54% faster). The calcite overgrowths from AFM experiments were then analyzed for corresponding MgCO3 compositions by Time-of-Flight Secondary Ion Mass Spectrometry. The data yield an inorganic baseline that quantifies the relation between Mg content and the solution concentration. Comparisons of the baseline Mg content to that of peptide-enriched overgrowths show the MgCO3 composition is enhanced by 50 to 70% (in acute and obtuse flanks respectively) in calcite grown in the presence of peptides. Comparisons of these measurements to the MgCO3 compositions reported by Mucci (1987, GCA) for 5-40?C synthetic seawater show that these differences are equivalent to the offset induced by a temperature change of several degrees. Two possible explanations for the enhanced Mg content in the presence of peptide are 1) step roughening increasing the kink density and 2) partial desolvation of the hydrated Mg ion, which lowers the energy barrier to incorporation.

  16. Two-phase flow and calcite deposition

    SciTech Connect

    Gudmudsson, J.S.; Granadso-G, E.; Ortiz-R, J.

    1984-04-01

    The literature on two-phase flow in geothermal wells shows that the Orkiszewski method has found wide application in state-of-the-art wellbore simulators. Such a simulator was developed and then used for the problem of wellbore deposition of calcite in the Miravalles geothermal field in Costa Rica. The output of wells suffering calcite deposition decreases slowly at early time but rapidly at late time. The simulator was also used to estimate the deliverability curve for a large diameter well in the Svartsengi geothemal field in Iceland. The view is presented that more accurate wellbore simulators will make new reservoir engineering studies possible in geothermal fields.

  17. Characterization of a lime-pozzolan plaster containing phase change material

    SciTech Connect

    Pavlíková, Milena; Pavlík, Zbyšek; Trník, Anton; Pokorný, Jaroslav; Černý, Robert

    2015-03-10

    A PCM (Phase Change Material) modified lime-pozzolan plaster for improvement of thermal energy storage of building envelopes is studied in the paper. The investigated plaster is composed of lime hydrate, pozzolan admixture based on metakaolin and mudstone, silica sand, water and paraffin wax encapsulated in polymer capsule. The reference plaster without PCM application is studied as well. The analyzed materials are characterized by bulk density, matrix density, total open porosity, compressive strength and pore size distribution. The temperature of phase change, heat of fusion and crystallization are studied using DSC (Difference Scanning Calorimetry) analysis performed in air atmosphere. In order to get information on materials hygrothermal performance, determination of thermal and hygric properties is done in laboratory conditions. Experimental data reveal a substantial improvement of heat storage capacity of PCM-modified plaster as compared to the reference material without PCM.

  18. Lime-pozzolana mortars in Roman catacombs: composition, structures and restoration

    SciTech Connect

    Sanchez-Moral, Sergio; Soler, Vicente; Garcia-Guinea, Javier

    2005-08-01

    Analyses of microsamples collected from Roman catacombs and samples of lime-pozzolana mortars hardened in the laboratory display higher contents in carbonated binder than other subaerial Roman monuments. The measured environmental data inside the Saint Callistus and Domitilla catacombs show a constant temperature of 15-17 deg C, a high CO{sub 2} content (1700 to 3500 ppm) and a relative humidity close to 100%. These conditions and particularly the high CO{sub 2} concentration speed-up the lime calcitization roughly by 500% and reduce the cationic diffusion to form hydrous calcium aluminosilicates. The structure of Roman catacomb mortars shows (i) coarser aggregates and thicker beds on the inside, (ii) thin, smoothed, light and fine-grained external surfaces with low content of aggregates and (iii) paintings and frescoes on the outside. The observed high porosity of the mortars can be attributed to cracking after drying linked with the high binder content. Hardened lime lumps inside the binder denote low water/mortar ratios for slaking. The aggregate tephra pyroclasts rich in aluminosilicate phases with accessorial amounts of Ba, Sr, Rb, Cu and Pb were analysed through X-ray diffraction (XRD), electron microprobe analysis (EMPA) and also by environmental scanning electron microscopy (ESEM) to identify the size and distribution of porosity. Results support procedures using local materials, special mortars and classic techniques for restoration purposes in hypogeal backgrounds.

  19. FULL SCALE DEMONSTRATION OF LIME STABILIZATION

    EPA Science Inventory

    The project objective was to demonstrate and evaluate the feasibility, economics, and benefits of stabilizing primary, waste activated, septic, and anaerobically digested sludges by lime addition. The project confirmed the findings of previous laboratory and pilot scale tests and...

  20. Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

    ERIC Educational Resources Information Center

    Wilkinson, Bruce H.

    1982-01-01

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

  1. Cyclic Cratonic Carbonates and Phanerozoic Calcite Seas.

    ERIC Educational Resources Information Center

    Wilkinson, Bruce H.

    1982-01-01

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

  2. Interaction of alcohols with the calcite surface.

    PubMed

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

    2015-02-01

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

  3. Solar bleaching of thermoluminescence of calcites

    NASA Astrophysics Data System (ADS)

    Liritzis, I.; Guibert, P.; Foti, F.; Schvoerer, M.

    1996-09-01

    Original results of solar bleaching of thermoluminescence (TL) of twelve Greek calcitic (limestone, marble) stone profiles have been obtained. The residual TL signal due to sunlight exposures (zero to 130 h) differs in samples, but in general follows an exponential decay form consisting of one or two components. The first component bleaches fast within the first 30-70 h and the second component bleaches slowly; the latter, occasionally, formed a residual plateau. The first exponential term decays with different rates ranging between 1 - 6 (%/h) for the 280C TL peak and slower, 0.1-0.3 (%/h) for the 350C TL peak. Phototransferred TL (PTTL) of the 280 and 350C TL peaks giving rise to a PTTL peak at around 180C, was observed. The residual TL glow curve shape variation as a function of daylight exposure time is provisionally used to further develop the method of dating carved megalithic masonry [1]. The solar bleached TL signal of calcites provides bleached TL curves characterestics which inhere useful information regarding dating of calcitic stones derived from archaeological sites, and contribute to the complex luminescence phenomenon in calcites.

  4. Evaluation of stripping and moisture damage in asphalt pavements treated with lime and antistripping agents

    SciTech Connect

    Ping, W.C.V.

    1989-01-01

    Moisture damage is a major problem for asphalt concrete pavements constructed throughout much of the United States. The seriousness of the problem is evidenced by the large number of research efforts conducted in the United States during the last ten years. As a result of these efforts and previous research, it has been concluded that hydrated lime and certain liquid antistrip additives are effective in protecting asphalt mixtures from stripping and moisture damage. Unfortunately, while there are only a relatively few basic types of tests being used to evaluate the resistance to moisture damage of asphalt-aggregate mixtures, there are many variations of each test and many different acceptance criteria being used. It is also apparent that these different basic tests do not yield the same results nor the same moisture damage predictions. Furthermore, the acceptance criteria often were arbitrarily established or, at best, were based primarily on past performance or the testing of materials with well established histories related to moisture damage. In recognition of these needs the research described in this report was undertaken to evaluate the effectiveness of hydrated lime and other selected antistripping additives under laboratory testing conditions, to evaluate the relationships between various moisture damage test values for a range of mixtures using different antistripping agents, and to monitor and field performance of the test sections for future long-term evaluation. The appropriate objectives were achieved from the research findings reported in this report. The effectiveness of hydrated lime and various selected antistripping additives were evaluated using the tensile strength ratios and the boiling test results. The conclusions and recommendations were drawn based on the findings from this study.

  5. Planktic Foraminiferal Sedimentation and Calcite Budget

    NASA Astrophysics Data System (ADS)

    Schiebel, R.

    2002-12-01

    Vertical flux and sedimentation rate of planktic foraminiferal tests is quantified on a global scale. The planktic foraminiferal test flux is a consequence of the population dynamics, and the differential settling modes for different species are a precondition for the differences in the regional flux rates. The average planktic foraminiferal calcite flux rate at the 100-m depth-level is estimated at 50% of the global-marine calcite flux and 6% of the total carbon flux. The most significant decrease in the planktic foraminiferal test flux rates between 100-700 m water depth possibly results from increased bacterially-mediated decomposition of cytoplasm and a decreasing pH in microenvironments within foraminiferal tests. Throughout most of the year, on average only 1-3% of the initially exported CaCO3 reaches the deep sea floor. Pulsed flux events, mass dumps of fast settling particles, yield a major contribution of tests to the formation of deep-sea sediments. On a global average, ~25% of the total calcite produced by planktic foraminifers arrives in the deep ocean and at the sediment surface. To complete the open-marine, particulate CaCO3 inventory, the contribution of coccolithophores, pteropods, and calcareous dinophytes is discussed. The global planktic foraminiferal calcite flux rate at 100 m depth amounts to 23-56% of the total open marine CaCO3 flux. The total planktic foraminiferal contribution of CaCO3 to global surface sediments is estimated at 0.36-0.88 Gt per year, ~30-80% of the total deep-marine calcite budget.

  6. Effect of micromorphological development on the elastic moduli of fly ash-lime stabilized bentonite

    SciTech Connect

    Baykal, G.I.

    1987-01-01

    The mineralogical and micromorphological changes occurring in fly ash-lime stabilized bentonite were observed and related to changes in elastic moduli of the stabilized mixture. Compacted fly ash, fly ash-lime, bentonite-lime, bentonite-fly ash, and bentonite-fly ash-lime mixtures were prepared and cured at 23C and 50C, for 1, 28, 90 and 180 days. The development of microstructure and cementitous crystals were observed by a scanning electron microscope, and energy dispersive spectrum analyzer and a X-ray diffractometer. The elastic moduli and strengths were obtained from unconsolidated undrained triaxial and unconfined compressive strength tests. The physical test results were compared with changes observed by scanning electron microscopy and X-ray diffraction. CSH gel Type I, II and III, ettringite, afwillite and tetracalcium aluminate thirteen hydrate crystals were identified in the cured specimens. The elastic modulus of the fly ash-lime stabilized bentonite was higher than the untreated bentonite and the increase in elastic modulus corresponded to the curing times when new cementitious crystals were observed. Acicular crystals (CSH Type I and II) and ettringite crystals spanned the pores and increased the contact points where blocky aggregates of equant crystals (CSH III) engulfed the fly ash grains providing support. The compressive strength increased, and the strain at a failure decreased resulting in an increase in the elastic modulus. Some fly ash grains providing support for montmorillonite aggregates dissolved and created weak spots in the matrix, causing a decrease in elastic modulus at longer curing periods. At 50C curing temperature the same cementitious crystals were observed as at 23C. However, the rate of the reactions increased considerably.

  7. Improved control of sucrose losses and clarified juice turbidity with lime saccharate in hot lime clarification of sugarcane juice and other comparisons with milk of lime

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A comparative investigation of adding milk of lime (MOL) versus lime saccharate (SACCH) in hot lime clarification of juice at a U.S. sugarcane factory was undertaken to quantify performance across the 2009 processing season after a preliminary factory study in 2008. SACCH was prepared by adding hyd...

  8. Effect of whole catchment liming on the episodic acidification of two adirondack streams

    USGS Publications Warehouse

    Newton, R.M.; Burns, D.A.; Blette, V.L.; Driscoll, C.T.

    1996-01-01

    During the fall of 1989 7.7Mg/ha of calcium carbonate was applied on two tributary catchments (40 ha and 60 ha) to Woods Lake, a small (25 ha) acidic headwater lake in the western Adirondack region of New York. Stream-water chemistry in both catchment tributaries responded immediately. Acid-neutralizing capacity (ANC) increased by more than 200 ??eq/L in one of the streams and more than 1000 ??eq/L in the other, from pre-liming values which ranged from -25 to +40 ??eq/L. The increase in ANC was primarily due to increases in dissolved Ca2+ concentrations. Most of the initial response of the streams was due to the dissolution of calcite that fell directly into the stream channels and adjacent wetlands. A small beaver impoundment and associated wetlands were probably responsible for the greater response observed in one of the streams. After the liming of subcatchmentIV (60 ha), Ca2+ concentrations increased with increasing stream discharge in the stream during fall rain events, suggesting a contribution from calcite dissolved within the soil and transported to the stream by surface runoff or shallow interflow. Concentrations of other ions not associated with the calcite (e.g. Na+) decreased during fall rain events, presumably due to mixing of solute-rich base flow with more dilute shallow interflow. The strong relation between changes in Ca2+ and changes in NO3- concentrations during spring snowmelt, (r2 = 0.93, slope = 0.96, on an equivalent basis) suggests that both solutes had a common source in the organic horizon of the soil. Increases in NO3- concentrations during snowmelt were balanced by increases in Ca2+ that was released either directly from the calcite or from exchange sites, mitigating episodic acidification of the stream. However, high ambient NO3- concentrations and relatively low ambient Ca2+ concentrations in the stream during the spring caused the stream to become acidic despite the CaCO3 treatment. In stream WO2 (40ha), Ca2+ concentrations were much higher than in stream WO4 because of the dissolution of calcite which fell directly into the upstream beaver pond and its associated wetlands. Calcium concentrations decreased as both NO3- concentrations and stream discharge increased, due to the dilution of Ca-enriched beaver pond water by shallow interflow. Despite this dilution, Ca2+ concentrations were high enough to more than balance strong acid anion (SO42-, NO3-, Cl-) concentrations, resulting in a positive ANC in this stream throughout the year. These data indicate that liming of wetlands and beaver ponds is more effective than whole catchment liming in neutralizing acidic surface waters. ?? 1996 Kluwer Academic Publishers.

  9. in situ Calcite Precipitation for Contaminant Immobilization

    SciTech Connect

    Yoshiko Fujita; Robert W. Smith

    2009-08-01

    in situ Calcite Precipitation for Contaminant Immobilization Yoshiko Fujita (Yoshiko.fujita@inl.gov) (Idaho National Laboratory, Idaho Falls, Idaho, USA) Robert W. Smith (University of Idaho-Idaho Falls, Idaho Falls, Idaho, USA) Subsurface radionuclide and trace metal contaminants throughout the U.S. Department of Energy (DOE) complex pose one of DOE’s greatest challenges for long-term stewardship. One promising stabilization mechanism for divalent trace ions, such as the short-lived radionuclide strontium-90, is co-precipitation in calcite. Calcite, a common mineral in the arid western U.S., can form solid solutions with trace metals. The rate of trace metal incorporation is susceptible to manipulation using either abiotic or biotic means. We have previously demonstrated that increasing the calcite precipitation rate by stimulating the activity of urea hydrolyzing microorganisms can result in significantly enhanced Sr uptake. Urea hydrolysis causes the acceleration of calcium carbonate precipitation (and trace metal co-precipitation) by increasing pH and alkalinity, and also by liberating the reactive cations from the aquifer matrix via exchange reactions involving the ammonium ion derived from urea: H2NCONH2 + 3H2O ? 2NH4+ + HCO3- + OH- urea hydrolysis >X:2Ca + 2NH4+ ? 2>X:NH4 + Ca2+ ion exchange Ca2+ + HCO3- + OH- ? CaCO3(s) + H2O calcite precipitation where >X: is a cation exchange site on the aquifer matrix. This contaminant immobilization approach has several attractive features. Urea hydrolysis is catalyzed by the urease enzyme, which is produced by many indigenous subsurface microorganisms. Addition of foreign microbes is unnecessary. In turn the involvement of the native microbes and the consequent in situ generation of reactive components in the aqueous phase (e.g., carbonate and Ca or Sr) can allow dissemination of the reaction over a larger volume and/or farther away from an amendment injection point, as compared to direct addition of the reactants at a well (which can lead to clogging). A final particularly attractive characteristic of this approach is its long-term sustainability; the remediation scheme is geared toward environments that are already saturated with respect to calcite, and in such systems the bulk of any newly precipitated calcite will remain stable once engineered manipulations cease. This means that the co-precipitated contaminants will be effectively sequestered over the long term. We are currently conducting integrated field, laboratory, and computational research to evaluate a) the relationships between urea hydrolysis rate, calcite precipitation rate, and trace metal partitioning under environmentally relevant conditions; and b) the coupling between flow/flux manipulations and calcite precipitate distribution and metal uptake. We are also assessing the application of geophysical and molecular biological tools to monitor the relevant chemical and physical processes. The primary emphasis is on field-scale processes, with the laboratory and modeling activities designed specifically to support the field studies. Field experiments are being conducted in perched water (vadose zone) at the Vadose Zone Research Park (VZRP) at the Idaho National Laboratory; the VZRP provides an uncontaminated setting that is an analog of the 90Sr-contaminated vadose zone at the Idaho Nuclear Technology and Engineering Center. A summary of results to date will be presented.

  10. Hydration and Chronic Pancreatitis

    MedlinePLUS

    Fact Sheet - Hydration and Chronic Pancreatitis by Kathianne Sellers Proper hydration is important in the health of ... fluid needs are 8 cups per day. Kathianne Sellers, R.D., was a nutritionist at the Pancreas ...

  11. Stable isotopic composition of meteoric calcites: Evidence for early mississippian climate change in the mission canyon formation, Montana

    NASA Astrophysics Data System (ADS)

    Smith, Tad M.; Dorobek, Steven L.

    1993-07-01

    The Lower Mississippian Mission Canyon Formation of central to southwestern Montana was deposited under dominantly semiarid to arid climatic conditions during Osagean to early Meramecian times. Following deposition, a pronounced climatic shift to more humid conditions occurred during middle Meramecian times. This climatic change is indicated by extensive, post-depositional karst fabrics and in the stable isotopic composition of early, meteoric calcite cements and diagenetically altered sediments. Early meteoric calcite cement in Mission Canyon limestones is generally nonluminescent and fills intergranular and fenestral porosity. Petrographic data indicate that this cement formed during intermittent subaerial exposure of the Mission Canyon platform during Osagean times. This initial generation of meteoric calcite cement has ?18O values from -8.1 to -2.6%. PDB. These data, and the oxygen isotopic values from nonluminescent skeletal grains and micrite in host limestone indicate that Osagean meteoric water may have had ?18O values as low as -6.0%. SMOW. A second generation of petrographicalty similar, but isotopically distinct, calcite cement fills biomolds and porosity within solution-collapse breccias in the Mission Canyon Formation. This cement generation postdates earlier nonluminescent Osagean calcite cement and is volumetrically most abundant near the top of the Mission Canyon Formation. ?18O values from these cements and from nonluminescent lime mudstone clasts and matrix in solution collapse breccias range from - 13.8 to - 8.2%. PDB. These data indicate that Meramecian meteoric water may have had ?18O values as low as - 12.0%. However, a higher-temperature burial overprint on the ?18O values of the calcite cement cannot he ruled out. The more positive ?18O values of the Osagean calcite components probably indicate warm and arid conditions during short-term [10 4(?) yr] subaerial exposure along intraformational sequence and parasequence boundaries. The more negative ?18O values from Meramecian calcite components and the extensive karst associated with the post-Mission Canyon unconformity may have developed because of cooler and more humid climatic conditions and possible rain-out effects during middle Meramecian times. A dramatic shift towards cooler and more humid climatic conditions may be coincident with the onset of major continental glaciation in the Early Carboniferous. The post-Mission Canyon unconformity has been attributed to a major fall in sea level that may have glacio-eustatic origins. Growth of continental glaciers during a time of global cooling would have caused migration of polar fronts further toward the paleoequator. These polar fronts in turn, would have pushed moist, mid-latitude weather systems toward the paleoequator, resulting in cooler, more humid conditions in low-latitude settings during "icehouse" times.

  12. Dissolution Kinetics of Biogenic Magnesian Calcites

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  13. The role of silicate surfaces on calcite precipitation kinetics

    NASA Astrophysics Data System (ADS)

    Stockmann, Gabrielle J.; Wolff-Boenisch, Domenik; Bovet, Nicolas; Gislason, Sigurdur R.; Oelkers, Eric H.

    2014-06-01

    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, labradorite, olivine, basaltic glass and peridotite rock. Calcite saturation was achieved by mixing a CaCl2-rich aqueous solution with a NaHCO3-Na2CO3 aqueous buffer in mixed-flow reactors containing 0.5-2 g of mineral, rock, or glass seeds. This led to an inlet fluid calcite saturation index of 0.6 and a pH equal to 9.1. Although the inlet fluid composition, flow rate, and temperature were identical for all experiments, the onset of calcite precipitation depended on the identity of the seeds present in the reactor. Calcite precipitated instantaneously and at a constant rate in the presence of calcite grains. Calcite precipitated relatively rapidly on labradorite, olivine, enstatite, and peridotite (mainly composed of Mg-olivine) surfaces, but more slowly on augite and basaltic glass. Calcite precipitation rates, however, became independent of substrate identity and mass over time, and all rates approach 10-9.68 0.08 mol/s for ?10 day long experiments and 10-9.21 0.2 mol/s for ?70 day long experiments. Scanning Electron Microscope images showed olivine, enstatite and peridotite surfaces to be covered extensively with calcite coatings at the end of the experiments. Less calcite was found on labradorite and augite, and the least on basaltic glass. In all cases, calcite precipitation occurs on the mineral, rock or glass surfaces. Calcite precipitation on these surfaces, however, negligibly affects the dissolution rates of the silicate grains. These results support ultramafic and basalt carbonation as a long-term carbon storage strategy, as calcite readily precipitates on the surfaces of minerals contained in these rocks without inhibiting their dissolution.

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

    USGS Publications Warehouse

    Reddy, Michael M.

    2012-01-01

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

  15. Frictional behavior of talc-calcite mixtures

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  16. Hydrate characterization research overview

    SciTech Connect

    Malone, R.D.

    1993-06-01

    Gas hydrate research has been focused primarily on the development of a basic understanding of hydrate formation and dissociation in the laboratory, as well as in the field. Laboratory research on gas hydrates characterized the physical system, which focused on creating methane hydrates samples, tetrahydrofuran (THF) hydrate samples, consolidated rock samples, frost base mixtures, water/ice-base mixtures, and water-base mixtures. Laboratory work produced measurements of sonic velocity and electrical resistivity of hydrates. As work progressed, areas, such as the Gulf of Mexico and the Guatemala Trench, where gas hydrates are likely to occur were identified, and specific high potential areas were targeted for detailed investigation. The testing of samples and recovered cores from such areas provided information for detection of hydrate formations in the natural environment. Natural gas hydrate samples have been tested for thermal properties, dissociation properties, fracture mechanics, and optical properties. Acoustical properties were investigated both in the laboratory and, as possible, in the field. Sonic velocity and electrical resistivity measurements will continue to be obtained. These activities have been undertaken in hydrate deposits on Alaska`s North Slope, the Gulf of Mexico and the US East coast offshore, as well as other gas hydrate target areas.

  17. 19. LOOKING NORTH ALONG ROAD BISECTING SITE; PEBBLE LIME SILO ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    19. LOOKING NORTH ALONG ROAD BISECTING SITE; PEBBLE LIME SILO ON THE RIGHT, MAIN SUPPLY BUILDING AND MACHINE SHOP ON THE LEFT. - Standard Lime & Stone Quarry, County Route 27, Millville, Jefferson County, WV

  18. 62. INTERIOR VIEW OF THE LIME KILN BUILDING, LOOKING AT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    62. INTERIOR VIEW OF THE LIME KILN BUILDING, LOOKING AT THE LIME KILNS AND MOTOR DRIVES FOR THE KILNS. (DATE UNKNOWN). - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  19. LIME KILN BUILDING, KILN BOTTOM SHOWING ROTATOR GEAR. (GEAR IS ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    LIME KILN BUILDING, KILN BOTTOM SHOWING ROTATOR GEAR. (GEAR IS POINTED DOWN FOR PROPER ORIENTATION). - Solvay Process Company, Lime Kiln Building, Between Willis & Milton Avenues, Solvay, Onondaga County, NY

  20. Understanding gas hydrate dissolution

    NASA Astrophysics Data System (ADS)

    Lapham, Laura; Chanton, Jeffrey; MacDonald, Ian; Martens, Christopher

    2010-05-01

    In order to understand the role gas hydrates play in climate change or their potential as an energy source, we must first understand their basic behaviors. One such behavior not well understood is their dissolution and the factors that control it. Theoretically, hydrates are stable in areas of high pressure, low temperature, moderate salt concentrations, and saturated methane. Yet in nature, we observe hydrate to outcrop seafloor sediments into overlying water that is under-saturated with respect to methane. How do these hydrates not dissolve away? To address this question, we combine both field and laboratory experiments. In the field, we have collected pore-waters directly surrounding gas hydrate outcrops and measured for in situ methane concentrations. This gives us an understanding of the concentration gradients, and thus methane flux, directly from the hydrate to the surrounding environment. From these samples, we found that methane concentrations decreased further from hydrate yet are always under-saturated with respect to methane hydrate. The resulting low methane gradients were then used to calculate low dissolution rates. This result suggests that hydrates are meta-stable in the environment. What controls their apparent meta-stability? We hypothesize that surrounding oils or microbial slimes help protect the hydrate and slow down their dissolution. To test this hypothesis, we conducted a series of laboratory experiments where hydrate was formed at in situ pressure and temperature and the source gas removed; first with no oils, then with oils. Dissolved methane concentrations were then measured in surrounding fluids over time and dissolution rates calculated. To date, both methane and mixed gas hydrate (methane, ethane, and propane) have similar dissolution rates of 0.12 mM/hr. Future experiments will add oils to determine how different hydrate dissolves with such contaminants. This study will further our understanding of factors that control hydrate stability in nature.

  1. 46 CFR 148.230 - Calcium oxide (lime, unslaked).

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Calcium oxide (lime, unslaked). 148.230 Section 148.230... MATERIALS THAT REQUIRE SPECIAL HANDLING Special Requirements for Certain Materials § 148.230 Calcium oxide (lime, unslaked). (a) When transported by barge, unslaked lime (calcium oxide) must be carried in...

  2. 46 CFR 148.230 - Calcium oxide (lime, unslaked).

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Calcium oxide (lime, unslaked). 148.230 Section 148.230... MATERIALS THAT REQUIRE SPECIAL HANDLING Special Requirements for Certain Materials § 148.230 Calcium oxide (lime, unslaked). (a) When transported by barge, unslaked lime (calcium oxide) must be carried in...

  3. 46 CFR 148.230 - Calcium oxide (lime, unslaked).

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Calcium oxide (lime, unslaked). 148.230 Section 148.230... MATERIALS THAT REQUIRE SPECIAL HANDLING Special Requirements for Certain Materials § 148.230 Calcium oxide (lime, unslaked). (a) When transported by barge, unslaked lime (calcium oxide) must be carried in...

  4. 46 CFR 148.230 - Calcium oxide (lime, unslaked).

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Calcium oxide (lime, unslaked). 148.230 Section 148.230... MATERIALS THAT REQUIRE SPECIAL HANDLING Special Requirements for Certain Materials § 148.230 Calcium oxide (lime, unslaked). (a) When transported by barge, unslaked lime (calcium oxide) must be carried in...

  5. LIME STABILIZATION AND ULTIMATE DISPOSAL OF MUNICIPAL WASTEWATER SLUDGES

    EPA Science Inventory

    Twenty-eight lime stabilization facilities were visited. None of these plants were originally designed for sludge lime stabilization. Lime stabilization was instituted either as a permanent sludge handling mechanism to replace a more costly process, as an interim sludge handling ...

  6. 46 CFR 148.04-23 - Unslaked lime in bulk.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Unslaked lime in bulk. 148.04-23 Section 148.04-23 Shipping COAST GUARD, DEPARTMENT OF HOMELAND SECURITY (CONTINUED) DANGEROUS CARGOES CARRIAGE OF SOLID HAZARDOUS MATERIALS IN BULK Special Additional Requirements for Certain Material § 148.04-23 Unslaked lime in bulk. (a) Unslaked lime in bulk must...

  7. Effects of calcite and magnesite application to a declining Masson pine forest on strongly acidified soil in Southwestern China.

    PubMed

    Huang, Yongmei; Kang, Ronghua; Ma, Xiaoxiao; Qi, Yu; Mulder, Jan; Duan, Lei

    2014-05-15

    Liming of strongly acidified soil under a Masson pine (Pinus massoniana Lamb.) forest was studied through a seven-year field manipulation experiment at Tieshanping, Chongqing in Southwestern China. To distinguish between the individual effects of Ca(2+) and Mg(2+) addition, we separately applied calcite (CaCO3) and magnesite (MgCO3), rather than using dolomite [CaMg(CO3)2]. Both calcite and magnesite additions caused a significant increase in pH and a decrease in dissolved inorganic monomeric aluminium (Ali) concentration of soil water. Ecological recovery included increases of herb biomass (both treatments) and Mg content in Masson pine needles (magnesite treatment only). However, the growth rate of Masson pine did not increase under either treatment, possibly because of nutrient imbalance due to phosphorus (P) deficiency or limited observation period. In China, acid deposition in forest ecosystems commonly coincides with large inputs of atmogenic Ca(2+), both enhancing Mg(2+) leaching. Calcite addition may further decrease the Mg(2+) availability in soil water, thereby exacerbating Mg(2+) deficiency in the acidified forest soils of southern and southwestern China. The effect of anthropogenic acidification of naturally acid forest soils on P availability needs further study. PMID:24631610

  8. Combustion of Methane Hydrate

    NASA Astrophysics Data System (ADS)

    Roshandell, Melika

    A significant methane storehouse is in the form of methane hydrates on the sea floor and in the arctic permafrost. Methane hydrates are ice-like structures composed of water cages housing a guest methane molecule. This caged methane represents a resource of energy and a potential source of strong greenhouse gas. Most research related to methane hydrates has been focused on their formation and dissociation because they can form solid plugs that complicate transport of oil and gas in pipelines. This dissertation explores the direct burning of these methane hydrates where heat from the combustion process dissociates the hydrate into water and methane, and the released methane fuels the methane/air diffusion flame heat source. In contrast to the pipeline applications, very little research has been done on the combustion and burning characteristics of methane hydrates. This is the first dissertation on this subject. In this study, energy release and combustion characteristics of methane hydrates were investigated both theoretically and experimentally. The experimental study involved collaboration with another research group, particularly in the creation of methane hydrate samples. The experiments were difficult because hydrates form at high pressure within a narrow temperature range. The process can be slow and the resulting hydrate can have somewhat variable properties (e.g., extent of clathration, shape, compactness). The experimental study examined broad characteristics of hydrate combustion, including flame appearance, burning time, conditions leading to flame extinguishment, the amount of hydrate water melted versus evaporated, and flame temperature. These properties were observed for samples of different physical size. Hydrate formation is a very slow process with pure water and methane. The addition of small amounts of surfactant increased substantially the hydrate formation rate. The effects of surfactant on burning characteristics were also studied. One finding from the experimental component of the research was that hydrates can burn completely, and that they burn most rapidly just after ignition and then burn steadily when some of the water in the dissociated zone is allowed to drain away. Excessive surfactant in the water creates a foam layer around the hydrate that acts as an insulator. The layer prevents sufficient heat flux from reaching the hydrate surface below the foam to release additional methane and the hydrate flame extinguishes. No self-healing or ice-freezing processes were observed in any of the combustion experiments. There is some variability, but a typical hydrate flame is receiving between one and two moles of water vapor from the liquid dissociated zone of the hydrate for each mole of methane it receives from the dissociating solid region. This limits the flame temperature to approximately 1800 K. In the theoretical portion of the study, a physical model using an energy balance from methane combustion was developed to understand the energy transfer between the three phases of gas, liquid and solid during the hydrate burn. Also this study provides an understanding of the different factors impacting the hydrate's continuous burn, such as the amount of water vapor in the flame. The theoretical study revealed how the water layer thickness on the hydrate surface, and its effect on the temperature gradient through the dissociated zone, plays a significant role in the hydrate dissociation rate and methane release rate. Motivated by the above mentioned observation from the theoretical analysis, a 1-D two-phase numerical simulation based on a moving front model for hydrate dissociation from a thermal source was developed. This model was focused on the dynamic growth of the dissociated zone and its effect on the dissociation rate. The model indicated that the rate of hydrate dissociation with a thermal source is a function of the dissociated zone thickness. It shows that in order for a continuous dissociation and methane release, some of the water from the dissociated zone needs to be drained. The results

  9. Gas Hydrate Nucleation Processes

    NASA Astrophysics Data System (ADS)

    David, R. E.; Zatsepina, O.; Phelps, T. J.

    2003-12-01

    The onset of gas hydrate nucleation is greatly affected by the thermal history of the water that forms its lattice structure. Hydrate formation experiments were performed in a 72 liter pressure vessel by bubbling carbon dioxide through a 1 liter column at hydrate formation pressures (1.4 to 3.7 MPa) and temperatures (275.0 to 278.0 K) to quantify this effect. They show that when even a fraction ( e. g. 20 %) of the water in which hydrate has formed was recently frozen and thawed, the overpressurization for nucleation was reduced by an average of 50 % versus experiments performed in distilled water. In those experiments where a lower overpressure is present when hydrate nucleated, they tended to form on the surface of bubbles, whereas when a higher amount of overpressure was necessary for hydrate to nucleate, they appeared to form abruptly on bubble surfaces as well as from the bulk liquid phase. In approximation of classical nucleation, hydrate formation could be described as occurring by the spontaneous joining together of arising components of the hydrate lattice. In water that was frozen, and kept at a low temperature (< 275 K), molecular simulation models predict the predominance of water molecules organized as penatmeters, a possible subunit of the hydrate lattice. Our results suggest that in nature, initiation of hydrate formation may be strongly influenced by temperature dependant pre-structuring of water molecules prior to their contact with gas.

  10. Controlling local packing and growth in calcium-silicate-hydrate gels.

    PubMed

    Ioannidou, Katerina; Pellenq, Roland J-M; Del Gado, Emanuela

    2014-02-28

    We investigate the development of gels under out-of-equilibrium conditions, such as calcium-silicate-hydrate (C-S-H) gels that form during cement hydration and are the major factor responsible for cement mechanical strength. We propose a new model and numerical approach to follow the gel formation upon precipitation and aggregation of nano-scale colloidal hydrates, whose effective interactions are consistent with forces measured in experiments at fixed lime concentrations. We use Grand Canonical Monte Carlo to mimic precipitation events during Molecular Dynamics simulations, with their rate corresponding to the hydrate production rate set by the chemical environment. Our results display hydrate precipitation curves that indeed reproduce the acceleration and deceleration regime typically observed in experiments and we are able to correctly capture the effect of lime concentration on the hydration kinetics and the gel morphology. Our analysis of the evolution of the gel morphology indicates that the acceleration is related to the formation of an optimal local crystalline packing that allows for large, elongated aggregates to grow and that is controlled by the underlying thermodynamics. The defects produced during precipitation favor branching and gelation that end up controlling the deceleration. The effects on the mechanical properties of C-S-H gels are also discussed. PMID:24652466

  11. Fertilizer and Lime: Why They Are Used.

    ERIC Educational Resources Information Center

    McCaslin, Judith Strand

    This unit teaching guide is designed to help teachers explain the principles of fertilizer and lime use. The first of four major sections is a teaching outline keyed to transparency masters and student handouts. Thirteen major areas are covered in the teaching outline: (1) plant needs; (2) uses of fertilizer; (3) nutrients for plant growth; (4)

  12. Fertilizer and Lime: Why They Are Used.

    ERIC Educational Resources Information Center

    McCaslin, Judith Strand

    This unit teaching guide is designed to help teachers explain the principles of fertilizer and lime use. The first of four major sections is a teaching outline keyed to transparency masters and student handouts. Thirteen major areas are covered in the teaching outline: (1) plant needs; (2) uses of fertilizer; (3) nutrients for plant growth; (4)…

  13. Use of wastes of the sugar industry as pozzolana in lime-pozzolana binders: Study of the reaction

    SciTech Connect

    Hernandez, J.F.M.; Middendorf, B.; Gehrke, M.; Budelmann, H.

    1998-11-01

    Mineralogical studies of different wastes of the sugar industry, mainly sugar cane bagasse ash and sugar cane straw ash, have shown that such by-products are likely to be pozzolanic. Their use in lime-pozzolana binders could become an interesting alternative for developing countries. This paper presents a study that was aimed at monitoring the reaction between lime and wastes of the sugar industry having pozzolanic properties by evaluating (1) content of calcium hydroxide, dependent on time; (2) development of the pore structure, dependent on time; (3) study on the reaction products at different stages; and (4) mechanical properties of hardened pastes. The presence of calcium hydroxide was confirmed by x-ray diffraction analysis and thermogravimetric analysis of powder from samples of hydrated lime-pozzolana pastes. The reaction products in hydrated pastes were observed in a scanning electron microscope, and the pore structure was assessed using a mercury intrusion porosimeter. The results of the study show that sugar cane bagasse ash does not act like a reactive pozzolana, mainly due to the presence of unburned material and carbon, whereas sugar cane straw ash shows good pozzolanic activity comparable to that of rice husk ash.

  14. Determination of the pozzolanic activity of fluid catalytic cracking residue. Thermogravimetric analysis studies on FC3R-lime pastes

    SciTech Connect

    Paya, J.; Monzo, J.; Borrachero, M.V.; Velazquez, S.; Bonilla, M

    2003-07-01

    Spent fluid catalytic cracking catalyst (FC3R) from a petrol refinery played a pozzolanic role in portland cement system as revealed by previous experimental data. In the present study, the pozzolanic activity of FC3R was investigated by means thermogravimetry (TG) of cured lime-FC3R pastes. The influence of pozzolan/lime ratio on the pozzolanic activity was investigated. Due to the chemical composition of FC3R is similar to metakaolin (MK), and knowing that MK has a high pozzolanic activity, the latter was used as a material of comparison in this study. The scope of the study is the determination of the pozzolanic activity of FC3R and the evaluation of amount and nature of pozzolanic products. The products obtained from the reaction between FC3R components (SiO{sub 2}/Al{sub 2}O{sub 3}) and calcium hydroxide (CH) have been characterized, finding that the main pozzolanic reaction product was similar to hydrated gehlenite (calcium aluminosilicate hydrate) CSH and CAH were also formed in the reaction. FC3R showed higher pozzolanic reactivity than metakaolin, for low-lime content pastes and early curing age. Thermogravimetry, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) became very useful techniques for evaluation of reactivity.

  15. A mild alkali treated jute fibre controlling the hydration behaviour of greener cement paste.

    PubMed

    Jo, Byung-Wan; Chakraborty, Sumit

    2015-01-01

    To reduce the antagonistic effect of jute fibre on the setting and hydration of jute reinforced cement, modified jute fibre reinforcement would be a unique approach. The present investigation deals with the effectiveness of mild alkali treated (0.5%) jute fibre on the setting and hydration behaviour of cement. Setting time measurement, hydration test and analytical characterizations of the hardened samples (viz., FTIR, XRD, DSC, TGA, and free lime estimation) were used to evaluate the effect of alkali treated jute fibre. From the hydration test, the time (t) required to reach maximum temperature for the hydration of control cement sample is estimated to be 860 min, whilst the time (t) is measured to be 1040 min for the hydration of a raw jute reinforced cement sample. However, the time (t) is estimated to be 1020 min for the hydration of an alkali treated jute reinforced cement sample. Additionally, from the analytical characterizations, it is determined that fibre-cement compatibility is increased and hydration delaying effect is minimized by using alkali treated jute fibre as fibre reinforcement. Based on the analyses, a model has been proposed to explain the setting and hydration behaviour of alkali treated jute fibre reinforced cement composite. PMID:25592665

  16. A mild alkali treated jute fibre controlling the hydration behaviour of greener cement paste

    NASA Astrophysics Data System (ADS)

    Jo, Byung-Wan; Chakraborty, Sumit

    2015-01-01

    To reduce the antagonistic effect of jute fibre on the setting and hydration of jute reinforced cement, modified jute fibre reinforcement would be a unique approach. The present investigation deals with the effectiveness of mild alkali treated (0.5%) jute fibre on the setting and hydration behaviour of cement. Setting time measurement, hydration test and analytical characterizations of the hardened samples (viz., FTIR, XRD, DSC, TGA, and free lime estimation) were used to evaluate the effect of alkali treated jute fibre. From the hydration test, the time (t) required to reach maximum temperature for the hydration of control cement sample is estimated to be 860 min, whilst the time (t) is measured to be 1040 min for the hydration of a raw jute reinforced cement sample. However, the time (t) is estimated to be 1020 min for the hydration of an alkali treated jute reinforced cement sample. Additionally, from the analytical characterizations, it is determined that fibre-cement compatibility is increased and hydration delaying effect is minimized by using alkali treated jute fibre as fibre reinforcement. Based on the analyses, a model has been proposed to explain the setting and hydration behaviour of alkali treated jute fibre reinforced cement composite.

  17. A mild alkali treated jute fibre controlling the hydration behaviour of greener cement paste

    PubMed Central

    Jo, Byung-Wan; Chakraborty, Sumit

    2015-01-01

    To reduce the antagonistic effect of jute fibre on the setting and hydration of jute reinforced cement, modified jute fibre reinforcement would be a unique approach. The present investigation deals with the effectiveness of mild alkali treated (0.5%) jute fibre on the setting and hydration behaviour of cement. Setting time measurement, hydration test and analytical characterizations of the hardened samples (viz., FTIR, XRD, DSC, TGA, and free lime estimation) were used to evaluate the effect of alkali treated jute fibre. From the hydration test, the time (t) required to reach maximum temperature for the hydration of control cement sample is estimated to be 860?min, whilst the time (t) is measured to be 1040?min for the hydration of a raw jute reinforced cement sample. However, the time (t) is estimated to be 1020?min for the hydration of an alkali treated jute reinforced cement sample. Additionally, from the analytical characterizations, it is determined that fibre-cement compatibility is increased and hydration delaying effect is minimized by using alkali treated jute fibre as fibre reinforcement. Based on the analyses, a model has been proposed to explain the setting and hydration behaviour of alkali treated jute fibre reinforced cement composite. PMID:25592665

  18. Zinc isotope fractionation during adsorption on calcite

    NASA Astrophysics Data System (ADS)

    Dong, S.; Wasylenki, L. E.

    2013-12-01

    Zinc is an important element as a nutrient in the marine biosphere. However, our understanding of its biogeochemical cycling in the oceans is relatively limited. The Zn stable isotope system holds the promise of providing novel insights, since published Zn isotopic values for various natural samples reveal significant fractionations in the marine environment. Surface seawater, basalts, shales, deep-sea clay sediments, sediment trap material, bulk plankton and zooplankton samples, and eolian dust fall within a tight range (?66/64Zn from -0.1 to 0.5), but modern ferromanganese crusts (?66/64Zn from 0.5 to 1.2), as well as carbonates (?66/64Zn from 0.3 to 1.4), are notably enriched in heavy Zn isotopes [1-4]. In this study we seek to constrain the mechanism by which carbonates are enriched in heavier isotopes. In particular, we have conducted experiments to quantify isotope fractionation during adsorption of Zn onto the surfaces of calcite crystals that are in equilibrium with solution. The adsorption experiments were carried out in a series of small-volume batch reactions in a clean laboratory environment, using high-purity reagents and calcite seed crystals. The calcite was equilibrated with the solution prior to addition of Zn at atmospheric CO2 pressure (i.e., in air) for 5 days until a stable pH of 8.3 was reached. Later, a small aliquot of dissolved ZnCl2 was added such that the solution remained undersaturated with respect to hydrozincite. Experimental duration varied among the replicates from 6 to 144 hours, and then all solids and solutions were separated by filtration, purified by ion exchange chromatography, and analyzed by MC-ICP-MS. Zn adsorbed on calcite is isotopically heavier than in the co-existing solutions, with ?68/66Zncalcite-solution of approximately 0.3. The variation of ?68/66Zncalcite-solution beyond 24 hours is insignificant, so we infer that isotopic equilibrium is reached by this time. Previous work strongly suggests that a difference in coordination number between dissolved Zn and adsorbed Zn is drives the observed fractionation. Elzinga and Reeder[5] determined using EXAFS (Extended X-ray Absorption Fine Structure) that Zn adsorbed to calcite surfaces is tetrahedrally coordinated, sharing three oxygens with the calcite surface. Meanwhile density functional theory calculations[6] predicted that tetrahedral Zn-O species should be heavier than octahedral Zn-O species. Thus we infer that equilibrium between octahedrally coordinated, dissolved Zn and tetrahedrally coordinated, adsorbed Zn is the mechanism of fractionation in our experiments. Our further studies will determine whether the isotopically heavy pool of adsorbed Zn becomes the Zn incorporated within carbonates; if so, then we are closer to understanding the mechanism by which carbonate rocks in nature are enriched in heavier isotopes of zinc. [1] Bermin et al., 2006, Chem. Geol. 226, 280. [2] Marchal et al., 2000, Geochem. Geophys. Geosyst. 1, 1999GC-000029. [3] Dong et al., 2013, Talanta 114, 103-109. [4] Pichat et al., 2003, Earth Planet. Sci. Lett. 210, 167-178. [5] Elzinga and Reeder, 2002, Geochim. Cosmochim. Acta 66, 3943-3954. [6] Schauble, 2003, EOS, Trans. AGU, Fall Meet. Suppl. 84(46), B12B-0781.

  19. Influence of water vapour and carbon dioxide on free lime during storage at 80 C, studied by Raman spectroscopy.

    PubMed

    Dubina, E; Korat, L; Black, L; Strupi-uput, J; Plank, J

    2013-07-01

    Micro-Raman spectroscopy has been used to follow the reaction of free lime (CaO) exposed for 24h to moist air at 80 C under conditions of different relative humidities (10-80% RH). X-ray diffraction and SEM imaging were applied as complementary techniques. The conversion of lime to calcium hydroxide and its subsequent carbonation to various calcium carbonate polymorphs was found to strongly depend on the relative humidity. At low RH (10-20%), only Raman spectroscopy revealed the formation of early amorphous CaCO3 which in the XRD patterns was detected only at ?40% RH. However, XRD analysis could identify the crystalline polymorphs formed at higher relative humidities. Thus, between 20 and 60% RH, all three CaCO3 polymorphs (calcite, aragonite and vaterite) were observed via XRD whereas at high relative humidity (80%), calcite was the predominant reaction product. The results demonstrate the usefulness of Raman spectroscopy in the study of minor cement constituents and their reaction products on air, especially of amorphous character. PMID:23639205

  20. Origins of hydration lubrication

    NASA Astrophysics Data System (ADS)

    Ma, Liran; Gaisinskaya-Kipnis, Anastasia; Kampf, Nir; Klein, Jacob

    2015-01-01

    Why is friction in healthy hips and knees so low? Hydration lubrication, according to which hydration shells surrounding charges act as lubricating elements in boundary layers (including those coating cartilage in joints), has been invoked to account for the extremely low sliding friction between surfaces in aqueous media, but not well understood. Here we report the direct determination of energy dissipation within such sheared hydration shells. By trapping hydrated ions in a 0.4-1 nm gap between atomically smooth charged surfaces as they slide past each other, we are able to separate the dissipation modes of the friction and, in particular, identify the viscous losses in the subnanometre hydration shells. Our results shed light on the origins of hydration lubrication, with potential implications both for aqueous boundary lubricants and for biolubrication.

  1. Methane Hydrate Field Program

    SciTech Connect

    2013-12-31

    This final report document summarizes the activities undertaken and the output from three primary deliverables generated during this project. This fifteen month effort comprised numerous key steps including the creation of an international methane hydrate science team, determining and reporting the current state of marine methane hydrate research, convening an international workshop to collect the ideas needed to write a comprehensive Marine Methane Hydrate Field Research Plan and the development and publication of that plan. The following documents represent the primary deliverables of this project and are discussed in summary level detail in this final report. • Historical Methane Hydrate Project Review Report • Methane Hydrate Workshop Report • Topical Report: Marine Methane Hydrate Field Research Plan • Final Scientific/Technical Report

  2. Origins of hydration lubrication.

    PubMed

    Ma, Liran; Gaisinskaya-Kipnis, Anastasia; Kampf, Nir; Klein, Jacob

    2015-01-01

    Why is friction in healthy hips and knees so low? Hydration lubrication, according to which hydration shells surrounding charges act as lubricating elements in boundary layers (including those coating cartilage in joints), has been invoked to account for the extremely low sliding friction between surfaces in aqueous media, but not well understood. Here we report the direct determination of energy dissipation within such sheared hydration shells. By trapping hydrated ions in a 0.4-1 nm gap between atomically smooth charged surfaces as they slide past each other, we are able to separate the dissipation modes of the friction and, in particular, identify the viscous losses in the subnanometre hydration shells. Our results shed light on the origins of hydration lubrication, with potential implications both for aqueous boundary lubricants and for biolubrication. PMID:25585501

  3. Removal of organic magnesium in coccolithophore calcite

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

    Coccolithophore calcite refers to the plates of calcium carbonate (CaCO3) produced by the calcifying phytoplankton, coccolithophores. The empirical study of the elemental composition has a great potential in the development of paleoproxies. However, the difficulties to separate coccolithophore carbonates from organic phases hamper the investigation of coccoliths magnesium to calcium ratios (Mg/Ca) in biogeochemical studies. Magnesium (Mg) is found in organic molecules in the cells at concentrations up to 400 times higher than in inorganically precipitated calcite in present-day seawater. The aim of this study was to optimize a reliable procedure for organic Mg removal from coccolithophore samples to ensure reproducibility in measurements of inorganic Mg in calcite. Two baseline methods comprising organic matter oxidations with (1) bleach and (2) hydrogen peroxide (H2O2) were tested on synthetic pellets, prepared by mixing reagent grade CaCO3 with organic matter from the non-calcifying marine algae Chlorella autotrophica and measured with an ICP-AES (inductively coupled plasma-atomic emission spectrometer). Our results show that treatments with a reductive solution [using hydroxylamine-hydrochloride (NH2OHHCl + NH4OH)] followed by three consecutive oxidations (using H2O2) yielded the best cleaning efficiencies, removing >99% of organic Mg in 24 h. P/Ca and Fe/Ca were used as indicators for organic contamination in the treated material. The optimized protocol was tested in dried coccolithophore pellets from batch cultures of Emiliania huxleyi, Calcidiscus leptoporus and Gephyrocapsa oceanica. Mg/Ca of treated coccolithophores were 0.151 0.018, 0.220 0.040, and 0.064 0.023 mmol/mol, respectively. Comparison with Mg/Ca literature coccolith values, suggests a tight dependence on modern seawater Mg/Ca, which changes as a consequence of different seawater origins (<10%). The reliable determination of Mg/Ca and Sr/Ca, and the low levels of organic contamination (Fe/Ca and P/Ca) make this protocol applicable to field and laboratory studies of trace elemental composition in coccolithophore calcite.

  4. Spectroscopic characterization of natural calcite minerals

    NASA Astrophysics Data System (ADS)

    Gunasekaran, S.; Anbalagan, G.

    2007-11-01

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

  5. Biogenic and synthetic high magnesium calcite - a review.

    PubMed

    Long, Xia; Ma, Yurong; Qi, Limin

    2014-01-01

    Systematic studies on the Mg distributions, the crystal orientations, the formation mechanisms and the mechanical properties of biogenic high-Mg calcites in different marine organisms were summarized in detail in this review. The high-Mg calcites in the hard tissues of marine organisms mentioned generally own a few common features as follows. Firstly, the Mg distribution is not uniform in most of the minerals. Secondly, high-Mg calcite biominerals are usually composed of nanoparticles that own almost the same crystallographic orientations and thus they behave like single crystals or mesocrystals. Thirdly, the formation of thermodynamically unstable high-Mg calcites in marine organisms under mild conditions is affected by three key factors, that is, the formation of amorphous calcium (magnesium) carbonate precursor, the control of polymorph via biomolecules and the high Mg/Ca ratios in modern sea. Lastly, the existence of Mg ions in the Mg-containing calcite may improve the mechanical properties of biogenic minerals. Furthermore, the key progress in the synthesis of high-Mg calcites in the laboratory based on the formation mechanisms of the biogenic high-Mg calcites was reviewed. Many researchers have realized the synthesis of high-Mg calcites in the laboratory under ambient conditions with the help of intermediate amorphous phase, mixed solvents, organic/inorganic surfaces and soluble additives. Studies on the structural analysis and formation mechanisms of thermodynamically unstable biogenic high-Mg calcite minerals may shed light on the preparation of functional materials with enhanced mechanical properties. PMID:24291472

  6. The Coordination of Mg in Foraminiferal Calcite

    NASA Astrophysics Data System (ADS)

    Branson, O.; Redfern, S. A.; Tyliszczak, T.; Sadekov, A.; Langer, G.; Elderfield, H.

    2012-12-01

    The Mg/Ca ratio in calcite shells ('tests') of foraminifera is an empirical ocean temperature proxy widely used to interpret palaeoclimates. We explore the distribution and local environment of Mg in foram tests using STXM and NEXAFS spectroscopy to test the fundamental assumptions behind the proxy, and shed light on the mechanisms underpinning this vital oceanographic tool. Throughout the development of the Mg/Ca proxy, it has been assumed that Mg in foraminifera tests substitutes directly into the calcite lattice (1). This assumption is based on XRD analyses of various high-Mg biogenic carbonates, where Mg concentrations are manifest in the shifted position of diffraction peaks (2, 3). The extrapolation of this trend to foraminiferal calcite links the proxy to inorganic precipitation experiments, and provides a theoretical mechanistic framework to understand the link between Mg/Ca and temperature: the substitution of Mg is endothermic, and favoured at higher temperatures. However, the concentration of Mg in most foraminifera (0-10 mmol/mol Mg/Ca) is below the detection limit of XRD methods, and the analogy to inorganic systems has not been explicitly tested. Electron microprobe (4-6), LA-ICP-MS (7) and high-resolution nanoSIMS mapping (Sadekov, unpub.) of foraminifera tests have revealed the presence of high 'trace element' bands running in plane with the test surface, enriched in Mg, Sr, S, organic molecules and other trace elements. This emphasises a key question highlighted by Dodd (1) when the proxy was still in its infancy: how is Mg incorporated into mineral skeletons? By direct substitution into the calcite lattice, interstitially in a separate distinct mineral phase, or associated with organic compounds? We address this fundamental question using scanning transmission X-ray microscopy (STXM) and X-ray absorption spectroscopy at ALS beamline 11.0.2 to examine the distribution and local atomic environment of Mg in two contrasting species of foraminifera. Our data conclusively demonstrate that the Mg in the high- and low-trace element bands in the two different species is incorporated in the same mode. Foraminiferal Mg K-edge spectra are most similar to that of dolomite, where Ca and Mg are interchangeable and both present in octahedral sites. This indicates that Mg directly substitutes for Ca in the calcite test, validating the assumptions underlying the use of the Mg/Ca proxy. The uniformity of Mg environment also sheds light on the drivers of Mg heterogeneity, suggesting that Mg banding is driven by fluctuations in medium chemistry, rather than any change in Mg incorporation mechanism. The ultimate cause of Mg heterogeneity remains an open question, however. 1. J. R. Dodd, J Paleontology, 1313-1329 (1967). 2. K. E. Chave, J Geol 62, 266-283 (1954). 3. J. Titschack, F. Goetz-Neunhoeffer, J. Neubauer, Am Min 96, 1028 (2011). 4. J. Lipps, P. Ribbe, J Paleontology 41, 492-496 (1967). 5. A. Y. Sadekov, S. M. Eggins, P. de Deckker, G3 6, Q12P06 (2005). 6. J. Erez, Rev Min Geochem 54, 115 (2003). 7. A. Y. Sadekov, S. M. Eggins, G. P. Klinkhammer, Y. Rosenthal, Earth Planet Sc Lett 292, 312-324 (2010).

  7. Gas Hydrates-bearing Sediments from Southern Hydrate Ridge (ODP Leg 204): Geochemical and Mineralogical Approach

    NASA Astrophysics Data System (ADS)

    Piñero, E.; Martinez-Ruiz, F.; Gràcia, E.; Larrasoaña, J. C.; Dañobeitia, J.

    2006-12-01

    Mineralogical and geochemical analyses of more than 500 samples were carried out in order to characterize the southern Hydrate Ridge sediments and to evaluate the role of sediment composition in fluid migration and gas hydrate (GH) distribution. Bulk and clay mineralogy were obtained by XRD and trace element contents by ICP-MS. Bulk mineral composition of southern Hydrate Ridge sediments does not change significantly from the summit to the flanks and slope basin. This composition is dominated by clays (30-60% ), quartz (25- 40% ), feldspars (10-25% ) and calcite (<5% ). Regarding the clay mineralogy, the most abundant mineral is detrital mica (50% ), whereas smectites, kaolinite and chlorite are less abundant (<30% ). Some noticeable trends are recognized in smectite content, increasing with depth at both flanks, from low values near the seafloor to high values (>40% ) downcore. Such increase is accompanied by a decrease in detrital mica content, suggesting the presence of deep fluid flows from below the accretionary complex. Sediments from all sites show high TOC contents from seafloor down to 50 mbsf. Within this interval, high CaCO3 contents and carbonate nodules are observed. High values of REE, Hf and Zr concentrations correlate with increasing terrigenous input, which resulted in coarse grain-size layers, identified as turbidites and formed by silty-clay sediments with different amounts of sand content (up to 10% ). The comparison between turbidite and gas hydrate distributions (inferred from IR imaging, disturbance fabrics and gas hydrate identification) suggests that GH predominantly form within the terrigenous coarser grain-size layers. At the summit, near the seafloor, where the highest GH content was observed (40% of pore volume), this trend is not recognizable, suggesting that gas-methane availability is high enough to generate GH even within finer grain-size layers.

  8. Energy efficient hydration process

    SciTech Connect

    Beimesch, W. E.; Hortel, T. C.

    1985-02-05

    A process for hydrating in a spray tower a water-wet mixture of materials, at least one of which is hydratable, which allows the mixture to be easily formed into the desired size and shape and easily and safely dried.

  9. Gas Hydrates Burning

    USGS Multimedia Gallery

    An image of gas hydrates burning. Gas hydrates are naturally-occurring “ice-like” combinations of natural gas and water that have the potential to provide an immense resource of natural gas from the world’s oceans and polar regions....

  10. Mallik Gas Hydrate Sample

    USGS Multimedia Gallery

    A sample of gas hydrates collected from Mallik, Canada. Gas hydrates are naturally-occurring “ice-like” combinations of natural gas and water that have the potential to provide an immense resource of natural gas from the world’s oceans and polar regions....

  11. Gas Hydrates Burning

    USGS Multimedia Gallery

    An image of gas hydrates burning. Gas hydrates are naturally-occurring ice-like combinations of natural gas and water that have the potential to provide an immense resource of natural gas from the worlds oceans and polar regions....

  12. TOUGH-Fx/Hydrate

    Energy Science and Technology Software Center (ESTSC)

    2005-02-01

    TOUGH-Fx/HYORATL can model the non-isothermal gas release. phase behavior and flow of fluids and heat in complex geologic media. The code can simulate production from natural gas hydrate deposits in the subsurtace (i.e., in the permafrost and in deep ocean sediments), as well as laboratory experiments of hydrate dissociation/formation in porous/fractured media. T006H-Fx/HYDRATE vi .0 includes both an equilibrium and a kinetic model of hydrate Ibmiation and dissociation. The model accounts for heat and upmore » to four mass components-- i.e., water, CH4, hydrate, and water-soluble inhibitors such as salts or alcohols. These are partitioned among four possible phases (gas phase, liquid phase, ice phase and hydrate phase). Hydrate dIssociation or formation, phase changes, and the corresponding thermal effects are fully described, as are the effects of inhibitors. The model can describe all possible hydrate dissociation mechanisms, i.e., depressurization, thermal stimulation, salting-out effects, and inhibItor-Induced effects.« less

  13. Phosphogypsum-fly ash cementitious binder -- Its hydration and strength development

    SciTech Connect

    Singh, M.; Garg, M.

    1995-05-01

    The paper deals with the formulation of a cementitious binder based on calcined phosphogypsum, flyash, hydrated lime and portland cement. Strength properties and hydration of the cementitious binder studies at room temperature and at 50 C in over 90% R.H are presented. It was found that the compressive strength of the cementitious binder was remarkably enhanced at 50 C than at 27 C. The hydration of the cementitious binder as studied by differential thermal analysis and scanning electron microscopy showed that the early age strength in the cementitious binder was due to the hardening of calcined gypsum and the hydration of portland cement while later age strength development was ascribed to the formation of ettringite and CSH.

  14. Fly ash as a liming material for corn production

    SciTech Connect

    Tarkalson, D.D.; Hergert, G.W.; Stevens, W.B.; McCallister, D.L.; Kackman, S.D.

    2005-05-01

    Fly ash produced as a by-product of subbituminous coal combustion can potentially serve as an alternative liming material without negatively affecting corn (Zea mays L.) production in areas where use of conventional liming materials can be uneconomical due to transportation costs. A study was conducted to determine if fly ash produced from the Nebraska Public Power District Gerald Gentleman Power Station located in Sutherland, NE could be used as an alternative liming material. Combinations of dry fly ash (DFA), wet fly ash (WFA), beet lime (by-product of sugar beet (Beta vulgaris L.) processing) (BL), and agricultural lime (AGL) were applied at rates ranging from 0.43 to 1.62 times the recommended lime rate to plots on four acidic soils (Anselmo fine sandy loam, Hord fine sandy loam, Holdrege sandy loam, and Valentine fine sand). Soil samples were collected to a depth of 0.2 m from plots and analyzed for pH before lime applications and twice periodically after lime application. The Hord and Valentine soils were analyzed for exchangeable Ca, Mg, K, Na,and Al for determination of percent Al saturation on selected treatments and sampling dates. Corn grain yields were determined annually. It is concluded that the fly ash utilized in this study and applied at rates in this study, increases soil pH comparable to agricultural lime and is an appropriate alternative liming material.

  15. Friction characteristics of Cd-rich carbonate films on calcite surfaces: implications for compositional differentiation at the nanometer scale

    PubMed Central

    2009-01-01

    Lateral Force Microscopy (LFM) studies were carried out on cleaved calcite sections in contact with solutions supersaturated with respect to otavite (CdCO3) or calcite-otavite solid solutions (SS) as a means to examine the potential for future application of LFM as a nanometer-scale mineral surface composition mapping technique. Layer-by-layer growth of surface films took place either by step advancement or by a surface nucleation and step advancement mechanisms. Friction vs. applied load data acquired on the films and the calcite substrate were successfully fitted to the Johnson Kendall Roberts (JKR) model for single asperity contacts. Following this model, friction differences between film and substrate at low loads were dictated by differences in adhesion, whereas at higher load they reflect differences in contact shear strength. In most experiments at fixed load, the film showed higher friction than the calcite surface, but the friction-load dependence for the different surfaces revealed that at low loads (0–40 nN), a calcian otavite film has lower friction than calcite; a result that is contrary to earlier LFM reports of the same system. Multilayer films of calcian-otavite displayed increasing friction with film thickness, consistent with the expectation that the film surface composition will become increasingly Cd-rich with increasing thickness. Both load- and thickness-dependence trends support the hypothesis that the contact shear strength correlates with the hydration enthalpy of the surface ions, thereby imparting friction sensitivity in the LFM to mineral-water interface composition. PMID:19549312

  16. Emission polarization study on quartz and calcite.

    NASA Technical Reports Server (NTRS)

    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.

  17. Effect of repeated steam hydration reactivation on CaO-based sorbents for CO2 capture.

    PubMed

    Materi?, By Vlatko; Sheppard, Carolyn; Smedley, Stuart I

    2010-12-15

    Samples of natural limestone and commercial calcium carbonate were subjected to successive calcination and carbonation reactions in a TGA and to repeated activity restoration by steam hydration. Steam hydration of spent lime, followed by heating in CO(2), was shown to be an effective method for repeatedly restoring high CO(2) capture activity to spent lime during a large number of CO(2) capture cycles. Steam hydration was also shown to reduce the decay rate of the CO(2) capture activity by increasing the rate of carbonation in the diffusion controlled regime. Repeated hydration-carbonation-calcination cycles led to a considerable expansion of the particles through the formation of large vesicles, likely to lead to high attrition levels when applied in fluidized beds. Based on SEM observation of the particles during hydration-carbonation-calcination cycling, a model was proposed for their progressive weakening. It was concluded that strategies to reduce this weakening must limit the growth of the cracks in the crystal as they are cycled repeatedly. PMID:21114320

  18. Corrosion protection of mild steel by a calcite layer

    SciTech Connect

    Keysar, S.; Hasson, D.; Semiat, R.; Bramson, D.

    1997-08-01

    Artificial calcite lining represents a novel technique for the rehabilitation of water mains. Calcite linings, similar to the commonly used cement-mortar linings, are of porous nature. The corrosion protection mechanisms of calcinite linings were investigated by polarization techniques, complemented by scanning electron microscopy observations and energy dispersive spectrometry analyses. The effect of time on lining durability was examined by exposure of coated mild steel (1020) coupons in a controlled flowing water system. Iron ion distributions in calcite sections, before and after exposure to water flow, indicate that the calcite corrosion protection mechanism is based mainly on accumulation of corrosion products inside the lining. At the calcite-metal interface, a protective film is formed. At the calcite-water interface, the calcite structure, being alkaline with respect to the water, promotes precipitation of the iron ions and blockage of the pores near that interface. The formation of this protective oxide film was evident from the polarization data which showed that both the anodic Tafel constant and the polarization resistance increase with time. This paper also examines the applicability of potentiodynamic and linear polarization techniques for the characterization of the corrosion protection of a porous lining, such as calcite. It is shown that these convenient electrochemical techniques provide reliable and meaningful corrosion protection information.

  19. Dissolution of coccolithophorid calcite by microzooplankton and copepod grazing

    NASA Astrophysics Data System (ADS)

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

    2008-01-01

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

  20. Preparation and evaluation of modified lime and silica-lime sorbents for mercury vapor emissions control

    SciTech Connect

    Ghorishi, S.B.; Singer, C.F.; Sedman, C.B.

    1999-01-01

    The paper discusses current efforts to improve the uptake of mercury species by increasing active sites and adding oxiditive species to the sorbent. (NOTE: Previous work showed that mercury chloride vapor is readily absorbed by calcium-based sorbents as an acid gas in environments typical of coal-fired boiler flue gas, white elemental mercury vapor is absorbed by calcium-based sorbents only when sulfur oxides are also present.) Preparation of modified lime and silica-lime sorbents and their behavior toward mercury species are compared to those of commercially available lime on a fixed-bed bench reactor. The implications of findings toward development of mutipollutant control technologies and planned field toward development of multipollutant control technologies and planned field pilot evaluations of more multipollutant control concepts are discussed.

  1. Hydration rate of obsidian.

    PubMed

    Friedman, I; Long, W

    1976-01-30

    The hydration rates of 12 obsidian samples of different chemical compositions were measured at temperatures from 95 degrees to 245 degrees C. An expression relating hydration rate to temperature was derived for each sample. The SiO(2) content and refractive index are related to the hydration rate, as are the CaO, MgO, and original water contents. With this information it is possible to calculate the hydration rate of a sample from its silica content, refractive index, or chemical index and a knowledge of the effective temperature at which the hydration occurred. The effective hydration temperature can be either measured or approximated from weather records. Rates have been calculated by both methods, and the results show that weather records can give a good approximation to the true EHT, particularly in tropical and subtropical climates. If one determines the EHT by any of the methods suggested, and also measures or knows the rate of hydration of the particular obsidian used, it should be possible to carry out absolute dating to +/- 10 percent of the true age over periods as short as several years and as long as millions of years. PMID:17782901

  2. Sugarcane factory performance of cold, intermediate, and hot lime clarification processes

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A comparative factory investigation of hot versus intermediate and cold lime clarification was undertaken to quantify performance. In cold liming, mixed cane juice (MJ) was incubated (8 min) and then limed in a lime tank (4 minutes), both at -IO5F. For intermediate liming, 50% of the MJ was heated (...

  3. Effect of Microorganism Sporosarcina pasteurii on the Hydration of Cement Paste.

    PubMed

    Lee, Jun Cheol; Lee, Chang Joon; Chun, Woo Young; Kim, Wha Jung; Chung, Chul-Woo

    2015-08-01

    Years of research have shown that the application of microorganisms increases the compressive strength of cement-based material when it is cured in a culture medium. Because the compressive strength is strongly affected by the hydration of cement paste, this research aimed to investigate the role of the microorganism Sporosarcina pasteurii in hydration of cement paste. The microorganism's role was investigated with and without the presence of a urea-CaCl2 culture medium (i.e., without curing the specimens in the culture medium). The results showed that S. pasteurii accelerated the early hydration of cement paste. The addition of the urea-CaCl2 culture medium also increased the speed of hydration. However, no clear evidence of microbially induced calcite precipitation appeared when the microorganisms were directly mixed with cement paste. PMID:25876598

  4. Methane Hydrates: Chapter 8

    USGS Publications Warehouse

    Boswell, Ray; Yamamoto, Koji; Lee, Sung-Rock; Collett, Timothy S.; Kumar, Pushpendra; Dallimore, Scott

    2008-01-01

    Gas hydrate is a solid, naturally occurring substance consisting predominantly of methane gas and water. Recent scientific drilling programs in Japan, Canada, the United States, Korea and India have demonstrated that gas hydrate occurs broadly and in a variety of forms in shallow sediments of the outer continental shelves and in Arctic regions. Field, laboratory and numerical modelling studies conducted to date indicate that gas can be extracted from gas hydrates with existing production technologies, particularly for those deposits in which the gas hydrate exists as pore-filling grains at high saturation in sand-rich reservoirs. A series of regional resource assessments indicate that substantial volumes of gas hydrate likely exist in sand-rich deposits. Recent field programs in Japan, Canada and in the United States have demonstrated the technical viability of methane extraction from gas-hydrate-bearing sand reservoirs and have investigated a range of potential production scenarios. At present, basic reservoir depressurisation shows the greatest promise and can be conducted using primarily standard industry equipment and procedures. Depressurisation is expected to be the foundation of future production systems; additional processes, such as thermal stimulation, mechanical stimulation and chemical injection, will likely also be integrated as dictated by local geological and other conditions. An innovative carbon dioxide and methane swapping technology is also being studied as a method to produce gas from select gas hydrate deposits. In addition, substantial additional volumes of gas hydrate have been found in dense arrays of grain-displacing veins and nodules in fine-grained, clay-dominated sediments; however, to date, no field tests, and very limited numerical modelling, have been conducted with regard to the production potential of such accumulations. Work remains to further refine: (1) the marine resource volumes within potential accumulations that can be produced through exploratory drilling programs; (2) the tools for gas hydrate detection and characterisation from remote sensing data; (3) the details of gas hydrate reservoir production behaviour through additional, well-monitored and longer duration field tests and (4) the understanding of the potential environmental impacts of gas hydrate resource development. The results of future production tests, in the context of varying market and energy supply conditions around the globe, will be the key to determine the ultimate timing and scale of the commercial production of natural gas from gas hydrates.

  5. Differences in the immobilization of arsenite and arsenate by calcite

    NASA Astrophysics Data System (ADS)

    Yokoyama, Yuka; Tanaka, Kazuya; Takahashi, Yoshio

    2012-08-01

    The sorption and coprecipitation experiments of arsenic (As) with calcite coupled with determinations of the chemical state of As both in the reaction fluid and in calcite were conducted to investigate the influence of the As oxidation state on its immobilization into calcite. The oxidation states of As in calcite and water were determined via As K-edge XANES and HPLC-ICP-MS analysis, respectively. The results of the sorption experiments at pH 8.2 show that only As(V) is distributed to calcite regardless of the As oxidation state in the solution. In coprecipitation experiments, As(V) is preferentially incorporated into calcite over a wide range of pH (7-12). On the other hand, the incorporation of As(III) into calcite is not observed at circumneutral pH. This difference between As(III) and As(V) is attributed to the fact that their dissolved species are neutral vs. negatively charged, respectively, at circumneutral pH (arsenite as H3AsO3; arsenate as H2AsO4- or HAsO42-). As the pH increases (>9), up to 33% of As(III)/Astotal ratio is partitioned into calcite or a precursor of calcite (metastable vaterite formed during the early stage of precipitation). The higher interaction of As with calcite at an alkaline pH compared with circumneutral pH is due to the negative charge of As(III) at alkaline pH. However, the As(III)/Astotal ratio decreases as time progresses and only As(V) can be found finally in calcite. The ratio of distribution coefficients of As(III) and As(V) into calcite (KAs(V)/KAs(III)) at pH 7 is larger than 2.1 103, suggesting that the oxidation state of As is a significant issue in considering the interaction between As and calcite in groundwater. Moreover, low KAs(III) shows that the sequestration of As via coprecipitation with calcite is not an important chemical process under reducing conditions, such as in the groundwaters in Bangladesh and other As-contaminated areas where As(III) is the dominant dissolved species of As. In the system spiked only with As(III), the XANES analysis detected As(V) in calcite, where the partitioning of As into calcite is very limited as stated above. Therefore, HPLC-ICP-MS and cyclic voltammetric measurements were performed to clarify the As(V)-incorporation mechanism in the As(III) system. As a result, the oxidation of As(III) to As(V) and the stabilization of As(V) in a solution in the presence of the Ca2+ ion are observed. These phenomena result from the formation of calcium arsenate complexes in the aqueous phase. This complexation is an important process for the coprecipitation of As with calcite. Hence, As is incorporated into calcite as As(V) even from the As(III) solution at circumneutral pH, wherein As(III) exists as neutral arsenite with little interaction with calcite.

  6. Hydrate morphology: Physical properties of sands with patchy hydrate saturation

    USGS Publications Warehouse

    Dai, S.; Santamarina, J.C.; Waite, William F.; Kneafsey, T.J.

    2012-01-01

    The physical properties of gas hydrate-bearing sediments depend on the volume fraction and spatial distribution of the hydrate phase. The host sediment grain size and the state of effective stress determine the hydrate morphology in sediments; this information can be used to significantly constrain estimates of the physical properties of hydrate-bearing sediments, including the coarse-grained sands subjected to high effective stress that are of interest as potential energy resources. Reported data and physical analyses suggest hydrate-bearing sands contain a heterogeneous, patchy hydrate distribution, whereby zones with 100% pore-space hydrate saturation are embedded in hydrate-free sand. Accounting for patchy rather than homogeneous hydrate distribution yields more tightly constrained estimates of physical properties in hydrate-bearing sands and captures observed physical-property dependencies on hydrate saturation. For example, numerical modeling results of sands with patchy saturation agree with experimental observation, showing a transition in stiffness starting near the series bound at low hydrate saturations but moving toward the parallel bound at high hydrate saturations. The hydrate-patch size itself impacts the physical properties of hydrate-bearing sediments; for example, at constant hydrate saturation, we find that conductivity (electrical, hydraulic and thermal) increases as the number of hydrate-saturated patches increases. This increase reflects the larger number of conductive flow paths that exist in specimens with many small hydrate-saturated patches in comparison to specimens in which a few large hydrate saturated patches can block flow over a significant cross-section of the specimen.

  7. Transformations in methane hydrates

    USGS Publications Warehouse

    Chou, I.-Ming; Sharma, A.; Burruss, R.C.; Shu, J.; Mao, Ho-kwang; Hemley, R.J.; Goncharov, A.F.; Stern, L.A.; Kirby, S.H.

    2000-01-01

    Detailed study of pure methane hydrate in a diamond cell with in situ optical, Raman, and x-ray microprobe techniques reveals two previously unknown structures, structure II and structure H, at high pressures. The structure II methane hydrate at 250 MPa has a cubic unit cell of a = 17.158(2) A?? and volume V = 5051.3(13) A??3; structure H at 600 MPa has a hexagonal unit cell of a = 11.980(2) A??, c = 9.992(3) A??, and V = 1241.9(5) A??3. The compositions of these two investigated phases are still not known. With the effects of pressure and the presence of other gases in the structure, the structure II phase is likely to dominate over the known structure I methane hydrate within deep hydrate-bearing sediments underlying continental margins.

  8. Withdrawing Nutrition, Hydration

    Cancer.gov

    Module eleven of the EPEC-O Self-Study Original Version discusses the general aspects of withholding or withdrawing of life-sustaining therapies, and presents a specific application to artificial nutrition and hydration.

  9. EVALUATION OF HAZARDOUS WASTE INCINERATION IN A LIME KILN: ROCKWELL LIME COMPANY

    EPA Science Inventory

    During a one-week test burn, hazardous waste was used as supplemental fuel and co-fired with petroleum coke in a lime kiln in eastern Wisconsin. Detailed sampling and analysis was conducted on the stack gas for principal organic hazardous constituents (POHCs), particulates, parti...

  10. Strontium Incorporation into Calcite Generated by Bacterial Ureolysis

    SciTech Connect

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

    2004-08-01

    Strontium incorporation into calcite generated by bacterial ureolysis was investigated as part of an assessment of a proposed remediation approach for 90Sr contamination in groundwater. Urea hydrolysis produces ammonium and carbonate and elevates pH, resulting in the promotion of calcium carbonate precipitation. Urea hydrolysis by the bacterium Bacillus pasteurii in a medium designed to mimic the chemistry of the Snake River Plain Aquifer in Idaho resulted in a pH rise from 7.5 to 9.1. Measured average distribution coefficients (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.

  11. COLOR REMOVAL FROM KRAFT PULPING EFFLUENT BY LIME ADDITION. CAPSULE REPORT

    EPA Science Inventory

    A full scale process for lime decolorization of kraft pulping total mill effluent was operated. Slaked lime addition was followed by primary sedimentation for removal of mixed fibrous and lime decolorization sludges. The clarified effluent subsequently underwent biochemical stabi...

  12. Magnesium inhibition of calcite dissolution kinetics

    SciTech Connect

    Arvidson, Rolf S.; Collier, Martin; Davis, Kevin J.; Vinson, Michael D.; Amonette, James E.; Luttge, Andreas

    2006-02-01

    We present evidence of inhibition of calcite dissolution by dissolved magnesium through direct observations of the (104) surface using atomic force microscopy (AFM) and vertical scanning interferometry (VSI). Far from equilibrium, the pattern of magnesium inhibition is dependent on solution composition and specific to surface step geometry. In CO2-free solutions (pH 8.8), dissolved magnesium brings about little inhibition even at concentrations of 0.8 x 10-3 molal. At the same pH, magnesium concentrations of less than 0.05 x 10-3 molal in carbonate-buffered solutions generate significant inhibition, although no changes in surface and etch pit morphology are observed. As concentrations exceed magnesite saturation, the dissolution rate shows little additional decrease; however, selective pinning of step edges results in unique etch-pit profiles, seen in both AFM and VSI datasets. Despite the decreases in step velocity, magnesium addition in carbonated solutions also appears to activate the surface by increasing the nucleation rate of new defects. These relationships suggest that the modest depression of the bulk rate measured by VSI reflects a balance between competing reaction mechanisms that simultaneously depress the rate through selective inhibition of step movement, but also enhance reactivity on terraces by lowering the energy barrier to new etch-pit formation.

  13. Kinetics of lime/bentonite pozzolanic reactions at 20 and 50 C: Batch tests and modeling

    SciTech Connect

    De Windt, Laurent; Deneele, Dimitri; Maubec, Nicolas

    2014-05-01

    The effects of duration (1100 days) and temperature (20 and 50 C) were assessed from batch tests for Ca-bentonite mixed with 10 wt.% lime. The pozzolanic processes were monitored over time by {sup 29}Si NMR (Cement Concr. Res. 42, 2012), TGA-DTA, XRD and chemical analysis. Modeling considered kinetics and thermodynamics of mineralogical transformations and cation exchange. Kinetic laws were dependent on pH and temperature (Arrhenius energy). Lime hydration occurs within hours, modifying the bentonite exchangeable population and increasing the pH. These alkaline conditions initiate the pozzolanic reactions in a second stage. The rate-limiting step is the dissolution kinetics of the bentonite minerals, i.e. a relatively fast and total consumption of cristobalite in parallel to a long-term slower dissolution of montmorillonite. First CSH and then CASH are formed consequently. Temperature speeds up the pozzolanic reaction kinetics by a factor 5 from 20 to 50 C, corresponding to an apparent activation energy of 4050 kJ/mol.

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

    PubMed

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

    2012-11-21

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

  15. Atomic Resolution of Calcium and Oxygen Sublattices of Calcite in Ambient Conditions by Atomic Force Microscopy Using qPlus Sensors with Sapphire Tips.

    PubMed

    Wastl, Daniel S; Judmann, Michael; Weymouth, Alfred J; Giessibl, Franz J

    2015-01-01

    Characterization and imaging at the atomic scale with atomic force microscopy in biocompatible environments is an ongoing challenge. We demonstrate atomically resolved imaging of the calcite (101̅4) surface plane using stiff quartz cantilevers ("qPlus sensors", stiffness k = 1280 N/m) equipped with sapphire tips in ambient conditions without any surface preparation. With 10 atoms in one surface unit cell, calcite has a highly complex surface structure comprising three different chemical elements (Ca, C, and O). We obtain true atomic resolution of calcite in air at relative humidity ranging from 20% to 40%, imaging atomic steps and single atomic defects. We observe a great durability of sapphire tips with their Mohs hardness of 9, only one step below diamond. Depending on the state of the sapphire tip, we resolve either the calcium or the oxygen sublattice. We determine the tip termination by comparing the experimental images with simulations and discuss the possibility of chemical tip identification in air. The main challenges for imaging arise from the presence of water layers, which form on almost all surfaces and have the potential to dissolve the crystal surface. Frequency shift versus distance spectra show the presence of at least three ordered hydration layers. The measured height of the first hydration layer corresponds well to X-ray diffraction data and molecular dynamic simulations, namely, ∼220 pm. For the following hydration layers we measure ∼380 pm for the second and third layer, ending up in a total hydration layer thickness of at least 1 nm. Understanding the influence of water layers and their structure is important for surface segregation, surface reactions including reconstructions, healing of defects, and corrosion. PMID:25816927

  16. Preheating and incubation of cane juice prior to liming: a comparison of intermediate and cold lime clarification.

    PubMed

    Eggleston, Gillian; Monge, Adrian; Pepperman, Armand

    2002-01-30

    In the U.S., cold lime clarification remains the clarification process of choice in raw sugar manufacturing. A comparative study of cold vs intermediate lime clarification was undertaken at a factory that operated intermediate liming (approximately 30% mixed juice (MJ) of pH 5.2 +/- 0.3 was preheated to 87-93 degrees C to help maintain clean limed juice heaters, incubated at approximately 54 degrees C, and then limed) but still had the pipes to revert to cold liming (MJ incubated and limed at approximately 40 degrees C) for this study. Hourly samples were collected over a 6 h sampling period across cold and intermediate clarification processes on two consecutive days, respectively, and this was repeated three times across the 1999 grinding season. A total of 1.57% less sucrose was lost to inversion reactions across intermediate rather than cold liming. In intermediate liming, which required approximately 4.6% less lime, preheating of only 30% of the MJ markedly removed color (-29%), dextran (-10%), and starch (-24%) and caused large flocs to form that settled faster in the clarifiers. Faster settling led to an impressive 4.6% (season average) more turbidity removal across the clarifiers in intermediate rather than cold liming. Intermediate clarified juice (CJ) turbidity (season average 2028 ICU +/- 675) was approximately half of cold CJ turbidity (average 3952 ICU +/- 1450) with over 2-fold more CJ turbidity control. Subsequent turbidity values and control were significantly improved in the final evaporator syrup samples too. For both processes, juice incubation caused approximately 10% color removal, but this was offset by color formation on liming, because of the alkaline degradation of invert; however, overall, more color was removed than formed in intermediate liming. Starch was reduced in the incubator tank, for both processes, because added filtrate reduced the acidity enabling natural diastase from the cane to degrade starch. Some dextran occasionally formed in the incubator tank, in both processes. Summed across measured parameters, intermediate liming appears to offer several advantages over cold liming. PMID:11804517

  17. Investigation of Copper Sorption by Sugar Beet Processing Lime Waste

    EPA Science Inventory

    In the western United States, sugar beet processing for sugar recovery generates a lime-based waste product (~250,000 Mg yr-1) that has little liming value in the region’s calcareous soils. This area has recently experienced an increase in dairy production, with dairi...

  18. 76 FR 82295 - Central Power & Lime LLC; Notice of Filing

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-12-30

    ... Energy Regulatory Commission Central Power & Lime LLC; Notice of Filing December 23, 2011. Take notice that on December 22, 2011, Central Power & Lime LLC, pursuant to sections 18 CFR 292.205(c) and 385.207... other than the Applicant. The Commission encourages electronic submission of protests and...

  19. Bioconversion of lime pretreated wheat straw to fuel ethanol

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Lime pretreatment and enzymatic saccharification methods were evaluated for conversion of wheat straw cellulose and hemicellulose to fermentable sugars. The maximum yield of monomeric sugars from wheat straw (8.6%, w/v) by lime pretreatment (100 mg/g straw, 121 deg C, 1 h) and enzymatic hydrolysis ...

  20. Investigation of copper sorption by sugar beet processing lime waste

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In the western US, sugar beet processing for sugar recovery generates a lime-based waste product (~250,000 megagrams/yr) that has little liming value in the region’s calcareous soils. This area has recently experienced an increase in dairy production, with dairies utilizing copper-based hoof baths ...

  1. Investigation of Copper Sorption by Sugar Beet Processing Lime Waste

    EPA Science Inventory

    In the western United States, sugar beet processing for sugar recovery generates a lime-based waste product (~250,000 Mg yr-1) that has little liming value in the regions calcareous soils. This area has recently experienced an increase in dairy production, with dairi...

  2. Engineering Properties of Bentonite Stabilized with Lime and Phosphogypsum

    NASA Astrophysics Data System (ADS)

    Kumar, Sujeet; Dutta, Rakesh Kumar; Mohanty, Bijayananda

    2014-12-01

    Engineering properties such as compaction, unconfined compressive strength, consistency limits, percentage swell, free swell index, the California bearing ratio and the consolidation of bentonite stabilized with lime and phosphogypsum are presented in this paper. The content of the lime and phosphogypsum varied from 0 to 10 %. The results reveal that the dry unit weight and optimum moisture content of bentonite + 8 % lime increased with the addition of 8 % phosphogypsum. The percentage of swell increased and the free swell index decreased with the addition of 8 % phosphogypsum to the bentonite + 8 % lime mix. The unconfined compressive strength of the bentonite + 8 % lime increased with the addition of 8 % phosphogypsum as well as an increase in the curing period up to 14 days. The liquid limit and plastic limit of the bentonite + 8 % lime increased, whereas the plasticity index remained constant with the addition of 8 % phosphogypsum. The California bearing ratio, modulus of subgrade reaction, and secant modulus increased for the bentonite stabilized with lime and phosphogypsum. The coefficient of the consolidation of the bentonite increased with the addition of 8 % lime and no change with the addition of 8 % phosphogypsum.

  3. Fly Ash as a Liming Material for Corn Production

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Fly ash produced as a by-product of sub-bituminous coal combustion can potentially serve as an alternative liming material without negatively affecting corn (Zea mays L.) production in areas where use of conventional liming materials can be uneconomical due to transportation costs. A study was cond...

  4. Mitigation of acid deposition: Liming of surface waters. Final report

    SciTech Connect

    Bartoshesky, J.; Price, R.; DeMuro, J.

    1989-05-01

    In recent years acid deposition has become a serious concern internationally. Scientific literature has documented the acidification of numerous lakes and streams in North America and Scandinavia resulting in the depletion or total loss of fisheries and other aquatic biota. Liming represents the only common corrective practice aimed specifically at remediating an affected acid receptor. This report reviews a range of liming technologies and liming materials, as well as the effect of surface-water liming on water quality and aquatic biota. As background to the liming discussion, the hydrologic cycle and the factors that make surface waters sensitive to acid deposition are also discussed. Finally, a brief review of some of the liming projects that have been conducted, or are currently in operation is presented, giving special emphasis to mitigation efforts in Maryland. Liming has been effectively used to counteract surface-water acidification in parts of Scandinavia, Canada, and the U.S. To date, liming has generally been shown to improve physical and chemical conditions and enhance the biological recovery of aquatic ecosystems affected by acidification.

  5. Effects of lime juice on malaria parasite clearance.

    PubMed

    Adegoke, S A; Oyelami, O A; Olatunya, O S; Adeyemi, L A

    2011-10-01

    One hundred and twenty children with acute uncomplicated malaria who were managed at the children's outpatient department of the Wesley Guild Hospital, Ilesa (a unit of Obafemi Awolowo University Teaching Hospitals' Complex, Ile-Ife, Osun state, Nigeria) were recruited into the study to determine the effects of lime juice on malaria parasite clearance. These children were randomized into treatment with World Health Organization recommended antimalarials (artemisinin combination therapy, ACT) either alone or with lime juice. Nine of them were lost to follow-up, four were in the group that were managed with ACT and lime, and five in the group that were managed on ACT alone. The average (SD) time to achieve >75% reduction in parasite load was significantly lower in patients on ACT and lime; 30.5??2.4?h against 38.6??3.3?h for those on ACT alone (p?lime juice achieved complete parasite clearance by 72?h of therapy (p?=?0.007), ten (18.2%) patients without lime had early treatment failure (p?=?0.003). There were no side effects with the use of lime juice. It may therefore be inferred, from this preliminary work, that lime juice when used with the appropriate antimalarial may enhance malaria parasite clearance especially in those with uncomplicated malaria. PMID:21413089

  6. Thermal behavior of biodegraded lime wood.

    PubMed

    Popescu, Carmen-Mihaela; Manoliu, Alexandru; Lisa, Gabriela; Gradinariu, Petronela; Vasile, Cornelia

    2010-06-16

    The effects of the soft-rot fungus Trichoderma viride Pers., on the thermal behavior of lime wood (Tillia cordata Mill.) were investigated. The lime wood pieces were inoculated with the fungus over a 12-week period. At pre-established time intervals two samples were withdrawn from the medium and analyzed by thermogravimetry and differential calorimetry, and the results were correlated with mass loss. Fungal activity was indicated by continuous decrease of sample mass. Modification of the wood because of the presence of the fungus was evidenced by structural changes that affected its thermal properties, both in respect to the hydrophilicity of the wood (evidenced mainly in desorption process) and in its decomposition behavior. The shape of DTG curves depends on the exposure time of wood to the action of microorganisms. The peak temperature assigned to the decomposition of wood components increases, while the global kinetic parameters for the main peak decrease with increasing exposure time of the wood to the attack by microorganisms. The increased characteristic temperatures of water desorption and cellulose decomposition processes and lower thermal stability could be explained by newly formed structures, mainly the oxidized ones. PMID:20451899

  7. Experimental investigation of sediment control on the saturation level of gas hydrate in sediments

    NASA Astrophysics Data System (ADS)

    Lu, H.; Ukita, T.; Noguchi, S.; Moudrakovski, I.; Shimada, T.; Ripmeester, J.; Ratcliffe, C.

    2010-12-01

    Except for those occurring at the seafloor, most natural gas hydrates form in sediments and are subject to the influence of the sediment. Investigations on natural gas hydrate have found that the saturation level of gas hydrate in sediments is closely related to the sediment type: comparatively enriched in coarse sediments such as sands but poorly saturated in fine sediments such as clay. However, due to the limitation of the current geological and geophysical investigations and the rarity of the recovery of intact hydrate samples, the knowledge about sediment control on hydrate saturation in sediments is still limited, and the mechanism is not yet understood. This research investigated the possible factors involved in sediment control on hydrate saturation using an experimental approach. The experiments were carried out with both natural and artificial sediments. The natural sediments were recovered from gas hydrate reservoirs in the Nankai Trough, offshore Japan, Cascadia, offshore Vancouver Island, K-G basin, offshore India, and offshore Andaman Island. The artificial sediments were prepared with quartz powder, a representative of silicates and aluminosilicates, kaolinite and Na-montmorillonite, representatives of clay minerals, and calcite, representative of carbonate minerals. Methane hydrate was synthesized in the artificial sediments under conditions simulating the reservoir of natural gas hydrate, and its saturation levels were determined from the gas amount released from a known volume of sediment. The results indicate that particle size and mineral composition are the two main factors affecting hydrate saturation in sediments. In the range from 20 to 250 ?m, the degree of conversion of water into hydrate increases dramatically with increase in particle size, from 3% to 82%, corresponding to a pore saturation from 4% to ~ 100%. Studies also found that the sorting effect of sediment particles can also play a certain role in affecting hydrate saturation, although not as significantly as particle size. With increasing clay content, hydrate saturation decreased dramatically. When the clay content is over 40%, the degree of pore water converted to hydrate is only about 2%, corresponding to hydrate saturation lower than 3%. The NMR proton relaxation times of water confined in silica sands, show a logarithmic relationship with particle size, and it was found that the samples with higher hydrate saturation are those with longer proton relaxation times.

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

    SciTech Connect

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

    1994-12-31

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

  9. Calcite crystal growth rate inhibition by polycarboxylic acids

    USGS Publications Warehouse

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

    2001-01-01

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

  10. Immobilization of lead and cadmium in solid residues from the combustion of refuse using lime and phosphate

    SciTech Connect

    O'Hara, M.J.; Surgi, M.R.

    1988-04-12

    This patent describes a method of immobilizing lead and cadmium in a free flowing particulate dry solid residue which maintains its free flowing particulate nature after the immobilizing treatment. The dry solid residue comprises fly ash and mixtures of fly ash with bottom ash resulting from the incineration of municipal waste, comprising contacting the dry solid residue with at least one water soluble phosphate in an amount equivalent to about 1 to about 8% by weight of phosphoric acid based on the total residue in the presence of a free lime source selected from the group consisting of lime, hydrated lime, flue gas scrubber product, and combinations thereof, in an amount sufficient to furnish from about 1 to about 25 parts by weight calcium hydroxide per 5 parts by weight of fly ash whereby the leaching of cadmium and lead is reduced to a level no more than 1 ppm cadium and 5 ppm lead as determined in an EPA test performed on the resulting dry treated residue.

  11. Uptake of chloride and carbonate ions by calcium monosulfoaluminate hydrate

    SciTech Connect

    Mesbah, Adel; Cau-dit-Coumes, Celine; Frizon, Fabien

    2012-08-15

    Decommissioning of old nuclear reactors may produce waste streams containing chlorides and carbonates, including radioactive {sup 36}Cl{sup -} and {sup 14}CO{sub 3}{sup 2-}. Their insolubilization by calcium monosulfoaluminate hydrate was investigated. Carbonates were readily depleted from the solution, giving at thermodynamic equilibrium monocarboaluminate, monocarboaluminate + calcite, or calcite only, depending on the initial ratio between the anion and calcium monosulfoaluminate hydrate. Chloride ions reacted more slowly and were precipitated as Kuzel's salt, Kuzel's and Friedel's salts, or Friedel's salt only. Rietveld refinement of X-Ray powder diffraction patterns was successfully used to quantify the phase distributions, which were compared to thermodynamic calculations. Moreover, analysing the lattice parameters of Kuzel's salt as a function of its chloride content showed the occurrence of a restricted solid solution towards the sulfate side with general formula 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}xCaCl{sub 2}{center_dot}(1 - x)CaSO{sub 4}{center_dot}(12 - 2x){center_dot}H{sub 2}O (0.36 {<=} x {<=} 0.50).

  12. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    SciTech Connect

    Chapman, Piers; *Morse, John W.

    2010-11-15

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

  13. Wetland vegetation responses to liming an Adirondack watershed

    SciTech Connect

    Mackun, I.R.

    1993-01-01

    Watershed liming as a long-term mitigation strategy to neutralize lake acidity, from increasing acid deposition, was initiated in North America at Woods Lake in the west central Adirondack region of New York. In October 1989, a dose of 10 MT lime (83.5% CaCO[sub 3]) ha[sup [minus]1] was aerially applied to 48% of the watershed. The wetlands adjacent to Woods Lake showed two distinct community types: one dominated by Chamaedaphne calyculata, and one dominated by graminoids and other herbaceous species. Within two years, liming did not alter the structure of either community type, and changed the cover or frequency of only 6 of 64 individual taxa. Most of these changes occurred in the herbaceous community type. The only strong positive response to liming was a nearly threefold increase in cover of the rhizomatous sedge Cladium mariscoides. The cover of Carex interior and Sphagnum spp. benefited from lime addition, while cover of Drosera intermedia and Muhlenbergia uniflora, and frequency of Hypericum canadense responded negatively to lime. Liming influenced the competitive release of only three taxa, all forbs with small growth forms. The tissue chemistry of foliage and twigs of Myrica gale, Chamaedaphne calyculata, and Carex stricta in the Chamaedaphne calyculata community type clearly illustrated species-specific patterns of nutrient accumulation and allocation both before and after liming. Concentrations of 17 of 20 elements responded to liming, although the responses varied among species and plant parts. Carex foliage was least responsive to liming, and Chamaedaphne twigs were most responsive. Elemental changes in plant tissues will be reflected in litter and many influence long-term nutrient dynamics in the wetland community.

  14. Natural gas hydrates

    SciTech Connect

    Sloan, E.D. Jr. )

    1991-12-01

    This paper reports on gas clathrates (commonly called hydrates), which are crystalline compounds that occur when water form a cage-like structure around smaller guest molecules. Gas hydrates of interest to the natural gas hydrocarbon industry are composed of water and eight molecules: methane, ethane, propane, isobutane, normal butane, nitrogen, carbon dioxide, and hydrogen sulfide. Hydrate formation is possible in any place where water exists with such molecules - in natural or artificial environments and at temperatures above and below 32{degrees} F when the pressure is elevated. Hydrates are considered a nuisance because they block transmission lines, plug blowout preventers, jeopardize the foundations of deepwater platforms and pipelines, cause tubing and casing collapse, and foul process heat exchangers, valves, and expanders. Common examples of preventive measures are the regulation of pipeline water content, unusual drilling-mud compositions, and large quantities of methanol injection into pipelines. We encounter conditions that encourage hydrate formation as we explore more unusual environments for gas and oil, including deepwater frontiers and permafrost regions.

  15. A novel determination of calcite dissolution kinetics in seawater

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  16. The differnces between bond lengths in biogenic and geologocal calcite.

    SciTech Connect

    Zlotoyabko, E.; Caspi, E. N.; Fieramosca, J. S.; Von Dreele, R. B.; Marin, F.; Mor, G.; Politi, Y.; Addadi, L.; Weiner, S.

    2010-01-01

    We used high-resolution neutron powder diffraction to accurately measure the atomic positions and bond lengths in biogenic and geological calcite. A special procedure for data analysis was developed in order to take into account the considerable amounts of magnesium present in all the investigated samples. As a result, in biogenic calcite we found some atomic bonds to have significantly different lengths as compared to those in geological calcite, after the contribution of magnesium is accounted for. The maximum effect (elongation up to 0.7%) was found for the C-O bonds. We also analyzed changes in frequencies and spectral widths of normal vibrations of carbonate groups in biogenic calcite (as compared to geological calcite) measured by Raman and Fourier transform IR techniques. Surprisingly, the frequency shifts after subtracting the magnesium contribution are close to zero. At the same time, substantial spectral broadening (up to 1.2%) in biogenic calcite as compared to geological samples was detected. Possible explanations for the experimental findings are discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

    Stable isotope (?18O and ?13C) 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 ?D and ?18O, dripwater Ca2+, pH, ?13C and TCO2, cave air pCO2 and ?13C, and farmed calcite ?18O and ?13C 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 ?13C 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 ??13C = -7 . A whole-cave "Hendy test" at distributed contemporaneous farming sites reveals that ventilation induces a +1.9 0.96 ?13C offset between calcite precipitated in a ventilation flow path and out of flow paths. Farmed calcite ?18O exhibits a +0.82 0.24 offset from values predicted by both theoretical calcite-water calculations and by laboratory-grown calcite [2]. Unlike calcite ?13C, 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 ? = 16.1(1000/T) - 24.6 We analyzed anions, cations, and trace elements in dripwater, bedrock, and farmed calcite to examine the relationships between net rainfall, drip rates, drip water chemistry, and calcite chemistry. Dripwater Mg/Ca and Sr/Ca ratios fall on coherent mixing lines between three geochemical endmembers: rainwater, dissolved dolomite, and dissolved limestone. Dripwater Sr/Ca vs. Mg/Ca ratios are also influenced by evaporative enrichment within the epikarst as a function of net rainfall amount [3]. Farmed calcite trace Cation/Ca ratios faithfully track short-term seasonal variations in dripwater chemistry for Na, Mg, Sr, Ba and U. However, speleothem calibrations are unique to each drip site regardless of proximity to one another, suggesting that individual speleothems are unlikely to be useful as a whole-cave hydrologic proxy. [1] Kowalczk, A. J., Froelich, P. N., 2010. Cave air ventilation and CO2 outgassing by radon-222 modeling: How fast do caves breathe? Earth & Planet. Sci. Lett. 289, 209-219. [2] Tremaine, D. M., Froelich, P. N., Wang, Y., 2011. Speleothem calcite farmed in situ: Modern calibration of ?18O and ?13C paleoclimate proxies in a continuously-monitored natural cave system. Geochim. Cosmochim. Acta 75, 4929-4950. [3] Tremaine, D. M., Froelich, P. N., 2012. Speleothem trace element signatures: A modern hydrologic geochemical study of cave drip waters and farmed calcite. Geochim. Cosmochim. Acta (submitted)

  18. HYDRATE CORE DRILLING TESTS

    SciTech Connect

    John H. Cohen; Thomas E. Williams; Ali G. Kadaster; Bill V. Liddell

    2002-11-01

    The ''Methane Hydrate Production from Alaskan Permafrost'' project is a three-year endeavor being conducted by Maurer Technology Inc. (MTI), Noble, and Anadarko Petroleum, in partnership with the U.S. DOE National Energy Technology Laboratory (NETL). The project's goal is to build on previous and ongoing R&D in the area of onshore hydrate deposition. The project team plans to design and implement a program to safely and economically drill, core and produce gas from arctic hydrates. The current work scope includes drilling and coring one well on Anadarko leases in FY 2003 during the winter drilling season. A specially built on-site core analysis laboratory will be used to determine some of the physical characteristics of the hydrates and surrounding rock. Prior to going to the field, the project team designed and conducted a controlled series of coring tests for simulating coring of hydrate formations. A variety of equipment and procedures were tested and modified to develop a practical solution for this special application. This Topical Report summarizes these coring tests. A special facility was designed and installed at MTI's Drilling Research Center (DRC) in Houston and used to conduct coring tests. Equipment and procedures were tested by cutting cores from frozen mixtures of sand and water supported by casing and designed to simulate hydrate formations. Tests were conducted with chilled drilling fluids. Tests showed that frozen core can be washed out and reduced in size by the action of the drilling fluid. Washing of the core by the drilling fluid caused a reduction in core diameter, making core recovery very difficult (if not impossible). One successful solution was to drill the last 6 inches of core dry (without fluid circulation). These tests demonstrated that it will be difficult to capture core when drilling in permafrost or hydrates without implementing certain safeguards. Among the coring tests was a simulated hydrate formation comprised of coarse, large-grain sand in ice. Results with this core showed that the viscosity of the drilling fluid must also be carefully controlled. When coarse sand was being cored, the core barrel became stuck because the drilling fluid was not viscous enough to completely remove the large grains of sand. These tests were very valuable to the project by showing the difficulties in coring permafrost or hydrates in a laboratory environment (as opposed to a field environment where drilling costs are much higher and the potential loss of equipment greater). Among the conclusions reached from these simulated hydrate coring tests are the following: Frozen hydrate core samples can be recovered successfully; A spring-finger core catcher works best for catching hydrate cores; Drilling fluid can erode the core and reduces its diameter, making it more difficult to capture the core; Mud must be designed with proper viscosity to lift larger cuttings; and The bottom 6 inches of core may need to be drilled dry to capture the core successfully.

  19. The relative merits of dolomitic and calcitic limestone in detoxifying and revegetating acidic, nickel- and copper-contaminated soils in the Sudbury mining and smelting region of Canada

    SciTech Connect

    McHale, D.; Winterhalder, K.

    1996-12-31

    Soils in the Sudbury mining and smelting region have been rendered phytotoxic and barren by acidification and Particulate metal contamination, but can be detoxified revegetated by the surface application of an growth is better on soil treated ground limestone. On certain barren sites, plant growth is better on soil treated with dolomitic limestone than with calcitic limestone and greenhouse experiments using mung beans (Vigna radiata) have shown superior root and shoot growth on certain contaminated soils when the limestone is dolomitic rather than calcitic. Results of experiments with species used in revegetation (Agrostis gigantea and Lotus corniculatus) suggest that leguminous species are more sensitive to Ca:Mg ratio than grasses, that the plant response to this ratio is greater at lowering liming levels, and that the response is more marked on more toxic soils. The effects of calcium:magnesium ratio of the limestone used in revegetating acidic, metal-contaminated soils are clearly complex, interactive and difficult to interpret. Further studies are needed, but meanwhile it is recommended that the practice of using dolomitic limestone to detoxify barren Sudbury soils be continued, since there is a risk of induced magnesium deficiency at certain sites when calcitic limestone is used.

  20. Lime kiln source characterization: Lime manufacturing industry Fourier transform infrared spectroscopy. Final report

    SciTech Connect

    Toney, M.L.

    1999-07-01

    The purpose of this testing program is to obtain uncontrolled and controlled hydrogen chloride (HCl) and speciated hydrocarbon Hazardous Air Pollutants (HAPs) emissions data from lime production plants to support a national emission standard for hazardous air pollutants (NESHAP). This report presents data from the Fourier Transform Infrared Spectroscopy (FTIR) measurements. FTIR source testing was conducted for the following purposes: Quantify HCl emission levels; and Gather screening (i.e., qualitative) data on other HAP emissions.

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

    NASA Astrophysics Data System (ADS)

    Nishio, Takashi; Naka, Kensuke

    2015-06-01

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

  2. Dynamics of protein hydration water

    NASA Astrophysics Data System (ADS)

    Wolf, M.; Emmert, S.; Gulich, R.; Lunkenheimer, P.; Loidl, A.

    2015-09-01

    We present the frequency- and temperature-dependent dielectric properties of lysozyme solutions in a broad concentration regime, measured at subzero temperatures, and compare the results with measurements above the freezing point of water and on hydrated lysozyme powder. Our experiments allow examining the dynamics of unfreezable hydration water in a broad temperature range. The obtained results prove the bimodality of the hydration shell dynamics. In addition, we find indications of a fragile-to-strong transition of hydration water.

  3. Mechanical and leaching behaviour of slag-cement and lime-activated slag stabilised/solidified contaminated soil.

    PubMed

    Kogbara, Reginald B; Al-Tabbaa, Abir

    2011-05-01

    Stabilisation/solidification (S/S) is an effective technique for reducing the leachability of contaminants in soils. Very few studies have investigated the use of ground granulated blast furnace slag (GGBS) for S/S treatment of contaminated soils, although it has been shown to be effective in ground improvement. This study sought to investigate the potential of GGBS activated by cement and lime for S/S treatment of a mixed contaminated soil. A sandy soil spiked with 3000mg/kg each of a cocktail of heavy metals (Cd, Ni, Zn, Cu and Pb) and 10,000mg/kg of diesel was treated with binder blends of one part hydrated lime to four parts GGBS (lime-slag), and one part cement to nine parts GGBS (slag-cement). Three binder dosages, 5, 10 and 20% (m/m) were used and contaminated soil-cement samples were compacted to their optimum water contents. The effectiveness of the treatment was assessed using unconfined compressive strength (UCS), permeability and acid neutralisation capacity (ANC) tests with determination of contaminant leachability at the different acid additions. UCS values of up to 800kPa were recorded at 28days. The lowest coefficient of permeability recorded was 510(-9)m/s. With up to 20% binder dosage, the leachability of the contaminants was reduced to meet relevant environmental quality standards and landfill waste acceptance criteria. The pH-dependent leachability of the metals decreased over time. The results show that GGBS activated by cement and lime would be effective in reducing the leachability of contaminants in contaminated soils. PMID:21420148

  4. Effect of lime concentration on gelatinized maize starch dispersions properties.

    PubMed

    Lobato-Calleros, C; Hernandez-Jaimes, C; Chavez-Esquivel, G; Meraz, M; Sosa, E; Lara, V H; Alvarez-Ramirez, J; Vernon-Carter, E J

    2015-04-01

    Maize starch was lime-cooked at 92 C with 0.0-0.40% w/w Ca(OH)2. Optical micrographs showed that lime disrupted the integrity of insoluble remnants (ghosts) and increased the degree of syneresis of the gelatinized starch dispersions (GSD). The particle size distribution was monomodal, shifting to smaller sizes and narrower distributions with increasing lime concentration. X-ray patterns and FTIR spectra showed that crystallinity decreased to a minimum at lime concentration of 0.20% w/w. Lime-treated GSD exhibited thixotropic and viscoelastic behaviour. In the linear viscoelastic region the storage modulus was higher than the loss modulus, but a crossover between these moduli occurred in the non-linear viscoelastic region. The viscoelastic properties decreased with increased lime concentration. The electrochemical properties suggested that the amylopectin-rich remnants and the released amylose contained in the continuous matrix was firstly attacked by calcium ions at low lime levels (<0.20% w/w), disrupting the starch gel microstructure. PMID:25442564

  5. On the complex conductivity signatures of calcite precipitation

    SciTech Connect

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

    2009-11-01

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

  6. The effect of additives on lime dissolution rates. Final report

    SciTech Connect

    Khang, S.J.

    1996-07-31

    Based on the previous years` studies concerning the efficiency of SO{sub 2} removal by spray dryers with high sulfur coal flue gas, the work for year five included investigations of lime dissolution rates at different slaking conditions and with the effect of additives. The prominent additives that have significant effects on lime dissolution rates were tested with the mini pilot spray drying absorber to see their effects on spray drying desulfurization applications. The mechanisms of these additive effects along with the properties of hygroscopic additives have been discussed and incorporated into the spray drying desulfurization model ``SPRAYMOD-M.`` Slaking conditions are very important factors in producing high quality lime slurry in spray drying desulfurization processes. At optimal slaking conditions, the slaked lime particles are very fine (3-5{mu}m) and the slaked lime has high BET surface areas which are beneficial to the desulfurization. The slaked lime dissolution rate experiments in our study are designed to determine how much lime can dissolve in a unit time if the initial lime surface area is kept constant. The purpose of the dissolution rate study for different additives is to find those effective additives that can enhance lime dissolution rates and to investigate the mechanisms of the dissolution rate enhancement properties for these additives. The applications of these additives on spray drying desulfurization are to further verify the theory that dissolution rate is a rate limiting step in the whole spray drying desulfurization process as well as to test the feasibility of these additives on enhancing SO{sub 2} removal in spray dryers.

  7. Leaching behavior of lime-fly ash mixtures

    SciTech Connect

    Daniels, J.L.; Das, G.P.

    2006-01-15

    As part of a larger investigation that included numerical and field-based components, the use of lime to reduce the leachability of a coal combustion fly ash was evaluated in the laboratory. The focus of this paper is on the experimental assessment of lime-fly ash leachability through sequential leach (SL), freeze-thaw (FT), and wet-dry (WD) leaching as well as multileachant sequential extraction (SE) tests. The results suggest that lime addition reduces the leachability for Cd, Se, and to some extent As. They also suggest that Cr is rendered more leachable with increasing lime content, for the conditions and low levels tested. It appears that there is a threshold lime content ({gt} 1.0%) that must be exceeded prior to reducing the leachability of As and Se. In particular, this threshold likely corresponds to the level at which appreciable cementitious reactions have developed. For example, in the case of As after the first cycle of leaching, the concentration was below the reporting limit (10 {mu} g/L) for 0% lime. However, at 0.5% lime amendment, the leached concentration increased to nearly 50 {mu} g/L. Subsequent lime additions reduced this concentration. No such threshold was observed for Cd leachability as was expected as a direct consequence of hydroxide precipitation, which is well established under the measured pH conditions. As such, Cd mobility is insensitive to the extent to which cementitious reactions are initiated. Overall, the results suggest that while lime stabilization may be effective for reducing leachability, sufficient amounts must be added; otherwise, the leachability of some constituents can actually be exacerbated.

  8. Regeneration of lime from sulfates for fluidized-bed combustion

    DOEpatents

    Yang, Ralph T.; Steinberg, Meyer

    1980-01-01

    In a fluidized-bed combustor the evolving sulfur oxides are reacted with CaO to form calcium sulfate which is then decomposed in the presence of carbonaceous material, such as the fly ash recovered from the combustion, at temperatures of about 900.degree. to 1000.degree. C., to regenerate lime. The regenerated lime is then recycled to the fluidized bed combustor to further react with the evolving sulfur oxides. The lime regenerated in this manner is quite effective in removing the sulfur oxides.

  9. [Hydration in clinical practice].

    PubMed

    Maristany, Cleof Prez-Portabella; Segurola Gurruchaga, Hegoi

    2011-01-01

    Water is an essential foundation for life, having both a regulatory and structural function. The former results from active and passive participation in all metabolic reactions, and its role in conserving and maintaining body temperature. Structurally speaking it is the major contributer to tissue mass, accounting for 60% of the basis of blood plasma, intracellular and intersticial fluid. Water is also part of the primary structures of life such as genetic material or proteins. Therefore, it is necessary that the nurse makes an early assessment of patients water needs to detect if there are signs of electrolyte imbalance. Dehydration can be a very serious problem, especially in children and the elderly. Dehydrations treatment with oral rehydration solution decreases the risk of developing hydration disorders, but even so, it is recommended to follow preventive measures to reduce the incidence and severity of dehydration. The key to having a proper hydration is prevention. Artificial nutrition encompasses the need for precise calculation of water needs in enteral nutrition as parenteral, so the nurse should be part of this process and use the tools for calculating the patient's requirements. All this helps to ensure an optimal nutritional status in patients at risk. Ethical dilemmas are becoming increasingly common in clinical practice. On the subject of artificial nutrition and hydration, there isn't yet any unanimous agreement regarding hydration as a basic care. It is necessary to take decisions in consensus with the health team, always thinking of the best interests of the patient. PMID:21428011

  10. Aluminum Sulfate 18 Hydrate

    ERIC Educational Resources Information Center

    Young, Jay A.

    2004-01-01

    A chemical laboratory information profile (CLIP) of the chemical, aluminum sulfate 18 hydrate, is presented. The profile lists physical and harmful properties, exposure limits, reactivity risks, and symptoms of major exposure for the benefit of teachers and students using the chemical in the laboratory.

  11. DEFINITIVE SOX CONTROL PROCESS EVALUATIONS: LIMESTONE, LIME, AND MAGNESIA FGD PROCESSES

    EPA Science Inventory

    The report gives economic and ground-to-ground energy evaluations of limestone slurry, lime slurry, and magnesia (producing sulfuric acid) flue gas desulfurization (FGD) processes. The lime slurry process, using purchased lime and lime calcined onsite, remains lower in capital in...

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

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

    Calcites build large deposits which have been observed in the rock record throughout geological time at various localities around the globe. Carbonate deposits have affected atmospheric carbon dioxide concentration. As it has been generally accepted, inorganic precipitation represents a source of carbon dioxide on short geological time scales and a sink of inorganic carbon at long time scales from millions to thousands of millions years. However, recent research indicates that calcite deposits may result from microbial calcification instead of inorganic precipitation. In this case the process may reduce atmospheric carbon dioxide on geologically short time scales. Thus the effect of carbonate sediment deposition on global carbon cycling depends on the origin of carbonate. Thus it is essential to understand the cause and the key parameters affecting calcite precipitation. The role of algae and bacteria in calcite formation in lakes has not been evaluated in detail. Some evidence, however, exists supporting precipitation of calcium carbonate by microbes as the origin of whiting. Several field studies on lakes have also produced puzzling results: The peaks of algal blooms were often not found at the same time as precipitation events of calcite. We suspect that parts of the discrepancies in the interpretation of field observations are due to the activity of autotrophic picoplankton. The unicellular autotrophic picoplankton (APP) is a ubiquitous component of pelagic ecosystems. But it has often been overlooked due to its small cell size of 0.2 - 2 ? m in diameter. Coccoid picocyanobacteria of the Synechococcus-type dominate the picoplankton community in most oligotrophic systems. Recently, laboratory experiments and field observations suggested that APP may play an important role in calcite precipitation. The aim of this study was to examine the influence of environmental factors such as saturation state, concentration of different dissolved ions and characteristics of the surface of cells on interaction between calcite and picocyanobacteria under both laboratory and field conditions. Laboratory experiments were performed with a picocyanobacteria strain Synechococcus-type. Using ion selective electrodes we monitored calcite precipitation induced by bacteria in the solutions of a different composition (calcium 0.7 - 48 mM, inorganic carbonate 6 - 35 ? M). Electron and atomic force microscopy measurements provided insight into the cell-mineral interface. Furthermore, quantitative investigations of the types and densities of proton binding sites on a bacterial surface will be reported from the acid-base titrations on bacteria. Results of these initial experiments are encouraging and demonstrate by direct measurements the potential of picocyanobacteria to precipitate calcite. The amount of the precipitated calcite varied in experiments with a different ratio of dissolved inorganic carbon and calcium. The microscopic observations provide some evidence that the cell walls of cyanobacteria act as a substrate of nucleation of calcite. Temporal and spatial correlations of cyanobacteria and calcite, as well as images of bacterial shape particles indicated that picoplankton plays an important role in calcite precipitation in Lake Lucerne. This class of phytoplankton has to be considered in studying the biogeochemical cycling of oligotrophic hardwater lakes.

  13. Sequestration of selenium on calcite surfaces revealed by nanoscale imaging

    NASA Astrophysics Data System (ADS)

    Putnis, Christine V.; Renard, Franois; King, Helen E.; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion

    2014-05-01

    Selenium is an important element because of its high toxicity in natural systems. In-situ atomic force microscopy observations of calcite surfaces during contact with selenium-bearing solutions demonstrate that selenium trapping can occur under conditions in which calcite both dissolves and precipitates. The contact of solutions containing selenium in two states of oxidation (either Se(IV ) or Se(V I)) onto a growing or dissolving calcite surface either changes the growth pattern or results in precipitates formed during dissolution. In the form of selenite (Se(IV )), but not as selenate (Se(IV )), selenium can be incorporated into calcite during growth. During dissolution, in the presence of selenate (Se(V I)), the precipitates formed remained small during the observation period. When injecting selenite (Se(IV )), the precipitates grew significantly, and were identified as CaSeO3H2O, based on SEM observations, Raman spectroscopy and thermodynamic calculations. An interpretation is proposed where dissolution of calcite increases the calcium concentration in a thin boundary layer in contact with the surface, allowing the precipitation of a selenium phase. This process of dissolution-precipitation provides a new mechanism for selenium sequestration and extends the range of thermodynamic conditions under which such a process is efficient.

  14. A Raman spectroscopic comparison of calcite and dolomite

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

  15. A Raman spectroscopic comparison of calcite and dolomite.

    PubMed

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

    2014-01-01

    Raman spectroscopy was used to characterize and differentiate the two minerals calcite and dolomite and the bands related to the mineral structure. The (CO3)(2-) group is characterized by four prominent Raman vibrational modes: (a) the symmetric stretching, (b) the asymmetric deformation, (c) asymmetric stretching and (d) symmetric deformation. These vibrational modes of the calcite and dolomite were observed at 1440, 1088, 715 and 278 cm(-1). The significant differences between the minerals calcite and dolomite are observed by Raman spectroscopy. Calcite shows the typical bands observed at 1361, 1047, 715 and 157 cm(-1), and the special bands at 1393, 1098, 1069, 1019, 299, 258 and 176 cm(-1) for dolomite are observed. The difference is explained on the basis of the structure variation of the two minerals. Calcite has a trigonal structure with two molecules per unit cell, and dolomite has a hexagonal structure. This is more likely to cause the splitting and distorting of the carbonate groups. Another cause for the difference is the cation substituting for Mg in the dolomite mineral. PMID:23988531

  16. Static Grain Growth in Contact Metamorphic Calcite: A Cathodoluminescence Study.

    NASA Astrophysics Data System (ADS)

    Vogt, B.; Heilbronner, R.; Herwegh, M.; Ramseyer, K.

    2009-04-01

    In the Adamello contact aureole, monomineralic mesozoic limestones were investigated in terms of grain size evolution and compared to results on numerical modeling performed by Elle. The sampled area shows no deformation and therefore represents an appropriate natural laboratory for the study of static grain growth (Herwegh & Berger, 2003). For this purpose, samples were collected at different distances to the contact to the pluton, covering a temperature range between 270 to 630C. In these marbles, the grain sizes increase with temperature from 5 m to about 1 cm as one approaches the contact (Herwegh & Berger, 2003). In some samples, photomicrographs show domains of variable cathodoluminescence (CL) intensities, which are interpreted to represent growth zonations. Microstructures show grains that contain cores and in some samples even several growth stages. The cores are usually not centered and the zones not concentric. They may be in touch with grain boundaries. These zonation patterns are consistent within a given aggregate but differ among the samples even if they come from the same location. Relative CL intensities depend on the Mn/Fe ratio. We assume that changes in trace amounts of Mn/Fe must have occurred during the grain size evolution, preserving local geochemical trends and their variations with time. Changes in Mn/Fe ratios can either be explained by (a) locally derived fluids (e.g. hydration reactions of sheet silicate rich marbles in the vicinity) or (b) by the infiltration of the calcite aggregates by externally derived (magmatic?) fluids. At the present stage, we prefer a regional change in fluid composition (b) because the growth zonations only occur at distances of 750-1250 m from the pluton contact (350-450C). Closer to the contact, neither zonations nor cores were found. At larger distances, CL intensities differ from grain to grain, revealing diagenetic CL patterns that were incompletely recrystallized by grain growth. The role of infiltration of magmatic fluids is also manifest in the vicinity of dikes, where intense zonation patterns are prominent in the marbles. The software Elle was developed to simulate microstructural evolution in rocks. The numerical model with the title "Grain boundary sweeping" was performed by M. Jessell and was found on http://www.materialsknowledge.org/elle. It displays the grain size evolution and the development of growth zonations during grain boundary migration of a 2D foam structure. This simulation was chosen because the driving force is the minimization of isotropic surface energies. It will be compared to the natural microstructures. At the last stage of the simulation the average grain and core sizes have increased. All, even the smallest grains, show growth zonations. Grains can be divided into two groups: (a) initially larger grains, increasing their grain size and maintaining their core size and (b) initially smaller grains with decreasing grain and decreasing core size. Group (a) grains show large areas swept by grain boundaries into the direction of small grains. Grain boundaries between large grains move more slowly. Their cores do not touch any grain boundaries. Cores of group (b) grains are in contact with the grain boundary network and are on the way to be consumed. In the numerical model and in the natural example similar features can be observed: The cores are not necessarily centered, the zonations are not necessarily concentric and some of the cores touch the grain boundary network. In the simulation, grain boundary migration velocity between large grains is smaller than between a large and a small grain. From this we would predict that - given enough time - a well sorted grain size distribution of increased grain size could be generated. But since many small grains occur we infer that this equilibrium has not been obtained. Analytical results of some natural samples that could be analyzed up to now indicate a relatively well sorted grain size distribution suggesting a more mature state of static grain growth. In comparison t

  17. Effect of microstructure and microchemistry on improvement of hydration and slag attack resistance of ilmenite-doped refractory limestone

    NASA Astrophysics Data System (ADS)

    Soltan, Abdel Monem; Serry, Mohamed

    2015-02-01

    This work studies densification, resistance to hydration and slag attack of 0.0-2.0 wt% ilmenite-doped lime refractories in relation to their thermal equilibrium and microfabric after firing at 1,400-1,700 C. XRF, XRD, SEM-EDAX, transmitted light microscopy and mercury intrusion methods were used to characterize the fired samples. The ternary diagram CaO-C2S-C4AF was applied to the thermal equilibrium data. The rates of hydration and attack by steel-slag were also assessed using cathode-luminescence microscope. Doping limestone with 0.5 wt% ilmenite leads maximizes the rate of densification after firing for 2 h at 1,600 C. A direct-bonded CaO-CaO network is found in the doped sample with separated islands of Ca-silicate, alumino-ferrite and TiO2-rich Ca, Mg- solid solutions all filling the pores and triple points of the lime grains. Due to the dense microstructure of the doped sample with the direct-bonded lime grains, hydration and slag-attack resistance are enhanced compared with the un-doped sample.

  18. EVALUATION OF LIME PRECIPITATION FOR TREATING BOILER TUBE CLEANING WASTES

    EPA Science Inventory

    The report gives results of an evaluation of lime precipitation for treating boiler tube cleaning wastes. In this project, wastewater samples were collected from six boiler tubeside chemical cleanings, using complexing and chelating agents. The samples represented: (1) ammoniacal...

  19. 63. INTERIOR VIEW OF THE LIME KILN BUILDING, LOOKING AT ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    63. INTERIOR VIEW OF THE LIME KILN BUILDING, LOOKING AT THE FIRE BOX AND KILN FOR DILLUTANT. APRIL 22, 1919. - United States Nitrate Plant No. 2, Reservation Road, Muscle Shoals, Muscle Shoals, Colbert County, AL

  20. A novel role for calcite in calcium homeostasis.

    PubMed

    Anderson, S; Appanna, V D; Huang, J; Viswanatha, T

    1992-08-10

    Calcium carbonate (CaCO3) minerals are known to be deposited in a wide array of different organisms, ranging from microbes to vertebrates [(1989) On Biomineralization, Oxford University Press, New York]. Calcite, aragonite and vaterite are the major crystalline structural polymorphs of CaCO3 associated with living systems, and participate in a variety of biological functions [(1989) Biomineralization: Chemical and Biochemical Perspectives, VCH Publishers, Weinham, Germany; (1991) Advances in Inorganic Chemistry 36, 137-200]. Here we report on the ability of a soil bacterium to synthesize calcite in a calcium-stressed environment. The elaboration of this exocellular crystalline residue enables the organism to regulate its calcium content. The attainment of calcium homeostasis via the exocellular deposition of bacterial calcite with unique crystal habits is a novel biological phenomenon. PMID:1644205

  1. Time and metamorphic petrology: Calcite to aragonite experiments

    USGS Publications Warehouse

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

    1992-01-01

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

  2. Shock, release, and tension response of soda lime glass

    SciTech Connect

    Dandekar, Dattatraya P.

    1998-07-10

    This work describes the result of shock wave experiments on soda lime glass in which the shock wave profiles were recorded simultaneously at or near the impact surface and the free surface of the glass specimen by means of multi-beam VISAR. Since earlier work indicated that the glass under shock compression does not follow the Gladstone-Dale model, these profiles provide accurate and self consistent values of transit times for shock, release, and tensile waves propagating in soda lime glass.

  3. Micromachining soda-lime glass by femtosecond laser pulses

    NASA Astrophysics Data System (ADS)

    Jia, Wei; Yu, Jian; Chai, Lu; Wang, Ching-Yue

    2015-08-01

    The physical process of forming a modified region in soda-lime glass was investigated using 1 kHz intense femtosecond laser pulses from a Ti: sapphire laser at 775 nm. Through the modifications induced by the femtosecond laser radiation using selective chemical etching techniques, we fabricated reproducible and defined microstructures and further studied their morphologies and etching properties. Moreover, a possible physical mechanism for the femtosecond laser modification in soda-lime glass was proposed.

  4. Nucleation and growth kinetics in synthesizing nanometer calcite

    NASA Astrophysics Data System (ADS)

    Lin, Rong-yi; Zhang, Jia-Yun; Zhang, Pei-xin

    2002-11-01

    The size of nanometer particles uniquely depends not only on the nucleus growth rate but also on the nucleation rate. This paper presents the effect of sodium tripolyphosphate on the microimages, synthesis reaction, nucleation and growth during the synthesizing of nanometer calcite using chemical analysis, SEM technique and Rosin-Ramuler probability statistics theory. The result showed that the calcium hydroxide carbonation reaction was inhibited by sodium tripolyphosphate adsorbed on the active growth sites. The SEM images revealed that the synthesizing of nanometer calcite was a multi-stable state process. When [Na 5P 3O 10]=0, 38.04 ?M, the tiny calcite nuclei re-dissolved and the nucleation rate was negative at the final stage. The supersaturation and the nucleation rate increased in proportion to the concentration of sodium tripolyphosphate. The presence of sodium tripolyphosphate accelerated the nucleation of calcite and inhibited the crystal growth. During the crystallization of nanoscale calcite, the fluctuation nucleation, nucleus growth and coarsening growth may take place in series for a fine particle. To a whole carbonation solution, these three steps may occur simultaneously. At the final stage of the nucleation, the calcite crystal growth was controlled by a short-range diffusion and an interface reaction. The Zener-Ham model could not correctly describe the crystal growth. At the coarsening growth stage, the Zener-Ham model could not correctly describe the crystal growth yet. Once the steady nucleus had been shaped in the solution, the crystal growth was determined by a long-range diffusion, and the growth process accorded with Zener-Ham model quite well.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  6. Microbially Induced Calcite Precipitation for Subsurface Immobilization of Contaminants

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  7. Soil liming as a measure to mitigate acid runoff

    SciTech Connect

    Warfvinge, P.; Sverdrup, H.

    1988-05-01

    Watershed liming is one method to decrease the acidity of surface waters. To gain an understanding of the mechanisms involved in terrestrial liming and to develop a tool for planning and evaluation, a mathematical model has been developed. The model includes key chemical processes such as limestone dissolution, cation-exchange reactions, and leaching and accumulation of dissolved species. The ability of the model to describe the short and long-term improvement in stream water quality following wetland liming is demonstrated by comparing the model calculations with data from two Swedish full-scale liming experiments. The influence of temporal hydrological and chemical variations on model output is assessed. The sensitivity of the system response to liming is analyzed with respect to three design parameters: the amount and the fineness of the liming material, and the fraction of the watershed that is treated. The simulations illustrate the importance of careful soil and hydrological characterization of treated watersheds to ensure that the limestone dose and the treated area are sufficient to ensure a satisfactory increase in stream pH and resistance to reacidification.

  8. Soil liming as a measure to mitigate acid runoff

    NASA Astrophysics Data System (ADS)

    Warfvinge, Per; Sverdrup, Harald

    1988-05-01

    Watershed liming is one method to decrease the acidity of surface waters. To gain an understanding of the mechanisms involved in terrestrial liming and to develop a tool for planning and evaluation, a mathematical model has been developed. The model includes key chemical processes such as limestone dissolution, cation-exchange reactions, and leaching and accumulation of dissolved species. The ability of the model to describe the short and long-term improvement in stream water quality following wetland liming is demonstrated by comparing the model calculations with data from two Swedish full-scale liming experiments. The influence of temporal hydrological and chemical variations on model output is assessed. The sensitivity of the system response to liming is analyzed with respect to three design parameters: the amount and the fineness of the liming material, and the fraction of the watershed that is treated. The simulations illustrate the importance of careful soil and hydrological characterization of treated watersheds to ensure that the limestome dose and the treated area are sufficient to ensure a satisfactory increase in stream pH and resistance to reacidification.

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

    NASA Astrophysics Data System (ADS)

    Wombacher, F.; Eisenhauer, A.; Bhm, F.; Gussone, N.; Regenberg, M.; Dullo, W.-Chr.; Rggeberg, A.

    2011-10-01

    This survey of magnesium stable isotope compositions in marine biogenic aragonite and calcite includes samples from corals, sclerosponges, benthic porcelaneous and planktonic perforate foraminifera, coccolith oozes, red algae, and an echinoid and brachiopod test. The analyses were carried out using MC-ICP-MS with an external repeatability of 0.22 (2SD for ? 26Mg; n = 37), obtained from a coral reference sample (JCp-1). Magnesium isotope fractionation in calcitic corals and sclerosponges agrees with published data for calcitic speleothems with an average ? 26Mg calcite-seawater = -2.6 0.3 that appears to be weakly related to temperature. With one exception ( Vaceletia spp.), aragonitic corals and sclerosponges also display uniform Mg isotope fractionations relative to seawater with ? 26Mg biogenic aragonite-seawater = -0.9 0.2. Magnesium isotopes in high-Mg calcites from red algae, echinoids and perhaps some porcelaneous foraminifera as well as in all low-Mg calcites (perforate foraminifera, coccoliths and brachiopods) display significant biological influences. For planktonic foraminifera, the Mg isotope data is consistent with the fixation of Mg by organic material under equilibrium conditions, but appears to be inconsistent with Mg removal from vacuoles. Our preferred model, however, suggests that planktonic foraminifera synthesize biomolecules that increase the energetic barrier for Mg incorporation. In this model, the need to remove large quantities of Mg from vacuole solutions is avoided. For the high-Mg calcites from echinoids, the precipitation of amorphous calcium carbonate may be responsible for their weaker Mg isotope fractionation. Disregarding superimposed biological effects, it appears that cation light isotope enrichments in CaCO 3 principally result from a chemical kinetic isotope effect, related to the incorporation of cations at kink sites. In this model, the systematics of cation isotope fractionations in CaCO 3 relate to the activation energy required for cation incorporation, which probably reflects the dehydration of the cation and the crystal surface and bond formation at the incorporation site. This kinetic incorporation model predicts (i) no intrinsic dependence on growth rate, unless significant back reaction upon slow growth reduces the isotope fractionation towards that characteristic for equilibrium isotope partitioning (this may be observed for Ca isotopes in calcites), (ii) a small decrease of isotope fractionation with increasing temperature that may be amplified if higher temperatures promote back reaction and (iii) a sensitivity to changes in the activation barrier caused by additives such as anions or biomolecules or by the initial formation of amorphous CaCO 3.

  10. Sulfated Macromolecules as Templates for Calcite Nucleation and Growth

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

    Mineralization of egg and seashells is controlled by an intimate association of inorganic materials with organic macromolecules. Among them, particular polyanionic sulfated macromolecules referred to as proteoglycans have been described to be involved in the calcification of these biominerals. The sulfated moieties of the proteoglycans are part of polymer chains constituted of building-blocks of disaccharide units, referred to as sulfated glycosaminoglycans (GAGs), which are covalently attached to a protein core. By using a sitting drop crystallization assay under controlled conditions of time, pH and reactants concentration, we have tested several sulfated and non-sulfated GAGs (i.e.: dermatan and keratan sulfate, hyaluronic acid and heparin), differing in their sulfonate and carboxylate degree and pattern, in their ability to modify calcium carbonate crystal morphology as observed under scanning electron microscopy. Without the addition of GAGs, regular \\{104\\} rhombohedral calcite crystals were obtained. When hyaluronic acid (HA), a non-sulfated but carboxylated GAG, was added, 20 mm long piles of unmodified calcite crystals were observed. When desulfated dermatan, which is an epimeric form of HA but shorter polymer, having their carboxylate groups in an inverted configuration, was added, isolated rhombohedral \\{104\\} calcite crystals showing rounded corners with planes oriented parallel to the c axis were observed. When dermatan sulfated was added, isolated calcite crystals exhibit a columnar morphology as a \\{hk0\\} cylinder with three \\{104\\} faces forming a cap at both ends. Heparin activity depends on the fraction added. Fast-moving heparin fraction (FM), is an undersulfated, low-molecular-weight heterogeneous polymer, while slow-moving heparin fraction (SM) is an high-molecular-weight homogeneous polymer rich in trisulfated-disaccharide units. When FM was added, isolated calcite crystals displayed rhombohedrical \\{104\\} faces but flat corners of \\{111\\} faces. The addition of the hypersulfated heparin SM induce the formation of large rosette-like aggregated calcite crystals, where the majority of the \\{104\\} faces appeared not to be lost, although aggregation is done by different kind of faces. It is concluded that, the variation of the sulfate and carboxylate content and configuration drastically changed the morphology of the calcite crystals. The production of calcite particles with defined morphologies could be interesting for the design of novel materials with desirable shape- and texture-depending properties. Granted by FONDAP 11980002.

  11. Cyanobacterial Calcite Precipitation - Laboratory Study on Different Spatial Scales

    NASA Astrophysics Data System (ADS)

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

    2003-12-01

    Lacustrine calcite precipitation with sedimentation rates up to 1 mm per year can result in large carbonate deposits. Varved lake sediments high in calcite content are now intensively studied as high-resolution continental archives for environmental change. Especially in oligotrophic hardwater lakes, eukaryotic and prokaryotic picoplankton was found to be important in the overall process of calcite precipitation. Rates and mechanisms of bacteria-surface mediated precipitation reactions, however, remain poorly understood. For interpreting geochemical and isotopic information stored in sediments, it is essential to know the carbonate precipitation mechanisms and the governing environmental factors. Thus, laboratory experiments with picoplankton under controlled conditions were combined with electron and atomic force microscopy in order to obtain insights into the details of the calcite precipitation mechanisms of cyanobacteria. This study aimed at evaluating the potential of such laboratory studies and investigating the influence of environmental parameters as a first step. Under carefully controlled chemical and physical conditions, precipitation of calcite was induced by adding cultures of picocyanobacteria to supersaturated solutions of CaCO3 at different CaCl2/NaHCO3 ratios. The cell suspensions were purged with an artificial atmosphere at constant CO2 concentration. Abiotic solutions were used as reference systems. Chemical conditions such as pH, calcium and carbonate concentrations were continuously monitored by ion selective electrodes. The influence of supersaturation in the range of ? = 2 - 20 on biogenic precipitation was quantified at different ratios of calcium (0.7 - 48 mM) /carbonate (6 ? M - 35 ? M). In a series of bulk experiments it was possible to detect critical values of supersaturation for the onset of precipitation both with and without cells, both in the range of ? = 5 - 10. The morphology of the precipitates was analyzed by scanning electron microscopy. Both, initial crystals (<500 nm) and larger grown crystals (>10 ? m) showed rhombohedral and hexagonal-prism shapes characteristic for calcite. Ultrathin-sections ( 100nm) of the cyanobacteria cells and the attached calcite crystals were prepared by Focused Ion Beam. This technique allowed us to preserve the cell wall - crystal interface as intact as possible in order to perform Transmission Electron Microscopy (TEM) analysis of the sections. Using TEM-Electron Energy Loss Spectroscopy, carbon bonds in both calcite crystals and cyanobacteria cells were detected and identified. The carbon absorption spectra are significantly different to discriminate the organic and inorganic carbon. Thus, the absorption peaks are the fingerprints of the analyzed material and can be used to analyze the transition zone between the cell and the particle.

  12. Long-Term Effects of a Watershed Liming Experiment on Soils and Surface Waters at Woods Lake, New York

    NASA Astrophysics Data System (ADS)

    Newton, R. M.

    2005-12-01

    In October 1989, approximately 1000 Mg of pelletized limestone was applied to two subcatchments of the Woods Lake Watershed located in the western Adirondacks of New York State. This experiment was designed to evaluate the effectiveness of calcite addition to watershed soils as a strategy to mitigate the effects of surface water acidification from acidic deposition. Woods Lake is 23 ha in size and lies within a 207 ha thin-till dominated watershed. In 1979 the lake was highly acidic (pH 4.8, ANC -8 ?eq/L). The watershed treatment followed two earlier lake liming experiments. These experiments successfully raised the pH and ANC of the lake but only for a short time as the residence time of water in the lake is only 174 days. Because calcite applied to the soil would be continuously exposed to precipitation falling on the land surface, it was hypothesized that watershed liming would have a much longer impact. The limed subcatchments (102 ha) were treated with limestone that had been crushed to the consistency of fine sand and pelletized with a lignosulfonate binder to form pellets 1.41 to 4.00 mm in diameter. The chemical composition of the pellets was approximately 82% CaCO3, 8% MgCO3, 4% organic binder, and 6% inorganic salts and insoluble silicate minerals. Application rates were targeted at 10 Mg CaCO3/ha but limefall collectors measured lower rates with a mean of 7.85 Mg/ha falling in subcatchment II and 3.42 Mg/ha in subcatchment IV. During the first two years after watershed liming lake pH averaged 6.62, ANC 138 ?eq/L and Ca2+ 119 ?eq/L. Samples collected during the summer of 2005 show that, even after 16 years, the lake has maintained its positive ANC (37.7 ?eq/L) and still has high concentrations of Ca2+ (151.7 ?eq/L). A viable fish population has also survived in this previously fishless lake. Even more surprising, soil samples collected in 2005 still have significant quantities of undissolved CaCO3. In the time since treatment, the CaCO3 has been displaced downward through the organic horizon of the soil through seasonal deposition of organic debris from above. It now lies within an Oa horizon having a pH of approximately 4.5. Organic coatings on the CaCO3 are likely inhibiting reactions with soil water. Some reaction must still be occurring as the pH is higher and exchangeable acidity lower in treated catchments as compared to untreated control catchments. The pH of the organic horizons in the control catchments is as low as 3.6 while the exchangeable acidity is as high as 11.2 meq/100 gm. Exchangeable acidity of organic horizons in the treated catchments is generally less than 2 meq/100 gm. Calcite weathering rates are likely lower in this field experiment than expected due to the presence of organic coatings on the mineral grain surfaces that are formed during organic decomposition reactions in the soil. Despite this, the rate of Ca2+ release from the treated catchments is high enough to maintain a positive ANC in the lake.

  13. Petrology of UHP calcite marble from the Kokchetav Massif

    NASA Astrophysics Data System (ADS)

    Aoki, K.; Adachi, T.; Kikuchi, M.; Ogasawara, Y.

    2004-12-01

    In the Kumdy-kol area, Kokchetav Massif, northern Kazakhstan, three types of UHP marbles have been described: diamond-bearing dolomite marble, Ti-clinohumite-bearing dolomitic marble (Ogasawara et al., 2000) and titanite-bearing calcite marble (Ogasawara et al., 2002). UHP calcite marble is distinguished from other types of UHP marbles by pure calcite (after aragonite) as a dominant carbonate phase. This calcite marble has unique evidence of UHP metamorphism; titanite with coesite exsolution and its precursor compositions indicated that the peak P-T conditions was > 6 GPa and 980-1250 C (Ogasawara et al., 2000; 2002). This rock shows typical granoblastic texture consisting of calcite, diopside, K-feldspar, titanite and symplectite (diopside + zoisite) after garnet. The peak assemblage was aragonite + diopside + K-feldspar + garnet + titanite. Based on the phase relations in the system CaO-MgO-TiO2-SiO2-CO2-H2O, aragonite + diopside + rutile tie-triangle is stable under UHP conditions and divides the compositional space into dolomite-bearing or dolomite-free tetrahedrons (Kikuchi et al., 2003). The presence of titanite in calcite marble means that P-T condition was located at the right-hand side of the reaction rutile + aragonite + coesite = titanite + CO2. Previously described titanite-bearing calcite marble is diamond-free (A-type) and is characterized by titanite with coesite exsolution (Ogasawara et al., 2002). Recently, we found a small amount of diamond in calcite marble (B-type) that is characterized by microdiamond in diopside, and by the lack of K-feldspar and low amount of titanite. No diamond occurs in titanite. Rutile, aragonite and calcite inclusions in titanite were found in titanite of B-type calcite marble. These three inclusion phases in titanite that were confirmed by laser Raman spectroscopy are the evidence for titanite formation reaction described above. This titanite forming reaction occurs at extremely low XCO2 conditions as 0.02. In B-type calcite marble, microdiamond occurs locally and its amount is low; only 61 grains were found in two thin sections. Distributions of titanite, K-feldspar and diamond are heterogeneous and seem to form layers. Diamond occurs in the domain where amounts of titanite and K-feldspar are relatively low. Low amount of microdiamond may be related with extremely low-XCO2 condition under UHP metamorphism. References Ishida et al. (2003: Journal of Metamorphic Geology, Vol. 21, p. 515-522. Kikuchi et al. (2003): EOS Transactions AGU, Vol. 84, F1532. Ogasawara et al. (2000): The Island Arc, Vol. 9, p 400-416. Ogasawara et al. (2002): American Mineralogist, Vol. 87, p. 454-461.

  14. Methane Clathrate Hydrate Prospecting

    NASA Technical Reports Server (NTRS)

    Duxbury, N.; Romanovsky, V.

    2003-01-01

    A method of prospecting for methane has been devised. The impetus for this method lies in the abundance of CH4 and the growing shortages of other fuels. The method is intended especially to enable identification of subpermafrost locations where significant amounts of methane are trapped in the form of methane gas hydrate (CH4(raised dot)6H2O). It has been estimated by the U.S. Geological Survey that the total CH4 resource in CH4(raised dot) 6H2O exceeds the energy content of all other fossil fuels (oil, coal, and natural gas from non-hydrate sources). Also, CH4(raised dot)6H2O is among the cleanest-burning fuels, and CH4 is the most efficient fuel because the carbon in CH4 is in its most reduced state. The method involves looking for a proxy for methane gas hydrate, by means of the combination of a thermal-analysis submethod and a field submethod that does not involve drilling. The absence of drilling makes this method easier and less expensive, in comparison with prior methods of prospecting for oil and natural gas. The proposed method would include thermoprospecting in combination with one more of the other non-drilling measurement techniques, which could include magneto-telluric sounding and/or a subsurface-electrical-resistivity technique. The method would exploit the fact that the electrical conductivity in the underlying thawed region is greater than that in the overlying permafrost.

  15. Anthropogenic oligotrophication via liming: Long-term phosphorus trends in acidified, limed, and neutral reference lakes in Sweden.

    PubMed

    Hu, Qian; Huser, Brian J

    2014-01-01

    Restoration of acidified lakes by liming does not, in many cases, improve productivity to a pre-acidified state. We hypothesize that the poor recovery detected in many of these lakes is due to constrained in-lake phosphorous (P) cycling caused by enhanced precipitation of metals in higher pH, limed waters. Long-term (1990-2012) data for 65 limed, circum-neutral (pH 6-8), and acidified lakes in Sweden were analyzed to determine trends for P and potential drivers of these trends. Limed lakes not only had lower mean values and stronger decreasing trends for total P than non-limed lakes, but they also had the highest percentage of decreasing trends (85%). A P release factor (Hypolimnetic P/Epilimnetic P) was developed to elucidate differences in internal P cycling between lake groups. Consistently, lower P release factors in limed lakes show limitation of internal P cycling during summer months that may be a factor limiting P bioavailability and thus productivity of these systems. PMID:25403973

  16. Rapid gas hydrate formation process

    DOEpatents

    Brown, Thomas D.; Taylor, Charles E.; Unione, Alfred J.

    2013-01-15

    The disclosure provides a method and apparatus for forming gas hydrates from a two-phase mixture of water and a hydrate forming gas. The two-phase mixture is created in a mixing zone which may be wholly included within the body of a spray nozzle. The two-phase mixture is subsequently sprayed into a reaction zone, where the reaction zone is under pressure and temperature conditions suitable for formation of the gas hydrate. The reaction zone pressure is less than the mixing zone pressure so that expansion of the hydrate-forming gas in the mixture provides a degree of cooling by the Joule-Thompson effect and provides more intimate mixing between the water and the hydrate-forming gas. The result of the process is the formation of gas hydrates continuously and with a greatly reduced induction time. An apparatus for conduct of the method is further provided.

  17. Bioremediation of Cd by microbially induced calcite precipitation.

    PubMed

    Kang, Chang-Ho; Han, Sang-Hyun; Shin, Yujin; Oh, Soo Ji; So, Jae-Seong

    2014-03-01

    Contamination by Cd is a significant environmental problem. Therefore, we examined Cd removal from an environmental perspective. Ureolysis-driven calcium carbonate precipitation has been proposed for use in geotechnical engineering for soil remediation applications. In this study, 55 calcite-forming bacterial strains were newly isolated from various environments. Biomineralization of Cd by calcite-forming bacteria was investigated in laboratory-scale experiments. A simple method was developed to determine the effectiveness of microbially induced calcite precipitation (MICP). Using this method, we determined the effectiveness of biomineralization for retarding the flow of crystal violet through a 25-mL column. When the selected bacteria were analyzed using an inductively coupled plasma optical emission spectrometer, high removal rates (99.95%) of Cd were observed following incubation for 48 h. Samples of solids that formed in the reaction vessels were examined using a scanning electron microscope. The CdCO3 compounds primarily showed a spherical shape. The results of this study demonstrate that MICP-based sequestration of soluble heavy metals via coprecipitation with calcite may be useful for toxic heavy metal bioremediation. PMID:24458656

  18. Bioremediation of Cd by microbially induced calcite precipitation.

    PubMed

    Kang, Chang-Ho; Han, Sang-Hyun; Shin, Yujin; Oh, Soo Ji; So, Jae-Seong

    2014-02-01

    Contamination by Cd is a significant environmental problem. Therefore, we examined Cd removal from an environmental perspective. Ureolysis-driven calcium carbonate precipitation has been proposed for use in geotechnical engineering for soil remediation applications. In this study, 55 calcite-forming bacterial strains were newly isolated from various environments. Biomineralization of Cd by calcite-forming bacteria was investigated in laboratory-scale experiments. A simple method was developed to determine the effectiveness of microbially induced calcite precipitation (MICP). Using this method, we determined the effectiveness of biomineralization for retarding the flow of crystal violet through a 25-mL column. When the selected bacteria were analyzed using an inductively coupled plasma optical emission spectrometer, high removal rates (99.95 %) of Cd were observed following incubation for 48 h. Samples of solids that formed in the reaction vessels were examined using a scanning electron microscope. The CdCO3 compounds primarily showed a spherical shape. The results of this study demonstrate that MICP-based sequestration of soluble heavy metals via coprecipitation with calcite may be useful for toxic heavy metal bioremediation. PMID:24293312

  19. Utricular otoconia of some amphibians have calcitic morphology

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  20. Aragonite / Calcite seas and the evolution of biomineralization

    NASA Astrophysics Data System (ADS)

    Balthasar, Uwe

    2015-04-01

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

  1. Cross-section of Calcite Crystal Covering in Jewel Cave

    USGS Multimedia Gallery

    Jewel Cave is currently the 3rd most extensive cave network in the world. It is believed to have formed completely underwater, thus leading to the extensive coating of calcite crystals. A cross-sectional view of the crystal coating can be seen in the center of the image, with the surface of the cal...

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

    PubMed

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

    2015-12-01

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

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

    PubMed Central

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

    1989-01-01

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

  4. Effect of Calcite Surfaces on Chiral Separtion of Amino Acids

    NASA Astrophysics Data System (ADS)

    Kwon, K.; Kubicki, J. D.

    2003-12-01

    Studies have suggested that mineral surfaces break chirality of biomolecules by selective adsorption of amino acids to mineral surfaces and mineral surfaces catalyze amino acid polymerization. Recently, a plausible chiral-separation of amino acids was proposed by showing aspartic acids adsorb selectively on chiral calcite surfaces (Hazen et al., 2001, P NATL ACAD SCI USA). However, the selective adsorption is still phenomenal observation without a theoretical model. We have applied molecular modeling tools to explain the selective adsorption in terms of structures and energetics of interactions between aspartic acids and calcite surfaces. Molecular dynamics (MD) simulations were used to obtain structures of L- and D-aspartic acids and calcite surfaces. The Universal Force Field with Ewald sum and canonical ensemble at 300K were used. Simulations were run with a time step of 1 fs for 100,000 steps. The charges of each atom were calculated every 300 steps using the charge equilibration method (QEq). The interactions between one type of aspartic acid (D or L) and a calcite surface ((21\\~{3}1) or (3\\~{1}\\~{2}1)) were simulated in a 3-D periodic box model. Gas-phase MD simulations predicted that D-aspartic acid has stronger binding energy (averaged internal energy of a system) than L-aspartic acid to calcite (21\\~{3}1) surface, while L-aspartic acid has stronger binding energy than D-aspartic acid to calcite (3\\~{1}\\~{2}1) surface. The gas-phase simulations are in a good agreement with the experimental observation of aspartic acids preferential adsorption in that lager binding energy corresponds to more adsorption. Because the adsorption occurs in solution, we simulated the interactions in solution by adding 451 water molecules in the lowest-energy configurations obtained from gas phase simulations. The solution simulations predicted a similar trend to the gas phase simulations, but the averaged binding-energy differences between D/L amino acids with calcite surfaces were within the range of energy deviation of each simulation. Therefore, molecular orbital calculations were carried out using the program GAMESS to calculate more accurate interaction-energies from minimum-energy configurations of solution-phase MD simulations. Molecular orbital calculations combined with MD simulations are expected to give a theoretical basis to understand the selective adsorption.

  5. Uranium Isotope Fractionation During Coprecipitation with Aragonite and Calcite

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  6. Gas hydrate cool storage system

    DOEpatents

    Ternes, M.P.; Kedl, R.J.

    1984-09-12

    The invention presented relates to the development of a process utilizing a gas hydrate as a cool storage medium for alleviating electric load demands during peak usage periods. Several objectives of the invention are mentioned concerning the formation of the gas hydrate as storage material in a thermal energy storage system within a heat pump cycle system. The gas hydrate was formed using a refrigerant in water and an example with R-12 refrigerant is included. (BCS)

  7. Gas hydrates: technology status report

    SciTech Connect

    Not Available

    1986-01-01

    The DOE Morgantown Energy Technology Center (METC) implemented a gas hydrates R and D program that emphasized an understanding of the resource through (1) an assessment of current technology, (2) the characterization of gas hydrate geology and reservoir engineering, and (3) the development of diagnostic tools and methods. Recovery of natural gas from gas hydrates will be made possible through (1) improved instrumentation and recovery methods, (2) developing the capability to predict production performance, and (3) field verification of recovery methods. Gas hydrates research has focused primarily on geology. As work progressed, areas where gas hydrates are likely to occur were identified, and specific high potential areas were targeted for detailed investigation. A Geologic Analysis System (GAS) was developed. GAS contains approximately 30 software packages and can manipulate and correlate several types of geologic and petroleum data into maps, graphics, and reports. The system also contains all well information currently available from the Alaskan North Slope area. Laboratory research on gas hydrates includes the characterization of the physical system, which focuses on creating synthetic methane hydrates and developing synthetic hydrate cores using tetrahydrofuran (THF), consolidated rock cores, frost base mixtures, water/ice-base mixtures, and water-base mixtures. Laboratory work produced measurements of the sonic velocity and electrical resistivity of these synthetic hydrates. During 1983, a sample from a natural hydrate core recovered from the Pacific coast of Guatemala was tested for these properties by DOE/METC. More recently, natural hydrate samples acquired from the Gulf of Mexico are being tested. Modeling and systems analysis work has focused on the development of GAS and preliminary gas hydrate production models. 23 refs., 18 figs., 6 tabs.

  8. Soil pH management without lime, a strategy to reduce greenhouse gas emissions from cultivated soils

    NASA Astrophysics Data System (ADS)

    Nadeem, Shahid; Bakken, Lars; Reent Köster, Jan; Tore Mørkved, Pål; Simon, Nina; Dörsch, Peter

    2015-04-01

    For decades, agricultural scientists have searched for methods to reduce the climate forcing of food production by increasing carbon sequestration in the soil and reducing the emissions of nitrous oxide (N2O). The outcome of this research is depressingly meagre and the two targets appear incompatible: efforts to increase carbon sequestration appear to enhance the emissions of N2O. Currently there is a need to find alternative management strategies which may effectively reduce both the CO2 and N2O footprints of food production. Soil pH is a master variable in soil productivity and plays an important role in controlling the chemical and biological activity in soil. Recent investigations of the physiology of denitrification have provided compelling evidence that the emission of N2O declines with increasing pH within the range 5-7. Thus, by managing the soil pH at a near neutral level appears to be a feasible way to reduce N2O emissions. Such pH management has been a target in conventional agriculture for a long time, since a near-neutral pH is optimal for a majority of cultivated plants. The traditional way to counteract acidification of agricultural soils is to apply lime, which inevitably leads to emission of CO2. An alternative way to increase the soil pH is the use of mafic rock powders, which have been shown to counteract soil acidification, albeit with a slower reaction than lime. Here we report a newly established field trail in Norway, in which we compare the effects of lime and different mafic mineral and rock powders (olivine, different types of plagioclase) on CO2 and N2O emissions under natural agricultural conditions. Soil pH is measured on a monthly basis from all treatment plots. Greenhouse gas (GHG) emission measurements are carried out on a weekly basis using static chambers and an autonomous robot using fast box technique. Field results from the first winter (fallow) show immediate effect of lime on soil pH, and slower effects of the mafic rocks. The plots with mafic rock powders have lower CO2 and N2O emissions as compared with calcite and dolomite. The experiment will be continued for several years under conventionally managed continuous grass, and is unique in its kind allowing to compare different strategies for pH management on GHG emissions.

  9. Dissolution enthalpies of synthetic magnesian calcites: Comparison with biogenic phases

    SciTech Connect

    Bischoff, W.D. . Geology Dept.); Wollast, R. )

    1992-01-01

    A series of synthetic magnesian calcites (0--15 mol% MgCO[sub 3]) were dissolved in weak acetic acid solutions to measure enthalpies of the reaction at 25 C. Heat released was 33.5 KJ/mol for calcite, decreasing to 33 KJ/mol for a Mg-Calcite of 2 mol% MgCO[sub 3], and increasing to 35 KJ/mol for a phase of 15 mol%. Excess enthalpies of formation Hf for these phases were calculated using calcite and magnesite as end-members. Values of Hf average about [minus]1 KJ/mol for the synthetic phases with a trend of increasingly negative values of Hf with Mg content. Excess entropies of formation Sf, corrected for excess entropies associated with ideal solid solutions, were calculated form available data on Gibbs free energies of formation and the values of Hf from this study. These values of Sf range from about [minus]2 J/mol-K for the phase with 2 mol% MgCO[sub 3] to [minus]5 J/mol-K at 15 mol%. The values of Sf suggest that some form of ordering (probably cation ordering) is obtained from these phases. In contrast, biogenic phases have positive values of Hf, increasing from about 1 KJ/mol for phases containing 5 mol% MgCO[sub 3] to 3 KJ/mol for those with 20 mol%. Values of Sf for the biogenic phases are positive, approximately 5 J/mol-K for a phase containing 15 mol% MgCO[sub 3]. For the biogenic phases, some form of disordering is suggested from the entropy calculations and may be the result of positional disordering is suggested from the entropy calculations and may be the result of positional disordering of the carbonate ion. The disorder in biogenic phases compared to the ordering in synthetic phases indicates significant structural differences that account for the higher solubilities of biogenic Mg-Calcites.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  11. Anomalous porosity preservation and preferential accumulation of gas hydrate in the Andaman accretionary wedge, NGHP-01 site 17A

    SciTech Connect

    Rose, Kelly K.; Johnson, Joel E.; Torres, Marta E.; Hong, WeiLi; Giosan, Liviu; Solomon, E.; Kastner, Miriam; Cawthern, Thomas; Long, Philip E.; Schaef, Herbert T.

    2014-12-01

    In addition to well established properties that control the presence or absence of the hydrate stability zone, such as pressure, temperature, and salinity, additional parameters appear to influence the concentration of gas hydrate in host sediments. The stratigraphic record at Site 17A in the Andaman Sea, eastern Indian Ocean, illustrates the need to better understand the role pore-scale phenomena play in the distribution and presence of marine gas hydrates in a variety of subsurface settings. In this paper we integrate field-generated datasets with newly acquired sedimentology, physical property, imaging and geochemical data with mineral saturation and ion activity products of key mineral phases such as amorphous silica and calcite, to document the presence and nature of secondary precipitates that contributed to anomalous porosity preservation at Site 17A in the Andaman Sea. This study demonstrates the importance of grain-scale subsurface heterogeneities in controlling the occurrence and distribution of concentrated gas hydrate accumulations in marine sediments, and document the importance that increased permeability and enhanced porosity play in supporting gas concentrations sufficient to support gas hydrate formation. The grain scale relationships between porosity, permeability, and gas hydrate saturation documented at Site 17A likely offer insights into what may control the occurrence and distribution of gas hydrate in other sedimentary settings.

  12. Lime enhances moving bed filters for mercury and dioxin control

    SciTech Connect

    Licata, A.; Goetz, E.; Nethe, L.P.

    1997-12-01

    Moving bed carbon filters were developed and used in Europe to control mercury and dioxin emissions from municipal waste combustors (MWCs), crematories, hazardous waste incinerators and power plants. Although some operating problems such as a potential for fires to form in the carbon beds have caused operators some concern, more stable bed materials are presently being produced which can maintain the moving bed filter`s capability in reducing mercury and dioxin emissions to very low levels while providing safe operations. Maerker Umwelttechnik GmbH (Maerker) and Dravo Lime Company (Dravo) have developed a pelletized form of Sorbalit{reg_sign} that replaces the carbon in moving bed filters and is effective in removing mercury, dioxins, and acid gases without the inherent problems of using a carbon only adsorbent system. Sorbalit pellets are a formulation of portland cement, lime, carbon, and sulfur compounds. These pellets are currently being successfully applied in a hazardous waste incinerator, a foundry, a crematory, and a contaminated soil treatment plant. This paper discusses the development of pellet technology and its application in moving bed filters. Safety aspects for the use of composite carbon/lime pellets will be discussed and a review of removal efficiencies among carbon alone, a composite carbon/lime material in a powder form, and composite carbon/lime adsorbents in a pellet form will be provided.

  13. Engineering properties of cement/lime-stabilized Egyptian soft clay

    NASA Astrophysics Data System (ADS)

    Mansour, M. A.; Samieh, A. M.; Matter, H. E.

    2015-09-01

    Soft clay formations are extensively located in many coastal areas around the world. The significant high compressibility and low shear strength of these formations impose challenging engineering problems. The deep cement/lime-mix-in-place method is one of the ground improvement techniques exhibiting successful use in stabilizing soft clay. Analysis and design of the deep mixing systems necessitate the identification of the additive content, the proportions of the lime to cement and the characteristics of the stabilized clay. This paper investigates experimentally the influence of adding lime and cement or cement alone, as stabilizing additives, on the engineering behavior of an Egyptian soft clay extracted from the north delta region. A series of laboratory tests were carried out considering, different additive contents of 8, 10, 12, and 14% of the dry weight, with different proportions of lime to cement of 50:50, 25:75 and 0:100. A series of unconfined compression strength tests were performed after different periods; one week, four weeks and 8 weeks, to assess the effect of curing period on the stabilized clay response. In addition, one dimensional consolidation tests were carried out to evaluate the compressibility properties of the stabilized clay. This study declared that the use of an additive content in the range of 12% and more is recommended to improve the characteristics of the considered Egyptian clay. It was pointed out that addition of lime and cement to soft clay significantly increases the strength characteristics and significantly reduces the compressibility characteristics of such clay.

  14. Hydration of small peptides

    NASA Astrophysics Data System (ADS)

    Wyttenbach, Thomas; Liu, Dengfeng; Bowers, Michael T.

    2005-02-01

    The results for the sequential hydration of small peptides (<15 residues) obtained in our group are reviewed and put in perspective with other work published in the literature where appropriate. Our findings are based on hydration equilibrium measurements in a high-pressure drift cell inserted into an electrospray mass spectrometer and on calculations employing molecular mechanics and density functional theory methods. It is found that the ionic functional groups typically present in peptides, the ammonium, guanidinium, and carboxylate groups, are the primary target of water molecules binding to peptides. Whereas the water-guanidinium binding energy is fairly constant at 9 +/- 1 kcal/mol, the water binding energy of an ammonium group ranges from 7 to 15 kcal/mol depending on how exposed the ammonium group is. A five-residue peptide containing an ammonium group is in favorable cases large enough to fully self-solvate the charge, but a pentapeptide containing a guanidinium group is too small to efficiently shield the charge of this much larger ionic group. The water-carboxylate interaction amounts to 13 kcal/mol with smaller values for a shielded carboxylate group. Both water bound to water in a second solvation shell and charge remote water molecules on the surface of the peptide are bound by 7-8 kcal/mol. The presence of several ionic groups in multiply charged peptides increases the number of favorable hydration sites, but does not enhance the water-peptide binding energy significantly. Water binding energies measured for the first four water molecules bound to protonated bradykinin do not show the declining trend typically observed for other peptides but are constant at 10 kcal/mol, a result consistent with a molecule containing a salt bridge with several good hydration sites. Questions regarding peptide structural changes as a function of number of solvating water molecules are discussed. Not much is known at present about the effect of individual water molecules on the conformation of peptides and on the stability of peptide zwitterions.

  15. Aragonite, breunnerite, calcite and dolomite in the CM carbonaceous chondrites: High fidelity recorders of progressive parent body aqueous alteration

    NASA Astrophysics Data System (ADS)

    Lee, Martin R.; Lindgren, Paula; Sofe, Mahmood R.

    2014-11-01

    Carbonate minerals in CM carbonaceous chondrite meteorites, along with the silicates and sulphides with which they are intergrown, provide a detailed record of the nature and evolution of parent body porosity and permeability, and the chemical composition, temperature and longevity of aqueous solutions. Fourteen meteorites were studied that range in petrologic subtype from mildly aqueously altered CM2.5 to completely hydrated CM2.0. All of them contain calcite, whereas aragonite occurs only in the CM2.5-CM2.2 meteorites and dolomite in the CM2.2-CM2.0. All of the aragonite crystals, and most of the calcite and dolomite grains, formed during early stages of parent body aqueous alteration by cementation of pores produced by the melting of tens of micrometre size particles of H2O-rich ice. Aragonite was the first carbonate to precipitate in the CM2.5 to CM2.2 meteorites, and grew from magnesium-rich solutions. In the least altered of these meteorites the aragonite crystals formed in clusters owing to physical restriction of aqueous fluids within the low permeability matrix. The strong correlation between the petrologic subtype of a meteorite, the abundance of its aragonite crystals and the proportion of them that have preserved crystal faces, is because aragonite was dissolved in the more altered meteorites on account of their higher permeability, and/or greater longevity of the aqueous solutions. Dolomite and breunnerite formed instead of aragonite in some of the CM2.1 and CM2.2 meteorites owing to higher parent body temperatures. The pore spaces that remained after precipitation of aragonite, dolomite and breunnerite cements were occluded by calcite. Following completion of cementation, the carbonates were partially replaced by phyllosilicates and sulphides. Calcite in the CM2.5-CM2.2 meteorites was replaced by Fe-rich serpentine and tochilinite, followed by Mg-rich serpentine. In the CM2.1 and CM2.0 meteorites dolomite, breunnerite and calcite were replaced by Fe-rich serpentine and Fe-Ni sulphide, again followed by Mg-rich serpentine. The difference between meteorites in the mineralogy of their replacive sulphides may again reflect greater temperatures in the parent body regions from where the more highly altered CMs were derived. This transition from Fe-rich to Mg-rich carbonate replacement products mirrors the chemical evolution of parent body solutions in response to consumption of Fe-rich primary minerals followed by the more resistant Mg-rich anhydrous silicates. Almost all of the CMs examined contain a second generation of calcite that formed after the sulphides and phyllosilicates and by replacement of remaining anhydrous silicates and dolomite (dedolomitization). The Ca and CO2 required for this replacive calcite is likely to have been sourced by dissolution of earlier formed carbonates, and ions may have been transported over metre-plus distances through high permeability conduits that were created by impact fracturing.

  16. Fluid mediated transformation of aragonitic cuttlebone to calcite

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    The aragonite to calcite transition has been studied extensively over the years because of its wide spectra of applications and of its significant geochemical interest. While studies of kinetics (e.g. Topor et al., 1981), thermodynamics (e.g. Wolf et al., 1996) and behavior of ions such as Sr and Mg (e.g. Yoshioka et al., 1986) have been made there are still unanswered questions regarding this reaction especially in the cases where the effects of fluid composition are considered. It is well known that when heated in air, aragonite transforms by a solid state reaction to calcite. The aragonite cuttlebone of the sepia officinalis that was used for our experiments undergoes a phase transition at ~370-390˚ C, measured by in situ heating experiments in a Philips X'pert X-ray powder diffractometer equipped with a HTK 1200 High temperature oven. Successive X-ray scans were taken at isothermal temperatures at 200C intervals. A similar temperature range was found by Vongsavat et al. 2006, who studied this transition in Acropora corals. It is possible however to promote this transition at considerably lower temperatures by means of a fluid mediated reaction where the replacement takes place by a dissolution-precipitation mechanism (Putnis & Putnis, 2007). We have successfully carried out hydrothermal experiments where cuttlebone has been converted to calcite at 200˚ C. Using the PhreeqC program we calculated the required composition of a solution that would be undersaturated with respect to aragonite and saturated with respect to calcite leading to dissolution of the aragonite and to a consequent precipitation of the new calcite phase, similar to the experiments described in an earlier study (Perdikouri et al, 2008). This reaction is not pseudomorphic and results in the destruction of the morphology, presumably due to the molar volume increase. A total transformation of the cuttlebone produced a fine calcite powder. The cuttlebone exhibits a unique microstructure, made up of interconnected chambers. The aragonite grown during biomineralization of the cuttlebone is interlaced with a β-chitin organic phase that provides the framework for the morphology that is observed. Experiments carried out with the same constant conditions but for different periods of time have revealed the evolution of the transformation to calcite. At shorter reaction times the product was made up of calcite powder and of well preserved aragonite septa, as was confirmed by powder X-ray diffraction. In other words, the vertical pillars appear to react at faster rates than the horizontal septa. It has been reported by Florek et al. 2008 that the septa contain higher quantities of β-chitin. The aim of this study is the investigation of these observations and the determination of the effect of the organic component on the kinetics of the aragonite to calcite transformation. Florek M., Fornal E., Gómez-Romero P., Zieba E., Paszkowicz W., Lekki J.,Nowak J., Kuczumow A. Materials Science and Engineering C, In Press (2008) Perdikouri C., Kasioptas A., Putnis C.V., Putnis A. Mineralogical Magazine 72, 111-114 (2008) Putnis A., Putnis C.V. Solid State Chemistry 180, 1783-1786 (2007) Topor N. D., Tolokonnikova L. I., Kadenatsi B. M. Journal of Thermal Analysis 20, 169-174 (1981) Vongsavat V., Winotai P., Meejoo S. Nuclear Instruments and Methods in Physics Research B 243, 167-173 (2006) Wolf G., Lerchner J., Schmidt H., Gamsjäger H., Königsberger E., Schmidt P. Journal of Thermal Analysis 46, 353-359 (1996) Yoshioka S., Ohde S., Kitano Y., Kanamori N. Marine Chemistry 18, 35-48 (1986)

  17. Carbonate "clumped" isotope signatures in aragonitic scleractinian and calcitic gorgonian deep-sea corals

    NASA Astrophysics Data System (ADS)

    Kimball, J.; Tripati, R. E.; Dunbar, R.

    2015-12-01

    Deep-sea corals are a potentially valuable archive of the temperature and ocean chemistry of intermediate and deep waters. Living in near constant temperature, salinity and pH, and having amongst the slowest calcification rates observed in carbonate-precipitating biological organisms, deep-sea corals can provide valuable constraints on processes driving mineral equilibrium and disequilibrium isotope signatures. Here we report new data to further develop "clumped" isotopes as a paleothermometer in deep-sea corals as well as to investigate mineral-specific, taxon-specific, and growth-rate related effects. Carbonate clumped isotope thermometry is based on measurements of the abundance of the doubly-substituted isotopologue 13C18O16O2 in carbonate minerals, analyzed in CO2 gas liberated on phosphoric acid digestion of carbonates and reported as Δ47 values. We analyzed Δ47 in live-collected aragonitic scleractinian (Enallopsammia sp.) and calcitic gorgonian (Isididae and Coralliidae) deep-sea corals, and compared results to published data for other aragonitic scleractinian taxa. Measured Δ47 values were compared to in situ temperatures and the relationship between Δ47 and temperature was determined for each group to investigate taxon-specific effects. We find that aragonitic scleractinian deep-sea corals exhibit higher values than calcitic gorgonian corals and the two groups of coral produce statistically different relationship between Δ47-temperature calibrations. These data are significant in the interpretation of all carbonate "clumped" isotope calibration data as they show that distinct Δ47-temperature calibrations can be observed in different materials recovered from the same environment and analyzed using the same instrumentation, phosphoric acid composition, digestion temperature and technique, CO2 gas purification apparatus, and data handling. There are three possible explanations for the origin of these different calibrations. The offset between the corals of different mineralogy is in the same direction as published theoretical predictions for the offset between calcite and aragonite, although the magnitude of the offset is different. One possibility is that the deep-sea coral results reflect that crystals may attain nominal mineral equilibrium clumped isotope signatures only under conditions of extremely slow growth. In that case, a possible explanation for the attainment of disequilibrium bulk isotope signatures and equilibrium clumped isotope signatures by deep-sea corals is that extraordinarily slow growth rates can promote the occurrence of isotopic reordering in the interfacial region of growing crystals. We also cannot rule out a component of a biological "vital-effect" influencing clumped isotope signatures in one or both orders of coral. Based on published experimental data and theoretical calculations, these biological "vital" effects could arise from kinetic isotope effects due to the source of carbon used for calcification, temperature- and pH-dependent rates of CO2 hydration and/or hydroxylation, calcifying fluid pH, the activity of carbonic anhydrase, the residence time of dissolved inorganic carbon in the calcifying fluid, and calcification rate. A third possible explanation is the occurrence of variable acid digestion fractionation factors. Although a recent study has suggested that dolomite, calcite, and aragonite may have similar clumped isotope acid digestion fractionation factors, the influence of acid digestion kinetics on Δ47 is a subject that warrants further investigation.

  18. Fracture-aperture alteration induced by calcite precipitation

    NASA Astrophysics Data System (ADS)

    Jones, T.; Detwiler, R. L.

    2013-12-01

    Mineral precipitation significantly alters the transport properties of fractured rock. Chemical solubility gradients that favor precipitation induce mineral growth, which decreases the local aperture and alters preferential flow paths. Understanding the resulting development of spatial heterogeneities is necessary to predict the evolution of transport properties in the subsurface. We present experimental results that quantify the relationship between mineral precipitation and aperture alteration in a transparent analog fracture, 7.62cm x 7.62cm, with a uniform aperture of ~200 μm. Prior to flow experiments, a pump circulated a super-saturated calcite solution over the bottom glass, coating the glass surface with calcite. This method of seeding resulted in clusters of calcite crystals with large reactive surface area and provided micro-scale variability in the aperture field. A continuous flow syringe pump injected a reactive fluid into the fracture at 0.5 ml/min. The fluid was a mixture of sodium bicarbonate (NaHCO3, 0.02M) and calcium chloride (CaCl2 0.0004M) with a saturation index, Ω, of 8.51 with respect to calcite. A strobed LED panel backlit the fracture and a high-resolution CCD camera monitored changes in transmitted light intensity. Light transmission techniques provided a quantitative measurement of fracture aperture over the flow field. Results from these preliminary experiments showed growth near the inlet of the fracture, with decreasing precipitation rates in the flow direction. Over a period of two weeks, the fracture aperture decreased by 17% within the first 4mm of the inlet. Newly precipitated calcite bridged individual crystal clusters and smoothed the reacting surface. This observation is an interesting contradiction to the expectation of surface roughening induced by mineral growth. Additionally, the aperture decreased uniformly across the width of the fracture due to the initial aperture distribution. Future experiments of precipitation within variable-aperture fields will investigate the dependency of growth patterns on heterogeneous aperture distributions. (a) Aperture strain (Δb/bi) after 14 days. Precipitation is concentrated near the inlet and decreases in the flow direction. (b) Width-averaged profiles of the initial and final aperture field show changes in aperture and smoothing that results from calcite precipitation between the initial discrete crystals.

  19. Hydration of a low-alkali CEM III/B-SiO{sub 2} cement (LAC)

    SciTech Connect

    Lothenbach, Barbara; Le Saout, Gwenn; Ben Haha, Mohsen; Figi, Renato; Wieland, Erich

    2012-02-15

    The hydration of a low-alkali cement based on CEM III/B blended with 10 wt.% of nanosilica has been studied. The nanosilica reacted within the first days and 90% of the slag reacted within 3.5 years. C-S-H (Ca/Si {approx} 1.2, Al/Si {approx} 0.12), calcite, hydrotalcite, ettringite and possibly straetlingite were the main hydrates. The pore water composition revealed ten times lower alkali concentrations than in Portland cements. Reducing conditions (HS{sup -}) and a pH value of 12.2 were observed. Between 1 month and 3.5 years of hydration more hydrates were formed due to the ongoing slag reaction but no significant differences in the composition of the pore solution or solid phase assemblage were observed. On the basis of thermodynamic calculations it is predicted that siliceous hydrogarnet could form in the long-term and, in the presence of siliceous hydrogarnet, also thaumasite. Nevertheless, even after 3.5 year hydration, neither siliceous hydrogarnet nor thaumasite have been observed.

  20. Some thermodynamical aspects of protein hydration water.

    PubMed

    Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Vasi, Cirino; Stanley, H Eugene; Chen, Sow-Hsin

    2015-06-01

    We study by means of nuclear magnetic resonance the self-diffusion of protein hydration water at different hydration levels across a large temperature range that includes the deeply supercooled regime. Starting with a single hydration shell (h = 0.3), we consider different hydrations up to h = 0.65. Our experimental evidence indicates that two phenomena play a significant role in the dynamics of protein hydration water: (i) the measured fragile-to-strong dynamic crossover temperature is unaffected by the hydration level and (ii) the first hydration shell remains liquid at all hydrations, even at the lowest temperature. PMID:26049527

  1. Some thermodynamical aspects of protein hydration water

    SciTech Connect

    Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Sebastiano; Vasi, Cirino; Stanley, H. Eugene; Chen, Sow-Hsin

    2015-06-07

    We study by means of nuclear magnetic resonance the self-diffusion of protein hydration water at different hydration levels across a large temperature range that includes the deeply supercooled regime. Starting with a single hydration shell (h = 0.3), we consider different hydrations up to h = 0.65. Our experimental evidence indicates that two phenomena play a significant role in the dynamics of protein hydration water: (i) the measured fragile-to-strong dynamic crossover temperature is unaffected by the hydration level and (ii) the first hydration shell remains liquid at all hydrations, even at the lowest temperature.

  2. Mallik Gas Hydrates Test Well

    USGS Multimedia Gallery

    A test-well for collecting gas hydrates in Mallik, Canada. Gas hydrates are naturally-occurring “ice-like” combinations of natural gas and water that have the potential to provide an immense resource of natural gas from the world’s oceans and polar regions....

  3. Ductile flow of methane hydrate

    USGS Publications Warehouse

    Durham, W.B.; Stern, L.A.; Kirby, S.H.

    2003-01-01

    Compressional creep tests (i.e., constant applied stress) conducted on pure, polycrystalline methane hydrate over the temperature range 260-287 K and confining pressures of 50-100 MPa show this material to be extraordinarily strong compared to other icy compounds. The contrast with hexagonal water ice, sometimes used as a proxy for gas hydrate properties, is impressive: over the thermal range where both are solid, methane hydrate is as much as 40 times stronger than ice at a given strain rate. The specific mechanical response of naturally occurring methane hydrate in sediments to environmental changes is expected to be dependent on the distribution of the hydrate phase within the formation - whether arranged structurally between and (or) cementing sediments grains versus passively in pore space within a sediment framework. If hydrate is in the former mode, the very high strength of methane hydrate implies a significantly greater strain-energy release upon decomposition and subsequent failure of hydrate-cemented formations than previously expected.

  4. Bubble migration during hydrate formation

    NASA Astrophysics Data System (ADS)

    Shagapov, V. Sh.; Chiglintseva, A. S.; Rusinov, A. A.

    2015-03-01

    A model of the process of migration of methane bubbles in water under thermobaric conditions of hydrate formation is proposed. The peculiarities of the temperature field evolution, migration rate, and changes in the radius and volume fraction of gas hydrate bubbles are studied. It is shown that, with a constant mass flow of gas from the reservoir bottom, for all parameters of the surfacing gas hydrate disperse system, there is a quasistationary pattern in the form of a "step"-like wave. Depending on the relationship of the initial gas bubble density with the average gas density in the hydrate composition determined by the depth from which bubbles rise to the surface, the final radius of hydrate particles may be larger or smaller than the initial gas bubble radii. It is established that the speed at which gas hydrate inclusions rise to the surface decreases by several times due to an increase in their weight during hydrate formation. The influence of the depth of the water reservoir whose bottom is a gas flow source on the dynamics of hydrate formation is studied.

  5. Hydration and physical performance.

    PubMed

    Murray, Bob

    2007-10-01

    There is a rich scientific literature regarding hydration status and physical function that began in the late 1800s, although the relationship was likely apparent centuries before that. A decrease in body water from normal levels (often referred to as dehydration or hypohydration) provokes changes in cardiovascular, thermoregulatory, metabolic, and central nervous function that become increasingly greater as dehydration worsens. Similarly, performance impairment often reported with modest dehydration (e.g., -2% body mass) is also exacerbated by greater fluid loss. Dehydration during physical activity in the heat provokes greater performance decrements than similar activity in cooler conditions, a difference thought to be due, at least in part, to greater cardiovascular and thermoregulatory strain associated with heat exposure. There is little doubt that performance during prolonged, continuous exercise in the heat is impaired by levels of dehydration >or= -2% body mass, and there is some evidence that lower levels of dehydration can also impair performance even during relatively short-duration, intermittent exercise. Although additional research is needed to more fully understand low-level dehydration's effects on physical performance, one can generalize that when performance is at stake, it is better to be well-hydrated than dehydrated. This generalization holds true in the occupational, military, and sports settings. PMID:17921463

  6. Ultrafast hydration dynamics of proteins

    NASA Astrophysics Data System (ADS)

    Zhong, Dongping

    2004-03-01

    Hydration dynamics of the water layer at the protein surface is important to protein structure and function. Recent studies of water-protein interactions have merged into a cohesive picture: Biological water molecules are not static but dynamic in nature. Previously limited time resolution did not fully resolve hydration processes. Here, we report our direct mapping of the hydration dynamics at a protein surface. The intrinsic tryptophan residue will be engineered to scan the protein surface by site-directed mutagenesis. Spatial and temporal hydration heterogeneity will for the first time be characterized in both native and molten globule states. Dynamical hydration patterns will be evaluated in terms of the local topography and chemical identity. These results will provide a molecular basis for the understanding of protein-water interactions, a topic central to protein science.

  7. Liming Poultry Manures to Kill Pathogens and Decrease Soluble Phosphorus

    SciTech Connect

    Maguire,R.; Hesterberg, D.; Gernat, A.; Anderson, K.; Wineland, M.; Grimes, J.

    2006-01-01

    Received for publication September 9, 2005. Stabilizing phosphorus (P) in poultry waste to reduce P losses from manured soils is important to protect surface waters, while pathogens in manures are an emerging issue. This study was conducted to evaluate CaO and Ca(OH){sub 2} for killing manure bacterial populations (pathogens) and stabilizing P in poultry wastes and to investigate the influence on soils following amendment with the treated wastes. Layer manure and broiler litter varying in moisture content were treated with CaO and Ca(OH){sub 2} at rates of 2.5, 5, 10, and 15% by weight. All treated wastes were analyzed for microbial plate counts, pH, and water-soluble phosphorus (WSP), while a few selected layer manures were analyzed by phosphorus X-ray absorption near edge structure (XANES). A loamy sand and a silt loam were amended with broiler litter and layer manure treated with CaO at rates of 0, 2.5, 5, 10, and 15% and soil WSP and pH were measured at times 1, 8, and 29 d. Liming reduced bacterial populations, with greater rates of lime leading to greater reductions; for example 10% CaO applied to 20% solids broiler litter reduced the plate counts from 793 000 to 6500 mL{sup -1}. Liming also reduced the WSP in the manures by over 90% in all cases where at least 10% CaO was added. Liming the manures also reduced WSP in soils immediately following application and raised soil pH. The liming process used successfully reduced plate counts and concerns about P losses in runoff following land application of these limed products due to decreased WSP.

  8. EVALUATION OF BIOAEROSOL COMPONENTS, GENERATION FACTORS, AND AIRBORNE TRANSPORT ASSOCIATED WITH LIME TREATMENT OF CONTAMINATED SEDIMENT

    EPA Science Inventory

    Lime treatment has been used in contaminated sediment management activities for many purposes such as dewatering, improvement of physical properties, and reducing contaminant mobility. Exothermic volatilization of volatile organic compounds from lime-treated sediment is well kno...

  9. REMOVAL OF BERYLLIUM FROM DRINKING WATER BY CHEMICAL COAGULATION AND LIME SOFTENING

    EPA Science Inventory

    The effectiveness of conventional drinking water treatment and lime softening was evaluated for beryllium removal from two drinking water sources. ar test studies were conducted to determine how common coagulants (aluminum sulfate and ferric chloride and lime softening performed ...

  10. Catalytic iron oxide for lime regeneration in carbonaceous fuel combustion

    DOEpatents

    Shen, Ming-Shing (Rocky Point, NY); Yang, Ralph T. (Middle Island, NY)

    1980-01-01

    Lime utilization for sulfurous oxides absorption in fluidized combustion of carbonaceous fuels is improved by impregnation of porous lime particulates with iron oxide. The impregnation is achieved by spraying an aqueous solution of mixed iron sulfate and sulfite on the limestone before transfer to the fluidized bed combustor, whereby the iron compounds react with the limestone substrate to form iron oxide at the limestone surface. It is found that iron oxide present in the spent limestone acts as a catalyst to regenerate the spent limestone in a reducing environment. With only small quantities of iron oxide the calcium can be recycled at a significantly increased rate.

  11. The solubility of Fish Produced High Magnesium Calcite in Seawater

    NASA Astrophysics Data System (ADS)

    Woosley, R. J.; Millero, F. J.; Grosell, M.

    2011-12-01

    Fish have been shown to produce high 10 to 30% magnesium calcite as part of the physiological mechanisms responsible for maintaining salt and water balance. The importance of this source to the marine carbon cycle is only now being considered. In this paper we report the first measurements of the solubility of this CaCO3 in seawater. The resulting solubility (pKsp = 5.85 0.07) is more than two times higher than aragonite and similar to the high magnesium calcite generated on the Bahamas Banks (pKsp = 5.90). This high solubility of fish produced CaCO3 renders it soluble in near surface (<2000 m) waters contributing to the input of carbonate to surface ocean waters, and at least partially explaining the increase in total alkalinity above the aragonite saturation horizon.

  12. U(VI) behaviour in hyperalkaline calcite systems

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    The behaviour of U(VI) in hyperalkaline fluid/calcite systems was studied over a range of U(VI) concentrations (5.27 × 10-5 μM to 42.0 μM) and in two high pH systems, young and old synthetic cement leachate in batch sorption experiments. These systems were selected to be representative of young- (pH 13.3) and old-stage (pH 10.5) leachate evolution within a cementitious geological disposal facility. Batch sorption experiments, modelling, extended X-ray absorption fine structure spectroscopy, electron microscopy, small angle X-ray scattering and luminescence spectroscopy were used to define the speciation of U(VI) across the systems of study. At the lowest concentrations (5.27 × 10-5 μM 232U(VI)) significant U removal was observed for both old and young cement leachates, and this was successfully modelled using a first order kinetic adsorption modelling approach. At higher concentrations (>4.20 μM) in the young cement leachate, U(VI) showed no interaction with the calcite surface over an 18 month period. Small angle X-ray scattering techniques indicated that at high U concentrations (42.0 μM) and after 18 months, the U(VI) was present in a colloidal form which had little interaction with the calcite surface and consisted of both primary and aggregated particles with a radius of 7.6 ± 1.1 and 217 ± 24 Å, respectively. In the old cement leachate, luminescence spectroscopy identified two surface binding sites for U(VI) on calcite: in the system with 0.21 μM U(VI), a liebigite-like Ca2UO2(CO3)3 surface complex was identified; at higher U(VI) concentrations (0.42 μM), a second binding site of undetermined coordination was identified. At elevated U(VI) concentrations (>2.10 μM) in old cement leachate, both geochemical data and luminescence spectroscopy suggested that surface mediated precipitation was controlling U(VI) behaviour. A focused ion beam mill was used to create a section across the U(VI) precipitate-calcite interface. Transmission electron microscope images of the section revealed that the calcite surface was coated with a nano crystalline, U containing phase. Selected area electron diffraction images of the U precipitate which was formed at a U(VI) concentration of 4.20 μM were consistent with the formation of calcium uranate. XAS spectroscopy at higher concentrations (⩾21.0 μM) suggested the formation of a second U(VI) phase, possibly a uranyl oxyhydroxide phase. These results indicated that in the young cement leachate, U(VI) did not react with the calcite surface unless U(VI) concentrations were very low (5.27 × 10-5 μM). At higher concentrations, speciation calculations suggested that U(VI) was significantly oversaturated and experimental observations confirmed it existed in a colloidal form that interacted with the mineral surface only weakly. In the old cement leachate systems at low concentrations batch sorption and luminescence data suggested that U(VI) removal was being driven by a surface complexation mechanism. However, at higher concentrations, spectroscopic methods suggest a combination of both surface complexation and surface mediated precipitation was responsible for the observed removal. Overall, U(VI) behaviour in hyperalkaline calcite systems is distinct from that at circumneutral pH conditions: at high pH and anything but low U(VI) concentrations, a surface mediated precipitation mechanism occurs; this is in contrast to circumneutral pH conditions where U(VI) surface complexation reactions tend to dominate.

  13. Understanding silicate hydration from quantitative analyses of hydrating tricalcium silicates.

    PubMed

    Pustovgar, Elizaveta; Sangodkar, Rahul P; Andreev, Andrey S; Palacios, Marta; Chmelka, Bradley F; Flatt, Robert J; d'Espinose de Lacaillerie, Jean-Baptiste

    2016-01-01

    Silicate hydration is prevalent in natural and technological processes, such as, mineral weathering, glass alteration, zeolite syntheses and cement hydration. Tricalcium silicate (Ca3SiO5), the main constituent of Portland cement, is amongst the most reactive silicates in water. Despite its widespread industrial use, the reaction of Ca3SiO5 with water to form calcium-silicate-hydrates (C-S-H) still hosts many open questions. Here, we show that solid-state nuclear magnetic resonance measurements of (29)Si-enriched triclinic Ca3SiO5 enable the quantitative monitoring of the hydration process in terms of transient local molecular composition, extent of silicate hydration and polymerization. This provides insights on the relative influence of surface hydroxylation and hydrate precipitation on the hydration rate. When the rate drops, the amount of hydroxylated Ca3SiO5 decreases, thus demonstrating the partial passivation of the surface during the deceleration stage. Moreover, the relative quantities of monomers, dimers, pentamers and octamers in the C-S-H structure are measured. PMID:27009966

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

    NASA Astrophysics Data System (ADS)

    Fried, Ruth; Mastai, Yitzhak

    2012-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Raitzsch, M.; Dueas-Bohrquez, A.; Reichart, G.-J.; de Nooijer, L. J.; Bickert, T.

    2010-03-01

    We investigated the effect of the calcium concentration in seawater and thereby the calcite saturation state (?) 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 ? at a gradient of -4.310-5 per ? unit. The DSr value of A. tepida does not change with ?, 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 ?, while DSr increases considerably with ? at a gradient of 0.009 per ? 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-sea benthic foraminifera typically used for paleostudies, the higher Ca concentrations in the past may potentially bias temperature reconstructions to a considerable degree. For instance, 25 Myr ago Mg/Ca ratios in A. tepida would have been 0.2 mmol/mol lower than today, due to the 1.5 times higher [Ca2+] of seawater, which in turn would lead to a temperature underestimation of more than 2 C.

  16. Interaction of copper with the surface of calcite

    SciTech Connect

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

    1981-05-01

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

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

    SciTech Connect

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

    1997-02-01

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

  18. Influence of chemical and physical characteristics of cement kiln dusts (CKDs) on their hydration behavior and potential suitability for soil stabilization

    SciTech Connect

    Peethamparan, Sulapha Olek, Jan Lovell, Janet

    2008-06-15

    The interaction of CKDs with a given soil depends on the chemical and physical characteristics of the CKDs. Hence, the characterization of CKDs and their hydration products may lead to better understanding of their suitability as soil stabilizers. In the present article, four different CKD powders are characterized and their hydration products are evaluated. A detailed chemical (X-ray diffraction), thermogravimetric and morphological (scanning electron microscope) analyses of both the CKD powders and the hydrated CKD pastes are presented. In general, high free-lime content ({approx} 14-29%) CKDs, when reacted with water produced significant amounts of calcium hydroxide, ettringite and syngenite. These CKDs also developed higher unconfined compressive strength and higher temperature of hydration compared to CKDs with lower amounts of free-lime. An attempt was made to qualitatively correlate the performance of CKD pastes with the chemical and physical characteristics of the original CKD powders and to determine their potential suitability as soil stabilizers. To that effect a limited unconfined compressive strength testing of CKD-treated kaolinite clays was performed. The results of this study suggest that both the compressive strength and the temperature of hydration of the CKD paste can give early indications of the suitability of particular CKD for soil stabilization.

  19. Imaging surface contacts: Power law contact distributions and contact stresses in quartz, calcite, glass and acrylic plastic

    USGS Publications Warehouse

    Dieterich, J.H.; Kilgore, B.D.

    1996-01-01

    A procedure has been developed to obtain microscope images of regions of contact between roughened surfaces of transparent materials, while the surfaces are subjected to static loads or undergoing frictional slip. Static loading experiments with quartz, calcite, soda-lime glass and acrylic plastic at normal stresses to 30 MPa yield power law distributions of contact areas from the smallest contacts that can be resolved (3.5 ??m2) up to a limiting size that correlates with the grain size of the abrasive grit used to roughen the surfaces. In each material, increasing normal stress results in a roughly linear increase of the real area of contact. Mechanisms of contact area increase are by growth of existing contacts, coalescence of contacts and appearance of new contacts. Mean contacts stresses are consistent with the indentation strength of each material. Contact size distributions are insensitive to normal stress indicating that the increase of contact area is approximately self-similar. The contact images and contact distributions are modeled using simulations of surfaces with random fractal topographies. The contact process for model fractal surfaces is represented by the simple expedient of removing material at regions where surface irregularities overlap. Synthetic contact images created by this approach reproduce observed characteristics of the contacts and demonstrate that the exponent in the power law distributions depends on the scaling exponent used to generate the surface topography.

  20. Carbon isotopic thermometry calibrated by dolomite-calcite solvus temperatures

    NASA Astrophysics Data System (ADS)

    Wada, Hideki; Suzuki, Kazuhiro

    1983-04-01

    The temperature dependence of carbon isotopic fractionations between calcite and graphite, and between dolomite and graphite are calibrated by the calcite-dolomite solvus geothermometry using marbles collected from the contact metamorphic aureole in the Kasuga area, central Japan. The carbon isotopic fractionations ( ?13CCc- Gr and ?13CDo? Gr) systematically decrease with increasing metamorphic temperature. The concordant relationships between the fractionations and solvus temperatures are approximately linear with T-2 over the temperature range. 400 to 680C: ?13CCc? Gr (%.) = 5.6 10 6 T-2 (K) - 2.4 ?13CDo? Gr (%.) = 5.9 10 6 T-2 ( K) - 1.9 These systematic relationships between fractionation and temperature suggest that carbon isotopic equilibria between carbonates and graphite were attained in many cases. The equation for the calcite-graphite system has a slope steeper than BOTTINGA'S (1969) results. It is, however, in good agreement with that of VALLEY and O'NEIL (1981) in the temperature range from 600 to 800C. Because of the relatively high sensitivity to temperature, these isotopic geothermometers are useful for determining the temperatures in moderate- to high-grade metamorphosed carbonate rocks.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    In this paper we show for the first time that calcite granules, produced by the earthworm Lumbricus terrestris, and commonly recorded at sites of archaeological interest, accurately reflect temperature and soil water ?18O values. Earthworms were cultivated in an orthogonal combination of two different (granule-free) soils moistened by three types of mineral water and kept at three temperatures (10, 16 and 20 C) for an acclimatisation period of three weeks followed by transfer to identical treatments and cultivation for a further four weeks. Earthworm-secreted calcite granules were collected from the second set of soils. ?18O values were determined on individual calcite granules (?18Oc) and the soil solution (?18Ow). The ?18Oc values reflect soil solution ?18Ow values and temperature, but are consistently enriched by 1.51 ( 0.12) in comparison to equilibrium in synthetic carbonates. The data fit the equation 1000 ln ? = [20.21 0.92] (103 T-1) - [38.58 3.18] (R2 = 0.95; n = 96; p < 0.0005). As the granules are abundant in modern soils, buried soils and archaeological contexts, and can be dated using U-Th disequilibria, the developed palaeotemperature relationship has enormous potential for application to Holocene and Pleistocene time intervals.

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

    PubMed

    Naidu, Sonia; Scherer, George W

    2014-12-01

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

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

    USGS Publications Warehouse

    Komor, S.C.

    1995-01-01

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

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

    PubMed Central

    Murai, Rie

    2013-01-01

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

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

    SciTech Connect

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

    2003-03-27

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

  6. 40 CFR 180.1232 - Lime-sulfur; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Lime-sulfur; exemption from the... Exemptions From Tolerances 180.1232 Lime-sulfur; exemption from the requirement of a tolerance. An exemption from the requirement of a tolerance is established for residues of lime-sulfur....

  7. 40 CFR 180.1232 - Lime-sulfur; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Lime-sulfur; exemption from the... Exemptions From Tolerances 180.1232 Lime-sulfur; exemption from the requirement of a tolerance. An exemption from the requirement of a tolerance is established for residues of lime-sulfur....

  8. 40 CFR 180.1232 - Lime-sulfur; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Lime-sulfur; exemption from the... Exemptions From Tolerances 180.1232 Lime-sulfur; exemption from the requirement of a tolerance. An exemption from the requirement of a tolerance is established for residues of lime-sulfur....

  9. 40 CFR 180.1232 - Lime-sulfur; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Lime-sulfur; exemption from the... Exemptions From Tolerances 180.1232 Lime-sulfur; exemption from the requirement of a tolerance. An exemption from the requirement of a tolerance is established for residues of lime-sulfur....

  10. 40 CFR 180.1232 - Lime-sulfur; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Lime-sulfur; exemption from the... Exemptions From Tolerances 180.1232 Lime-sulfur; exemption from the requirement of a tolerance. An exemption from the requirement of a tolerance is established for residues of lime-sulfur....

  11. Water, Hydration and Health

    PubMed Central

    Popkin, Barry M.; D’Anci, Kristen E.; Rosenberg, Irwin H.

    2010-01-01

    This review attempts to provide some sense of our current knowledge of water including overall patterns of intake and some factors linked with intake, the complex mechanisms behind water homeostasis, the effects of variation in water intake on health and energy intake, weight, and human performance and functioning. Water represents a critical nutrient whose absence will be lethal within days. Water’s importance for prevention of nutrition-related noncommunicable diseases has emerged more recently because of the shift toward large proportions of fluids coming from caloric beverages. Nevertheless, there are major gaps in knowledge related to measurement of total fluid intake, hydration status at the population level, and few longer-term systematic interventions and no published random-controlled longer-term trials. We suggest some ways to examine water requirements as a means to encouraging more dialogue on this important topic. PMID:20646222

  12. Interaction of copper with the surface of calcite

    SciTech Connect

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

    1981-12-01

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

  13. Strontium isotope fractionation of planktic foraminifera and inorganic calcite

    NASA Astrophysics Data System (ADS)

    Bhm, Florian; Eisenhauer, Anton; Tang, Jianwu; Dietzel, Martin; Krabbenhft, Andre; Kisakrek, Basak; Horn, Christian

    2012-09-01

    We have investigated the strontium isotope fractionation (?88/86Srcarb-aq) between inorganic calcite and aqueous Sr2+ ions by precipitation experiments at a constant temperature of 25 C and precipitation rates (R) ranging from 102.3 to 104.2 ?mol/m2/h. Strontium isotope ratios were measured using the 87Sr-84Sr double spike technique. It was found that strontium isotope fractionation in these calcites is strongly dependent on the precipitation rate: ?Sr carb-aq =-0.08?log(R[?mol/m/h])+0.08 The measured ?88/86Sr values are significantly correlated with previously measured ?44/40Ca and Sr/Ca values of the same calcite samples: ?Sr=+0.18??Ca-0.01 ?Sr=-1.5?KdSr-0.03 The slope of 88Sr/86Sr versus 44Ca/40Ca fractionation is 0.18 0.04 and compatible with a kinetic fractionation during dehydration of the strontium and calcium ions, but not with isotope fractionation in a diffusive boundary layer. Using published equilibrium ?44/40Cacarb-aq and KdSr values we estimate the equilibrium isotope fractionation of strontium to be very close to zero (?88/86Sreq(carb-aq) = -0.01 0.06). This estimate is confirmed by strontium isotope values of natural inorganic calcites that precipitated very slowly in basalts of the ocean crust. The results from the inorganic calcites are used to explain strontium isotope fractionation of planktic foraminifera. Specimens of two warm water species (Globigerinoides ruber and Globigerinoides sacculifer) were picked from the Holocene section of a Caribbean sediment core. We found no significant difference in ?88/86Sr between the two species. In addition, G. ruber specimens from Marine Isotope Stage 2 in the same core show ?88/86Sr values identical to the Holocene specimens. The strontium isotopes of both foraminifera species are strongly fractionated (?88/86Srcarb-aq = -0.248 0.005) when compared to published data of other major marine calcifiers. Applying the results from the inorganic precipitation experiments we find that the strong foraminiferal strontium isotope fractionation can be explained by calcification in a largely open system at high precipitation rates, comparable in magnitude to rates known from scleractinian reef corals. This interpretation is in good agreement with the kinetic calcification model for planktic foraminifera by Kisakrek et al. (2011), which was based on calcium isotopes and elemental Sr/Ca ratios.

  14. Hydrothermal replacement of calcite by Mg-carbonates

    NASA Astrophysics Data System (ADS)

    Jonas, Laura; Mueller, Thomas; Dohmen, Ralf

    2014-05-01

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

  15. Reactive uptake of acetic acid on calcite and nitric acid reacted calcite aerosol in an environmental reaction chamber.

    PubMed

    Prince, Amy Preszler; Kleiber, Paul D; Grassian, Vicki H; Young, Mark A

    2008-01-01

    The heterogeneous chemistry of gas-phase acetic acid with CaCO(3)(calcite) aerosol was studied under varying conditions of relative humidity (RH) in an environmental reaction chamber. Infrared spectroscopy showed the loss of gas-phase reactant and the appearance of a gaseous product species, CO(2). The acetic acid is observed to adsorb onto the calcite aerosol through both a fast and a slow uptake channel. While the fast channel is relatively independent of RH, the slow channel exhibits enhanced uptake and reaction as the RH is increased. In additional experiments, the calcite aerosol was exposed to both nitric and acetic acids in the presence of water vapor. The rapid conversion of the particulate carbonate to nitrate and subsequent deliquescence significantly enhances the uptake and reaction of acetic acid. These results suggest a possible mechanism for observed correlations between particulate nitrate and organic acids in the atmosphere. Calcium rich mineral dust may be an important sink for simple organic acids. PMID:18075693

  16. LIME SPRAY DRYER FLUE GAS DESULFURIZATION COMPUTER MODEL USERS MANUAL

    EPA Science Inventory

    The report describes a lime spray dryer/baghouse (FORTRAN) computer model that simulates SO2 removal and permits study of related impacts on design and economics as functions of design parameters and operating conditions for coal-fired electric generating units. The model allows ...

  17. K'qizaghetnu Ht'ana (Stories from Lime Village).

    ERIC Educational Resources Information Center

    Bobby, Pete; And Others

    A cross section of Athabascan life as related by eight inhabitants of Lime Village, Alaska, is given in this document. The short narratives are printed in English and in Dena'ina. Illustrations accompany the text. The stories tell of making eagle feather robes, birchbark or mooseskin boats, a raincoat from black bear intestines, and boots from…

  18. Coal conversion of a multiple burner lime kiln

    SciTech Connect

    Jones, G.; Thornton, L.W.

    1984-02-01

    During 1982 Ash Grove Cement Company contracted with Wagester, Walker, Thornton and Company to convert a Calcimatic rotating hearth kiln at its Portland, Oregon lime plant from gas/oil to coal firing. Increasing costs of natural gas and No. 6 fuel oil made this conversion mandatory if the plant was to remain competitive. Unique features of this project are the distributors of pulverized coal to eighteen small burners around the inner and outer perimeters of the doughnut-shaped kiln, and the attrition-dryer-pulverizer mill. Ash Grove, a century-old lime and cement producer headquartered in Overland Park, Kansas (Kansas City area), looked at various schemes for multiple burner firing before employing Wagester, Walker, Thornton and Company. W.W.T. of Pittsburgh, Pennsylvania was formed in 1980 by acquiring the Solid Fuels Division of the Pullman Swindell Corporation. This division had been active in developing solid fuel firing for brick tunnel kilns, principally in the Southeast. They continue to supply such systems firing wood waste as well as coal to the brick industry and have also converted two Calcimatic lime kilns for Dixie Lime, Sumterville, Florida, a fluid bed calciner for Texas Gulf in Aurora, North Carolina, and a chrome concentrate kiln for Diamond Chemicals at Castle Hayne, North Carolina. Testing and a proposal have been made for INMETCO, Elwood City, Pennsylvania, on an annular hearth furnace for direct reduction of iron ore to metallic iron.

  19. Method for lime stabilization of wastewater treatment plant sludges

    SciTech Connect

    Wurtz, W.O.

    1981-12-22

    A method for the lime stabilization of wastewater sludge, includes the steps of dewatering sludge so as to produce a sludge cake containing from about 10 to 60% by weight of dry solids and rapidly and intimately mixing and reacting the sludge cake with calcium oxide so as to produce stabilized sludge pellets. An apparatus for performing the process is also provided.

  20. 27 CFR 9.27 - Lime Kiln Valley.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2011-04-01 2011-04-01 false Lime Kiln Valley. 9.27 Section 9.27 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS AMERICAN VITICULTURAL AREAS Approved American Viticultural Areas 9.27...

  1. 27 CFR 9.27 - Lime Kiln Valley.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Lime Kiln Valley. 9.27 Section 9.27 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX AND TRADE BUREAU, DEPARTMENT OF THE TREASURY LIQUORS AMERICAN VITICULTURAL AREAS Approved American Viticultural Areas 9.27...

  2. Distribution of polycyclic aromatic hydrocarbons in lime spray dryer ash

    SciTech Connect

    Ping Sun; Panuwat Taerakul; Linda K. Weavers; Harold W. Walker

    2005-10-01

    Four lime spray dryer (LSD) ash samples were collected from a spreader stoker boiler and measured for their concentrations of 16 U.S. EPA specified polycyclic aromatic hydrocarbons (PAHs). Results showed that the total measured PAH concentration correlated with the organic carbon content of the LSD ash. Each LSD ash sample was then separated using a 140 mesh sieve into two fractions: a carbon-enriched fraction ({gt}140 mesh) and a lime-enriched fraction ({lt}140 mesh). Unburned carbon was further separated from the carbon-enriched fraction with a lithiumheteropolytungstate (LST) solution. PAH measurements on these different fractions showed that unburned carbon had the highest PAH concentrations followed by the carbon-enriched fraction, indicating that PAHs were primarily associated with the carbonaceous material in LSD ash. However, detectable levels of PAHs were also found in the lime-enriched fraction, suggesting that the fine spray of slaked lime may sorb PAH compounds from the flue gas in the LSD process. 37 refs., 5 figs., 4 tabs.

  3. Lime pretreatment and fermentation of enzymatically hydrolyzed sugarcane bagasse.

    PubMed

    Rabelo, Sarita C; Maciel Filho, Rubens; Costa, Aline C

    2013-03-01

    Sugarcane bagasse was subjected to lime (calcium hydroxide) pretreatment and enzymatic hydrolysis for second-generation ethanol production. A central composite factorial design was performed to determine the best combination of pretreatment time, temperature, and lime loading, as well as to evaluate the influence of enzymatic loadings on hydrolysis conversion. The influence of increasing solids loading in the pretreatment and enzymatic hydrolysis stages was also determined. The hydrolysate was fermented using Saccharomyces cerevisiae in batch and continuous mode. In the continuous fermentation, the hydrolysates were concentrated with molasses. Lime pretreatment significantly increased the enzymatic digestibility of sugarcane bagasse without the need for prior particle size reduction. In the optimal pretreatment conditions (90 h, 90 C, 0.47 glime/g bagasse) and industrially realistic conditions of hydrolysis (12.7 FPU/g of cellulase and 7.3 CBU/g of ?-glucosidase), 139.6 kglignin/ton raw bagasse and 126.0 kg hemicellulose in the pretreatment liquor per ton raw bagasse were obtained. The hydrolysate from lime pretreated sugarcane bagasse presented low amounts of inhibitors, leading to ethanol yield of 164.1 kgethanol/ton raw bagasse. PMID:23334836

  4. Variable Rate Lime Application in Louisiana Sugarcane Production Systems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Precision agriculture may offer sugarcane growers a management system that decreases costs and maximizes profits, while minimizing any potential negative environmental impact. The utility of variable-rate (VR) lime application in the initial production year (plant cane) of a 3-yr sugarcane crop cyc...

  5. Shock-wave properties of soda-lime glass

    SciTech Connect

    Grady, D.E.; Chhabildas, L.C.

    1996-11-01

    Planar impact experiments and wave profile measurements provided single and double shock equation of state data to 30 GPa. Both compression wave wave profile structure and release wave data were used to infer time-dependent strength and equation of state properties for soda-lime glass.

  6. CHARACTERIZATION OF CARBIDE LIME TO IDENTIFY SULFITE OXIDATION INHIBITORS

    EPA Science Inventory

    The report gives results of a study of carbide lime--a by-product of acetylene manufacture, primarily calcium hydroxide--used in a flue gas desulfurization (FGD) system at Louisville Gas and Electric (LGE). The study was undertaken to: identify sulfite ion oxidation inhibitors in...

  7. EFFECTS OF LIME (CAO) ON THE ENDOTOXIN LEVELS OF BIOSOLIDS

    EPA Science Inventory

    Lime addition is a common practice for treating biosolids in order to meet EPA 503 requirements for land application. Since this treatment kills the majority of microorganisms, will it increase the level of endotoxins present in biosolids? And, if endotoxin levels are increased, ...

  8. Variable-Rate Lime Application for Louisiana Sugarcane Production Systems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Precision agriculture may offer sugarcane growers a management system that decreases costs and maximizes profits, while minimizing any potential negative environmental impact. Variable rate (VR) application of lime and fertilizers is one area in which significant advantages may be realized. A seri...

  9. K'qizaghetnu Ht'ana (Stories from Lime Village).

    ERIC Educational Resources Information Center

    Bobby, Pete; And Others

    A cross section of Athabascan life as related by eight inhabitants of Lime Village, Alaska, is given in this document. The short narratives are printed in English and in Dena'ina. Illustrations accompany the text. The stories tell of making eagle feather robes, birchbark or mooseskin boats, a raincoat from black bear intestines, and boots from

  10. COMPUTERIZED SHAWNEE LIME/LIMESTONE SCRUBBING MODEL USERS MANUAL

    EPA Science Inventory

    The manual gives a general description of a computerized model for estimating design and cost of lime or limestone scrubber systems for flue gas desulfurization (FGD). It supplements PB80-123037 by extending the number of scrubber options which can be evaluated. It includes spray...

  11. HAZARDOUS WASTE COMBUSTION IN INDUSTRIAL PROCESSES: CEMENT AND LIME KILNS

    EPA Science Inventory

    The report summarizes the results of several studies relating to hazardous waste combustion in cement and lime kilns. The tests included in the study are four kilns tested by the U.S. Environmental Protection Agency, four kilns tested by State agencies or the kiln operator, two C...

  12. Hydrates represent gas source, drilling hazard

    SciTech Connect

    Bagirov, E.; Lerche, I.

    1997-12-01

    Gas hydrates look like ordinary ice. However, if a piece of such ice is put into warm water its behavior will be different from the ordinary melting of normal ice. In contrast, gas hydrates cause bubbles in the warm water, which indicates the high content of gas in the hydrate crystals. The presence of four components is required: gas itself, water, high pressure, and low temperature. The paper discusses how hydrates form, hydrates stability, South Caspian hydrates, and hydrates hazards for people, ships, pipelines, and drilling platforms.

  13. New waste based clinkers: Belite and lime formulations

    SciTech Connect

    Raupp-Pereira, Fabiano; Ball, Richard James Rocha, Joao; Labrincha, Joao A.; Allen, Geoffrey C.

    2008-04-15

    This work describes the formulation of new belite-based (CR2) and lime-based (CR3) cementitious materials derived from industrial wastes, such as sludges (generated in the Al-anodising and surface coating industrial processes, potable water filtration/cleaning operations and in marble sawing processes) and foundry sand. Powder mixtures were prepared and fired at different temperatures. For comparison, similar formulations were prepared with pre-treated and commercially available natural raw materials and processed in similar conditions. The thermal process was followed by differential scanning calorimetry (DSC) and high-temperature powder X-ray diffraction (HT-XRD) studies. The CR2 clinker was found to contain belite as the main cementitious phase, the main polymorph being identified by NMR. The CR3 clinker contained common cementitious phases, such as C{sub 3}A and C{sub 3}S, but free lime and calcium aluminium oxide sulphates were also identified by high temperature XRD and NMR. Then the corresponding cement was prepared and the evolution of the mechanical strength with time was evaluated. The lime-based cement obtained from wastes shows a stronger hardening character than the standard material, which tends to show dusting phenomena due to the presence of a reasonable amount of free lime (as the result of its expansive reaction with ambient moisture). Some fluxing impurities (e.g. alkalis) present in the waste materials improve the overall reactivity of the mixture and induces the combination of the lime in CR3. Raman, XPS and FIB techniques were used to fully characterise the aged cements.

  14. Obsidian hydration dates glacial loading?

    USGS Publications Warehouse

    Friedman, I.; Pierce, K.L.; Obradovich, J.D.; Long, W.D.

    1973-01-01

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming . The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow.

  15. Obsidian Hydration: A New Paleothermometer

    SciTech Connect

    Anovitz, Lawrence {Larry} M; Riciputi, Lee R; Cole, David R; Fayek, Mostafa; Elam, J. Michael

    2006-01-01

    The natural hydration of obsidian was first proposed as a dating technique for young geological and archaeological specimens by Friedman and Smith (1960), who noted that the thickness of the hydrated layer on obsidian artifacts increases with time. This approach is, however, sensitive to temperature and humidity under earth-surface conditions. This has made obsidian hydration dating more difficult, but potentially provides a unique tool for paleoclimatic reconstructions. In this paper we present the first successful application of this approach, based on combining laboratory-based experimental calibrations with archaeological samples from the Chalco site in the Basin of Mexico, dated using stratigraphically correlated 14C results and measuring hydration depths by secondary ion mass spectrometry. The resultant data suggest, first, that this approach is viable, even given the existing uncertainties, and that a cooling trend occurred in the Basin of Mexico over the past 1450 yr, a result corroborated by other paleoclimatic data.

  16. Obsidian hydration dates glacial loading?

    PubMed

    Friedman, I; Pierce, K L; Obradovich, J D; Long, W D

    1973-05-18

    Three different groups of hydration rinds have been measured on thin sections of obsidian from Obsidian Cliff, Yellowstone National Park, Wyoming. The average thickness of the thickest (oldest) group of hydration rinds is 16.3 micrometers and can be related to the original emplacement of the flow 176,000 years ago (potassium-argon age). In addition to these original surfaces, most thin sections show cracks and surfaces which have average hydration rind thicknesses of 14.5 and 7.9 micrometers. These later two hydration rinds compare closely in thickness with those on obsidian pebbles in the Bull Lake and Pinedale terminal moraines in the West Yellowstone Basin, which are 14 to 15 and 7 to 8 micrometers thick, respectively. The later cracks are thought to have been formed by glacial loading during the Bull Lake and Pinedale glaciations, when an estimated 800 meters of ice covered the Obsidian Cliff flow. PMID:17806883

  17. Hydration water and microstructure in calcium silicate and aluminate hydrates

    NASA Astrophysics Data System (ADS)

    Fratini, Emiliano; Ridi, Francesca; Chen, Sow-Hsin; Baglioni, Piero

    2006-09-01

    Understanding the state of the hydration water and the microstructure development in a cement paste is likely to be the key for the improvement of its ultimate strength and durability. In order to distinguish and characterize the reacted and unreacted water, the single-particle dynamics of water molecules in hydrated calcium silicates (C3S, C2S) and aluminates (C3A, C4AF) were studied by quasi-elastic neutron scattering, QENS. The time evolution of the immobile fraction represents the hydration kinetics and the mobile fraction follows a non-Debye relaxation. Less sophisticated, but more accessible and cheaper techniques, like differential scanning calorimetry, DSC, and near-infrared spectroscopy, NIR, were validated through QENS results and they allow one to easily and quantitatively follow the cement hydration kinetics and can be widely applied on a laboratory scale to understand the effect of additives (i.e., superplasticizers, cellulosic derivatives, etc) on the thermodynamics of the hydration process. DSC provides information on the free water index and on the activation energy involved in the hydration process while the NIR band at 7000 cm-1 monitors, at a molecular level, the increase of the surface-interacting water. We report as an example the effect of two classes of additives widely used in the cement industry: superplasticizers, SPs, and cellulose derivatives. SPs interact at the solid surface, leading to a consistent increment of the activation energy for the processes of nucleation and growth of the hydrated phases. In contrast, the cellulosic additives do not affect the nucleation and growth activation energy, but cause a significant increment in the water availability: in other words the hydration process is more efficient without any modification of the solid/liquid interaction, as also evidenced by the 1H-NMR. Additional information is obtained by scanning electron microscopy (SEM), ultra small angle neutron scattering (USANS) and wide angle x-ray scattering (WAXD) that characterize how additives affect both the hydrated microstructure development and the original grain size. In particular, SPs alter the morphology of the hydrated phases, which no longer grow with the classic fibrillar structure on the grain surface, but nucleate in solution as globular structures. All this information converges in a quantitative, and at molecular level, description of the mechanisms involved in the setting process of one of the materials most widely used by human beings.

  18. Hydrate formation and growth in pores

    NASA Astrophysics Data System (ADS)

    Jung, Jong-Won; Santamarina, J. Carlos

    2012-04-01

    Gas hydrates consist of guest gas molecules encaged in water cages. Methane hydrate forms in marine and permafrost sediments. In this study, we use optical, mechanical and electrical measurements to monitor hydrate formation and growth in small pores to better understand the hydrate pore habit in hydrate-bearing sediments. Hydrate formation in capillary tubes exposes the complex and dynamic interactions between nucleation, gas diffusion and gas solubility. The observation of hydrate growth in a droplet between transparent plates shows that the hydrate shell does not grow homogeneously but advances in the form of lobes that invade the water phase; in fact, the hydrate shell must be discontinuous and possibly cracked to justify the relatively fast growth rates observed in these experiments. Volume expansion during hydrate formation causes water to flow out of menisci; expelled water either spreads on the surface of water-wet substrates and forms a thin hydrate sheet, or remains next to menisci when substrates are oil-wet. Hydrate formation is accompanied by ion exclusion, yet, there is an overall increase in electrical resistance during hydrate formation. Hydrate growth may become salt-limited in trapped water conditions; in this case, aqueous brine and gas CH4 may be separated by hydrate and the three-phase system remains stable within the pore space of sediments.

  19. Crystallization of a polymorphic hydrate system.

    PubMed

    Tian, F; Qu, H; Louhi-Kultanen, M; Rantanen, J

    2010-02-01

    Nitrofurantoin can form two monohydrates, which have the same chemical composition and molar ratio of water, but differ in the crystal arrangements. The two monohydrates (hydrates I and II) could be produced independently via evaporative crystallization, where supersaturation and solvent composition were both found to have an effect. Hydrate I showed much slower crystallization than hydrate II. During cooling crystallization, the nucleation and growth of hydrate II was again dominant, consuming all supersaturation and leading to no hydrate I formation. Seeding of hydrate I during cooling crystallization was also applied, but the hydrate I seeds were not able to initiate its nucleation rather than dissolving into crystallizing solution. Although solubility tests revealed that hydrate II is more stable than hydrate I due to its lower solubility (110 +/- 4 and 131 +/- 12 microg/mL for hydrates II and I, respectively), this difference is rather small. Therefore, the small free energy difference between the two hydrates, together with the slow crystallization of hydrate I, both lead to a hindrance of hydrate I formation. Furthermore, the crystal structure of hydrate II demonstrated a higher H-bonding extent than hydrate I, suggesting its more favorable crystallization. This is in good agreement with experimental results. PMID:19569226

  20. Characterization of an expansive clay treated with lime: Effect of compaction on the swelling pressure

    NASA Astrophysics Data System (ADS)

    Kechouane, Z.; Nechnech, A.

    2015-03-01

    This work focuses on the study of the compaction effect on the stabilization of a highly expansive clay soil by adding lime. To this end, we used two types of swelling clay soils, the first one is intact and the other derivative (reconstituted, prepared from a natural soil and bentonite mixture with the following proportions: 70 and 30%. The results of the recorded dometric tests show that the incorporation of the lime reduces the soil swelling pressures at each dosing lime in agreement with many reported previous studies. The contents of lime greatly affect swelling; indeed for a dosage of 6% lime the swelling pressures are reduced by 27% for the sample of disturbed soil. The compaction test performed on the reconstituted incorporated lime soil shows that for a dosage of 2% lime, we have a reduction of the swelling pressure of 96%.

  1. Hydrate control in deepwater drilling

    SciTech Connect

    1997-09-01

    Gas-hydrate formation during deepwater offshore drilling and production is a well-recognized operational hazard. In water depths greater than 1,000 ft, seabed conditions of pressure and temperature become conducive to gas-hydrate formation. In a well-control situation, although the kick fluid leaves the formation at a high temperature, it can cool to seabed temperature with an extended shut-in period. With high enough hydrostatic pressure at the mudline, hydrates could form in the blowout-preventer (BOP) stack and choke and kill lines, as has been observed in field operations. The current practice in deepwater drilling is to suppress the hydrate-formation temperature by use of highly saline drilling fluids formulated from NaCl or other salts. This solution is applicable for the Gulf of Mexico but insufficient for the conditions encountered in Norwegian deep waters. At extreme water depths or extremely low mudline temperatures, this thermodynamic inhibition alone may not be sufficient to prevent hydrate formation. Instead, the use of kinetic inhibitors or crystal modifiers, in conjunction with thermodynamic inhibitors, may allow successful operations in such an environment. The definition of kinetic inhibitors (to distinguish them from the classic thermodynamic inhibitors, such as polar compounds and electrolytes) comes from the effect of the chemicals on the nucleation and growth of natural gas hydrates, both of which are time-dependent, stochastic processes. The paper describes deepwater drilling fluids, polar and surface-active additives, kinetic inhibition and crystal modifiers, laboratory measurements, and test results.

  2. The sensitized luminescence of manganese-activated calcite

    USGS Publications Warehouse

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

    1947-01-01

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

  3. Freshwater-phreatic calcite cementation, Schooner Cays, Bahamas

    SciTech Connect

    Budd, D.A.

    1985-02-01

    Freshwater-phreatic calcite cementation is an active process on 700 and 2700 yr-old ooid-sand islands in the Schooner Cays, Bahamas. Cement fabrics and textures indicate a general, four-stage model of pore infilling. (1) The precipitation of isolated, decimicron-sized, rhombohedrons of calcite on grain surfaces forms an incipient circumgranular cement. (2) Continued precipitation enlarges crystal sizes and forms new rhombohedral crystals, resulting in a continuous circumgranular rim of cement. (3) Additional cementation quickly masks the circumgranular fabric, producing a partial pore-filling mosaic. (4) The remaining pore space is occluded with a mosaic of calcite cement. Petrographic evidence for the earlier circumgranular rim of cement is not necessarily apparent after the last stage of cementation. Empty pores and all four stages of phreatic-zone cementation were observed in the diagenetically immature 700 yr-old rocks, but only stages 2 through 4 were observed in the diagenetically more mature 2700 yr-old phreatic zone samples. Cements are distributed homogeneously within each pore at every stage, yet because each pore may proceed through the four stages at different rates, each pore can be at a different stage of infilling. This results in an inhomogeneous distribution of cement between pores during the initial stages of cementation. Recognition of a cement stratigraphy similar to that described here should aid in the identification of freshwater-phreatic diagenesis in ancient carbonate rock sequences. Variability in the amount of freshwater-phreatic cement between pores should be expected and not interpreted as the product of different paragenetic sequences.

  4. Dynamic recrystallization processes of calcitic fossils in deformed marble

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Here we report dynamic recrystallization processes of calcitic fossils in weakly to fully recrystallized marbles to discuss the survivability of fossils and possible recognition of former fossils in fully recrystallized marbles. The marble is from the early Paleozoic sequence in the Jeongseon area of South Korea. Each crinoid stem in a weakly or non-recrystallized marble cut perpendicular to its length appears as a donut shape and consists of five calcite grains (300-500m in size) with the same c-axis but different a-axis orientations. The misorientation angle between adjacent grains in a crinoid stem is 40-50. The outer and inner diameters of the donut-shaped crinoid stems are about 900 and 500 m, respectively. The recrystallization processes initiate on grain boundaries as bulging recrystallization while transgranular subgrain walls form within lattice-distorted grains. New grains also nucleate on twin boundaries and subgrain boundaries. Some subgrain walls become grain boundaries as they collect more dislocations with subgrain boundary migration. The newly recrystallized grains grow to reach a steady-state grain size of 20-50m. In fully recrystallized and deformed marbles, the crinoid stems occur as elongated donut-shaped calcite aggregates. The crinoid stems can be recognized by their size larger than that of recrystallized matrix grains (5-20m), With a higher degree of dynamic recrystallization, the randomness of the misorientation angle distribution of the recrystallized grains within a crinoid stem increases, indicating weaker lattice preferred orientation. We are trying to test whether lattice orientation maps (or AVA diagrams) can be used to recognize former fossil traces in fully recrystallized marbles.

  5. Strain rate dependent calcite microfabric evolution at natural conditions

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

    Crystal plastic deformational behaviour of calcite has been the focus of many experimental studies. Different strain rates, pressure and temperature conditions have been addressed to investigate a wide range of deformation regimes. However, a direct comparison with natural fault rocks remains difficult because of extreme differences between experimental and natural strain rates. A flanking structure developed in almost pure calcite marble on Syros (Cyclades, Greece). Due to rotation of a planar feature (crack) a heterogeneous strain field in the surrounding area occurred resulting in different strain domains and the formation of the flanking structure. Assuming that deformation was active continuously during the development of the flanking structure, the different strain domains correspond to different strain-rate domains. The outcrop thus represents the final state of a natural experiment and gives us a great opportunity to get natural constraints on strain rate dependent deformation behaviour of calcite. Comparing the microfabrics in the 1 to 2.5 cm thick shear zone and the surrounding host rocks, which formed under the same metamorphic conditions but with different strain rates, is the central focus of this study. Due to the extreme variation in strain and strain rate, different microstructures and textures can be observed corresponding to different deformation mechanisms. With increasing strain rate we observe a change in dominant deformation mechanism from dislocation glide to dislocation creep and finally diffusion creep. Additionally, a change from subgrain rotation to bulging recrystallization can be observed in the dislocation creep regime. Crystallographic preferred orientations (CPO) and the grade of intracrystalline deformation were measured on a FEI Quanta 3D FEG instrument equipped with an EDAX Digiview IV EBSD camera. At all strain rates clear CPOs developed leading to the assumption that calcite preferentially deforms within the dislocation creep field. However, we can also find clear evidence for grain size sensitive deformation mechanisms at smaller grain sizes (3.6 ?m) consistent with experimental observations and determined flaw laws. The results of this study are compared with experimental data, closing the gap between experimental and natural geological strain rates.

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

    PubMed

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

    2002-01-23

    The spatial and temporal variations in calcite (calcium carbonate) solubility within the Dee basin of NE Scotland were assessed using water chemistry data gathered from a network of 59 sites monitored for water quality from June 1996 to May 1997. Calcite solubility, expressed in terms of a saturation index (SIcalcite), was determined from measured streamwater pH, Gran alkalinity and calcium concentrations and water temperature. In general, the waters of the Dee system are undersaturated with respect to calcite, though the saturation index is higher during the summer months indicating a dependency on flow conditions and biological activity. Under low-flow conditions, the streamwaters are dominated by water derived from the lower soil horizons and deeper groundwater stores and therefore, ions such as Gran alkalinity and calcium are at their highest concentrations as they are derived mainly from bedrock weathering. The influence of biological activity on the carbonate system is also evident as the observed pH and estimated EpCO2 values indicate strong seasonal patterns, with the highest pH and lowest EpCO2 values occurring during the summer low-flow periods. Only at three sites in the lowland region of the catchment, during the summer low-flow period, are the waters oversaturated. As such, the Dee system represents an extreme 'end-member' case when compared to many UK rivers that span both under- and oversaturated conditions during the year. Regression analysis highlights a systematic change in the SIcalcite-pH relationship in a broad east-west direction across the Dee system. At sites draining the relatively impermeable upland areas, the regression of SIcalcite against pH gives a straight line with a gradient in the range 1.6-2.4. Correspondingly, under the most extreme alkaline conditions found at sites draining lowland agricultural areas, a straight-line relationship exists but with a gradient of unity. It is concluded that these changes in the SIcalcite-pH relationship are due to variations in the bicarbonate system induced by the flow conditions and biological activity. Given the waters are undersaturated, then calcite precipitation and hence phosphorus co-precipitation cannot occur within the water column. PMID:11846077

  7. Energy resource potential of natural gas hydrates

    USGS Publications Warehouse

    Collett, T.S.

    2002-01-01

    The discovery of large gas hydrate accumulations in terrestrial permafrost regions of the Arctic and beneath the sea along the outer continental margins of the world's oceans has heightened interest in gas hydrates as a possible energy resource. However, significant to potentially insurmountable technical issues must be resolved before gas hydrates can be considered a viable option for affordable supplies of natural gas. The combined information from Arctic gas hydrate studies shows that, in permafrost regions, gas hydrates may exist at subsurface depths ranging from about 130 to 2000 m. The presence of gas hydrates in offshore continental margins has been inferred mainly from anomalous seismic reflectors, known as bottom-simulating reflectors, that have been mapped at depths below the sea floor ranging from about 100 to 1100 m. Current estimates of the amount of gas in the world's marine and permafrost gas hydrate accumulations are in rough accord at about 20,000 trillion m3. Disagreements over fundamental issues such as the volume of gas stored within delineated gas hydrate accumulations and the concentration of gas hydrates within hydrate-bearing strata have demonstrated that we know little about gas hydrates. Recently, however, several countries, including Japan, India, and the United States, have launched ambitious national projects to further examine the resource potential of gas hydrates. These projects may help answer key questions dealing with the properties of gas hydrate reservoirs, the design of production systems, and, most important, the costs and economics of gas hydrate production.

  8. Environmental controls on the Emiliania huxleyi calcite mass

    NASA Astrophysics Data System (ADS)

    Horigome, M. T.; Ziveri, P.; Grelaud, M.; Baumann, K.-H.; Marino, G.; Mortyn, P. G.

    2013-06-01

    Although ocean acidification is expected to impact (bio)calcification by decreasing the seawater carbonate ion concentration, [CO32-], there exists evidence of non-uniform response of marine calcifying plankton to low seawater [CO32-]. This raises questions on the role of environmental factors other than acidification and on the complex physiological responses behind calcification. Here we investigate the synergistic effect of multiple environmental parameters, including temperature, nutrient (nitrate and phosphate) availability, and seawater carbonate chemistry on the coccolith calcite mass of the cosmopolitan coccolithophore Emiliania huxleyi, the most abundant species in the world ocean. We use a suite of surface (late Holocene) sediment samples from the South Atlantic and southwestern Indian Ocean taken from depths lying well above the modern lysocline. The coccolith calcite mass in our results presents a latitudinal distribution pattern that mimics the main oceanographic features, thereby pointing to the potential importance of phosphorus and temperature in determining coccolith mass by affecting primary calcification and possibly driving the E. huxleyi morphotype distribution. This evidence does not necessarily argue against the potentially important role of the rapidly changing seawater carbonate chemistry in the future, when unabated fossil fuel burning will likely perturb ocean chemistry beyond a critical point. Rather our study highlights the importance of evaluating the combined effect of several environmental stressors on calcifying organisms to project their physiological response(s) in a high CO2 world and improve interpretation of paleorecords.

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

    NASA Astrophysics Data System (ADS)

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

    2001-08-01

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

  10. The coordination and distribution of B in foraminiferal calcite

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  11. Environmental controls on the Emiliania huxleyi calcite mass

    NASA Astrophysics Data System (ADS)

    Horigome, M. T.; Ziveri, P.; Grelaud, M.; Baumann, K.-H.; Marino, G.; Mortyn, P. G.

    2014-04-01

    Although ocean acidification is expected to impact (bio) calcification by decreasing the seawater carbonate ion concentration, [CO32-], there is evidence of nonuniform response of marine calcifying plankton to low seawater [CO32-]. This raises questions about the role of environmental factors other than acidification and about the complex physiological responses behind calcification. Here we investigate the synergistic effect of multiple environmental parameters, including seawater temperature, nutrient (nitrate and phosphate) availability, and carbonate chemistry on the coccolith calcite mass of the cosmopolitan coccolithophore Emiliania huxleyi, the most abundant species in the world ocean. We use a suite of surface (late Holocene) sediment samples from the South Atlantic and southwestern Indian Ocean taken from depths lying above the modern lysocline (with the exception of eight samples that are located at or below the lysocline). The coccolith calcite mass in our results presents a latitudinal distribution pattern that mimics the main oceanographic features, thereby pointing to the potential importance of seawater nutrient availability (phosphate and nitrate) and carbonate chemistry (pH and pCO2) in determining coccolith mass by affecting primary calcification and/or the geographic distribution of E. huxleyi morphotypes. Our study highlights the importance of evaluating the combined effect of several environmental stressors on calcifying organisms to project their physiological response(s) in a high-CO2 world and improve interpretation of paleorecords.

  12. Crystallographic orientation inhomogeneity and crystal splitting in biogenic calcite

    PubMed Central

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

    2013-01-01

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

  13. Acceleration of calcite kinetics by abalone nacre proteins

    SciTech Connect

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

    2005-06-09

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

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

    SciTech Connect

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

    2013-01-01

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

  16. LOW VELOCITY SHPERE IMPACT OF SODA LIME SILICATE GLASS

    SciTech Connect

    Morrissey, Timothy G; Fox, Ethan E; Wereszczak, Andrew A; Vuono, Daniel J

    2012-01-01

    This report summarizes TARDEC-sponsored work at Oak Ridge National Laboratory (ORNL) during the FY11 involving low velocity ( 30 m/s or 65 mph) ball impact testing of Starphire soda lime silicate glass. The intent was to better understand low velocity impact response in the Starphire for sphere densities that bracketed that of rock. Five sphere materials were used: borosilicate glass, soda-lime silicate glass, steel, silicon nitride, and alumina. A gas gun was fabricated to produce controlled velocity delivery of the spheres against Starphire tile targets. Minimum impact velocities to initiate fracture in the Starphire were measured and interpreted in context to the kinetic energy of impact and the elastic property mismatch between the any of the five sphere-Starphire-target combinations.

  17. Hazardous waste incineration in industrial processes: cement and lime kilns

    SciTech Connect

    Mournighan, R.E.; Peters, J.A.; Branscome, M.R.; Freeman, H.

    1985-07-01

    With more liquid wastes due to be banned from land disposal facilities, expanding hazardous waste incineration capacity becomes increasingly important. At the same time, industrial plants are increasingly seeking to find new sources of lower cost fuel, specifically from the disposal of hazardous wastes with heating value. The Hazardous Waste Engineering Research Laboratory (HWERL) is currently evaluating the disposal of hazardous wastes in a wide range of industrial processes. The effort includes sampling stack emissions at cement, lime and aggregate plants, asphalt plants and blast furnaces, which use waste as a supplemental fuel. This research program is an essential part of EPA's determination of the overall environmental impact of various disposal options available to industry. This paper summarizes the results of the HWERL program of monitoring emissions from cement and lime kilns burning hazardous wastes as fuel.

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

    NASA Astrophysics Data System (ADS)

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

    2013-04-01

    Low-Mg calcite (LMC; < 5 mol% Mg), commonly observed during time intervals of "calcite seas," since the beginning of the Paleozoic Era, is a good indicator of low Mg/Ca ratio (< 2) in seawater. Calcite seas were coincident with times of active seawater-basalt interactions along mid-ocean ridges at high temperatures, which extract Mg from seawater and release Ca to it. In the modern aragonite sea, most carbonate minerals precipitate at the seafloor, including deposits from cold seep environments are primarily either aragonite or high-Mg calcite (HMC). Here, we report the finding of non-skeletal LMC from cold seeps in Alaminos Canyon block 601 (AC 601), 2200 m below the sea surface on northern Gulf of Mexico (GOM) continental slope. Low-Mg calcite usually represents the only carbonate mineral in the studied samples. Dominant allochems in these seep carbonates are peloids, grain aggregates, pelagic forams, and fragments of mollusks and echinoids. The limestone is heavily cemented. The observed cements include micrite, microspar, mosaic, bladed, fan, and needle cements. The dissolution of grains and cements was observed. Not only originally aragonitic mollusks shells, but also carbonate cement have been dissolved. The aerobic oxidation of reduced chemical species such as methane and H2S is responsible for an increase in pCO2 and a decrease of pH, leading to local carbonate dissolution. The occurrence of oxic conditions is confirmed by the presence of negative Ce anomalies of the carbonates. Further, we report on analyses showing that the ambient porewater Mg/Ca ratio actually governs the carbonate mineralogy. The occurrence of LMC may be attributed to the brine fluids, which is relatively Mg-depleted (Mg/Ca mole ratio is below 0.7) compared to pore fluid of the subsurface sediments from the reference site (Mg/Ca mole ratio is above 4.1) that usually produce HMC. The 87Sr/86Sr values of LMC (mean = 0.708001, sd = 0.000034, n=2) are significantly lower than that of the seawater (0.709175). Strong deviation of the Sr isotope ratios of LMC from seawater is interpreted as the modification of the strontium from less radiogenic sources like older marine sediments and/or the locally abundant Jurassic salt. Therefore, we speculate that the seep fluids at the studied site most likely have a deep origin and may also have been influenced by dissolved halite during their ascent through conduits along the margins of salt bodies. The understanding of the processes that control the LMC precipitation in the GOM will also contribute to an improved understanding of the presence or absence of LMC in other oceans margin settings today, and in geological deposits as well.

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

    USGS Publications Warehouse

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

    1981-01-01

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

  20. Flavor chemistry of lemon-lime carbonated beverages.

    PubMed

    Hausch, Bethany J; Lorjaroenphon, Yaowapa; Cadwallader, Keith R

    2015-01-14

    The most potent aroma-active components of Sprite (SP), Sierra Mist (SM), and 7UP (7UP) were identified. Aroma extracts were prepared by liquidliquid continuous extraction/solvent-assisted flavor evaporation (LLCE/SAFE). Twenty-eight compounds were detected by gas chromatographyolfactometry (GC-O) with linalool (floral, lavender), octanal (pungent orange), and 2,3-dehydro-1,8-cineole (minty) determined to be predominant aroma compounds based on their high flavor dilution (FD) factors by aroma extract dilution analysis (AEDA). The data indicate that lemon-lime flavor is composed of a small number of compounds (22 at the most in SM), and only a subset of these may be important because many compounds were detected only at low FD factors. Predominant aroma compounds (23) were quantified using static headspace solid phase microextraction (SPME) combined with stable isotope dilution assays (SIDA). In contrast to FD factors, the calculated odor-activity values (OAVs) indicate that octanal and limonene make the greatest contribution to the overall aroma of lemon-lime carbonated beverages, followed by nonanal, decanal, linalool, 1,8-cineole, and geranyl acetate. The results demonstrate that lemon-lime carbonated beverages share many of the same compounds but the relative abundance of these compounds varies by brand. PMID:25494537

  1. Energy reduction in beet sugar processing by cossette liming

    SciTech Connect

    Randall, J.M.; Camirand, W.M.; Neumann, H.J.

    1981-01-01

    Under appropriate conditions of temperature and fresh Ca(OH)/sub 2/ application, demethylation occurs in the pectin in the cell walls of sugar beet cossettes, allowing Ca/sup 2 +/ to precipitate the pectin as calcium pectate. The calcium pectate will not degrade and pass into solution during subsequent hot extraction of sugar from the cossettes. This retention of pectin in the pulp was shown by 10 to 20% increases in solids weight in the pulp for a number of processing conditions. The toughened pulp produced by retention of calcium pectate allowed easier mechanical dewatering of the pulp which could save considerably on the heat normally required to dry the pulp for cattle feed. Beyond data reported in this paper, there are qualitative indications that the sugar juice extracted from limed cossettes is purer than standard juice, for pectin and colloidal materials remain in the pulp. Thus, much less purification of the juice with lime would be necessary than is required in standard beet-sugar processing, and the current 2% CaO used for purification may be cut almost in half. This represents another energy saving, for production of CaO at the factory is a major consumer of energy. These, along with other possible energy savings resulting from cossette liming (such as less water used for extraction, cold extraction, ion exchange of the purer juice), could produce an overall saving up to 20% of the energy currently used in beet-sugar processing. Some of these possibilities will be further investigated.

  2. Well log evaluation of natural gas hydrates

    SciTech Connect

    Collett, T.S.

    1992-10-01

    Gas hydrates are crystalline substances composed of water and gas, in which a solid-water-lattice accommodates gas molecules in a cage-like structure. Gas hydrates are globally widespread in permafrost regions and beneath the sea in sediment of outer continental margins. While methane, propane, and other gases can be included in the clathrate structure, methane hydrates appear to be the most common in nature. The amount of methane sequestered in gas hydrates is probably enormous, but estimates are speculative and range over three orders of magnitude from about 100,000 to 270,000,000 trillion cubic feet. The amount of gas in the hydrate reservoirs of the world greedy exceeds the volume of known conventional gas reserves. Gas hydrates also represent a significant drilling and production hazard. A fundamental question linking gas hydrate resource and hazard issues is: What is the volume of gas hydrates and included gas within a given gas hydrate occurrence? Most published gas hydrate resource estimates have, of necessity, been made by broad extrapolation of only general knowledge of local geologic conditions. Gas volumes that may be attributed to gas hydrates are dependent on a number of reservoir parameters, including the areal extent ofthe gas-hydrate occurrence, reservoir thickness, hydrate number, reservoir porosity, and the degree of gas-hydrate saturation. Two of the most difficult reservoir parameters to determine are porosity and degreeof gas hydrate saturation. Well logs often serve as a source of porosity and hydrocarbon saturation data; however, well-log calculations within gas-hydrate-bearing intervals are subject to error. The primary reason for this difficulty is the lack of quantitative laboratory and field studies. The primary purpose of this paper is to review the response of well logs to the presence of gas hydrates.

  3. Well log evaluation of natural gas hydrates

    SciTech Connect

    Collett, T.S.

    1992-10-01

    Gas hydrates are crystalline substances composed of water and gas, in which a solid-water-lattice accommodates gas molecules in a cage-like structure. Gas hydrates are globally widespread in permafrost regions and beneath the sea in sediment of outer continental margins. While methane, propane, and other gases can be included in the clathrate structure, methane hydrates appear to be the most common in nature. The amount of methane sequestered in gas hydrates is probably enormous, but estimates are speculative and range over three orders of magnitude from about 100,000 to 270,000,000 trillion cubic feet. The amount of gas in the hydrate reservoirs of the world greedy exceeds the volume of known conventional gas reserves. Gas hydrates also represent a significant drilling and production hazard. A fundamental question linking gas hydrate resource and hazard issues is: What is the volume of gas hydrates and included gas within a given gas hydrate occurrence Most published gas hydrate resource estimates have, of necessity, been made by broad extrapolation of only general knowledge of local geologic conditions. Gas volumes that may be attributed to gas hydrates are dependent on a number of reservoir parameters, including the areal extent ofthe gas-hydrate occurrence, reservoir thickness, hydrate number, reservoir porosity, and the degree of gas-hydrate saturation. Two of the most difficult reservoir parameters to determine are porosity and degreeof gas hydrate saturation. Well logs often serve as a source of porosity and hydrocarbon saturation data; however, well-log calculations within gas-hydrate-bearing intervals are subject to error. The primary reason for this difficulty is the lack of quantitative laboratory and field studies. The primary purpose of this paper is to review the response of well logs to the presence of gas hydrates.

  4. Dissociation heat transfer characteristics of methane hydrates

    SciTech Connect

    Kamath, V.A.; Holder, G.D.

    1987-02-01

    Knowledge of the interfacial heat transfer phenomenon during the dissociation of gas hydrates is essential in modeling the hydrate dissociation process. Such knowledge has applications in natural gas processing, storage, or transportation; in the drilling and recovery of oil and gas in the presence of gas hydrates; in the desalination of sea water; and in the production of natural gas from hydrate reservoirs. The process of hydrate dissociation is a unique phenomenon in which gas and water are simultaneously produced at the dissociated hydrate surface and play an important role in the mechanism of heat transfer to hydrates. An earlier study of propane hydrate dissociation showed that hydrate dissociation is a heat-transfer-limited process and somewhat similar to the nucleate boiling of liquids. In the present study, heat transfer limitations for methane hydrate dissociation were studied for two reasons. First, a comparison of the results of this study with propane hydrate was desired. Second, the effect of hydrate structure and gas molecule type on the rate of heat transfer during hydrate dissociation was sought.

  5. Effects of hydration on mitral valve prolapse.

    PubMed

    Lax, D; Eicher, M; Goldberg, S J

    1993-08-01

    We investigated the effect of hydration on mitral valve prolapse (MVP). Ten subjects with documented diagnosis of MVP were studied before and after oral hydration with 1 L of fluid. Increased weight and cardiac output were present after hydration. Results showed that all 10 subjects with diagnosis of MVP before hydration continued to have MVP after hydration; however, subtle changes were detected, especially on auscultation. Seven of 9 subjects (with cardiac examination recorded before and after hydration) had auscultatory findings of MVP before hydration. No detectable auscultatory change after hydration was present in one subject; in six subjects a loss of either a click or a murmur was detected after hydration. All subjects had echocardiographically detected MVP before hydration; evidence of MVP on two-dimensional or M-mode examination persisted after hydration in all 10 subjects. Minor changes in the echocardiographic examination (M-mode n = 2, Doppler n = 1) were detected in three subjects. Thus we found that hydration of subjects with MVP did not alter the overall diagnosis; however, changes occurred, especially on auscultation. This suggests that alterations in hydration may affect auscultatory expression of MVP and could explain, in part, the variable auscultatory findings in patients with MVP. PMID:8338013

  6. Complex gas hydrate from the Cascadia margin.

    PubMed

    Lu, Hailong; Seo, Yu-taek; Lee, Jong-won; Moudrakovski, Igor; Ripmeester, John A; Chapman, N Ross; Coffin, Richard B; Gardner, Graeme; Pohlman, John

    2007-01-18

    Natural gas hydrates are a potential source of energy and may play a role in climate change and geological hazards. Most natural gas hydrate appears to be in the form of 'structure I', with methane as the trapped guest molecule, although 'structure II' hydrate has also been identified, with guest molecules such as isobutane and propane, as well as lighter hydrocarbons. A third hydrate structure, 'structure H', which is capable of trapping larger guest molecules, has been produced in the laboratory, but it has not been confirmed that it occurs in the natural environment. Here we characterize the structure, gas content and composition, and distribution of guest molecules in a complex natural hydrate sample recovered from Barkley canyon, on the northern Cascadia margin. We show that the sample contains structure H hydrate, and thus provides direct evidence for the natural occurrence of this hydrate structure. The structure H hydrate is intimately associated with structure II hydrate, and the two structures contain more than 13 different hydrocarbon guest molecules. We also demonstrate that the stability field of the complex gas hydrate lies between those of structure II and structure H hydrates, indicating that this form of hydrate is more stable than structure I and may thus potentially be found in a wider pressure-temperature regime than can methane hydrate deposits. PMID:17230188

  7. Retrofit costs for lime/limestone FGD and lime spray drying at coal-fired utility boilers

    SciTech Connect

    Emmel, T.E.; Jones, J.W.

    1990-01-01

    The paper gives results of a research program the objective of which was to significantly improve engineering cost estimates currently being used to evaluate the economic effects of applying SO2 controls to existing coal-fired utility boilers. The costs of retrofitting conventional lime/limestone wet flue gas desulfurization (L/LS FGD) and lime spray drying (LSD) FGD at 100-200 coal-fired power plants are being estimated under this program. The retrofit capital cost estimating procedures used for L/LS FGD and LSD FGD make two cost adjustments to current procedures used to estimate FGD costs: cost adders (for items not normally included in FGD system costs; e.g., demolition and relocation of existing facilities) and cost multipliers (to adjust capital costs for site access, congestion, and underground obstructions).

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

    NASA Astrophysics Data System (ADS)

    Renard, Francois; Putnis, Christine; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hvelmann, Jrn; Sarret, Graldine

    2015-04-01

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

  9. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    SciTech Connect

    Gorman, Brian P

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer growth mechanism was confirmed by grazing incidence X-ray diffraction, µ-Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, and electron diffraction. Extended time studies out to 45 days confirmed the epitaxial relationship of the overgrowth layer with the substrate. Under NSW conditions, overgrowths were found to have ~0.4 to 0.8 nm / hr growth rates and accommodating 4 at% Mg, resulting in a highly strained overgrowth layer. Following the initial layer by layer growth mechanism, the growth changes to Stranski-Krastanov type after a critical thickness of approximately 100 nm.

  10. Predicting Calcite (CaCO3) Requirements of Sphagnum Peat Moss from pH Titration Curves

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Liming materials are required to neutralize acidity in peat moss to make it a suitable substrate for growing container crops. A series of time-consuming incubations of peat:lime mixtures are typically used to determine the liming rate to achieve a desired pH. Our objective was to evaluate the util...

  11. Natural Gas Hydrates Update 1998-2000

    EIA Publications

    2001-01-01

    Significant events have transpired on the natural gas hydrate research and development front since "Future Supply Potential of Natural Gas Hydrates" appeared in Natural Gas 1998 Issues and Trends and in the Potential Gas Committee's 1998 biennial report.

  12. [Hypodermoclysis hydration in the elderly].

    PubMed

    Brugnolli, Anna; Bevilacqua, Anita; Clodig, Majda; Danielis, Matteo

    2012-01-01

    Hydration with hypodermoclysis in elderly patients. Hypodermoclysis is a technique which consists in the administration of fluids into the subcutaneous tissue for the treatment of mild to moderate dehydration. The article starts from the case of a 74 year old man that, after a stroke, was unable to eat or drink, and was then hydrated with continuous hypodermoclysis for 45 days, obtaining a recovery of the clinical and psychological conditions. An update of the available knowledge on hypodermoclisis, together with some comments on the clinical case are presented. PMID:23164967

  13. Gas Hydrate and Pore Pressure

    NASA Astrophysics Data System (ADS)

    Tinivella, Umberta; Giustiniani, Michela

    2014-05-01

    Many efforts have been devoted to quantify excess pore pressures related to gas hydrate dissociation in marine sediments below the BSR using several approaches. Dissociation of gas hydrates in proximity of the BSR, in response to a change in the physical environment (i.e., temperature and/or pressure regime), can liberate excess gas incrising the local pore fluid pressure in the sediment, so decreasing the effective normal stress. So, gas hydrate dissociation may lead to excess pore pressure resulting in sediment deformation or failure, such as submarine landslides, sediment slumping, pockmarks and mud volcanoes, soft-sediment deformation and giant hummocks. Moreover, excess pore pressure may be the result of gas hydrate dissociation due to continuous sedimentation, tectonic uplift, sea level fall, heating or inhibitor injection. In order to detect the presence of the overpressure below the BSR, we propose two approachs. The fist approach models the BSR depth versus pore pressure; in fact, if the free gas below the BSR is in overpressure condition, the base of the gas hydrate stability is deeper with respect to the hydrostatic case. This effect causes a discrepancy between seismic and theoretical BSR depths. The second approach models the velocities versus gas hydrate and free gas concentrations and pore pressure, considering the approximation of the Biot theory in case of low frequency, i.e. seismic frequency. Knowing the P and S seismic velocity from seismic data analysis, it is possibile to jointly estimate the gas hydrate and free gas concentrations and the pore pressure regime. Alternatively, if the S-wave velocity is not availbale (due to lack of OBS/OBC data), an AVO analysis can be performed in order to extract information about Poisson ratio. Our modeling suggests that the areas characterized by shallow waters (i.e., areas in which human infrastructures, such as pipelines, are present) are significantly affected by the presence of overpressure condition. Moreover, the knoweledge of seismic velocities can be considered an powerful tool to detect the overpressure in case that the pore pressure is equal to the hydrostatic pressure plus the 50% of the difference between the lithostatic and the hydrostatic pressure. In conclusions, an accurate analysis of the BSR nature and the pore pressure are required to improve the reliability of the gas-phase estimation for different target, such as gas hydrate and free gas exploitations and environmental studies.

  14. Hydration of highly charged ions

    PubMed Central

    Hofer, Thomas S.; Weiss, Alexander K.H.; Randolf, Bernhard R.; Rode, Bernd M.

    2011-01-01

    Based on a series of ab initio quantum mechanical charge field molecular dynamics (QMCF MD) simulations, the broad spectrum of structural and dynamical properties of hydrates of trivalent and tetravalent ions is presented, ranging from extreme inertness to immediate hydrolysis. Main group and transition metal ions representative for different parts of the periodic system are treated, as are 2 threefold negatively charged anions. The results show that simple predictions of the properties of the hydrates appear impossible and that an accurate quantum mechanical simulation in cooperation with sophisticated experimental investigations seems the only way to obtain conclusive results. PMID:22298911

  15. Photoelectron spectroscopy of hydrated electrons

    NASA Astrophysics Data System (ADS)

    Shreve, Alexander T.; Yen, Terry A.; Neumark, Daniel M.

    2010-06-01

    We report a systematic study of the photoelectron spectroscopy of hydrated electrons in liquid water jets using multiple precursors and photodetachment wavelengths. Hydrated electrons were generated in and detached from liquid microjets using two photons from a single nanosecond laser pulse at 266 or 213 nm. Solutions of 50 to 250 mM potassium hexacyanoferrate(II) or potassium iodide were used to provide precursor anions. All of our experimental conditions yield similar results, giving a mean vertical binding energy of 3.6 ± 0.1 eV at a temperature of ˜280 K, a slightly higher value than in recent reports.

  16. Advanced mineral calciner for regeneration of lime. Topical technical report, May 1992-August 1993

    SciTech Connect

    Namazian, M.; Kelly, J.T.; Woodworth, R.

    1994-10-01

    Pulp and paper market growth and process changes require low cost incremental capacity lime regeneration units. Existing rotary kiln lime regeneration technology is costly to install and operate, especially at the lower capacity needed for the pulp and paper growth market. If this capacity need is not met by a cost effective and environmentally clean system, an 8 BCF potential gas market could move off-shore. The Advanced Mineral Calciner (AMC) is an environmentally clean, low capital and low operating cost lime regeneration system that is well suited to meeting this projected market. To quantify the benefits of the AMC, in small-scale a 100 lb/hr test system was built and operated. The product lime was subjected to standard industry tests to evaluate the extent of reaction and level of reactivity. The results showed that the lime produced by AMC has low unreacted core and good reactivity, compared to lime produced by rotary kilns.

  17. Methods to determine hydration states of minerals and cement hydrates

    SciTech Connect

    Baquerizo, Luis G.; Matschei, Thomas; Scrivener, Karen L.; Saeidpour, Mahsa; Thorell, Alva; Wadsö, Lars

    2014-11-15

    This paper describes a novel approach to the quantitative investigation of the impact of varying relative humidity (RH) and temperature on the structure and thermodynamic properties of salts and crystalline cement hydrates in different hydration states (i.e. varying molar water contents). The multi-method approach developed here is capable of deriving physico-chemical boundary conditions and the thermodynamic properties of hydrated phases, many of which are currently missing from or insufficiently reported in the literature. As an example the approach was applied to monosulfoaluminate, a phase typically found in hydrated cement pastes. New data on the dehydration and rehydration of monosulfoaluminate are presented. Some of the methods used were validated with the system Na{sub 2}SO{sub 4}–H{sub 2}O and new data related to the absorption of water by anhydrous sodium sulfate are presented. The methodology and data reported here should permit better modeling of the volume stability of cementitious systems exposed to various different climatic conditions.

  18. Characteristics and reactivity of rapidly hydrated sorbent for semidry flue gas desulfurization

    SciTech Connect

    Jie Zhang; Changfu You; Suwei Zhao; Changhe Chen; Haiying Qi

    2008-03-01

    The semidry flue gas desulfurization (FGD) process has many advantages over the wet FGD process for moving sulfur dioxide emissions from pulverized coal-fired power plants. Semidry FGD with a rapidly hydrated sorbent was studied in a pilot-scale circulating fluidized bed (CFB) experimental facility. The sorbent was made from lumps of lime and coal fly ash. The desulfurization efficiency was measured for various operating parameters, including the sorbent recirculation rate and the water spray method. The experimental results show that the desulfurization efficiencies of the rapidly hydrated sorbent were 1.5-3.0 times higher than a commonly used industrial sorbent for calcium to sulfur molar ratios from 1.2 to 3.0, mainly due to the higher specific surface area and pore volume. The Ca(OH){sub 2} content in the cyclone separator ash was about 2.9% for the rapidly hydrated sorbent and was about 0.1% for the commonly used industrial sorbent, due to the different adhesion between the fine Ca(OH){sub 2} particles and the fly ash particles, and the low cyclone separation efficiency for the fine Ca(OH){sub 2} particles that fell off the sorbent particles. Therefore the actual recirculation rates of the active sorbent with Ca(OH){sub 2} particles were higher for the rapidly hydrated sorbent, which also contributed to the higher desulfurization efficiency. The high fly ash content in the rapidly hydrated sorbent resulted in good operating stability. The desulfurization efficiency with upstream water spray was 10-15% higher than that with downstream water spray. 20 refs., 7 figs., 1 tab.

  19. Calcite orientations and composition ranges within teeth across Echinoidea

    PubMed Central

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

    2016-01-01

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

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

    PubMed

    Hincke, Maxwell T

    2013-12-01

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

  1. Shock-induced effects in calcite from Cactus Crater

    NASA Technical Reports Server (NTRS)

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

    1980-01-01

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

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

    SciTech Connect

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

    2001-04-29

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

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

    SciTech Connect

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

    1993-07-01

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

  4. Short-term responses of wetland vegetation after liming of an Adirondack watershed

    SciTech Connect

    Mackun, I.R.; Leopold, D.J.; Raynal, D.J. )

    1994-08-01

    Watershed liming has been suggested as a long-term mitigation strategy for lake acidity, particularly in areas subject to high levels of acidic deposition. However, virtually no information has been available on the impacts of liming on wetland vegetation. In 1989, 1100 Mg of limestone (83.5% CaCO[sub 3]) were aerially applied to 48% (100 ha) of the Woods Lake watershed in the west-central Adirondack region of New York as part of the first comprehensive watershed liming study in North America. We inventoried wetland vegetation in 1.0-m[sup 2] plots before liming and during the subsequent 2 yr. Within this period liming influenced the cover, frequency, or importance values of only 6 of 64 wetland taxa. The cover of Sphagnum spp. and of the cespitose sedge Carex interior decreased in control relative to limed plots, and cover of the rhizomatous sedge Cladium mariscoides increased nearly threefold in limed areas. These two sedges, which are relatively tall, are characteristic of more calcareous habitats. Cover of the grass Muhlenbergia uniflora, cover and importance were adversely affected or inhibited by lime. It is unclear whether liming directly inhibited the growth of these three small-statured species, or whether the adverse effects of lime were mediated through shifts in competitive interactions with other species. The limited responses that we observed to liming, along with changes that occurred in control plots over the study period, may indicate that in the short term watershed liming was no more of a perturbation than the environmental factors responsible for natural annual variation in wetland communities.

  5. Precipitation of calcite induced by Synechocystis sp. PCC6803.

    PubMed

    Han, Zuozhen; Yan, Huaxiao; Zhou, Shixue; Zhao, Hui; Zhang, Yan; Zhang, Ningning; Yao, Chuankai; Zhao, Lin; Han, Chunyan

    2013-10-01

    Calcite with laminate structure was successfully prepared by culturing Synechocystis sp. PCC6803 with different concentrations of calcium chloride (CaCl₂) in BG11 media. S. PCC6803 was examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), laser confocal scanning microscope (LCSM) and energy dispersive spectroscopy (EDS). The effects of Ca²⁺ concentrations and pH values on calcification were investigated and the micro morphs of the CaCO₃ crystals were observed by means of SEM. These results showed that CaCO₃ crystals could be more easily formed with increasing the concentration of CaCl₂ in S. PCC6803 culture solution. S. PCC6803 could largely bind calcium ions, most of which were present in extracellular polymeric substances and on the cell wall. Inside the cells there were a lot of circular areas rich in calcium ions without the crystallization of calcium. Some cells produced a thicker gelatinous sheath outside of the translucent organic thin layer. And the cells inside also produced major changes that the original chloroplasts were almost transformed into starch grains whose sizes were from 0.5 to 1 μm with relatively uniform in sizes. At the same time the cell sizes significantly reduced to only about 8-9 μm almost changing to half of its original diameters. The calcite crystals with a highly preferred orientation induced by S. PCC6803 were observed with X-ray diffraction (XRD). A critical implication was that S. PCC6803 could induce bio-calcification and then mediate the further growth of CaCO₃ crystals in the biological system. PMID:23543209

  6. Biotic Control of Skeletal Growth by Scleractinian Corals in AragoniteCalcite Seas

    PubMed Central

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

    2014-01-01

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

  7. Catalytic biomineralization of fluorescent calcite by the thermophilic bacterium Geobacillus thermoglucosidasius.

    PubMed

    Yoshida, Naoto; Higashimura, Eiji; Saeki, Yuichi

    2010-11-01

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

  8. [Research on Raman spectra of calcite phase transition at high pressure].

    PubMed

    Wang, Shi-Xia; Zheng, Hai-Fei

    2011-08-01

    The present research studied the process of phase transition from calcite-I to calcite-III under the condition of high hydrostatic pressure using hydrothermal diamond anvil cell and Raman spectrum technique. The hydrothermal diamond anvil cell is the most useful instrument to observe sample in-situation under high temperature and high pressure. The authors can get effective results from this instrument and pursue further research. The method of Raman spectra is the most useful measure tool and it can detect the material according to the spectrum. The result shows that three characteristic Raman peaks of calcite-I move to high-position with adding pressure. Water media in system becomes frozen at the pressure of 1103 MPa, and there is no change in the structure of calcite-I. The abrupt change of characteristic Raman peaks of calcite-I happens when the system pressure reaches 1752 MPa, and changed characteristic Raman peaks explain that calcite-I changes to calcite-III. There are two types of calcite-III, and type A happens in the system because of the effect of hydrostatic pressure. The characteristic Raman peak in different areas of minerals shows that the degree of phase transition becomes larger from inner part to edge part. The research also shows the advantage of hydrothermal diamond anvil cell and Raman spectrum for qualitative analysis of mineral structure using in-situ technique. PMID:22007398

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

    SciTech Connect

    Kolodny, Y.; Kaplan, I. R.

    1981-04-01

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

  10. Influence of etidronic acid and tartaric acid on the growth of different calcite morphologies

    NASA Astrophysics Data System (ADS)

    Ukrainczyk, Marko; Stelling, Jan; Vu?ak, Marijan; Neumann, Thomas

    2013-04-01

    The influence of organic additives on the crystal growth of different calcite morphologies in two crystallization processes operating under steady state and batch mode is described. The crystal growth kinetics and overgrown morphological observations of rhombohedral, scalenohedral and prismatic calcite seed crystals in the systems containing etidronic acid (HEDP) and tartaric acid (TA) were investigated. The crystallization systems were of low supersaturations (SI<1.1) and of moderate pH (8.0). Kinetic parameters of the crystal growth in the presence of selected additives, such as reduction of the growth rates, rate constant and reduced critical supersaturation were calculated and correlated with additive concentration and different calcite seeds. The results indicate strong interactions of HEDP molecules and weak but specific interactions of TA for calcite surfaces. Interactions occur at the step edges which finally results in the expression of near-{hk0} faces and highly polar faces, consisting of solely Ca layer on the surface, stabilised by TA and HEDP molecules, respectively. The affinity of both additives is significantly higher for scalenohedral and prismatic calcite in contrast to rhombohedral calcite seeds. The effect of calcite seed morphology was attributed to different surface energetics of the predominant crystal faces of the studied calcite seeds.

  11. Formation of hydrates during deepwater drilling operations

    SciTech Connect

    Barker, J.W.; Gomez, R.K.

    1989-03-01

    Two deepwater wells in widely separated geographical areas have experienced natural gas hydrate information during drilling operations. In both cases, hydrates, ice-like mixtures of natural gas and water, plugged subsea equipment, causing difficulties in subsequent operations. The potential for hydrate formation merits consideration during planning and conducting of deepwater drilling operations.

  12. 75 FR 9886 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-04

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... Methane Hydrate Advisory Committee is to provide advice on potential applications of methane hydrate...

  13. 77 FR 40032 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-06

    ... Methane Hydrate Advisory Committee AGENCY: Office of Fossil Energy, Department of Energy. ACTION: Notice of open meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee.... SUPPLEMENTARY INFORMATION: Purpose of the Committee: The purpose of the Methane Hydrate Advisory Committee is...

  14. The effect of liming on antibacterial and hormone levels in wastewater biosolids.

    PubMed

    Olszewski, Jennifer M; Lozano, Nuria; Haines, Christine; Rice, Clifford P; Ramirez, Mark; Torrents, Alba

    2013-01-01

    This study analyzes the effect of liming on levels of triclocarban (TCC), triclosan (TCS), estrone (E1), and progesterone (P), two antimicrobial agents and two natural hormones, respectively. Factors studied include lime particle size, mixing time, and overall lime contact time. The study results suggest that coarse lime may be more active than fine lime due to less interaction with surrounding air. Both TCS and TCC concentrations were lower in coarse limed samples versus unlimed samples and the decrease was a function of time. A similar, but statistically insignificant trend in TCC and TCS levels was observed in fine lime samples with respect to unlimed samples. Liming was also found to decrease apparent E1 levels, with more notable decreases in samples amended with coarse lime. P-levels significantly increased after 1-day of contact time, stabilizing over the next 14days of the study period. This increase and stabilization of P-levels was attributed to the pH and moisture-driven conversion of more chemically complex steroids into P. PMID:23485235

  15. Long-term field-scale experiment on using lime filters in an agricultural catchment.

    PubMed

    Kirkkala, Teija; Ventel, Anne-Mari; Tarvainen, Marjo

    2012-01-01

    The River Ylneenjoki catchment in southwest Finland is an area with a high agricultural nutrient load. We report here on the nutrient removal performance of three on-site lime-sand filters (F1, F2, and F3), established within or on the edge of the buffer zones. The filters contain burnt lime (CaO) or spent lime [CaO, Ca(OH), and CaCO]. Easily soluble lime results in a high pH level (>11) and leads to an efficient precipitation of soluble phosphorus (P) from the runoff. Water samples were taken from the inflow and outflow of each site in different hydrological situations. The length of the monitoring period was 4 yr for F1, 6 yr for F2, and 1.5 yr for F3. F1 and F2 significantly reduced the suspended solids (SS), total P (PTOT), and dissolved reactive P (DRP) in the treated water. The proportional reduction (%) varied but was usually clearly positive. Filter F3 was divided into two equal parts, one containing burnt lime and the other spent lime. Both filter parts removed PTOT and SS efficiently from the water; the burnt-lime part also removed DRP. The mixed-lime part removed DRP for a year, but then the efficiency decreased. The effect of filters on nitrogen compounds varied. We conclude that sand filters incorporating lime can be used together with buffer zones to reduce both P and SS load to watercourses. PMID:22370403

  16. Diagenetic calcite from the Chazyan Group (Vermont): an example of aragonite alteration in a greenhouse ocean

    NASA Astrophysics Data System (ADS)

    Tobin, Kenneth J.; Walker, Kenneth R.

    1998-11-01

    Marine diagenetic calcite with both a calcitic (low-to-intermediate Mg) and aragonitic origin was examined from the middle Ordovician buildups of the Chazyan Group in Vermont. All marine phases have elevated Sr (up to 1800 ppm) compared with that observed from marine precipitates in other middle Ordovician units. Stromatoporoids (labechiids), which were originally aragonitic, have higher Sr values than phases with an original calcite mineralogy (trilobites, marine cement). Additional evidence supporting precursor mineralogy interpretations includes elevated Mg values (up to 3.6 mole% MgCO 3) and the presence of microdolomite in interpreted calcitic phases. Originally aragonitic precipitates have lower Mg values and most significantly lack microdolomite. This study demonstrates the presence of elevated Sr values in marine precipitates that formed during a period when calcite, not aragonite, was the dominant physiochemically precipitated calcium carbonate mineralogy that formed from sea water. Elevated Sr is attributable to at least a partially open system diagenetic stabilization of biogenic aragonite.

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

    SciTech Connect

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

    2014-01-23

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

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

    USGS Publications Warehouse

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

    1951-01-01

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

  19. Attraction between hydrated hydrophilic surfaces

    NASA Astrophysics Data System (ADS)

    Kanduč, Matej; Schneck, Emanuel; Netz, Roland R.

    2014-08-01

    According to common knowledge, hydrophilic surfaces repel via hydration forces while hydrophobic surfaces attract, but mounting experimental evidence suggests that also hydrophilic surfaces can attract. Using all-atom molecular dynamics simulations at prescribed water chemical potential we study the crossover from hydration repulsion to hydrophobic attraction for planar polar surfaces of varying stiffness and hydrogen-bonding capability. Rescaling the partial charges of the polar surface groups, we cover the complete spectrum from very hydrophobic surfaces (characterized by contact angles θ ≃ 135°) to hydrophilic surfaces exhibiting complete wetting (θ = 0°). Indeed, for a finite range θadh < θ < 90°, we find a regime where hydrophilic surfaces attract at sub-nanometer separation and stably adhere without intervening water. The adhesive contact angle θadh depends on surface type and lies in the range 65° < θadh < 80°, in good agreement with experiments. Analysis of the total number of hydrogen bonds (HBs) formed by water and surface groups rationalizes this crossover between hydration repulsion and hydrophilic attraction in terms of a subtle balance: Highly polar surfaces repel because of strongly bound hydration water, less polar hydrophilic surfaces attract because water-water HBs are preferred over surface-water HBs. Such solvent reorganization forces presumably underlie also other important phenomena, such as selective ion adsorption to interfaces as well as ion pair formation.

  20. Hydration rind dates rhyolite flows.

    PubMed

    Friedman, I

    1968-02-23

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago. PMID:17768978

  1. Hydration rind dates rhyolite flows

    USGS Publications Warehouse

    Friedman, I.

    1968-01-01

    Hydration of obsidian has been used to date rhyolite flows, containing obsidian or porphyritic glass, at Glass Mountain (Medicine Lake Highlands) and Mono Lake, California. The method is simple and rapid and can be used to date flows that erupted between 200 and approximately 200,000 years ago.

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

    SciTech Connect

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

    1999-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

    The styles and mechanisms of deformation associated with many variably dolomitized limestone shear systems are strongly controlled by strain partitioning between dolomite and calcite. Here, we present experimental results from the deformation of four composite materials designed to address the role of dolomite on the strength of limestone. Composites were synthesized by hot isostatic pressing mixtures of dolomite (Dm) and calcite powders (% Dm: 25%-Dm, 35%-Dm, 51%-Dm, and 75%-Dm). In all composites, calcite is finer grained than dolomite. The synthesized materials were deformed in torsion at constant strain rate (3נ10-4 and 1נ10-4s-1), high effective pressure (262MPa), and high temperature (750C) to variable finite shear strains. Mechanical data show an increase in yield strength with increasing dolomite content. Composites with <75% dolomite (the remaining being calcite), accommodate significant shear strain at much lower shear stresses than pure dolomite but have significantly higher yield strengths than anticipated for 100% calcite. The microstructure of the fine-grained calcite suggests grain boundary sliding, accommodated by diffusion creep and dislocation glide. At low dolomite concentrations (i.e. 25%), the presence of coarse-grained dolomite in a micritic calcite matrix has a profound effect on the strength of composite materials as dolomite grains inhibit the superplastic flow of calcite aggregates. In high (>50%) dolomite content samples, the addition of 25% fine-grained calcite significantly weakens dolomite, such that strain can be partially localized along narrow ribbons of fine-grained calcite. Deformation of dolomite grains by shear fracture is observed; there is no intracrystalline deformation in dolomite irrespective of its relative abundance and finite shear strain.

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

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

    NASA Astrophysics Data System (ADS)

    Renard, Franois; Putnis, Christine V.; Montes-Hernandez, German; Ruiz-Agudo, Encarnacion; Hovelmann, Jrn; Sarret, Graldine

    2015-06-01

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

  6. Thermal properties of methane gas hydrates

    USGS Publications Warehouse

    Waite, William F.

    2007-01-01

    Gas hydrates are crystalline solids in which molecules of a guest species occupy and stabilize cages formed by water molecules. Similar to ice in appearance (fig. 1), gas hydrates are stable at high pressures and temperatures above freezing (0C). Methane is the most common naturally occurring hydrate guest species. Methane hydrates, also called simply gas hydrates, are extremely concentrated stores of methane and are found in shallow permafrost and continental margin sediments worldwide. Brought to sea-level conditions, methane hydrate breaks down and releases up to 160 times its own volume in methane gas. The methane stored in gas hydrates is of interest and concern to policy makers as a potential alternative energy resource and as a potent greenhouse gas that could be released from sediments to the atmosphere and ocean during global warming. In continental margin settings, methane release from gas hydrates also is a potential geohazard and could cause submarine landslides that endanger offshore infrastructure. Gas hydrate stability is sensitive to temperature changes. To understand methane release from gas hydrate, the U.S. Geological Survey (USGS) conducted a laboratory investigation of pure methane hydrate thermal properties at conditions relevant to accumulations of naturally occurring methane hydrate. Prior to this work, thermal properties for gas hydrates generally were measured on analog systems such as ice and non-methane hydrates or at temperatures below freezing; these conditions limit direct comparisons to methane hydrates in marine and permafrost sediment. Three thermal properties, defined succinctly by Briaud and Chaouch (1997), are estimated from the experiments described here: - Thermal conductivity, ?: if ? is high, heat travels easily through the material. - Thermal diffusivity, ?: if ? is high, it takes little time for the temperature to rise in the material. - Specific heat, cp: if cp is high, it takes a great deal of heat to raise the temperature of the material.

  7. Physical activity, hydration and health.

    PubMed

    Marcos, Ascensión; Manonelles, Pedro; Palacios, Nieves; Wärnberg, Julia; Casajús, José A; Pérez, Margarita; Aznar, Susana; Benito, Pedro J; Martínez-Gomez, David; Ortega, Francisco B; Ortega, Eduardo; Urrialde, Rafael

    2014-01-01

    Since the beginning of mankind, man has sought ways to promote and preserve health as well as to prevent disease. Hydration, physical activity and exercise are key factors for enhancing human health. However, either a little dose of them or an excess can be harmful for health maintenance at any age. Water is an essential nutrient for human body and a major key to survival has been to prevent dehydration. However, there is still a general controversy regarding the necessary amount to drink water or other beverages to properly get an adequate level of hydration. In addition, up to now the tools used to measure hydration are controversial. To this end, there are several important groups of variables to take into account such as water balance, hydration biomarkers and total body water. A combination of methods will be the most preferred tool to find out any risk or situation of dehydration at any age range. On the other hand, physical activity and exercise are being demonstrated to promote health, avoiding or reducing health problems, vascular and inflammatory disea ses and helping weight management. Therefore, physical activity is also being used as a pill within a therapy to promote health and reduce risk diseases, but as in the case of drugs, dose, intensity, frequency, duration and precautions have to be evaluated and taken into account in order to get the maximum effectiveness and success of a treatment. On the other hand, sedentariness is the opposite concept to physical activity that has been recently recognized as an important factor of lifestyle involved in the obesogenic environment and consequently in the risk of the non-communicable diseases. In view of the literature consulted and taking into account the expertise of the authors, in this review a Decalogue of global recommendations is included to achieve an adequate hydration and physical activity status to avoid overweight/obesity consequences. PMID:24972459

  8. Mesoscale texture of cement hydrates

    PubMed Central

    Ioannidou, Katerina; Krakowiak, Konrad J.; Bauchy, Mathieu; Hoover, Christian G.; Masoero, Enrico; Yip, Sidney; Ulm, Franz-Josef; Levitz, Pierre; Pellenq, Roland J.-M.; Del Gado, Emanuela

    2016-01-01

    Strength and other mechanical properties of cement and concrete rely upon the formation of calcium–silicate–hydrates (C–S–H) during cement hydration. Controlling structure and properties of the C–S–H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C–S–H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C–S–H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C–S–H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C–S–H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials. PMID:26858450

  9. Mesoscale texture of cement hydrates.

    PubMed

    Ioannidou, Katerina; Krakowiak, Konrad J; Bauchy, Mathieu; Hoover, Christian G; Masoero, Enrico; Yip, Sidney; Ulm, Franz-Josef; Levitz, Pierre; Pellenq, Roland J-M; Del Gado, Emanuela

    2016-02-23

    Strength and other mechanical properties of cement and concrete rely upon the formation of calcium-silicate-hydrates (C-S-H) during cement hydration. Controlling structure and properties of the C-S-H phase is a challenge, due to the complexity of this hydration product and of the mechanisms that drive its precipitation from the ionic solution upon dissolution of cement grains in water. Departing from traditional models mostly focused on length scales above the micrometer, recent research addressed the molecular structure of C-S-H. However, small-angle neutron scattering, electron-microscopy imaging, and nanoindentation experiments suggest that its mesoscale organization, extending over hundreds of nanometers, may be more important. Here we unveil the C-S-H mesoscale texture, a crucial step to connect the fundamental scales to the macroscale of engineering properties. We use simulations that combine information of the nanoscale building units of C-S-H and their effective interactions, obtained from atomistic simulations and experiments, into a statistical physics framework for aggregating nanoparticles. We compute small-angle scattering intensities, pore size distributions, specific surface area, local densities, indentation modulus, and hardness of the material, providing quantitative understanding of different experimental investigations. Our results provide insight into how the heterogeneities developed during the early stages of hydration persist in the structure of C-S-H and impact the mechanical performance of the hardened cement paste. Unraveling such links in cement hydrates can be groundbreaking and controlling them can be the key to smarter mix designs of cementitious materials. PMID:26858450

  10. Excimer laser ablation rate and corneal hydration.

    PubMed

    Dougherty, P J; Wellish, K L; Maloney, R K

    1994-08-15

    During excimer laser photorefractive keratectomy, dehydration of the cornea begins as soon as the epithelium is removed. Corneal hydration might affect the excimer laser ablation rate, which could affect the accuracy of correction. We studied the effect of corneal hydration on the excimer laser ablation rate in bovine eyes. To control hydration, bovine corneoscleral rims were equilibrated in dextran solutions of varying concentrations. One button trephined from each rim underwent laser ablation. Hydrated tissue ablation rates (amount of collagen, ground substance, and water removed per pulse) and dry component ablation rates (amount of collagen and ground substance removed per pulse) were calculated from mass removed. The hydrated tissue ablation rate at physiologic hydration was 0.40 micron/pulse. As corneal hydration increased, the hydrated tissue ablation rate increased by 5.6 micrograms/cm2/pulse per increase in unit corneal hydration (simple linear regression analysis, P = .0001). The dry component ablation rate decreased linearly by 0.82 microgram/cm2/pulse per unit increase in corneal hydration (simple linear regression analysis, P = .0001). Both clinical data and theoretical arguments imply that dry component ablation rate determines refractive outcome after photorefractive keratectomy. Since the dry component ablation rate increases as the cornea dries, significant dehydration of the cornea before ablation might lead to relative overcorrections of myopia. Surgeons should use a technique that minimizes changes in hydration to maximize the predictability of excimer laser photorefractive keratectomy. PMID:8053462

  11. Lime and fly ash stabilization of wastewater treatment sludge

    SciTech Connect

    Burns, H.; Gremminger, L.

    1994-01-11

    This invention provides a process meeting the EPA's PFRP standard for WWTS treatment thereby producing a readily usable end-product in either soil-like form or semi-impermeable low load bearing, mass form. The process includes mixing WWTS with lime and fly ash, to cause a temperature increase to above 70 C for at least 30 minutes and to cause the pH to exceed 12 for at least 2 hours. The end-product may be compacted to produce an semi-impermeable, durable mass or the soil-like product may be used as landfill cover material. 3 figs.

  12. Improvement of tropical soils with waste ash and lime

    SciTech Connect

    Nicholson, P.G.; Ding, M.

    1997-12-31

    The special environment in Hawaii produces some tropical soils which often have poor engineering properties including high swelling potential, high plasticity, low strength, etc. On the island of Oahu, municipal solid waste (MSW) is incinerated to reduce the total volume for landfill conservation while generating electricity to supplement the islands energy needs. Productive use of these wastes, together with locally available lime and/or cement, are being considered as possible admixtures to stabilize those undesirable soils. Utilization of this waste ash could have significant environmental benefits and result in considerable cost savings, while providing a low cost stabilizer for geotechnical applications.

  13. Improvement in hardness of soda-lime-silica glass

    SciTech Connect

    Chakraborty, Riya; De, Moumita; Roy, Sudakshina; Dey, Arjun; Biswas, Sampad K.; Middya, Tapas Ranjan; Mukhopadhyay, Anoop K.

    2012-06-05

    Hardness is a key design parameter for structural application of brittle solids like glass. Here we report for the first time the significant improvement of about 10% in Vicker's hardness of a soda-lime-silica glass with loading rate in the range of 0.1-10 N.s{sup -1}. Corroborative dark field optical and scanning electron microscopy provided clue to this improvement through evidence of variations in spatial density of shear deformation band formation as a function of loading rate.

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

    SciTech Connect

    B.D. Marshall; K. Futa

    2001-02-07

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

  15. Handbook of gas hydrate properties and occurrence

    SciTech Connect

    Kuustraa, V.A.; Hammershaimb, E.C.

    1983-12-01

    This handbook provides data on the resource potential of naturally occurring hydrates, the properties that are needed to evaluate their recovery, and their production potential. The first two chapters give data on the naturally occurring hydrate potential by reviewing published resource estimates and the known and inferred occurrences. The third and fourth chapters review the physical and thermodynamic properties of hydrates, respectively. The thermodynamic properties of hydrates that are discussed include dissociation energies and a simplified method to calculate them; phase diagrams for simple and multi-component gases; the thermal conductivity; and the kinetics of hydrate dissociation. The final chapter evaluates the net energy balance of recovering hydrates and shows that a substantial positive energy balance can theoretically be achieved. The Appendices of the Handbook summarize physical and thermodynamic properties of gases, liquids and solids that can be used in designing and evaluating recovery processes of hydrates. 158 references, 67 figures, 47 tables.

  16. Simulation of SO sub 2 removal via hydrated lime slurries in a spray dryer absorber flue gas desulfurization system

    SciTech Connect

    Shih, Hang-Shin.

    1989-01-01

    The objective of this study was to numerically analyze an SO{sub 2} removal process by combining a two phase gas-solid reaction (dry particle) stage with a three phase gas-liquid-solid reaction (wet particle) stage. The SO{sub 2} removal process in a spray dryer absorber flue gas desulfurization system was simulated and studied by the mathematical model developed. This model involves the simulation of the evaporation of water from atomized slurry droplets, the absorption/reaction of SO{sub 2} in the slurry droplets, and the transport phenomena in both wet and dry particle stages. Two stages of evaporation which include a constant-drying period and a falling-rate drying period were described by the corresponding mass and heat transfer relations. The absorption/reaction of SO{sub 2} in the wet particle stage was modeled using the modified Ramachandran and Sharma's film model. The grain model was adopted to evaluate the SO{sub 2} removal rate in the dry particle stage. The model predictions were compared with experimental data taken over a wide range of operating conditions.

  17. Thermal conductivity of hydrate-bearing sediments

    USGS Publications Warehouse

    Cortes, D.D.; Martin, A.I.; Yun, T.S.; Francisca, F.M.; Santamarina, J.C.; Ruppel, C.

    2009-01-01

    A thorough understanding of the thermal conductivity of hydrate-bearing sediments is necessary for evaluating phase transformation processes that would accompany energy production from gas hydrate deposits and for estimating regional heat flow based on the observed depth to the base of the gas hydrate stability zone. The coexistence of multiple phases (gas hydrate, liquid and gas pore fill, and solid sediment grains) and their complex spatial arrangement hinder the a priori prediction of the thermal conductivity of hydrate-bearing sediments. Previous studies have been unable to capture the full parameter space covered by variations in grain size, specific surface, degree of saturation, nature of pore filling material, and effective stress for hydrate-bearing samples. Here we report on systematic measurements of the thermal conductivity of air dry, water- and tetrohydrofuran (THF)-saturated, and THF hydrate-saturated sand and clay samples at vertical effective stress of 0.05 to 1 MPa (corresponding to depths as great as 100 m below seafloor). Results reveal that the bulk thermal conductivity of the samples in every case reflects a complex interplay among particle size, effective stress, porosity, and fluid-versus-hydrate filled pore spaces. The thermal conductivity of THF hydrate-bearing soils increases upon hydrate formation although the thermal conductivities of THF solution and THF hydrate are almost the same. Several mechanisms can contribute to this effect including cryogenic suction during hydrate crystal growth and the ensuing porosity reduction in the surrounding sediment, increased mean effective stress due to hydrate formation under zero lateral strain conditions, and decreased interface thermal impedance as grain-liquid interfaces are transformed into grain-hydrate interfaces. Copyright 2009 by the American Geophysical Union.

  18. Pockmark formation and evolution in deep water Nigeria: Rapid hydrate growth versus slow hydrate dissolution

    NASA Astrophysics Data System (ADS)

    Sultan, N.; Bohrmann, G.; Ruffine, L.; Pape, T.; Riboulot, V.; Colliat, J.-L.; De Prunel, A.; Dennielou, B.; Garziglia, S.; Himmler, T.; Marsset, T.; Peters, C. A.; Rabiu, A.; Wei, J.

    2014-04-01

    In previous works, it has been suggested that dissolution of gas hydrate can be responsible for pockmark formation and evolution in deep water Nigeria. It was shown that those pockmarks which are at different stages of maturation are characterized by a common internal architecture associated to gas hydrate dynamics. New results obtained by drilling into gas hydrate-bearing sediments with the MeBo seafloor drill rig in concert with geotechnical in situ measurements and pore water analyses indicate that pockmark formation and evolution in the study area are mainly controlled by rapid hydrate growth opposed to slow hydrate dissolution. On one hand, positive temperature anomalies, free gas trapped in shallow microfractures near the seafloor and coexistence of free gas and gas hydrate indicate rapid hydrate growth. On the other hand, slow hydrate dissolution is evident by low methane concentrations and almost constant sulfate values 2 m above the Gas Hydrate Occurrence Zone.

  19. Mechanism of atomic force microscopy imaging of three-dimensional hydration structures at a solid-liquid interface

    NASA Astrophysics Data System (ADS)

    Fukuma, Takeshi; Reischl, Bernhard; Kobayashi, Naritaka; Spijker, Peter; Canova, Fillippo Federici; Miyazawa, Keisuke; Foster, Adam S.

    2015-10-01

    Here we present both subnanometer imaging of three-dimensional (3D) hydration structures using atomic force microscopy (AFM) and molecular dynamics simulations of the calcite-water interface. In AFM, by scanning the 3D interfacial space in pure water and recording the force on the tip, a 3D force image can be produced, which can then be directly compared to the simulated 3D water density and forces on a model tip. Analyzing in depth the resemblance between experiment and simulation as a function of the tip-sample distance allowed us to clarify the contrast mechanism in the force images and the reason for their agreement with water density distributions. This work aims to form the theoretical basis for AFM imaging of hydration structures and enables its application to future studies on important interfacial processes at the molecular scale.

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

    SciTech Connect

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

    1985-01-01

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

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

    PubMed Central

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

    2014-01-01

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

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

    PubMed

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

    2014-01-01

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

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

    PubMed

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

    2015-02-01

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

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

    PubMed

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

    2016-04-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-12-01

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

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

    PubMed

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

    2007-01-01

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

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

    PubMed

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

    2011-09-01

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

  8. Substrate pH and butterfly bush response to dolomitic lime or steel slag amendment

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Steel slag is a fertilizer amendment with a high concentration of calcium oxide, and thus capable of raising substrate pH similar to dolomitic lime. Steel slag, however, contains higher concentrations of some nutrients, such as iron, manganese, and silicon, compared to dolomitic lime. The objectiv...

  9. Effects of liming on forage availability and nutrient content in a forest impacted by acid rain.

    PubMed

    Pabian, Sarah E; Ermer, Nathan M; Tzilkowski, Walter M; Brittingham, Margaret C

    2012-01-01

    Acidic deposition and subsequent forest soil acidification and nutrient depletion can affect negatively the growth, health and nutrient content of vegetation, potentially limiting the availability and nutrient content of forage for white-tailed deer (Odocoileus virginianus) and other forest herbivores. Liming is a mitigation technique that can be used to restore forest health in acidified areas, but little is known about how it affects the growth or nutrient content of deer forage. We examined the effects of dolomitic limestone application on the growth and chemical composition of understory plants in an acidified forest in central Pennsylvania, with a focus on vegetative groups included as white-tailed deer forage. We used a Before-After-Control-Impact study design with observations 1 year before liming and up to 5 years post-liming on 2 treated and 2 untreated 100-ha sites. Before liming, forage availability and several nutrients were below levels considered optimal for white-tailed deer, and many vegetative characteristics were related to soil chemistry. We observed a positive effect of liming on forb biomass, with a 2.7 fold increase on limed sites, but no biomass response in other vegetation groups. We observed positive effects of liming on calcium and magnesium content and negative effects on aluminum and manganese content of several plant groups. Responses to liming by forbs and plant nutrients show promise for improving vegetation health and forage quality and quantity for deer. PMID:22761890

  10. EVALUATION OF SOLIDS DEWATERING FOR A PILOT-SCALE THIOSORBIC LIME SO2 SCRUBBER

    EPA Science Inventory

    The paper gives results of an evaluation of solids dewatering for a pilot-scale thiosorbic lime SO2 scrubber. Pilot plant data showed that the dissolved magnesium in thiosorbic lime caused deterioration of solids dewatering properties. The slurry settling rate increased when the ...

  11. 77 FR 45715 - Application of Key Lime Air Corporation for Commuter Authority

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-01

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF TRANSPORTATION Office of the Secretary Application of Key Lime Air Corporation for Commuter Authority AGENCY: Department... not issue an order finding Key Lime Air Corporation fit, willing, and able, and awarding it a...

  12. DELIMING OF BOUND AND UN-BOUND LIME FROM WHITE HIDE

    Technology Transfer Automated Retrieval System (TEKTRAN)

    White hide deliming requires the removal of un-bound lime as well as bound lime. This can be accomplished sequentially by washing the hides in pure water followed by an appropriate deliming solution. The objective of this paper is to determine the optimal wash parameters for each using a mathemati...

  13. Barley seedling growth in soils amended with fly ash or agricultural lime followed by acidification

    SciTech Connect

    Renken, R.R.; McCallister, D.L.; Tarkalson, D.D.; Hergert, G.W.; Marx, D.B.

    2006-05-15

    Calcium-rich coal combustion fly ash can be used as an amendment to neutralize soil acidity because of its oxides and carbonate content, but its aluminum content could inhibit plant growth if soil pH values fall below optimal agronomic levels. This study measured root and shoot growth of an acid-sensitive barley (Hordeum vulgare L. 'Kearney') grown in the greenhouse on three naturally acid soils. The soils were either untreated or amended with various liming materials (dry fly ash, wet fly ash, and agricultural lime) at application rates of 0, .5, 1, and 1.5 times the recommended lime requirement, then treated with dilute acid solutions to simulate management-induced acidification. Plant growth indexes were measured at 30 days after planting. Root mass per plant and root length per plant were greater for the limed treatments than in the acidified check. Root growth in the limed treatments did not differ from root growth in the original nonacidified soils. Top mass per plant in all limed soils was either larger than or not different from that in the original nonacidified soils. Based on top mass per plant, no liming material or application rate was clearly superior. Both fly ash and agricultural lime reduced the impact of subsequent acidification on young barley plants. Detrimental effects of aluminum release on plant growth were not observed. Calcium-rich fly ash at agronomic rates is an acceptable acid-neutralizing material with no apparent negative effects.

  14. Effects of Liming on Forage Availability and Nutrient Content in a Forest Impacted by Acid Rain

    PubMed Central

    Pabian, Sarah E.; Ermer, Nathan M.; Tzilkowski, Walter M.; Brittingham, Margaret C.

    2012-01-01

    Acidic deposition and subsequent forest soil acidification and nutrient depletion can affect negatively the growth, health and nutrient content of vegetation, potentially limiting the availability and nutrient content of forage for white-tailed deer (Odocoileus virginianus) and other forest herbivores. Liming is a mitigation technique that can be used to restore forest health in acidified areas, but little is known about how it affects the growth or nutrient content of deer forage. We examined the effects of dolomitic limestone application on the growth and chemical composition of understory plants in an acidified forest in central Pennsylvania, with a focus on vegetative groups included as white-tailed deer forage. We used a Before-After-Control-Impact study design with observations 1 year before liming and up to 5 years post-liming on 2 treated and 2 untreated 100-ha sites. Before liming, forage availability and several nutrients were below levels considered optimal for white-tailed deer, and many vegetative characteristics were related to soil chemistry. We observed a positive effect of liming on forb biomass, with a 2.7 fold increase on limed sites, but no biomass response in other vegetation groups. We observed positive effects of liming on calcium and magnesium content and negative effects on aluminum and manganese content of several plant groups. Responses to liming by forbs and plant nutrients show promise for improving vegetation health and forage quality and quantity for deer. PMID:22761890

  15. Dissolution of lime into synthetic coal ash slags

    SciTech Connect

    Elliott, L.; Wang, Shen Mao; Wall, T.; Lucas, J.

    1996-12-31

    One of the alternate processes presently being investigated to produce electrical power from coal is Integrated Gasification Combined Cycle (IGCC). The ash that remains when the coal is gasified in this process, is removed by granulating the molten ash at 1400 - 1500{degrees}C, To reduce the melting temperature of the coal ash to this level, a flux, usually limestone, is added with the cow to the gasifier. The rate of dissolution of the flux is uncertain. This paper reports the investigation of the rate of time dissolution into synthetic coal ashes, consisting of SiO{sub 2}, Al{sub 2}O{sub 3} and CaO. Results previously reported have shown that the free dissolution of fine particles (50-200 {mu}m) is mass transfer controlled. To investigate forced dissolution, a high temperature viscometer was used to rotate a cylinder of lime in the molten slag for a given period. At temperatures between 1450{degrees}C and 1656{degrees}C, reaction products of 3CaO.SiO{sub 2}/3CaOAl{sub 2}O{sub 3}, 2CaO.SiO{sub 2}/3CaO.Al{sub 2}O{sub 3}/12CaO,7Al{sub 2}O{sub 3} form around the lime pellet. The concentration gradient involved in the mass transfer was defined, and initial studies of the diffusion coefficients were completed.

  16. Computerized Shawnee lime/limestone scrubbing model users manual

    SciTech Connect

    Anders, W.L.; Torstrick, R.L.

    1981-03-01

    The manual gives a general description of a computerized model for estimating design and cost of lime or limestone scrubber systems for flue gas desulfurization (FGD). It supplements PB80-123037 by extending the number of scrubber options which can be evaluated. It includes spray tower and venturi/spray-tower absorbers, forced oxidation systems, systems with absorber loop additives (MgO or adipic acid), revised design and economic premises, and other changes reflecting process improvements and variations. It describes all inputs and outputs, along with detailed procedures for using the model and all its options. The model is based on prototype scrubber data from the EPA/Shawnee test facility and should be useful to utility companies, as well as to architectural and engineering contractors who are involved in selecting and designing FGD facilities. As key features, the model provides estimates of capital investment and operating revenue requirements. It also provides a material balance, equipment list, and a breakdown of costs by processing areas. The primary uses of the model are to project comparative economics of lime and limestone FGD processes and to evaluate system alternatives prior to the development of a detailed design.

  17. Late Mississippian lime mud mounds, Pitkin Formation, northern Arkansas

    SciTech Connect

    Manger, W.L.; Ar, V.P.; Webb, G.E.

    1984-04-01

    Carbonates deposited under shallow, open shelf conditions during the Late Mississippian in northern Arkansas exhibit numerous discrete to coalescing lime mud mounds up to 20 m (65 ft) high and tens of meters in diameter. The mounds are composed of a carbonate mud core, typically with fenestrate texture, entrapped by a loosely organized framework dominated by cystoporate bryozoans and rugose corals in the lower part, and by blue-green algae and cryptostomous bryozoans in the upper part. Disarticulated crinozoan detritus is common throughout the core, suggesting that these organisms also contributed to entrapment of lime mud. During deposition, the mud core was indurated enough to support and preserve vertical burrows. Also, rubble of core mudstone is found on the flanks of some mounds, suggesting some erosion. Intermound lithology is a shoaling-upward sequence dominated by oolitic and bioclastic grainstones and packstones. Shale is also present in minor amounts. The Pitkin mounds, interbedded with these intermound sequences, developed contemporaneously with them. Depositional relief was probably less than 3 m (10 ft). The mounds expanded laterally during periods of quieter water; their growth was impeded during times of higher energy. Contacts of the mound and intermound lithologic characteristics are sharp, truncating surfaces. Mound deposition ended with the onset of high energy conditions throughout the region.

  18. Santaclaraite, a new calcium-manganese silicate hydrate from California.

    USGS Publications Warehouse

    Erd, Richard C.; Ohashi, Y.

    1984-01-01

    Santaclaraite, ideally CaMn4(Si5O14(OH))(OH).H2O, occurs as pink and tan veins and masses in Franciscan chert in the Diablo Range, Santa Clara and Stanislaus counties, California. It is associated with four unidentified Mn silicates, Mn-howieite, quartz, braunite, calcite, rhodochrosite, kutnahorite, baryte, harmotome, chalcopyrite and native copper. Santaclaraite is triclinic, space group B1, a 15.633(1), b 7.603(1) , c 12.003(1) A, alpha 109.71(1)o, beta 88.61(1)o, gamma 99.95(1) o, V 1322.0(3) A3; Z = 4. The strongest lines of the X-ray pattern are 7.04(100), 3.003(84), 3.152(80), 7.69(63), 3.847(57) A. Crystals are lamellar to prismatic (flattened on (100)), with good cleavage on (100) and (010); H. 61/2 Dcalc. 3.398 g/cm3, Dmeas. 3.31 (+ or -0.01); optically biaxial negative, alpha 1.681, beta 1.696, gamma 1.708 (all + or - 0.002), 2Valpha 83 (+ or -1)o. Although chemically a hydrated rhodonite, santaclaraite dehydrates to Mn-bustamite at approx 550oC (in air) . Santaclaraite is a five-tetrahedral-repeat single-chain silicate and has structural affinities with rhodonite, nambulite, marsturite, babingtonite and inesite.-J.A.Z.

  19. Arbuscular Mycorrhizal Fungal Communities in the Roots of Maize Lines Contrasting for Al Tolerance Grown in Limed and Non-Limed Brazilian Oxisoil.

    PubMed

    Gomes, Eliane A; Oliveira, Christiane A; Lana, Ubiraci G P; Noda, Roberto W; Marriel, Ivanildo E; de Souza, Francisco A

    2015-07-01

    Aluminum (Al) toxicity is one of the greatest limitations to agriculture in acid soils, particularly in tropical regions. Arbuscular mycorrhizal fungi (AMF) can supply plants with nutrients and give protection against Al toxicity. The aim of this work was to evaluate the effects of soil liming (i.e., reducing Al saturation) on the AMF community composition and structure in the roots of maize lines contrasting for Al tolerance. To this end, we constructed four 18S rDNA cloning libraries from L3 (Al tolerant) and L22 (Al sensitive) maize lines grown in limed and non-limed soils. A total of 790 clones were sequenced, 69% belonging to the Glomeromycota phylum. The remaining sequences were from Ascomycota, which were more prominent in the limed soil, mainly in the L3 line. The most abundant AM fungal clones were related to the family Glomeraceae represented by the genera uncultured Glomus followed by Rhizophagus and Funneliformis. However, the most abundant operational taxonomic units with 27% of the Glomeromycota clones was affiliated to genus Racocetra. This genus was present in all the four libraries, but it was predominant in the non-limed soils, suggesting that Racocetra is tolerant to Al toxicity. Similarly, Acaulospora and Rhizophagus were also present mostly in both lines in non-limed soils. The community richness of AMF in the non-limed soils was higher than the limed soil for both lines. The results suggest that the soil Al saturation was the parameter that mostly influences the AMF species composition in the soils in this study. PMID:25674805

  20. Measuring Carbon and Oxygen Isotope Uptake into Inorganic Calcite using Crystal Growth Experiments

    NASA Astrophysics Data System (ADS)

    Baker, E. B.; Watkins, J. M.

    2014-12-01

    Carbon and oxygen isotopes measured on natural calcite crystals provide a record of paleo-environment conditions. Despite the importance of measuring stable isotopes in calcite for paleo-environment reconstructions, there is neither a general theory nor an experimental data set that fully separates the effects of pH, temperature, and precipitation rate on isotope discrimination during calcite growth. Many stable isotope studies of calcite have focused on either carbon or oxygen isotope compositions individually, but few have measured both carbon and oxygen isotope uptake in the same set of crystals. We are precipitating inorganic calcite across a range in temperature, pH, and precipitation rate to guide the development of a general theory for combined carbon and oxygen isotope uptake into calcite crystals grown on laboratory timescales. In our experiments, dissolved inorganic carbon (DIC) is added to an aqueous solution (15 mM CaCl2 + 5 mM NH4Cl) by CO2 bubbling. Once a critical supersaturation is reached, calcite crystals nucleate spontaneously and grow on the beaker walls. A key aspect of this experimental approach is that the ?13C of DIC is relatively constant throughout the crystal growth period, because there is a continuous supply of DIC from the CO2-bearing bubbles. Carbonic anhydrase, an enzyme promoting rapid equilibration of isotopes between DIC and water, was added to ensure that the solution remained isotopically equilibrated during calcite growth. We have conducted experiments at T = 25C and pH = 8.3 - 9.0. We observe that the fractionation of oxygen isotopes between calcite and water decreases with increasing pH, consistent with available data from experiments in which the enzyme carbonic anhydrase was used. Our results for carbon isotopes extend the available data set, which previously ranged from pH 6.62 to 7.75, to higher pH. At pH 8.3, we observe that calcite is isotopically heavier than DIC with respect to carbon isotopes by about 0.25. At pH 9.0, calcite is isotopically indistinguishable from, or perhaps slightly lighter than, DIC. We will present data from additional high-pH experiments and discuss the results in the context of recently developed ion-by-ion growth models for calcite.

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

    USGS Publications Warehouse

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

    1990-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Meyer, H. J.

    1984-05-01

    The effects of 34 different additives on the growth rate of calcite were investigated. An initial growth rate of about one crystal monolayer (3 10 -8 cm) per minute was adjusted at a constant supersaturation which was maintained by a control circuit. Then the impurity was added step by step and the reduction of the growth rate was measured. The impurity concentration necessary to reduce the initial growth rate by a certain percentage increased in the order Fe 2+, ATP, P 3O 5-10, P 2O 4-7, (PO 3) 6-6, Zn 2+, ADP, Ce 3+, Pb 2+, carbamyl phosphate, Fe 3+, PO 3-4, Co 2+, Mn 2+, Be 2+, ?-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.

  3. Calcium isotope ratios in calcitic tests of benthic foraminifers

    NASA Astrophysics Data System (ADS)

    Gussone, Nikolaus; Filipsson, Helena L.

    2010-02-01

    We analysed Ca isotope ratios of the infaunal foraminiferal species Cassidulina laevigata, Elphidium spp., Gyroidinoides spp., and Uvigerina peregrina as well as the epifaunal Cibicidoides wuellerstorfi over a depth-temperature gradient. The calcium isotope ratios of the benthic foraminifers' tests show a distinct anomaly around 4 C. This anomaly is observed in both epi- and infaunal species, but there are also characteristic differences between both. The ?44/40Ca characteristics of benthic foraminifers may be explained by the interference of temperature and carbonate chemistry of the fluid on Ca isotope fractionation. We suggest that Ca isotope composition of benthic foraminifer tests is dominantly controlled by temperature at temperatures higher than 5 C, while in the temperature range below 5 C, calcite saturation ( ?Cc) becomes an increasingly important controlling factor, due to the non linear shape of the ?Cc- ?44/40Ca relation of actively transported calcium. The potential applicability of Ca isotope ratios in benthic foraminifers for reconstruction of either temperatures or ?44/40Ca sw is limited by the complex fractionation pattern below 5 C. However, due to the minor temperature dependence in the temperature range above 5 C, benthic foraminifers might provide a possible alternative archive for ?44Ca sw avoiding some uncertainties associated with planktic records (relocation, habitat/calcification depth, short time climate variability) as long as a defined bottom water temperature above 5 C can be secured.

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

    PubMed

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

    2015-11-01

    Alkaline flocculation holds great potential as a low-cost harvesting method for marine microalgae biomass production. Alkaline flocculation is induced by an increase in pH and is related to precipitation of calcium and magnesium salts. In this study, we used the diatom Phaeodactylum tricornutum as model organism to study alkaline flocculation of marine microalgae cultured in seawater medium. Flocculation started when pH was increased to 10 and flocculation efficiency reached 90% when pH was 10.5, which was consistent with precipitation modeling for brucite or Mg(OH)2. Compared to freshwater species, more magnesium is needed to achieve flocculation (>7.5mM). Zeta potential measurements suggest that brucite precipitation caused flocculation by charge neutralization. When calcium concentration was 12.5mM, flocculation was also observed at a pH of 10. Zeta potential remained negative up to pH 11.5, suggesting that precipitated calcite caused flocculation by a sweeping coagulation mechanism. PMID:26310384

  5. Ultrasonic Observation of the Calcite-Aragonite Transition

    NASA Technical Reports Server (NTRS)

    Ahrens, T. J.; Katz, S.

    1963-01-01

    Elastic-wave velocities were measured as a function of pressure by ultrasonic pulse Interferometry in Solenhofen and Manilus limestone specimens to pressures of 27 and 38 kb. Longitudinal velocities decrease sharply from 5.3 km/sec at a mean pressure of 4 kb to a minimum of 4.8 km/sec at 8 kb. Transverse velocities decrease from 3.1 to 2.9 km/sec. At the minimum bulk and rigidity moduli are 25 and 20 per cent below their 4-kb values. A density increase of 1.7 per cent is associated with this minimum. The observed effects are attributed to the calcite-aragonite transition, and they may be due to an inherent property of the material, a component of which undergoes a polymorphic transition, the low- and high-pressure phases coexisting over a considerable pressure range. This may be an additional mechanism to account for low-velocity zones in the earth?s interior.

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

    NASA Astrophysics Data System (ADS)

    Rostom, Fatma; Ryne, Anja; Dysthe, Dag Kristian; Renard, Franois

    2013-01-01

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

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

    DOE PAGESBeta

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

    2015-08-20

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

  8. Multiple stage multiple filter hydrate store

    DOEpatents

    Bjorkman, H.K. Jr.

    1983-05-31

    An improved hydrate store for a metal halogen battery system is disclosed which employs a multiple stage, multiple filter means for separating the halogen hydrate from the liquid used in forming the hydrate. The filter means is constructed in the form of three separate sections which combine to substantially cover the interior surface of the store container. Exit conduit means is provided in association with the filter means for transmitting liquid passing through the filter means to a hydrate former subsystem. The hydrate former subsystem combines the halogen gas generated during the charging of the battery system with the liquid to form the hydrate in association with the store. Relief valve means is interposed in the exit conduit means for controlling the operation of the separate sections of the filter means, such that the liquid flow through the exit conduit means from each of the separate sections is controlled in a predetermined sequence. The three separate sections of the filter means operate in three discrete stages to provide a substantially uniform liquid flow to the hydrate former subsystem during the charging of the battery system. The separation of the liquid from the hydrate causes an increase in the density of the hydrate by concentrating the hydrate along the filter means. 7 figs.

  9. Multiple stage multiple filter hydrate store

    DOEpatents

    Bjorkman, Jr., Harry K. (Birmingham, MI)

    1983-05-31

    An improved hydrate store for a metal halogen battery system is disclosed which employs a multiple stage, multiple filter means or separating the halogen hydrate from the liquid used in forming the hydrate. The filter means is constructed in the form of three separate sections which combine to substantially cover the interior surface of the store container. Exit conduit means is provided in association with the filter means for transmitting liquid passing through the filter means to a hydrate former subsystem. The hydrate former subsystem combines the halogen gas generated during the charging of the battery system with the liquid to form the hydrate in association with the store. Relief valve means is interposed in the exit conduit means for controlling the operation of the separate sections of the filter means, such that the liquid flow through the exit conduit means from each of the separate sections is controlled in a predetermined sequence. The three separate sections of the filter means operate in three discrete stages to provide a substantially uniform liquid flow to the hydrate former subsystem during the charging of the battery system. The separation of the liquid from the hydrate causes an increase in the density of the hydrate by concentrating the hydrate along the filter means.

  10. Gas hydrate cool storage system

    DOEpatents

    Ternes, Mark P. (Knoxville, TN); Kedl, Robert J. (Oak Ridge, TN)

    1985-01-01

    This invention is a process for formation of a gas hydrate to be used as a cool storage medium using a refrigerant in water. Mixing of the immiscible refrigerant and water is effected by addition of a surfactant and agitation. The difficult problem of subcooling during the process is overcome by using the surfactant and agitation and performance of the process significantly improves and approaches ideal.

  11. Pre-desilication and digestion of gibbsitic bauxite with lime in sodium aluminate liquor

    NASA Astrophysics Data System (ADS)

    Pan, Xiao-lin; Yu, Hai-yan; Dong, Kai-wei; Tu, Gan-feng; Bi, Shi-wen

    2012-11-01

    The effect of lime on the pre-desilication and digestion of gibbsitic bauxite in synthetic sodium aluminate liquor at different temperatures was investigated. The bauxite is comprised of gibbsite, aluminogoethite, hematite, kaolin, quartz, and minor boehmite. Lime increases the desilication efficiency of the bauxite during the pre-desilication process by promoting the conversion of sodalite and cancrinite to hydrogarnet. Desilication reactions during the digestion process promoted by lime result in the loss of Al2O3 entering the red mud, but the amount of aluminogoethite-to-hematite conversion promoted by lime leads to the increase of aluminogoethitic Al2O3 entering the digested liquor. The alumina digestion rate at 245C is higher than that at 145C due to the more pronounced conversion of aluminogoethite to hematite. The soda consumption during the digestion process decreases due to lime addition, especially at higher temperatures.

  12. Gas hydrates: Technology status report

    SciTech Connect

    Not Available

    1987-01-01

    In 1983, the US Department of Energy (DOE) assumed the responsibility for expanding the knowledge base and for developing methods to recover gas from hydrates. These are ice-like mixtures of gas and water where gas molecules are trapped within a framework of water molecules. This research is part of the Unconventional Gas Recovery (UGR) program, a multidisciplinary effort that focuses on developing the technology to produce natural gas from resources that have been classified as unconventional because of their unique geologies and production mechanisms. Current work on gas hydrates emphasizes geological studies; characterization of the resource; and generic research, including modeling of reservoir conditions, production concepts, and predictive strategies for stimulated wells. Complementing this work is research on in situ detection of hydrates and field tests to verify extraction methods. Thus, current research will provide a comprehensive technology base from which estimates of reserve potential can be made, and from which industry can develop recovery strategies. 7 refs., 3 figs., 6 tabs.

  13. Micelle Structure and Hydrophobic Hydration.

    PubMed

    Long, Joshua A; Rankin, Blake M; Ben-Amotz, Dor

    2015-08-26

    Despite the ubiquity and utility of micelles self-assembled from aqueous surfactants, longstanding questions remain regarding their surface structure and interior hydration. Here we combine Raman spectroscopy with multivariate curve resolution (Raman-MCR) to probe the hydrophobic hydration of surfactants with various aliphatic chain lengths, and either anionic (carboxylate) or cationic (trimethylammonium) head groups, both below and above the critical micelle concentration. Our results reveal significant penetration of water into micelle interiors, well beyond the first few carbons adjacent to the headgroup. Moreover, the vibrational C-D frequency shifts of solubilized deuterated n-hexane confirm that it resides in a dry, oil-like environment (while the localization of solubilized benzene is sensitive to headgroup charge). Our findings imply that the hydrophobic core of a micelle is surrounded by a highly corrugated surface containing hydrated non-polar cavities whose depth increases with increasing surfactant chain length, thus bearing a greater resemblance to soluble proteins than previously recognized. PMID:26222042

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

    NASA Astrophysics Data System (ADS)

    Purgstaller, Bettina; Mavromatis, Vasileios; Dietzel, Martin

    2015-04-01

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

  15. Fundamentals and applications of gas hydrates.

    PubMed

    Koh, Carolyn A; Sloan, E Dendy; Sum, Amadeu K; Wu, David T

    2011-01-01

    Fundamental understanding of gas hydrate formation and decomposition processes is critical in many energy and environmental areas and has special importance in flow assurance for the oil and gas industry. These areas represent the core of gas hydrate applications, which, albeit widely studied, are still developing as growing fields of research. Discovering the molecular pathways and chemical and physical concepts underlying gas hydrate formation potentially can lead us beyond flowline blockage prevention strategies toward advancing new technological solutions for fuel storage and transportation, safely producing a new energy resource from natural deposits of gas hydrates in oceanic and arctic sediments, and potentially facilitating effective desalination of seawater. The state of the art in gas hydrate research is leading us to new understanding of formation and dissociation phenomena that focuses on measurement and modeling of time-dependent properties of gas hydrates on the basis of their well-established thermodynamic properties. PMID:22432618

  16. Development of Alaskan gas hydrate resources

    SciTech Connect

    Kamath, V.A.; Sharma, G.D.; Patil, S.L.

    1991-06-01

    The research undertaken in this project pertains to study of various techniques for production of natural gas from Alaskan gas hydrates such as, depressurization, injection of hot water, steam, brine, methanol and ethylene glycol solutions through experimental investigation of decomposition characteristics of hydrate cores. An experimental study has been conducted to measure the effective gas permeability changes as hydrates form in the sandpack and the results have been used to determine the reduction in the effective gas permeability of the sandpack as a function of hydrate saturation. A user friendly, interactive, menu-driven, numerical difference simulator has been developed to model the dissociation of natural gas hydrates in porous media with variable thermal properties. A numerical, finite element simulator has been developed to model the dissociation of hydrates during hot water injection process.

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

    ERIC Educational Resources Information Center

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

    1979-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

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

    USGS Publications Warehouse

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

    1989-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2011-03-01

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

  1. Experimental investigation of surface energy and subcritical crack growth in calcite

    NASA Astrophysics Data System (ADS)

    RYne, Anja; Bisschop, Jan; Dysthe, Dag Kristian

    2011-04-01

    Subcritical cracking behavior and surface energies are important factors in geological processes, as they control time-dependent brittle processes and the long-term stability of rocks. In this paper, we present experimental data on subcritical cracking in single calcite crystals exposed to glycol-water mixtures with varying water content. We find upper bounds for the surface energy of calcite that decrease with increasing water concentration and that are systematically lower than values obtained from molecular dynamics simulations. The relation of surface energy to water concentration can explain water weakening in chalks. The rate of subcritical crack growth in calcite is well described by a reaction rate model. The effect of increasing water on crack velocity is to lower the threshold energy release rate required for crack propagation. The slope of the crack velocity curve remains unaffected, something which strongly suggests that the mechanism for subcritical cracking in calcite does not depend on the water concentration.

  2. Strain improvement of Sporosarcina pasteurii for enhanced urease and calcite production.

    PubMed

    Achal, V; Mukherjee, A; Basu, P C; Reddy, M Sudhakara

    2009-07-01

    Phenotypic mutants of Sporosarcina pasteurii (previously known as Bacillus pasteurii) (MTCC 1761) were developed by UV irradiation to test their ability to enhance urease activity and calcite production. Among the mutants, Bp M-3 was found to be more efficient compared to other mutants and wild-type strain. It produced the highest urease activity and calcite production compared to other isolates. The production of extracellular polymeric substances and biofilm was also higher in this mutant than other isolates. Microbial sand plugging results showed the highest calcite precipitation by Bp M-3 mutant. Scanning electron micrography, energy-dispersive X-ray and X-ray diffraction analyses evidenced the direct involvement of bacteria in CaCO3 precipitation. This study suggests that calcite production by the mutant through biomineralization processes is highly effective and may provide a useful strategy as a sealing agent for filling the gaps or cracks and fissures in any construction structures. PMID:19408027

  3. Kinetic and Thermodynamic Study of Calcite Marble Samples from Lesser Himalayas

    NASA Astrophysics Data System (ADS)

    Fahad, M.; Iqbal, Y.

    2014-02-01

    A kinetic and thermodynamic study of selected calcite marble samples from Lesser Himalayas has been performed using thermogravimetric and differential thermal analyses at heating rates of and . The minero-petrography of calcite grains, phase analysis, chemical analysis, and minor impurities determination were carried out using thin-section polarized light microscopy, X-ray diffraction, X-ray fluorescence, and electron microprobe analysis, respectively. The calcite content of the investigated marble samples varied from 97.50 mass% to 98.70 mass%. The activation energy, , for the decomposition process increased from to and from to for heating rates of and , respectively, with decreasing calcite content. The activation energy values obtained in the present study were in good agreement with previous studies.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  5. The promotion effect of coexisting hygroscopic composition on the reaction between oxalic acid and calcite during humidifying process

    NASA Astrophysics Data System (ADS)

    Ma, Q.; He, H.

    2012-12-01

    Internally mixed oxalic acid with mineral dust has been frequently detected in field measurements (Sullivan and Prather, 2007; Wang et al., 2012; Yang et al., 2009). Meanwhile, Furukawa and Takahashi (Furukawa and Takahashi, 2011) found that most of the oxalic acid in mineral mixture is present as metal oxalate complexes in the aerosols, however, the formation mechanism of these complexes is not well known. It was reported that cloud process of H2C2O4/CaCO3 mixture could lead to the formation of calcium oxalate (Gierlus et al., 2012). Recently, we used Raman spectroscopy to investigate the hygroscopic behavior of H2C2O4/CaCO3 mixture below saturation condition as well as the effect of coexisting hygroscopic compositions, e.g. Ca(NO3)2, NaCl, NH4NO3, and (NH4)2SO4. It was found that there was no interaction between H2C2O4 and calcite without third component during humidifying process under ambient condition. In contrast, the presence of coexisting Ca(NO)3, NaCl, or NH4NO3 could promote the reaction between H2C2O4 and calcite by providing an aqueous circumstance after deliquescence, resulting in the formation of calcium oxalate hydrates. Moreover, substitution of strong acid (HNO3) by medium acid (H2C2O4) occurred when water vapor was absorbed in Ca(NO3)2/H2C2O4 mixture (Ma and He, 2012). As for (NH4)2SO4, there existed a competition effect between (NH4)2SO4 and H2C2O4 for the reaction with CaCO3. CaCO3 was preferentially reacted with (NH4)2SO4 to form gypsum in the solution, while the residual NH4+ and C2O42- ions were bonded to (NH4)2C2O4 after efflorescence. These results implies a potential formation pathway of metal oxalate complexes in the atmosphere and also suggests that synergistic effect between different constituents in humidifying process of mixed particles should be considered in future hygroscopic behavior studies.

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

    USGS Publications Warehouse

    Busenberg, E.; Niel, Plummer L.

    1985-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2014-05-01

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

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

    NASA Astrophysics Data System (ADS)

    Neal, Colin

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

  10. Calcite genesis in the Upper Freeport coal bed as indicated by stable isotope geochemistry

    SciTech Connect

    Dulong, F.T.; Spiker, E.C.; Cecil, C.B.; Stanton, R.W.

    1985-01-01

    The grinding and sizing in float-sink testing of the Upper Freeport coal bed physically separates calcite of different origins. The different origins are distinguished by different isotopic compositions. The isotopic compositions of calcite indicates at least two, possibly three, stages of calcite formation in the Upper Freeport coal bed. Calcite samples obtained from cleat, and isolated from 8x100 mesh-1.8 specific gravity sink fraction and -100 mesh size fraction, are enriched in /sup 13/C. The dispersion in /sup 18/O values for all three sample types, as measured by the standard deviation, is 2.7 per mil relative to SMOW, which may indicate similar temperature of formation. In contrast, calcite from the 1.275 specific gravity float fraction is depleted in /sup 13/C (mean = -4.6 per mil), indicative of CO/sub 2/ generated from the oxidation of organic matter. The standard deviation of /sup 18/O values for these samples is 9.2 per mil, probably indicating variation in the temperature of formation. Limestone samples associated with the Upper Freeport coal bed are slightly depleted in /sup 13/C (mean = -3.1 per mil). Genesis of calcite in the coal apparently resulted from biotic, as well as, thermogenic processes. A second stage of calcite formation, resulting from fermentation and methanogenesis is in cleat, and in the 8x100 mesh-1.8 specific gravity sink and -100 mesh size fractions. Part of the calcite in the 1.275 specific gravity float fraction may have formed from thermally generated CO/sub 2/ released during coalification.

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

    USGS Publications Warehouse

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

    2005-01-01

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

  12. Experimental study of the aragonite to calcite transition in aqueous solution

    NASA Astrophysics Data System (ADS)

    Perdikouri, Christina; Kasioptas, Argyrios; Geisler, Thorsten; Schmidt, Burkhard C.; Putnis, Andrew

    2011-10-01

    The experimental replacement of aragonite by calcite was studied under hydrothermal conditions at temperatures between 160 and 200 C using single inorganic aragonite crystals as a starting material. The initial saturation state and the total [Ca 2+]:[CO 32-] ratio of the experimental solutions was found to have a determining effect on the amount and abundance of calcite overgrowths as well as the extent of replacement observed within the crystals. The replacement process was accompanied by progressive formation of cracks and pores within the calcite, which led to extended fracturing of the initial aragonite. The overall shape and morphology of the parent aragonite crystal were preserved. The replaced regions were identified with scanning electron microscopy and Raman spectroscopy. Experiments using carbonate solutions prepared with water enriched in 18O (97%) were also performed in order to trace the course of this replacement process. The incorporation of the heavier oxygen isotope in the carbonate molecule within the calcite replacements was monitored with Raman spectroscopy. The heterogeneous distribution of 18O in the reaction products required a separate study of the kinetics of isotopic equilibration within the fluid to obtain a better understanding of the 18O distribution in the calcite replacement. An activation energy of 109 kJ/mol was calculated for the exchange of oxygen isotopes between [C 16O 32-] aq and [H 218O] and the time for oxygen isotope exchange in the fluid at 200 C was estimated at 0.9 s. Given the exchange rate, analyses of the run products imply that the oxygen isotope composition in the calcite product is partly inherited from the oxygen isotope composition of the aragonite parent during the replacement process and is dependent on access of the fluid to the reaction interface rather than equilibration time. The aragonite to calcite fluid-mediated transformation is described by a coupled dissolution-reprecipitation mechanism, where aragonite dissolution is coupled to the precipitation of calcite at an inwardly moving reaction interface.

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

    SciTech Connect

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

    2009-01-01

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

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

    SciTech Connect

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

    2009-04-22

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

  15. Physical Properties of Gas Hydrates: A Review

    DOE PAGESBeta

    Gabitto, Jorge F.; Tsouris, Costas

    2010-01-01

    Memore » thane gas hydrates in sediments have been studied by several investigators as a possible future energy resource. Recent hydrate reserves have been estimated at approximately 10 16   m 3 of methane gas worldwide at standard temperature and pressure conditions. In situ dissociation of natural gas hydrate is necessary in order to commercially exploit the resource from the natural-gas-hydrate-bearing sediment. The presence of gas hydrates in sediments dramatically alters some of the normal physical properties of the sediment. These changes can be detected by field measurements and by down-hole logs. An understanding of the physical properties of hydrate-bearing sediments is necessary for interpretation of geophysical data collected in field settings, borehole, and slope stability analyses; reservoir simulation; and production models. This work reviews information available in literature related to the physical properties of sediments containing gas hydrates. A brief review of the physical properties of bulk gas hydrates is included. Detection methods, morphology, and relevant physical properties of gas-hydrate-bearing sediments are also discussed.« less

  16. Excavation of methane hydrate using COIL

    NASA Astrophysics Data System (ADS)

    Josui, Kazuya; Miyakawa, Naoomi; Tei, Kazuyoku; Sugimoto, Daichi; Fujioka, Tomoo

    2006-02-01

    Methane hydrate is a energy resource distributed even in the resource-less countries such as Japan and India. The energy is necessary to extract the methane from the methane hydrate and COIL is the unique solution for the extraction tool, because fuels of COIL can be produced from the natural energy without the fossil energy resources. The experimental results of laser light-methane hydrate interaction, multi kW laser light transmission through 1 km optical fiber, and the estimation of the extracted methane by radiation of the multi hundreds kW COIL output on the methane hydrate layer, will be reported.

  17. Desalination utilizing clathrate hydrates (LDRD final report).

    SciTech Connect

    Simmons, Blake Alexander; Bradshaw, Robert W.; Dedrick, Daniel E.; Cygan, Randall Timothy; Greathouse, Jeffery A.; Majzoub, Eric H.

    2008-01-01

    Advances are reported in several aspects of clathrate hydrate desalination fundamentals necessary to develop an economical means to produce municipal quantities of potable water from seawater or brackish feedstock. These aspects include the following, (1) advances in defining the most promising systems design based on new types of hydrate guest molecules, (2) selection of optimal multi-phase reactors and separation arrangements, and, (3) applicability of an inert heat exchange fluid to moderate hydrate growth, control the morphology of the solid hydrate material formed, and facilitate separation of hydrate solids from concentrated brine. The rate of R141b hydrate formation was determined and found to depend only on the degree of supercooling. The rate of R141b hydrate formation in the presence of a heat exchange fluid depended on the degree of supercooling according to the same rate equation as pure R141b with secondary dependence on salinity. Experiments demonstrated that a perfluorocarbon heat exchange fluid assisted separation of R141b hydrates from brine. Preliminary experiments using the guest species, difluoromethane, showed that hydrate formation rates were substantial at temperatures up to at least 12 C and demonstrated partial separation of water from brine. We present a detailed molecular picture of the structure and dynamics of R141b guest molecules within water cages, obtained from ab initio calculations, molecular dynamics simulations, and Raman spectroscopy. Density functional theory calculations were used to provide an energetic and molecular orbital description of R141b stability in both large and small cages in a structure II hydrate. Additionally, the hydrate of an isomer, 1,2-dichloro-1-fluoroethane, does not form at ambient conditions because of extensive overlap of electron density between guest and host. Classical molecular dynamics simulations and laboratory trials support the results for the isomer hydrate. Molecular dynamics simulations show that R141b hydrate is stable at temperatures up to 265K, while the isomer hydrate is only stable up to 150K. Despite hydrogen bonding between guest and host, R141b molecules rotated freely within the water cage. The Raman spectrum of R141b in both the pure and hydrate phases was also compared with vibrational analysis from both computational methods. In particular, the frequency of the C-Cl stretch mode (585 cm{sup -1}) undergoes a shift to higher frequency in the hydrate phase. Raman spectra also indicate that this peak undergoes splitting and intensity variation as the temperature is decreased from 4 C to -4 C.

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

    NASA Astrophysics Data System (ADS)

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

    2003-05-01

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

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

    PubMed

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

    2014-11-28

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

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

    SciTech Connect

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

    2014-11-28

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

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

    PubMed

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

    2003-01-01

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

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

    USGS Publications Warehouse

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

    2003-01-01

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

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

    SciTech Connect

    Mitchell-Tapping, H.J.

    1983-09-01

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

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

    SciTech Connect

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

    1991-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-10-01

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

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

    SciTech Connect

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

    2010-12-01

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

  7. Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

    USGS Publications Warehouse

    Lee, J.Y.; Yun, T.S.; Santamarina, J.C.; Ruppel, C.

    2007-01-01

    The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

  8. Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

    ERIC Educational Resources Information Center

    Barlag, Rebecca; Nyasulu, Frazier

    2011-01-01

    The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such

  9. Observations related to tetrahydrofuran and methane hydrates for laboratory studies of hydrate-bearing sediments

    NASA Astrophysics Data System (ADS)

    Lee, J. Y.; Yun, T. S.; Santamarina, J. C.; Ruppel, C.

    2007-06-01

    The interaction among water molecules, guest gas molecules, salts, and mineral particles determines the nucleation and growth behavior of gas hydrates in natural sediments. Hydrate of tetrahydrofuran (THF) has long been used for laboratory studies of gas hydrate-bearing sediments to provide close control on hydrate concentrations and to overcome the long formation history of methane hydrate from aqueous phase methane in sediments. Yet differences in the polarizability of THF (polar molecule) compared to methane (nonpolar molecule) raise questions about the suitability of THF as a proxy for methane in the study of hydrate-bearing sediments. From existing data and simple macroscale experiments, we show that despite its polar nature, THF's large molecular size results in low permittivity, prevents it from dissolving precipitated salts, and hinders the solvation of ions on dry mineral surfaces. In addition, the interfacial tension between water and THF hydrate is similar to that between water and methane hydrate. The processes that researchers choose for forming hydrate in sediments in laboratory settings (e.g., from gas, liquid, or ice) and the pore-scale distribution of the hydrate that is produced by each of these processes likely have a more pronounced effect on the measured macroscale properties of hydrate-bearing sediments than do differences between THF and methane hydrates themselves.

  10. Waters of Hydration of Cupric Hydrates: A Comparison between Heating and Absorbance Methods

    ERIC Educational Resources Information Center

    Barlag, Rebecca; Nyasulu, Frazier

    2011-01-01

    The empirical formulas of four cupric hydrates are determined by measuring the absorbance in aqueous solution. The Beer-Lambert Law is verified by constructing a calibration curve of absorbance versus known Cu[superscript 2+](aq) concentration. A solution of the unknown hydrate is prepared by using 0.2-0.3 g of hydrate, and water is added such…

  11. The conversion process of hydrocarbon hydrates into CO2 hydrates and vice versa: thermodynamic considerations.

    PubMed

    Schicks, J M; Luzi, M; Beeskow-Strauch, B

    2011-11-24

    Microscopy, confocal Raman spectroscopy and powder X-ray diffraction (PXRD) were used for in situ investigations of the CO(2)-hydrocarbon exchange process in gas hydrates and its driving forces. The study comprises the exposure of simple structure I CH(4) hydrate and mixed structure II CH(4)-C(2)H(6) and CH(4)-C(3)H(8) hydrates to gaseous CO(2) as well as the reverse reaction, i.e., the conversion of CO(2)-rich structure I hydrate into structure II mixed hydrate. In the case of CH(4)-C(3)H(8) hydrates, a conversion in the presence of gaseous CO(2) from a supposedly more stable structure II hydrate to a less stable structure I CO(2)-rich hydrate was observed. PXRD data show that the reverse process requires longer initiation times, and structural changes seem to be less complete. Generally, the exchange process can be described as a decomposition and reformation process, in terms of a rearrangement of molecules, and is primarily induced by the chemical potential gradient between hydrate phase and the provided gas phase. The results show furthermore the dependency of the conversion rate on the surface area of the hydrate phase, the thermodynamic stability of the original and resulting hydrate phase, as well as the mobility of guest molecules and formation kinetics of the resulting hydrate phase. PMID:21928801

  12. Incorporation of ammonium fluoride into clathrate hydrate lattices and its significance in inhibiting hydrate formation.

    PubMed

    Park, Seongmin; Lim, Dongwook; Seo, Yongwon; Lee, Huen

    2015-05-25

    The stability of hydrate frameworks is influenced by guest molecules capable of hydrogen bonding with surrounding water molecules. Four remarkable features from the ammonium fluoride incorporation into a crystalline hydrate matrix provide important information on the thermodynamic stability, formation kinetics, structural characteristics, and molecular behavior in clathrate hydrate systems. PMID:25913716

  13. INDEX OF REFRACTION OF SHOCK LOADED SODA-LIME GLASS

    SciTech Connect

    Alexander, C. S.

    2009-12-28

    Soda-lime glass (SLG) is a potential low-cost VISAR window for use at moderate shock pressures (up to 2430 GPa) where the material remains transparent. In order for SLG to be practical as a VISAR window, the correction factor, which describes the frequency correction related to the strain dependence of the refractive index, and hence the index of refraction itself, must be characterized as a function of pressure. Characterization data are reported in this paper and compared to previous results. The present data show good agreement with those of Dandekar [J. Appl. Phys. 84, 6614 (1998)] and separate study results by Gibbons and Ahrens [J. Geophys. Res. 76, 5489 (1971)] up to 7 GPa. However, at stresses over 7 GPa, marked discrepancies are evident between the present data and that of Gibbons and Ahrens. Differences in test methods may explain these discrepancies.

  14. Fragrance mix reactions and lime allergic contact dermatitis.

    PubMed

    Swerdlin, Amy; Rainey, David; Storrs, Frances J

    2010-01-01

    Allergic contact dermatitis due to citrus fruits is rare, but has been reported in cooks and bartenders. We report an interesting case of a bartender with hand dermatitis who had an allergic contact sensitivity to lime peel, fragrance mix I, and fragrance mix II. Most reported cases of citrus peel allergy are due to d-limonene, which makes up the majority of the peel oil. However, our patient had an allergic reaction to geraniol, which is a minor component of the peel oil and is present in fragrance mix I. It is important to consider a contact sensitivity to citrus in patients who have positive reactions to fragrance mix I and II and who are occupationally exposed to citrus fruits. An initial positive reaction to fragrance mixes should prompt further testing to citrus in these individuals. PMID:20646673

  15. Dispersion of thermooptic coefficients of soda-lime-silica glasses

    SciTech Connect

    Ghosh, G.

    1995-01-01

    The thermooptic coefficients, i.e., the variation of refractive index with temperature (dn/dT), are analyzed in a physically meaningful model for two series of soda-lime-silica glasses. 25Na{sub 2}O{center_dot}xCaO{center_dot}(75 {minus} x)SiO{sub 2} and (25 {minus} x)Na{sub 2}O{center_dot}xCaO {center_dot} 75SiO{sub 2}. This model is based on three physical parameters--the thermal expansion coefficient and excitonic and isentropic optical bands that are in the vacuum ultraviolet region--instead of on consideration of the temperature coefficient of electronic polarizability, as suggested in 1960. This model is capable of predicting and analyzing the thermooptic coefficients throughout the transmission region of the optical glasses at any operating temperature.

  16. National uranium resource evaluation, Lime Hills Quadrangle, Alaska

    SciTech Connect

    Hinderman, T.K.

    1982-04-01

    The Lime Hills Quadrangle in south-central Alaska was evaluated to identify geologic environments favorable for the occurrence of uranium. The study used data from aerial radiometric surveys, geochemical sampling, published geologic maps, and ground geologic examinations. A small drainage at the head of the Post River in the northeastern part of the quadrangle was found to be favorable for the occurrence of fluvial placer uranium deposits. Samples of black sand from the area contained up to 0.7% U/sub 3/O/sub 8/. Quaternary gravels elsewhere in the quadrangle may also have placer potential; at the present time they are unevaluated. Anomalous concentrations of uranium, up to 540 ppM U/sub 3/O/sub 8/, occur in stream sediments collected from drainages of the south end of the Tired Pup batholith. The region is considered favorable for the occurrence of supergene uranium mineralization, probably of the authigenic type.

  17. Low Velocity Sphere Impact of a Soda Lime Silicate Glass

    SciTech Connect

    Wereszczak, Andrew A; Fox, Ethan E; Morrissey, Timothy G; Vuono, Daniel J

    2011-10-01

    This report summarizes TARDEC-sponsored work at Oak Ridge National Laboratory (ORNL) during the FY11 involving low velocity (< 30 m/s or < 65 mph) ball impact testing of Starphire soda lime silicate glass. The intent was to better understand low velocity impact response in the Starphire for sphere densities that bracketed that of rock. Five sphere materials were used: borosilicate glass, soda-lime silicate glass, steel, silicon nitride, and alumina. A gas gun was fabricated to produce controlled velocity delivery of the spheres against Starphire tile targets. Minimum impact velocities to initiate fracture in the Starphire were measured and interpreted in context to the kinetic energy of impact and the elastic property mismatch between the any of the five sphere-Starphire-target combinations. The primary observations from this low velocity (< 30 m/s or < 65 mph) testing were: (1) Frictional effects contribute to fracture initiation. (2) Spheres with a lower elastic modulus require less force to initiate fracture in the Starphire than spheres with a higher elastic modulus. (3) Contact-induced fracture did not initiate in the Starphire SLS for impact kinetic energies < 150 mJ. Fracture sometimes initiated or kinetic energies between {approx} 150-1100 mJ; however, it tended to occur when lower elastic modulus spheres were impacting it. Contact-induced fracture would always occur for impact energies > 1100 mJ. (4) The force necessary to initiate contact-induced fracture is higher under dynamic or impact conditions than it is under quasi-static indentation conditions. (5) Among the five used sphere materials, silicon nitride was the closest match to 'rock' in terms of both density and (probably) elastic modulus.

  18. Landfill methane oxidation response to vegetation, fertilization, and liming

    SciTech Connect

    Hilger, H.A.; Wollum, A.G.; Barlaz, M.A.

    2000-02-01

    Landfills are the fourth largest global source and the largest US source (USDOE, 1997) of anthropogenic CH{sub 4} emissions. Since gram-for-gram, CH{sub 4} has 21 times the 100-yr global-warming potential of CO{sub 2} (USEPA, 1990). CH{sub 4} release into the atmosphere has important implications for global climate change. This study was conducted to evaluate the effects of vegetation, N fertilizers, and lime addition on landfill CH{sub 4} oxidation. Columns filled with compacted sandy loam and sparged with synthetic landfill gas were used to simulate a landfill cover. Grass-topped and bare-soil columns reduced inlet CH{sub 4} by 47 and 37%, respectively, at peak uptake; but the rate for both treatments was about 18% at steady state. Nitrate and NH{sub 4} amendments induced a more rapid onset of CH{sub 4} oxidation relative to KCl controls. However, at steady state, NH{sub 4} inhibited CH{sub 4} oxidation in bare columns but not in grassed columns. Nitrate addition produced no inhibitory effects. Lime addition to the soil consistently enhanced CH{sub 4} oxidation. In all treatments, CH{sub 4} consumption increased to a peak value, then declined to a lower steady-state value; and all gassed columns developed a pH gradient. Neither nutrient depletion nor protozoan grazing could explain the decline from peak oxidation levels. Ammonium applied to grassed cover soil can cause transient reductions in CH{sub 4} uptake, but there is no evidence that the inhibition persists. The ability of vegetation to mitigate NH{sub 4} inhibition indicates that results from bare-soil tests may not always generalize to vegetated landfill caps.

  19. A coupled THMC model of a heating and hydration laboratory experiment in unsaturated compacted FEBEX bentonite

    SciTech Connect

    Zheng, L.; Samper, J.; Montenegro, L.; Fernandez, A.M.

    2010-05-01

    Unsaturated compacted bentonite is foreseen by several countries as a backfill and sealing material in high-level radioactive waste repositories. The strong interplays between thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes during the hydration stage of a repository call for fully coupled THMC models. Validation of such THMC models is prevented by the lack of comprehensive THMC experiments and the difficulties of experimental methods to measure accurately the chemical composition of bentonite porewater. We present here a non-isothermal multiphase flow and multicomponent reactive solute transport model for a deformable medium of a heating and hydration experiment performed on a sample of compacted FEBEX bentonite. Besides standard solute transport and geochemical processes, the model accounts for solute cross diffusion and thermal and chemical osmosis. Bentonite swelling is solved with a state-surface approach. The THM model is calibrated with transient temperature, water content and porosity data measured at the end of the experiment. The reactive transport model is calibrated with porewater chemical data derived from aqueous extract data. Model results confirm that thermal osmosis is relevant for the hydration of FEBEX bentonite while chemical osmosis can be safely neglected. Dilution and evaporation are the main processes controlling the concentration of conservative species. Dissolved cations are mostly affected by calcite dissolution-precipitation and cation exchange reactions. Dissolved sulphate is controlled by gypsum/anhydrite dissolution-precipitation. pH is mostly buffered by protonation/deprotonation via surface complexation. Computed concentrations agree well with inferred aqueous extract data at all sections except near the hydration boundary where cation data are affected by a sampling artifact. The fit of Cl{sup -} data is excellent except for the data near the heater. The largest deviations of the model from inferred aqueous extract data occur for dissolved SO{sub 4}{sup 2-} which is underpredicted by the model. There are uncertainties on the amount of gypsum available for dissolution and its dissolution mechanism (kinetics or local equilibrium).

  20. A coupled THMC model of a heating and hydration laboratory experiment in unsaturated compacted FEBEX bentonite

    NASA Astrophysics Data System (ADS)

    Zheng, Liange; Samper, Javier; Montenegro, Luis; Fernndez, Ana Mara

    2010-05-01

    SummaryUnsaturated compacted bentonite is foreseen by several countries as a backfill and sealing material in high-level radioactive waste repositories. The strong interplays between thermal (T), hydrodynamic (H), mechanical (M) and chemical (C) processes during the hydration stage of a repository call for fully coupled THMC models. Validation of such THMC models is prevented by the lack of comprehensive THMC experiments and the difficulties of experimental methods to measure accurately the chemical composition of bentonite porewater. We present here a non-isothermal multiphase flow and multicomponent reactive solute transport model for a deformable medium of a heating and hydration experiment performed on a sample of compacted FEBEX bentonite. Besides standard solute transport and geochemical processes, the model accounts for solute cross diffusion and thermal and chemical osmosis. Bentonite swelling is solved with a state-surface approach. The THM model is calibrated with transient temperature, water content and porosity data measured at the end of the experiment. The reactive transport model is calibrated with porewater chemical data derived from aqueous extract data. Model results confirm that thermal osmosis is relevant for the hydration of FEBEX bentonite while chemical osmosis can be safely neglected. Dilution and evaporation are the main processes controlling the concentration of conservative species. Dissolved cations are mostly affected by calcite dissolution-precipitation and cation exchange reactions. Dissolved sulphate is controlled by gypsum/anhydrite dissolution-precipitation. pH is mostly buffered by protonation/deprotonation via surface complexation. Computed concentrations agree well with inferred aqueous extract data at all sections except near the hydration boundary where cation data are affected by a sampling artifact. The fit of Cl - data is excellent except for the data near the heater. The largest deviations of the model from inferred aqueous extract data occur for dissolved SO42- which is underpredicted by the model. There are uncertainties on the amount of gypsum available for dissolution and its dissolution mechanism (kinetics or local equilibrium).

  1. Stabilization of Oklahoma expensive soils using lime and class C fly ash

    SciTech Connect

    Buhler, R.L.; Cerato, A.B.

    2007-01-15

    This study uses lime and class C fly ash, an industrial byproduct of electric power production produced from burning lignite and subbituminous coal, to study the plasticity reduction in highly expensive natural clays from Idabel, Oklahoma. This study is important, especially in Oklahoma, because most of the native soils are expansive and cause seasonal damage to roadways and structures. The addition of lime or fly ash helps to arrest the shrinkage and swelling behavior of soil. Four soil samples with the same AASHTO classification were used in this study to show shrinkage variability within a soil group with the addition of lime and class C fly ash. The plasticity reduction in this study was quantified using the linear shrinkage test. It was found that soils classified within the same AASHTO group had varying shrinkage characteristics. It was also found that both lime and fly ash reduced the lienar shrinkage, however, the addition of lime reduced the linear shrinkage to a greater degree than the same percentage of class C fly ash. Even though it takes much less lime than fly ash to reduce the plasticity of a highly expansive soil, it may be less expensive to utilize fly ash, which is a waste product of electric power production. Lime also has a lower unit weight than fly ash so weight percentage results may be misleading.

  2. [Wet FGD process on rotating-stream-tray tower with magnesium-enhanced lime].

    PubMed

    Sun, W; Wu, Z; Tan, T

    2001-05-01

    Wet flue gas desulfurization(FGD) process with magnesium-enhanced lime slurry was conducted on a rotating-stream-tray tower. Changes of SO2 removal efficiency and slurry pH with time were experimentally determined. Effects of magnesium sulfate concentration were investigated and the lime utilization was calculated according to experimental data. In comparison with lime FGD process, adding magnesium sulfate could effectively enhance SO2 removal efficiency; when the adequate magnesium sulfate concentration was 0.2 mol/L, the removal efficiency was more than 60% with two rotating-stream-trays, while the removal efficiency of lime process was only 45%. To achieve higher SO2 removal efficiency, the slurry pH should be controlled between 6.0 and 7.5. Magnesium sulfate could also promote lime dissolution, slow down descent of slurry pH and increase lime utilization; when magnesium sulfate concentration was 0.2 mol/L, lime utilization could be increased by more than 5 percentage point under adequate conditions. PMID:11507892

  3. Liming as an advanced treatment for sludge sanitisation: helminth eggs elimination--Ascaris eggs as model.

    PubMed

    Capizzi-Banas, S; Deloge, M; Remy, M; Schwartzbrod, J

    2004-01-01

    The presence of helminth eggs (Ascaris eggs) in sewage sludge may constitute a sanitary risk when used as agricultural fertiliser. Sanitisation of sewage sludge can be achieved by treatment with quick lime, a process that destroys sludge pathogens in two ways: pH increase and temperature rise. Among the pathogens of epidemiological relevance, Ascaris eggs are the most resistant to liming, and, hence, may serve as indicators of hygienic quality of biosolids. This research aims at defining, between 50 degrees C and 60 degrees C, the time required in the case of limed sludge to obtain a product with a negligible level of viable Ascaris eggs. To achieve this objective, investigations on inactivation kinetics of Ascaris eggs were conducted in the following products: contaminated milk of lime; naturally contaminated sludge treated with slaked lime and heat; naturally contaminated sludge treated with quick lime; and sludge treated at full scale with quick lime. For the inactivation kinetics where a negligible level of Ascaris eggs was reached, the inactivation threshold was determined. Depending on the experimental situation, the inactivation threshold period was found to fluctuate between 5 and 75 min at 55 degrees C and between 1 and 8 min at 60 degrees C. PMID:15276741

  4. Hydration of the stratum corneum.

    PubMed

    Batt, M D; Fairhurst, E

    1986-12-01

    Synopsis Topically applied water, occlusion and topically applied glycerol were used to investigate and characterize some of the changes which occur in the hydrated stratum corneum. The effects of these treatments were monitored using non-invasive techniques under controlled conditions. The Servomed Evaporimeter was used to determine natural water flux from the skin surface before and after treatment. The performance of the Evaporimeter in this type of study had previously been improved by attaching a paper baffle to the detector. This eliminated the variance in output caused by atmospheric movement. Experiments were carried out at temperatures below the threshold of thermal sweating and emotional sweating was minimized. Skin surface topography was characterized by means of a new type of profilometer. The instrument's design allowed a diamond stylus to traverse the living skin surface without significantly altering its structure. Changes in skin surface roughness were further elucidated using scanning electron microscopy and macrophotography. In vivo penetration of glycerol was assessed by chemical analysis of stratum corneum layers of treated skin. Samples were obtained by sequential stripping of the stratum corneum using adhesive tape. Topically applied water produced only a transient benefit because of rapid evaporation. More prolonged hydration was achieved by suppressing transepidermal water loss with polyethylene film. This occlusive hyperhydration was characterized by a significant reduction in profile roughness and by a smoother macroscopic appearance. Glycerol achieved the same effects by reducing the magnitude of the natural water flux from the skin surface and by reducing the rate of evaporation of water from applied aqueous glycerol solution or cosmetic product. Both effects were seen as the result of lowered water activity in the proximity of glycerol. Smoothing effects of glycerol on the skin surface, and improved appearance, persisted for at least 24 h. This persistence was explained by evidence for diffusion of glycerol into the stratum corneum where it formed a reservoir. Hydration of the skin is known to affect its barrier function and thereby exert a profound effect on penetration of both lipophilic and hydrophilic molecules. Clinically, this effect may be achieved using liberal applications of occlusive petroleum jelly and ointments. The results presented in this paper suggest that the use of humectants could achieve useful hydration using cosmetically acceptable materials. PMID:19457222

  5. Hydration management at the end of life.

    PubMed

    Lanuke, Kathryn; Fainsinger, Robin L; DeMoissac, Donna

    2004-04-01

    The management of parenteral hydration at the end of life remains controversial. The debate centers on whether and/or how often patients should be hydrated, the volume of hydration received, and the benefit verses side effects of parenteral hydration. In order to clarify the routine practice of physicians involved in the end-of-life care in Edmonton, Alberta, Canada, we investigated the routine management of hydration by attending physicians caring for patients dying in a palliative care unit (PCU) at Norwood Capital Care, and in acute care wards at the Royal Alexandra Hospital (RAH) both while receiving and while not receiving consult advice from the Palliative Care Program. We conducted a retrospective chart review of 50 consecutive patients who died in each of the 3 sites included in the study. Data from the last 7 days prior to and including the date of death (day 0) was recorded. The majority of patients at all sites received hydration. The volume of hydration ordered in the Norwood PCU site was significantly different compared to both RAH groups on all days studied (p < 0.005). The RAH palliative care group showed a trend for lower hydration volumes compared to the RAH acute care group with significant differences on days 1 and 2 (p < 0.05). Throughout the week, for all of the hydrated patients in the Norwood PCU site, hypodermoclysis (HDC) was ordered; for nearly all of the hydrated patients in the RAH acute care group, intravenous (IV) hydration was ordered; and for approximately one third of the hydrated RAH palliative care consult group HDC was ordered, and for the remainder IV hydration was ordered. The RAH acute care group represented the largest percentage of hydrated patients receiving diuretics while the Norwood hospice site represented the lowest. The data raise the possibility that more patients in the RAH acute care group were overhydrated and may have developed symptoms such as edema, ascites, and respiratory distress. This study suggests that hydration at the end of life is managed differently in different settings of care and highlights areas for education to improve management. PMID:15130203

  6. A natural hydrate dissolution experiment on complex multi-component hydrates on the sea floor

    NASA Astrophysics Data System (ADS)

    Hester, K. C.; Peltzer, E. T.; Walz, P. M.; Dunk, R. M.; Sloan, E. D.; Brewer, P. G.

    2009-11-01

    Dissolution of natural hydrate cores was measured using time-lapse photography on the seafloor at Barkley Canyon (850 m depth and 4.17 C). Two types of hydrate fabrics in close contact with one another were studied: a "yellow" hydrate stained with condensate oil and a "white" hydrate. From thermogenic origins, both fabrics contained methane as well as heavier hydrocarbons. These multi-component hydrates were calculated to be well within p- T stability conditions (<200 m water depth needed at 4.17 C). While stable in pressure and temperature, the hydrates were bathed in under-saturated seawater, which promoted dissolution. The flux of gas from the shrinking yellow hydrate core was 0.15 0.01 mmol gas/m 2 s, while the white hydrate dissolved faster at 0.25 0.02 mmol gas/m 2 s. To determine the controlling mechanism for the observed changes in the hydrate cores, experimental results were compared with an engineering correlation for convective mass transfer. Using water velocity as a fitting parameter, the correlation agreed well with results from a previous dissolution experiment on well-characterized synthetic hydrates. Even with a number of other unknowns, when applied to the natural hydrate, the mass transfer correlation predicted the dissolution rate within 20%. This seafloor-based experiment, along with visual observations of seafloor hydrate dissolution over a 3-day period, were used to further understand the fate of natural seafloor hydrates exposed on the seafloor. By showing that mass transfer is the rate-controlling mechanism for dissolution of these natural hydrate outcrops, proper hydrodynamic calculations can be employed to give a refined estimate on hydrate dissolution rates.

  7. Gas hydrates in ocean bottom sediments

    SciTech Connect

    MacLeod, M.K.

    1982-12-01

    Gas hydrates belong to a special category of chemical substances known as inclusion compounds. An inclusion compound is a physical combination of molecules in which one component becomes trapped inside the other. In gas hydrates, gas molecules are physically trapped inside an expanded lattice of water molecules. The pressures and temperatures beneath Artic water depths greater than 1,100 ft (335 m) and subtropical water depths greater than 2,000 ft (610 m) are suitable for the formation of methane hydrate. Theoretical depths to the base of a gas hydrate layer in ocean bottom sediments are determined by assuming: (1) a constant hydrostatic pressure gradient, (2) two typical hydrothermal gradients, (3) variable geothermal gradients, and (4) pure methane hydrated with connate seawater. In addition to pressure and geothermal gradient, other variables affecting the stability of gas hydrate are examined. These variables are hydrothermal gradient, sediment thermal conductivity, heat flow, hydrate velocity, gas composition, and connate water salinity. If these variables are constant in a lateral direction and the above assmptions are valid, a local geothermal gradient can be determined if the depth to the base of a gas hydrate is known. The base of the gas hydrate layer is seen on seismic profiles as an anomalous reflection nearly parallel to the ocean bottom, cross-cutting geologic bedding plane reflections, and generally increasing in sub-ocean bottom time with increasing water depth. The acoustic impedance is a result of the relatively fast velocity hydrate layer overlying slower velocity sediments. In addition, free gas may be trapped beneath the hydrate, thereby enhancing the reflection.

  8. Deep lime incorporation methods for neutralization of acidic minesoils. Final report, October 1987-May 1992

    SciTech Connect

    Dollhopf, D.J.

    1992-05-01

    There is concern that acidic minesoils limed to only the 30 cm depth may not provide sufficient root zone for either optimum plant growth or long-term plant establishment. It was shown that agricultural discs, chisel plows (subsoilers) and moldboard plows can incorporate lime efficiency to the 10 to 25 cm minesoil depth. One very large tandem disc having 91 cm diameter blades successfully neutralized acidic minesoil to the 30 cm depth. Tractors mounted rototillers commonly used in agricultural production can efficiently incorporate lime to the 25 cm minesoil depth.

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2009-04-01

    Fluoride is naturally abundant, encountered in rocks, soil and fresh and ocean water. Calcite crystals, during crystal growth may incorporate fluoride ions into their lattice (Okumura et al., 1983). In situ atomic force microscopy (AFM) has been used to study the growth and dissolution of calcite {104} surfaces in aqueous solutions in the presence of fluoride, using a fluid cell in which the supersaturated and the understaturated solutions respectively, flow over a freshly cleaved calcite crystal. For growth experiments, supersaturation index (S.I.) with respect to calcite was equal to 0.89 and the initial solution pH 10.2. The crystal growth rates were measured from the closure of the rhombohedral etch pits along the [010] direction induced by an initial dissolution step using pure water. The spreading rate of 2-dimensional nuclei was also measured along the same direction. In the presence of low fluoride concentrations (?0.33 mM), the crystal growth rate of calcite was unaffected. At higher concentrations (up to 5 mM) growth rate decreased substantially to 50% of the rate in the absence of fluoride. Potential fluoride sorption over the calcite surface may ascribe the decrease of growth rates. Dissolution experiments were conducted at pH= 7.2 and dissolution rates of calcite were measured from the spreading of rhombohedral etch pits along both [010] and [42] directions. The presence of low concentrations of fluoride (?1.1 mM) in the undersaturated solutions enhanced the dissolution rate along the [42] direction by 50% in comparison with pure water. The morphology of rhombohedral etch pits changed to hexagonal in the presence of fluoride in the undersaturated solutions. The AFM dissolution experiments suggested that the fluoride ions adsorbed onto the calcite surface. Further increase of fluoride concentrations (up to 1.6 mM) resulted in the decrease of the calcite dissolution rate by 60% in both [010] and [42] directions. Reference: Okumura, M, Kitano, Y., Idogaki, M., 1983. Inorporation of fluoride ions into calcite - Effect of organic materials and magnesium ions in a parent solution. Geochemical Journal 17, 257-263.

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

    SciTech Connect

    B. Peterman; R. Moscati

    2000-08-10

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

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

    NASA Astrophysics Data System (ADS)

    Candelier, Yael; Minoletti, Fabrice; Hermoso, Michael

    2013-04-01

    Previous works on the biogeochemistry of the ubiquist coccolithophore Calcidiscus leptoporus quantified an oxygen isotope fractionation of about -2.2 with respect to equilibrium. New cultures experiments and core top study of this taxon enable the calibration of the temperature dependance recorded in ?18O of this coccolith providing a new tool to decipher surfaces water temperatures through the Cenozoic. These findings, concordant in the two approaches show a reduced range of vital effect (-1.1 ). Other cultured and isolated species (Gephyrocapsa oceanica, Emiliania huxleyi and C.pelagicus) show similar patterns that raise the question of a possible overestimation of isotopic disequilibria in coccolith calcite. A promising research topic in palaeoceanography consists of exploiting interspecific isotopic fractionation because species respond differently to ambient changes in carbonate system chemistry. While E.huxleyi or G.oceanica are isotopically sensitive to changes in dissolved inorganic carbon speciation or concentration, others such as C.leptoporus remains almost unaffected. This may indicate that in addition to traditional ?18O temperature proxy, coccolith interspecific isotopic offsets can provide an innovative means to constrain the carbonate chemistry of the mixed-layer. We investigated this hypothesis with a study case of the last Pleistocene deglaciation that appears to be a good candidate by his abrupt changes in temperatures, oxygen isotope composition of seawater and atmospheric pCO2. While numerous studies have investigated climate changes at high latitudes, we present here the first coccoliths-based isotopic record of mixed-layer temperature at the border of North Atlantic Subtropical Gyre (southwards of the polar front). From Site DSDP 607 we successfully isolated fractions of coccolithophore species C.leptoporus, G.oceanica, E. huxleyi and C.pelagicus over the last 17 kyr. Oxygen isotope variations from these fractions exhibit a shift of about -1.9 between the Younger Dryas and the Early Holocene SSTs that can be translated into a warming of about 7-8 C. This result closely matches with previously reported temperatures derived from foraminiferal and alkenone records and confirms that coccoliths can be used as a complementary or alternative substrate to foraminiferal shells for isotopic analyses and paleoclimate reconstructions. Differential oxygen and carbon isotopic offsets between Calcidiscus spp. and small Noelaerhabdacea coccoliths are almost constant and present an overall agreement with culture predictions. Although further results are needed this may imply that an increase of about 80 ppm pCO2 as recorded in Antarctica ice sheet over this time period is not sufficient to effect variations in calcification and intensity of fractionation in these two common species.

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

    USGS Publications Warehouse

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

    2001-01-01

    Deposits of calcite and opal are present as coatings on open fractures and lithophysal cavities in unsaturated-zone tuffs at Yucca Mountain, Nevada, site of a potential high-level radioactive waste repository. Outermost layers of calcite and opal have radiocarbon ages of 16,000 to 44,000 years before present and thorium-230/uranium ages of 28,000 to more than 500,000 years before present. These ages are young relative to the 13-million-year age of the host rocks. Multiple subsamples from the same outer layer typically show a range of ages with youngest ages from the thinnest subsamples. Initial uranium-234/uranium-238 activity ratios between 1 and 9.5 show a distinct negative correlation with thorium-230/uranium age and are greater than 4 for all but one sample younger than 100,000 years before present. These data, along with micrometer-scale layering and distinctive crystal morphologies, are interpreted to indicate that deposits formed very slowly from water films migrating through open cavities. Exchanges of carbon dioxide and water vapor probably took place between downward-migrating liquids and upward-migrating gases at low rates, resulting in oversaturation of mineral constituents at crystal extremities and more or less continuous deposition of very thin layers. Therefore, subsamples represent mixtures of older and younger layers on a scale finer than sampling techniques can resolve. Slow, long-term rates of deposition (less than about 5 millimeters of mineral per million years) are inferred from subsamples of outermost calcite and opal. These growth rates are similar to those calculated assuming that total coating thicknesses of 10 to 40 millimeters accumulated over 12 million years. Calcite has a wide range of delta carbon-13 values from about -8.2 to 8.5 per mil and delta oxygen-18 values from about 10 to 21 per mil. Systematic microsampling across individual mineral coatings indicates basal (older) calcite tends to have the largest delta carbon-13 values and smallest delta oxygen-18 values compared to calcite from intermediate and outer positions. Basal calcite has relatively small strontium-87/strontium-86 ratios, between 0.7105 and 0.7120, that are similar to the initial isotopic compositions of the strontium-rich tuff units, whereas outer calcite has more radiogenic strontium-87/strontium-86 ratios between 0.7115 and 0.7127. Isotopic compositions of strontium, oxygen, and carbon in the outer (youngest) unsaturated-zone calcite are coincident with those measured in Yucca Mountain calcrete, which formed by pedogenic processes. The physical and isotopic data from calcite and opal indicate that they formed from solutions of meteoric origin percolating through a limited network of connected fracture pathways in the unsaturated zone rather than by inundation from ascending ground water originating in the saturated zone. Mineral assemblages, textures, and distributions within the unsaturated zone are distinctly different from those deposited below the water table at Yucca Mountain. The calcite and opal typically are present only on footwall surfaces of a small fraction of fractures and only on floors of a small fraction of lithophysal cavities. The similarities in the carbon, oxygen, and strontium isotopic compositions between fracture calcite and soil-zone calcite, as well as the gradation of textures from detritus-rich micrite in the soil to detritus-free spar 10 to 30 meters below the surface, also support a genetic link between the two depositional environments. Older deposits contain oxygen isotope compositions that indicate elevated temperatures of mineral formation during the early stages of deposition; however, in the youngest deposits these values are consistent with deposition under geothermal gradients similar to modern conditions. Correlations between mineral ages and varying Pleistocene climate conditions are not apparent from the current data. Cumulative evidence from calcite and opal deposits indicate

  14. Gas Hydrates Research Project in Japan

    USGS Multimedia Gallery

    Scientists from AIST, JOGMEC, Georgia Tech, and the USGS prepare to analyze pressure cores as part of a multi-year gas hydrates research project in Japan. This photo shows the pressure core storage chambers, which contain hydrate-bearing sediment samples obtained from the Nankai Trough offshore Japa...

  15. 78 FR 37536 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-06-21

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of...

  16. 78 FR 26337 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-05-06

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... Meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. The Federal... of the Methane Hydrate Advisory Committee is to provide advice on potential applications of...

  17. 76 FR 59667 - Methane Hydrate Advisory Committee

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-09-27

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF ENERGY Methane... Meeting. SUMMARY: This notice announces a meeting of the Methane Hydrate Advisory Committee. Federal... of the Committee: The purpose of the Methane Hydrate Advisory Committee is to provide advice...

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

    USGS Publications Warehouse

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

    2007-01-01

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

  19. The role of citrate and phthalate during Co(II) coprecipitation with calcite

    NASA Astrophysics Data System (ADS)

    Lee, Young J.; Reeder, Richard J.

    2006-05-01

    The influence of citrate and phthalate on Co coprecipitation with calcite was investigated using a combination of batch experiments, Fourier-transform infra-red (FT-IR) spectroscopy, and thermogravimetric analysis (TGA) over a wide range of precipitation rates. Steady-state growth conditions (at constant [Ca], [Co], DIC, and pH) were generally achieved within 3-5 h, after which Co(II) partitioning into calcite was evaluated. Only minor differences are observed in the partition coefficient ( Kd) trends with and without citrate and phthalate as a function of calcite precipitation rate except at very low rates. Slight inhibition of calcite growth is observed in the presence of citrate or phthalate, which can be attributed to adsorption at surface sites. TGA curves for samples coprecipitated with citrate show a significant mass loss between 375 and 550 C, whereas the weight-loss curves for the Co-phthalate coprecipitates are indistinguishable from those of the organic-free Co coprecipitates. This indicates that citrate is incorporated into calcite during calcite crystallization, whereas phthalate is excluded. FT-IR spectra for the sample with citrate show a broad absorption in the range 3700-3100 cm -1, which is attributable to water molecules coordinated to citrate coprecipitated with calcite. The preferential incorporation of citrate over phthalate likely reflects differences in both aqueous speciation and conformation of the carboxylate groups. This new finding may provide new insight to the factors that control the behavior of macromolecules and their incorporation into the structure of calcium carbonate during biomineralization.

  20. Effect of Mg on the Grain Growth and Dislocation Creep of Calcite

    NASA Astrophysics Data System (ADS)

    Xu, L.

    2004-12-01

    We tested the effect of variations in the amount of the solute impurity (Mg) on grain growth and strength of calcite aggregate. Synthetic marbles were produced by hot isostatic pressing mixtures of powders of calcite and dolomite at 850 C and 300 MPa confining pressure for different intervals (2 to 30 hrs). The HIP treatment resulted in homogeneous aggregates of calcite with Mg content from 0.5 to 17 mol%. Stress stepping tests and constant strain rate tests were used to examine the effect of Mg content on the dislocation creep of calcite. The grain growth rate under static conditions was decreased with Mg content from 7 to 17 mol%, indicating perhaps that grain boundary mobility is suppressed by the solute drag effect. In the diffusion creep at stresses below 40 Mpa, the strength of calcite decreases with increasing Mg content owing to the difference in grain size at 800 C and 300 MPa confining pressure. The contribution of dislocation creep increases with increasing stress, and the transition between diffusion and dislocation creep occurs at higher stresses for the samples with higher magnesium content and smaller grain size. The creep data were fit assuming a composite flow law consisting of a linear combination of diffusion and dislocation creep and a single-valued grain size. The best agreement was obtained by using a dislocation creep law with exponential dependence of strain rate on stress (e.g. Peierls law). More evidence from microstructure is needed to identify the dominant deformation mechanism conclusively. Most of the samples were compressed up to strains of 0.25; small recrystallized grains are formed resulting in a bimodal grain size distribution in some of the deformed samples. Preliminary data shows that the recrystallized grain sizes are smaller for Mg-calcite compared with that of pure calcite. This study will help to understand the effect of impurities on grain-g