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Sample records for accelerated carbonate dissolution

  1. Accelerated Carbonate Dissolution as a CO2 Separation and Sequestration Strategy

    SciTech Connect

    Caldeira, K G; Knauss, K G; Rau, G H

    2004-02-18

    process is geochemically equivalent to continental and marine carbonate weathering which will otherwise naturally consume anthropogenic CO{sub 2}, but over many millennia (e.g. [7,8,9]). We identify the enhanced form of this process as Accelerated Weathering of Limestone or accelerated carbonate dissolution. Previously, it has been shown that accelerated carbonate dissolution can effectively convert a significant fraction of US CO{sub 2} emissions to long-term storage as bicarbonate in the ocean, while avoiding or possibly reversing environmental impacts associated with either the ongoing passive or the proposed active injection of CO{sub 2} into the ocean [6,10]. Being analogous to the widespread use of wet limestone to desulfurize flue gas, accelerated carbonate dissolution reactors could be retrofitted to many existing coastal power plants at a typical cost estimated to be $20-$30/tonne CO{sub 2} mitigated [5,11]. This paper further explores limestone availability, cost, transportation, and reaction kinetics as well as ocean and environmental impacts, and the overall economics and practicality of accelerated carbonate dissolution CO{sub 2} mitigation.

  2. 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.

  3. CALCIUM CARBONATE DISSOLUTION RATE IN LIMESTONE CONTRACTORS

    EPA Science Inventory

    The rate of carbonate mineral dissolution from limestone was studied using a rotating disk apparatus and samples of limestone of varied composition. he purpose of this study was to determine the effect of limestone composition on the kinetics of carbonate mineral dissolution. he ...

  4. CALCIUM CARBONATE DISSOLUTION RATE IN LIMESTONE CONTACTORS

    EPA Science Inventory

    The rate of carbonate mineral dissolution from limestone was studied using a rotating disk apparatus and samples of limestone of varied composition. The purpose of this study was to determine the effect of limestone composition on the kinetics of carbonate mineral dissolution. Th...

  5. Carbonate ions and arsenic dissolution by groundwater

    USGS Publications Warehouse

    Kim, M.-J.; Nriagu, J.; Haack, S.

    2000-01-01

    solutions. The effects of pH and redox conditions on As dissolution were examined. Results showed that As was not leached significantly out of the Marshall Sandstone samples after 3 d using either deionized water or groundwater, but As was leached efficiently by sodium bicarbonate, potassium bicarbonate, and ferric chloride solutions. The leaching rate with sodium bicarbonate was about 25% higher than that with potassium bicarbonate. The data indicated that bicarbonate ion was involved primarily in As dissolution and that hydroxyl radical ion did not affect As dissolution to any significant degree. The amount of As leached was dependent upon the sodium bicarbonate concentration, increasing with reaction time for each concentration. Significant As leaching was found in the extreme pH ranges of <1.9 and 8.0-10.4. The resulting arseno-carbonate complexes formed were stable in groundwater.

  6. Helium enrichment during convective carbon dioxide dissolution

    NASA Astrophysics Data System (ADS)

    Larson, T.; Hesse, M. A.

    2013-12-01

    Motivated by observed variations of the CO2/He ratios in natural carbon dioxide (CO2) reservoirs, such as the Bravo Dome field in northeastern New Mexico, we have performed laboratory experiments equilibrating gas mixtures containing Helium (He) and CO2 with water, at close to ambient conditions in a closed system. The experimental design allows for continuous measurement of headspace pressure as well as timed interval measurements of the CO2/He ratios and the δ13C value of CO2 in the headspace. Results from three dissolution experiments are reported: 1) pure Helium system, 2) 98% CO2 + 2% Nitrogen system, and 3) 97% CO2 and 3% Helium. Final equilibrated experimental results are compared to theoretical results obtained using Henry's Law relationships. The evolution of the amount of dissolved CO2 computed from gas pressure and gas compositions are in good agreement with Henry's Law relationships. For example, the CO2 + N2 system was initially pressurized with pure CO2 to 1323 mbar and after six days it equilibrated to a measured headspace pressure of 596 mbar. This compares very well with a calculated equilibrium headspace pressure of 592 mbar for this system. The CO2 + He system was pressurized to 1398 mbar CO2 and after six days equilibrated to a measured headspace pressure of 397 mbar. This measured pressure is slightly higher than the predicted equilibrated headspace pressure of 341 mbar, indicating a possible leak in the system during this particular experiment. In both experiments the initial pH of the water was 9.3 and the final equilibrated pH was 5.4. The δ13C value of equilibrated headspace CO2 was within 0.25‰ of its starting δ13C value, demonstrating insignificant carbon isotope fractionation at low pH. Measured Helium/ CO2 ratios throughout the CO2+Helium experiment preserve a non-linear trend of increasing He/ CO2 ratios through time that correlate very well with the measured pressure drop from CO2 dissolution. This indicates that gas composition

  7. Dissolution kinetics of calcium carbonate in equatorial Pacific sediments

    SciTech Connect

    Berelson, W.M.; Hammond, D.E.; McManus, J.; Kilgore, T.E. )

    1994-06-01

    Calcium carbonate dissolution exerts a major influence on the carbonate chemistry of seawater and is an important factor in regulating atmospheric CO2 concentration. The authors use a numerical model, based on an estimate of k determined from benthic chamber flux measurements, the distribution of CO3 2-in the water column and percent of CaCO3 in the sediments, to derive the total alkalinity flux from Pacific Ocean sediments. The significance of this budget is discussed as are the following questions: what is the rate of calcium carbonate dissolution on the deep sea floor what controls carbonate dissolution, organic carbon rain rates, or bottom water carbonate ion concentration what is the equations that relates carbonate dissolution to degree of undersaturation and what is the associate rate constant 43 refs., 10 figs., 4 tabs.

  8. Accelerated carbonation of brucite in mine tailings for carbon sequestration.

    PubMed

    Harrison, Anna L; Power, Ian M; Dipple, Gregory M

    2013-01-01

    Atmospheric CO(2) is sequestered within ultramafic mine tailings via carbonation of Mg-bearing minerals. The rate of carbon sequestration at some mine sites appears to be limited by the rate of CO(2) supply. If carbonation of bulk tailings were accelerated, large mines may have the capacity to sequester millions of tonnes of CO(2) annually, offsetting mine emissions. The effect of supplying elevated partial pressures of CO(2) (pCO(2)) at 1 atm total pressure, on the carbonation rate of brucite [Mg(OH)(2)], a tailings mineral, was investigated experimentally with conditions emulating those at Mount Keith Nickel Mine (MKM), Western Australia. Brucite was carbonated to form nesquehonite [MgCO(3) · 3H(2)O] at a rate that increased linearly with pCO(2). Geochemical modeling indicated that HCO(3)(-) promoted dissolution accelerated brucite carbonation. Isotopic and aqueous chemistry data indicated that equilibrium between CO(2) in the gas and aqueous phases was not attained during carbonation, yet nesquehonite precipitation occurred at equilibrium. This implies CO(2) uptake into solution remains rate-limiting for brucite carbonation at elevated pCO(2), providing potential for further acceleration. Accelerated brucite carbonation at MKM offers the potential to offset annual mine emissions by ~22-57%. Recognition of mechanisms for brucite carbonation will guide ongoing work to accelerate Mg-silicate carbonation in tailings. PMID:22770473

  9. Abiotic carbonate dissolution traps carbon in a semiarid desert

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  10. Abiotic carbonate dissolution traps carbon in a semiarid desert

    PubMed Central

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

    2016-01-01

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

  11. Convective dissolution of carbon dioxide in saline aquifers

    NASA Astrophysics Data System (ADS)

    Neufeld, Jerome A.; Hesse, Marc A.; Riaz, Amir; Hallworth, Mark A.; Tchelepi, Hamdi A.; Huppert, Herbert E.

    2010-11-01

    Geological carbon dioxide (CO2) storage is a means of reducing anthropogenic emissions. Dissolution of CO2 into the brine, resulting in stable stratification, increases storage security. The dissolution rate is determined by convection in the brine driven by the increase of brine density with CO2 saturation. We present a new analogue fluid system that reproduces the convective behaviour of CO2-enriched brine. Laboratory experiments and high-resolution numerical simulations show that the convective flux scales with the Rayleigh number to the 4/5 power, in contrast with a classical linear relationship. A scaling argument for the convective flux incorporating lateral diffusion from downwelling plumes explains this nonlinear relationship for the convective flux, provides a physical picture of high Rayleigh number convection in a porous medium, and predicts the CO2 dissolution rates in CO2 accumulations. These estimates of the dissolution rate show that convective dissolution can play an important role in enhancing storage security.

  12. In situ calcium carbonate dissolution in the Pacific Ocean

    SciTech Connect

    Feely, R. A.; Sabine, Chris; Lee, K.; Millero, F. J.; Lamb, M. F.; Greeley, D.; Bullister, J.L.; Key, Robert; Peng, T.-H.; Kozyr, Alexander; Ono, Tsueno

    2002-01-01

    Over the past several years researchers have been working to synthesize the WOCE/ JGOFS global CO2 survey data to better understand carbon cycling processes in the oceans. The Pacific Ocean data set has over 35,000 sample locations with at least two carbon parameters, oxygen, nutrients, CFC tracers, and hydrographic parameters. In this paper we estimate the in situ CaCO3 dissolution rates in the Pacific Ocean water column. Calcium carbonate dissolution rates ranging from 0.01 1.1 mmol kg1 yr1 are observed in intermediate and deepwater beginning near the aragonite saturation horizon. In the North Pacific Intermediate Water between 400 and 800 m, CaCO3 dissolution rates are more than 7 times faster than observed in middle and deep water depths (average = 0.051 mmol kg1 yr1). The total amount of CaCO3 that is dissolved within the Pacific is determined by integrating excess alkalinity throughout the water column. The total inventory of CaCO3 added by particle dissolution in the Pacific Ocean, north of 40S, is 157 Pg C. This amounts to an average dissolution rate of approximately 0.31 Pg C yr1. This estimate is approximately 74% of the export production of CaCO3 estimated for the Pacific Ocean. These estimates should be considered to be upper limits for in situ carbonate dissolution in the Pacific Ocean, since a portion of the alkalinity increase results from inputs from sediments.

  13. Kinetics of Carbon Dissolution of Coke in Molten Iron

    NASA Astrophysics Data System (ADS)

    Jang, Dongik; Kim, Yumkyum; Shin, Minsoo; Lee, Joonho

    2012-12-01

    The effect of temperature on the dissolution rate of carbon from coke in molten iron was investigated using a sampling technique in the temperature range of 1723 K to 1923 K (1450 °C to 1650 °C). The dissolution rate of carbon from coke in molten iron increased as the temperature increased. At 1923 K (1650 °C), the rate-determining step was the mass transfer of carbon in the boundary layer adjacent to the metal-carbon interface. At 1723 K (1450 °C), the rate-determining step changed from the mass transfer to the interfacial chemical reaction as the reaction proceeded. At 1823 K (1550 °C), both reaction steps affected the apparent reaction rates. Sulfur dissolution did not affect the carbon dissolution rates in molten iron, so it was considered that the sulfur adsorption at the metal/coke interface was not so significant. The apparent activation energy of the carbon dissolution of coke in molten iron was estimated to be 442 kJ/mol.

  14. Dissolution rates of carbonated hydroxyapatite in hydrochloric acid.

    PubMed

    Hankermeyer, Christine R; Ohashi, Kevin L; Delaney, David C; Ross, John; Constantz, Brent R

    2002-02-01

    Osteoclasts have been shown to dissolve efficiently and effectively the mineral phase of bone by locally controlling the environment surrounding the cell. Although this mineral phase has been identified and well characterized as carbonated hydroxyapatite, there is little understanding of the factors that affect the dissolution properties of this mineral phase. Mimicking the mechanism by which osteoclasts dissolve the mineral phase of bone may provide insight into methods for the decalcification of atherosclerotic mineral deposits in the vascular system. Accordingly, a detailed characterization of the effects of various chemical and mechanical parameters on the dissolution of carbonated hydroxyapatite mineral was investigated in this study. Increases in the mineral dissolution rate (2-10 times) were associated with increases in dissolving solution [H+], osmolality, temperature, and flow rate. Mineral dissolution rate increases (5-8 times) were associated with greater surface area of the mineral and mechanical agitation of the dissolving solution. PMID:11771694

  15. Mesogenetic dissolution: Its role in porosity development in carbonate reservoirs

    SciTech Connect

    Mazzullo, S.J. ); Harris, P.M. )

    1992-05-01

    Models of porosity formation in carbonate rocks have stressed subaerial exposure and attendant shallow meteoric diagenesis. Porosity formation also occurs in deep-burial, or mesogenetic, settings as a result of dissolution enlargement of preexisting pores (porosity enhancement) and creation of new pore systems. Brines charged with organic acids, carbon dioxide, and/or hydrogen sulfide derived from organic matter diagenesis and thermochemical sulfate reduction are the likely fluids causing significant mesogenetic dissolution. Enhanced and newly created mesogenetic pore types can mimic pore types formed in shallow meteoric environments, and therefore, the mesogenetic origin of some porosity may go unrecognized.

  16. Dissolution of Spent Nuclear Fuel in Carbonate-Peroxide Solution

    SciTech Connect

    Soderquist, Chuck Z.; Hanson, Brady D.

    2010-01-31

    This study shows that spent UO2 fuel can be completely dissolved in a carbonate-peroxide solution apparently without attacking the metallic Mo-Tc-Ru-Rh-Pd fission product phase. Samples of spent nuclear fuel were pulverized and sieved to a uniform size, then duplicate aliquots were weighed into beakers for analysis. One set was dissolved in near-boiling 10M nitric acid, and the other set was dissolved in a solution of ammonium carbonate and hydrogen peroxide at room temperature. All the resulting fuel solutions were then analyzed for Sr-90, Tc-99, Cs-137, plutonium, and Am-241. For all the samples, the concentrations of Cs-137, Sr-90, plutonium, and Am-241 were the same for both the nitric acid dissolution and the ammonium carbonate-hydrogen peroxide dissolution, but the technetium concentration of the ammonium carbonate-hydrogen peroxide fuel solution was only about 25% of the same fuels dissolved in hot nitric acid.

  17. Dissolution rates of coals and graphite in Fe-C-S melts in direct ironmaking: Influence of melt carbon and sulfur on carbon dissolution

    NASA Astrophysics Data System (ADS)

    Wu, C.; Sahajwalla, V.

    2000-04-01

    Carbon dissolution from graphite and coals was investigated by using a carburizer cover technique in an induction furnace. The intent of the study was to investigate the influence of factors governing the rate of carbon dissolution from carbonaceous materials, especially coals, into Fe-C-S melts. The factors studied were the initial melt carbon and sulfur concentrations and the wettability between carbonaceous materials and the melt. It was found that graphite dissolves markedly faster than coal. The rate of carbon dissolution from graphite could be decreased by increasing the sulfur in the melt. Also, poor wetting could retard the rate of carbon dissolution by reducing the surface area for mass transfer. Carbon dissolution from graphite is controlled by mass transfer in the liquid boundary layer adjacent to the solid/liquid interface. The rate of carbon dissolution from coal is more sensitive to the molten iron composition. A higher initial melt carbon and sulfur content retards the rate of carbon dissolution from coal more significantly than from graphite. However, the rate constant of coal char dissolution does not show a strong dependence on the wettability. Carbon dissolution from coals is most likely governed by a mixed-control mechanism that includes liquid-side mass transfer. The mechanisms underlying the influence of bath sulfur on carbon dissolution from graphite and coals are discussed.

  18. Late Pleistocene carbonate dissolution in the Venezuela Basin, Caribbean Sea

    SciTech Connect

    Cofer-Shabica, N.B.; Peterson, L.C.

    1985-01-01

    Piston cores from water depths greater than 4000 m in the Venezuela Basin (Caribbean Sea) provide continuous late Pleistocene records of carbonate dissolution and accumulation. The authors examination of multiple dissolution indices indicate that, at least for the last 150,000 years, dissolution of carbonate in the Venezuela Basin has been more intense during interglacial than glacial periods, a pattern opposite to more general observations from the deep Atlantic and Gulf of Mexico. By virtue of its shallow sill depth (1815 m), the Venezuela Basin is relatively isolated from the mainstream of Atlantic thermohaline circulation, and presently is filled with homogeneous, relatively warm (3.8/sup 0/C) waters primarily derived from Upper North Atlantic Deep Water. During the last glacial, the enhanced preservation of carbonate in the Venezuela Basin suggests the presence of a less corrosive, more oxygenated water mass in the Atlantic near sill depth. However, this simple interpretations is potentially complicated by past changes in the rain of biogenic materials from surface waters to the deep basin in what must be an essentially closed system below sill depth. Their observations of increased interglacial dissolution may help to explain previously noted discrepancies in the local glacial to interglacial amplitude of delta/sup 18/O variations recorded by coccoliths and planktonic foraminifera.

  19. Carbonate dissolution rates at the deep ocean floor

    NASA Astrophysics Data System (ADS)

    Boudreau, Bernard P.

    2013-02-01

    This paper reexamines experimental data on the seawater dissolution of CaCO3-bearing sediment beds to establish that the dependence of the calcite dissolution rate is linearly dependent on the calcite saturation state of the overlying water. This linearity is inherent to the original data and is not the result of an error in the solubility product for calcite. A comparison between these linear kinetics and the rate of solute transport across the benthic boundary layer further reveals that the overall rate of dissolution at ocean depths below the saturation horizon is controlled by boundary layer transfer. A carbonate mass-balance model for the sediment-water interface, which includes both kinetics and boundary layer effects, predictively reproduces the currently observed CaCO3 depth distribution for two test areas in the oceans. These findings allow important simplifications in modeling CO2 neutralization in the oceans.

  20. Karstification without carbonic acid: bedrock dissolution by gypsum- driven dedolomitization

    USGS Publications Warehouse

    Bischoff, J.L.; Julia, R.; Shanks, Wayne C.; Rosenbauer, R.J.

    1994-01-01

    The primary karst-forming process at Lake Banyoles is dedolomitization of basement rocks driven by gypsum dissolution. Karstification takes place along the subsurface contact between the gypsiferous Beuda Formation and the dolomitic Perafita Formation. This process is here recognized for the first time to cause karstification on a large scale; this is significant because it proceeds without the addition of soil-generated carbonic acid. -from Authors

  1. Boron isotope fractionation in magma via crustal carbonate dissolution

    PubMed Central

    Deegan, Frances M.; Troll, Valentin R.; Whitehouse, Martin J.; Jolis, Ester M.; Freda, Carmela

    2016-01-01

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to −41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle. PMID:27488228

  2. Boron isotope fractionation in magma via crustal carbonate dissolution.

    PubMed

    Deegan, Frances M; Troll, Valentin R; Whitehouse, Martin J; Jolis, Ester M; Freda, Carmela

    2016-01-01

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ(11)B values down to -41.5‰, reflecting preferential partitioning of (10)B into the assimilating melt. Loss of (11)B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports (11)B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ(11)B melt values in arc magmas could flag shallow-level additions to the subduction cycle. PMID:27488228

  3. Boron isotope fractionation in magma via crustal carbonate dissolution

    NASA Astrophysics Data System (ADS)

    Deegan, Frances M.; Troll, Valentin R.; Whitehouse, Martin J.; Jolis, Ester M.; Freda, Carmela

    2016-08-01

    Carbon dioxide released by arc volcanoes is widely considered to originate from the mantle and from subducted sediments. Fluids released from upper arc carbonates, however, have recently been proposed to help modulate arc CO2 fluxes. Here we use boron as a tracer, which substitutes for carbon in limestone, to further investigate crustal carbonate degassing in volcanic arcs. We performed laboratory experiments replicating limestone assimilation into magma at crustal pressure-temperature conditions and analysed boron isotope ratios in the resulting experimental glasses. Limestone dissolution and assimilation generates CaO-enriched glass near the reaction site and a CO2-dominated vapour phase. The CaO-rich glasses have extremely low δ11B values down to ‑41.5‰, reflecting preferential partitioning of 10B into the assimilating melt. Loss of 11B from the reaction site occurs via the CO2 vapour phase generated during carbonate dissolution, which transports 11B away from the reaction site as a boron-rich fluid phase. Our results demonstrate the efficacy of boron isotope fractionation during crustal carbonate assimilation and suggest that low δ11B melt values in arc magmas could flag shallow-level additions to the subduction cycle.

  4. Dissolution-Driven Permeability Reduction of a Fractured Carbonate Caprock

    PubMed Central

    Ellis, Brian R.; Fitts, Jeffrey P.; Bromhal, Grant S.; McIntyre, Dustin L.; Tappero, Ryan; Peters, Catherine A.

    2013-01-01

    Abstract Geochemical reactions may alter the permeability of leakage pathways in caprocks, which serve a critical role in confining CO2 in geologic carbon sequestration. A caprock specimen from a carbonate formation in the Michigan sedimentary Basin was fractured and studied in a high-pressure core flow experiment. Inflowing brine was saturated with CO2 at 40°C and 10 MPa, resulting in an initial pH of 4.6, and had a calcite saturation index of −0.8. Fracture permeability decreased during the experiment, but subsequent analyses did not reveal calcite precipitation. Instead, experimental observations indicate that calcite dissolution along the fracture pathway led to mobilization of less soluble mineral particles that clogged the flow path. Analyses of core sections via electron microscopy, synchrotron-based X-ray diffraction imaging, and the first application of microbeam Ca K-edge X-ray absorption near edge structure, provided evidence that these occlusions were fragments from the host rock rather than secondary precipitates. X-ray computed tomography showed a significant loss of rock mass within preferential flow paths, suggesting that dissolution also removed critical asperities and caused mechanical closure of the fracture. The decrease in fracture permeability despite a net removal of material along the fracture pathway demonstrates a nonintuitive, inverse relationship between dissolution and permeability evolution in a fractured carbonate caprock. PMID:23633894

  5. Dissolution-Driven Permeability Reduction of a Fractured Carbonate Caprock

    SciTech Connect

    Ellis, Brian R; Fitts, Jeffrey P; Bromhal, Grant S; McIntyre, Dustin L; Tappero, Ryan; Peters, Catherine

    2013-04-01

    Geochemical reactions may alter the permeability of leakage pathways in caprocks, which serve a critical role in confining CO{sub 2} in geologic carbon sequestration. A caprock specimen from a carbonate formation in the Michigan sedimentary Basin was fractured and studied in a high-pressure core flow experiment. Inflowing brine was saturated with CO{sub 2} at 40°C and 10 MPa, resulting in an initial pH of 4.6, and had a calcite saturation index of −0.8. Fracture permeability decreased during the experiment, but subsequent analyses did not reveal calcite precipitation. Instead, experimental observations indicate that calcite dissolution along the fracture pathway led to mobilization of less soluble mineral particles that clogged the flow path. Analyses of core sections via electron microscopy, synchrotron-based X-ray diffraction imaging, and the first application of microbeam Ca K-edge X-ray absorption near edge structure, provided evidence that these occlusions were fragments from the host rock rather than secondary precipitates. X-ray computed tomography showed a significant loss of rock mass within preferential flow paths, suggesting that dissolution also removed critical asperities and caused mechanical closure of the fracture. The decrease in fracture permeability despite a net removal of material along the fracture pathway demonstrates a nonintuitive, inverse relationship between dissolution and permeability evolution in a fractured carbonate caprock.

  6. Acceleration of Fe-silicate mineral dissolution for CO2 sequestration via microbial siderophore production

    NASA Astrophysics Data System (ADS)

    Torres, M. A.; Nealson, K. H.; West, A.

    2013-12-01

    While the dissolution of silicate minerals will ultimately neutralize anthropogenic CO2 emissions, the slow natural timescale of this process limits its ability to mitigate any of the societal impacts of high atmospheric pCO2. As a result, much research has been focused on developing ways to significantly accelerate silicate mineral dissolution rates. Harnessing the effects of microbial activity is one particularly attractive strategy because research has shown that microbes can appreciably accelerate mineral dissolution rates and they require little external energy input. At present, one major hurdle in the development of microbe-based CO2 sequestration techniques is the observation that bacteria only accelerate dissolution rates under particular culturing conditions. In this work, natural and genetic mutant strains of the bacterial genera Shewanella, Pseudomonas, and Marinobacter are used to identify the geochemical and genetic factors that underlie the 'accelerated-weathering phenotype' in order to support the development of microbe-based CO2 sequestration techniques using olivine as a model mineral. Preliminary results suggest that microbial siderophore production at circum-neutral pH results in significantly accelerated olivine dissolution rates.

  7. Experimental observations of dolomite dissolution in geologic carbon sequestration conditions

    NASA Astrophysics Data System (ADS)

    Luhmann, A. J.; Kong, X.; Tutolo, B. M.; Saar, M. O.; Seyfried, W. E.

    2013-12-01

    One sequestration scenario proposed to reduce CO2 emissions involves injecting CO2 into saline formations or hydrocarbon reservoirs, where dolomite frequently occurs. To better understand fluid-mineral interactions in these sequestration settings, we have conducted a series of single-pass, flow-through experiments on dolomite core samples with CO2-bearing brine. An important component of the experimental design was to maintain the fabric of the rock so as to more accurately simulate fluid flow in natural dolomite-bearing systems. Seven experiments were conducted at 100°C and a pore-fluid pressure of 150 bars with a fluid containing 1 molal NaCl and 0.6 molal dissolved CO2. Flow rates ranged from 0.01 to 1 ml/min. Each experiment was terminated before dissolution breakthrough, but permeability increased by approximately an order of magnitude for all experiments. In general, Ca and Mg concentrations were initially high, but then decreased with reaction progress. We hypothesize that time-dependent changes in fluid chemistry reflect reduction in reactive surface area. Fluid chemistry also indicates preferential removal of Ba, Mn, and Sr with respect to Ca and Mg. In the extreme case, 70% of the Ba was removed from one core, while only 3% of the Ca, Mg, or the entire core mass was removed by dissolution. Ongoing work is focused on identifying elemental distributions throughout the rock to better understand the dissolution process. With fluid chemistry and BET surface area, we model dissolution rate as a function of core length using reactive transport simulations and compare our whole rock, far from equilibrium dissolution rates with analogous data reported in the literature. Finally, X-ray computed tomography images enable reconstructions of dissolution patterns, and they are being used to explore the effect of pore space heterogeneity on flow path development. Geologic carbon sequestration in dolomite will produce significant dissolution at the brine/CO2 interface

  8. An Alternative Mechanism for Accelerated Carbon Sequestration in Concrete

    SciTech Connect

    Haselbach, Liv M.; Thomle, Jonathan N.

    2014-07-01

    The increased rate of carbon dioxide sequestration (carbonation) is desired in many primary and secondary life applications of concrete in order to make the life cycle of concrete structures more carbon neutral. Most carbonation rate studies have focused on concrete exposed to air under various conditions. An alternative mechanism for accelerated carbon sequestration in concrete was investigated in this research based on the pH change of waters in contact with pervious concrete which have been submerged in carbonate laden waters. The results indicate that the concrete exposed to high levels of carbonate species in water may carbonate faster than when exposed to ambient air, and that the rate is higher with higher concentrations. Validation of increased carbon dioxide sequestration was also performed via thermogravimetric analysis (TGA). It is theorized that the proposed alternative mechanism reduces a limiting rate effect of carbon dioxide dissolution in water in the micro pores of the concrete.

  9. Accelerating Mineral Carbonation Using Carbonic Anhydrase.

    PubMed

    Power, Ian M; Harrison, Anna L; Dipple, Gregory M

    2016-03-01

    Carbonic anhydrase (CA) enzymes have gained considerable attention for their potential use in carbon dioxide (CO2) capture technologies because they are able to catalyze rapidly the interconversion of aqueous CO2 and bicarbonate. However, there are challenges for widespread implementation including the need to develop mineralization process routes for permanent carbon storage. Mineral carbonation of highly reactive feedstocks may be limited by the supply rate of CO2. This rate limitation can be directly addressed by incorporating enzyme-catalyzed CO2 hydration. This study examined the effects of bovine carbonic anhydrase (BCA) and CO2-rich gas streams on the carbonation rate of brucite [Mg(OH)2], a highly reactive mineral. Alkaline brucite slurries were amended with BCA and supplied with 10% CO2 gas while aqueous chemistry and solids were monitored throughout the experiments (hours to days). In comparison to controls, brucite carbonation using BCA was accelerated by up to 240%. Nesquehonite [MgCO3·3H2O] precipitation limited the accumulation of hydrated CO2 species, apparently preventing BCA from catalyzing the dehydration reaction. Geochemical models reproduce observed reaction progress in all experiments, revealing a linear correlation between CO2 uptake and carbonation rate. Data demonstrates that carbonation in BCA-amended reactors remained limited by CO2 supply, implying further acceleration is possible. PMID:26829491

  10. Dissolution driven convection for carbon dioxide sequestration: the stability problem

    NASA Astrophysics Data System (ADS)

    Mandre, Shreyas; Guo, Xinjun; Slim, Anja

    2013-11-01

    The dissolution-driven convection in porous media is potentially a rate limiting process for sequestering carbon dioxide in underground aquifers. Super critical carbon dioxide introduced in the aquifer is lighter than the water that fills the surrounding porous rock, and hence quickly rises to the top. However, the solution of carbon dioxide in water is heavier than water. Hence, as the layer of carbon dioxide dissolves in the water, convection may ensue. The threshold criteria for convection is obscured by the continually changing background density profile as the carbon dioxide diffuses through the pores. Commonly used techniques such as frozen coefficient analysis or non-modal theories using transient amplifications yield substantially different results for the threshold, which has been the cause of a debate in the scientific community. We present a general theory for the linear stability of non-autonomous systems and apply it to dissolution driven convection. The theory unifies the classical modal stability theory using eigenvalues, the non-modal approaches using optimal growth of energy and the frozen coefficient analysis. We settle the debate, and demonstrate the existence of a threshold time for convection to commence.

  11. Carbonate mineral dissolution kinetics in high pressure experiments

    NASA Astrophysics Data System (ADS)

    Dethlefsen, F.; Dörr, C.; Schäfer, D.; Ebert, M.

    2012-04-01

    The potential CO2 reservoirs in the North German Basin are overlain by a series of Mesozoic barrier rocks and aquifers and finally mostly by Tertiary and Quaternary close-to-surface aquifers. The unexpected rise of stored CO2 from its reservoir into close-to-surface aquifer systems, perhaps through a broken well casing, may pose a threat to groundwater quality because of the acidifying effect of CO2 dissolution in water. The consequences may be further worsening of the groundwater quality due to the mobilization of heavy metals. Buffer mechanisms counteracting the acidification are for instance the dissolution of carbonates. Carbonate dissolution kinetics is comparably fast and carbonates can be abundant in close-to-surface aquifers. The disadvantages of batch experiments compared to column experiments in order to determine rate constants are well known and have for instance been described by v. GRINSVEN and RIEMSDIJK (1992). Therefore, we have designed, developed, tested, and used a high-pressure laboratory column system to simulate aquifer conditions in a flow through setup within the CO2-MoPa project. The calcite dissolution kinetics was determined for CO2-pressures of 6, 10, and 50 bars. The results were evaluated by using the PHREEQC code with a 1-D reactive transport model, applying a LASAGA (1984) -type kinetic dissolution equation (PALANDRI and KHARAKA, 2004; eq. 7). While PALANDRI and KHARAKA (2004) gave calcite dissolution rate constants originating from batch experiments of log kacid = -0.3 and log kneutral = -5.81, the data of the column experiment were best fitted using log kacid = -2.3 and log kneutral = -7.81, so that the rate constants fitted using the lab experiment applying 50 bars pCO2 were approximately 100 times lower than according to the literature data. Rate constants of experiments performed at less CO2 pressure (pCO2 = 6 bars: log kacid = -1.78; log kneutral = -7.29) were only 30 times lower than literature data. These discrepancies in the

  12. Tuning the dissolution kinetics of wollastonite via chelating agents for CO2 sequestration with integrated synthesis of precipitated calcium carbonates.

    PubMed

    Zhao, Huangjing; Park, Youngjune; Lee, Dong Hyun; Park, Ah-Hyung Alissa

    2013-09-28

    Carbon mineralization has recently received much attention as one of the most promising options for CO2 sequestration. The engineered weathering of silicate minerals as a means of permanent carbon storage has unique advantages such as the abundance of naturally occurring calcium and magnesium-bearing minerals and the formation of environmentally-benign and geologically stable solids via a thermodynamically favored carbonation reaction. However, several challenges need to be overcome to successfully deploy carbon mineralization on a large scale. In particular, the acceleration of the rate-limiting mineral dissolution step along with process optimization is essential to ensure the economic feasibility of the proposed carbon storage technology. In this study, the effect of various types of chelating agents on the dissolution rate of calcium-bearing silicate mineral, wollastonite, was explored to accelerate its weathering rate. It was found that chelating agents such as acetic acid and gluconic acid significantly improved the dissolution kinetics of wollastonite even at a much diluted concentration of 0.006 M by complexing with calcium in the mineral matrix. Calcium extracted from wollastonite was then reacted with a carbonate solution to form precipitated calcium carbonate (PCC), while tuning the particle size and the morphological structure of PCC to mimic commercially available PCC-based filler materials. PMID:23925694

  13. Kinetic model of carbonate dissolution in Martian meteorite ALH84001

    NASA Astrophysics Data System (ADS)

    Kopp, R. E.; Humayun, M.

    2003-09-01

    The magnetites and sulfides located in the rims of carbonate globules in the Martian meteorite ALH84001 have been claimed as evidence of past life on Mars. Here, we consider the possibility that the rims were formed by dissolution and reprecipitation of the primary carbonate by the action of water. To estimate the rate of these solution-precipitation reactions, a kinetic model of magnesite-siderite carbonate dissolution was applied and used to examine the physicochemical conditions under which these rims might have formed. The results indicate that the formation of the rims could have taken place in < 50 yr of exposure to small amounts of aqueous fluids at ambient temperatures. Plausible conditions pertaining to reactions under a hypothetical ancient Martian atmosphere (1 bar CO 2), the modern Martian atmosphere (8 mbar CO 2), and the present terrestrial atmosphere (0.35 mbar CO 2) were explored to constrain the site of the process. The results indicated that such reactions likely occurred under the latter two conditions. The possibility of Antarctic weathering must be entertained, which, if correct, would imply that the plausibly biogenic minerals (single-domain magnetite of characteristic morphology and sulfide) reported from the rims may be the products of terrestrial microbial activity. This model is discussed in terms of the available isotope data and found to be compatible with the formation of ALH84001 rims. Particularly, anticorrelated variations of radiocarbon with δ 13C indicate that carbonate in ALH84001 was affected by solution-precipitation reactions immediately after its initial fall (˜13,000 yr ago) and then again during its recent exposure prior to collection.

  14. Reassessing the dissolution of marine carbonates: II. Reaction kinetics

    NASA Astrophysics Data System (ADS)

    Gehlen, M.; Bassinot, F. C.; Chou, L.; McCorkle, D.

    2005-08-01

    We studied dissolution kinetics of the carbonate fraction >150 μm of sediments sampled along two bathymetric transects in the eastern tropical Atlantic: the Sierra Leone Rise (SLR) and the Cape Verde Plateau (CVP). The reaction was followed by monitoring solution pH during freedrift experiments lasting between 46 and 50 h (20 °C, pCO 2≈3100 ppm and 1 atm pressure). The alkalinity reached at the end of the dissolution experiments ranged between 2.444 and 2.798 meq/kg sw. The dissolution time series was extrapolated to equilibrium by fitting an empirical relation to the data. The estimated asymptotic concentration products ([Ca 2+] ∞×[CO 32-] ∞, for t→∞ and dA/dt=0) range from 4.27×10 -7 to 6.77×10 -7 mol 2/kg sw2. These asymptotic concentration products are comparable with the stoichiometric concentration product of aragonite (6.56×10 -7 mol 2/kg sw2) and calcite (4.37 (±0.22)×10 -7 mol 2/kg sw2) derived for the same sediment material during long-term equilibration experiments. They are indicative of the presence of trace amounts of a higher solubility carbonate phase in sediments of the shallow stations (SLR station A, 2637 m; CVP station M, 3104 m). While it is likely that this phase is aragonite, the presence of authigenic carbonate precipitated in contact with supersaturated bottom waters cannot be excluded. Calcite is the main dissolving carbonate mineral in sediments from deeper stations. The order of reaction is always greater than unity. It varies between 1.4 (SLR station C) and 2.8 (CVP station M2), with an average n=2.3±0.4. The higher order reaction is explained in terms of a multiphase system. Specific rate constants range from 0.09 to 0.53 meq/m 2/d.

  15. Dissolution of Calcite in the Twilight Zone: Bacterial Control of Dissolution of Sinking Planktonic Carbonates Is Unlikely

    PubMed Central

    Bissett, Andrew; Neu, Thomas R.; de Beer, Dirk

    2011-01-01

    We investigated the ability of bacterial communities to colonize and dissolve two biogenic carbonates (Foraminifera and oyster shells). Bacterial carbonate dissolution in the upper water column is postulated to be driven by metabolic activity of bacteria directly colonising carbonate surfaces and the subsequent development of acidic microenvironments. We employed a combination of microsensor measurements, scanning electron microscopy (SEM), confocal laser scanning microscopy (CLSM) and image analysis and molecular documentation of colonising bacteria to monitor microbial processes and document changes in shell surface topography. Bacterial communities rapidly colonised shell surfaces, forming dense biofilms with extracellular polymeric substance (EPS) deposits. Despite this, we found no evidence of bacterially mediated carbonate dissolution. Dissolution was not indicated by Ca2+ microprofiles, nor was changes in shell surface structure related to the presence of colonizing bacteria. Given the short time (days) settling carbonate material is actually in the twilight zone (500–1000 m), it is highly unlikely that microbial metabolic activity on directly colonised shells plays a significant role in dissolving settling carbonates in the shallow ocean. PMID:22102861

  16. Reassessing the dissolution of marine carbonates: I. Solubility

    NASA Astrophysics Data System (ADS)

    Gehlen, M.; Bassinot, F. C.; Chou, L.; McCorkle, D.

    2005-08-01

    We studied the solubility of the [63-150 μm] and the greater than 150 μm size fractions of sediments from two bathymetric transects in the eastern tropical Atlantic (Sierra Leone rise and Cape Verde Plateau). Both fractions are made mainly of foraminiferal shells and fragments. We determined the calcite crystallinity (full width at half maximum of XRD (104) calcite peak) of the >150 μm size fraction. Equilibration experiments were carried out in artificial seawater (20 °C, pCO 2=3100 ppm) for up to 57 days starting from undersaturation with respect to calcite and supersaturation with respect to aragonite. Experiments starting from supersaturation yielded concentration products close to aragonite solubility for sediments from the shallowest stations, suggesting the presence of trace levels of aragonite in these samples. Concentration products computed for the deeper stations were intermediate between aragonite and calcite solubility. Our results indicate the formation of a high-Mg coating. The equilibration period was too short to allow the complete recrystallization of these Mg-rich overgrowths. Experiments initiated from undersaturation yield concentration products that are between 4% and 24% higher than the reported stoichiometric concentration product of synthetic calcite. These differences between estimates of calcite stoichiometric solubility products are explained in terms of variations in experimental conditions (artificial versus natural seawater) and related choices of carbonic acid dissociation constants. They do not reflect a true difference in solubility between biogenic and synthetic calcite. The thinning of the foraminiferal calcite (104) XRD peak from 0.168°( 2θ) to 0.148°( 2θ) along the depth transects is interpreted as reflecting an improvement in calcite crystallinity. This and the change in specific surface area are consistent with the progressive change of the carbonate assemblage. The evolution of the bulk composition of the carbonate

  17. Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

    NASA Astrophysics Data System (ADS)

    Turchyn, Alexandra V.; DePaolo, Donald J.

    2011-11-01

    Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ 44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ 44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ 44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ 44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these

  18. Experimental Dissolution of Fine-Fraction Carbonate Sediments From the Paleocene

    NASA Astrophysics Data System (ADS)

    Schneider, L. J.; Bralower, T. J.

    2007-12-01

    Pelagic carbonates play a vital role in sequestering CO2 and buffering the oceans through dissolution. The dominant component of deep-sea carbonates is calcareous nannofossils, a group that plays an important role in biostratigraphy, paleoecology and paleoceanography. The composition of assemblages is readily altered by dissolution in the water column, on the seafloor, and within the sediment column. It is therefore necessary to have some understanding of changes in the assemblage composition that may have occurred as well as the dissolution processes involved. Previous studies utilized experiments to constrain the susceptibility of nannofossil taxa during dissolution. While they noted general patterns related to ultrastructure, little is known about how dissolution affects fine-fraction carbonates at the scale of individual crystals of calcite. In this study we use long-term dissolution experiments to recreate dissolution of Paleocene nannofossils from the Indian Ocean in the water through sediment column. This assemblage is diverse and has a range of delicate to robust species and several different calcite morphologies. Detailed observations of subtle changes in the calcite crystals of nannofossils in the SEM reveal information on dissolution processes in pelagic carbonates and the factors that render specific morphologies more susceptible to dissolution. The morphologic alterations of nannofossil species in the light microscope can be used to create a quantitative index for dissolution. This index is based upon etching of rims, the presence of central areas, and the relative abundance of resistant taxa. A quantitative, rather than a subjective, dissolution index will help determine the preservational state of pelagic carbonates from the Paleocene.

  19. Effect of a magnetic field on the dissolution kinetics of carbon dioxide in aqueous solutions

    SciTech Connect

    Kruglitskii, N.N.; Kolomiets, A.A.; Kul'skii, L.A.; Rubezhanskii, K.A.; Zhantalai, B.P.

    1986-02-01

    This paper gives an account of an investigation into the effect of a magnetic field on the rate of dissolution of carbon dioxide in aqueous solutions. The CO/sub 2/ pressure in the system was maintained by a Hoffer valve. The method used for studying the dissolution kinetics of carbon dioxide in aqueous solutions is described. The specific rate of dissolution of carbon dioxide in solutions exposed to a magnetic field is lower than in solutions not so exposed. There is a tendency for the equilibrium solubility of CO/sub 2/ to increase in solutions exposed to a magnetic field.

  20. Dispersion Caused by Carbon Dioxide During Secondary Alumina Dissolution: A Lab-Scale Research

    NASA Astrophysics Data System (ADS)

    Yang, Youjian; Gao, Bingliang; Wang, Zhaowen; Shi, Zhongning; Hu, Xianwei; Yu, Jiangyu

    2014-06-01

    Secondary alumina is the byproduct of dry scrubbing in aluminum smelting. Secondary alumina has superior dissolution characteristics to primary alumina. Secondary alumina dissolves in pieces in molten cryolite, which results in larger contact area and better diffusion kinetics. In this work, the dissolution phenomenon of primary alumina, secondary alumina, and primary alumina doped with sodium carbonate or calcium carbonate (mass ratio = 10:1, 20:1) was observed and compared to estimate carbon-induced dispersion in industrial secondary alumina. Temperature fluctuations during sample dissolution were measured to evaluate the benefits of preheating on alumina dissolution. It was found that carbon mixed in secondary alumina significantly influences the dispersion of alumina particles at the moment of feeding, and thermodynamic analysis also shows that the combustion heat from carbon facilitates dispersion.

  1. Dissolution behaviour of magnetite film formed over carbon steel in dilute organic acid media

    NASA Astrophysics Data System (ADS)

    Prince, A. A. M.; Velmurugan, S.; Narasimhan, S. V.; Ramesh, C.; Murugesan, N.; Raghavan, P. S.; Gopalan, R.

    2001-03-01

    Magnetite is the major corrosion product formed over the carbon steel in the primary heat transport system of the pressurized heavy water reactor (PHWR). This magnetite usually accumulates radioactivity during reactor operation. The dissolution of the host magnetite is achieved by chemical formulations in order to get rid of the radioactivity trapped in the oxide; the underlying base metal also participates in the process by contributing electron to reduce the ferric ion or by undergoing corrosion. In the present study, the role of base metal in the dissolution of magnetite in various chelating agents has been investigated. The liberated hydrogen was measured by using an amperometric hydrogen sensor. The magnetite dissolution rate and the corrosion rate of carbon steel in the formulations were calculated. The effect of temperature, pH and concentration of the chelating agents on the magnetite film dissolution was studied in detail. The mechanism of base metal aided magnetite dissolution is discussed.

  2. Dissolution along fracture systems in Turonian-Campanian carbonates in Brazil

    NASA Astrophysics Data System (ADS)

    Hilario Rego Bezerra, Francisco; Cazarin, Caroline; Nogueira, Francisco; Rabelo, Juliana; Bertotti, Giovanni; Bisdom, Kevin; Silva, Carlos; Maia, Rubson

    2015-04-01

    Dissolution occurs by the action of diagenetic fluids of diverse nature along faults. When this process affects carbonate rocks, karst systems develop. Many karst systems evolve from dissolution of selected zones to pervasive karstification and to later burial and diagenesis. These systems resulted from coalesced, collapsed caves that may reach several thousand meters long and more than 100 m thick. We studied the dissolution along faults and fractures in the Turonian-Campanian carbonates in the Potiguar Basin, Brazil. We used an integrated multidisciplinary approach in outcrops and core samples, which combined Quickbird satellite imagery analysis, structural and sedimentary-facies mapping, and petrographic. The units investigated here presents a variety of carbonate facies, which include mudstones to bioclastic, peloidal, intraclastic, and oolitic grainstones. Our results indicate that dissolution occurred along N-S, NE-, and E-W-trending faults, which provided vertical leaching pathways of increased secondary porosity and permeability. Dissolution led to mechanical breakdown and collapse of carbonate blocks, which resulted in the infilling of clastic sediments and formation of collapse breccia in caves. The dissolution led to widespread karstification of the carbonate unit. We conclude that karstified faults and preferential sedimentary facies form the karst system, which makes the karst geometry predictable. We suggest that similar patterns may occur in other paleokarst systems.

  3. In-life pteropod shell dissolution as an indicator of past ocean carbonate saturation

    NASA Astrophysics Data System (ADS)

    Wall-Palmer, Deborah; Smart, Christopher W.; Hart, Malcolm B.

    2013-12-01

    Recent concern over the effects of ocean acidification upon calcifying organisms has highlighted the aragonitic shelled thecosomatous pteropods as being at a high risk. Both in-situ and laboratory studies have shown that an increased dissolved CO2 concentration, leading to decreased water pH and low carbonate concentration, causes reduced calcification rates and enhanced dissolution in the shells of living pteropods. In fossil records unaffected by post-depositional dissolution, this in-life shell dissolution can be detected. Here we present the first evidence of variations of in-life pteropod shell dissolution due to variations in surface water carbonate concentration during the Late Pleistocene by analysing the surface layer of pteropod shells in marine sediment cores from the Caribbean Sea and Indian Ocean. In-life shell dissolution was determined by applying the Limacina Dissolution Index (LDX) to the sub-tropical pteropod Limacina inflata. Average shell size information shows that high in-life dissolution is accompanied by smaller shell sizes in L. inflata, which may indicate a reduction in calcification rate. Comparison of the LDX profile to Late Pleistocene Vostok atmospheric CO2 concentrations, shows that in-life pteropod dissolution is closely associated to variations in past ocean carbonate saturation. This study confirms the findings of laboratory studies, showing enhanced shell dissolution and reduced calcification in living pteropods when surface ocean carbonate concentrations were lower. Results also demonstrate that oceanic pH levels that were less acidic and changing less rapidly than those predicted for the 21st Century, negatively affected pteropods during the Late Pleistocene.

  4. Lithologic controls on morphology of pressure-dissolution surfaces (stylolites and dissolution seams) in Paleozoic carbonate rocks from the mideastern United States

    SciTech Connect

    Railsback, L.B. )

    1993-05-01

    Examination of pressure-dissolution surfaces (stylolites and dissolution seams) in carbonate rocks from the mideastern US demonstrates that the morphology of these surfaces varies with rock fabric. In limestones, pressure dissolution causes suturing of intergranular contacts at the microscopic scale and formation of macroscopic pressure-dissolution surfaces. Pressure dissolution thus modifies limestone fabric, and it contributes to destruction of porosity in two ways, by eliminating intergranular space at sites of dissolution and by providing cement to fill pores elsewhere. In addition to these petrologic effects, pressure-dissolution surfaces (1) can generate bedding planes, (2) can account for significant thicknesses of lost section in stratigraphic reconstructions, and (3) can be of economic significance by modifying reservoir properties, by serving as barriers to petroleum migration, and by acting as seals for reservoirs. This paper examines lithologic controls on morphology of stylolites and dissolution seams in relatively undeformed carbonate rocks. It thus addresses many of the same problems on which Buxton and Sibley (1981) focused, but it quantifies, rather than categorizes, morphology of pressure-dissolution surfaces, and examines a more general sample suite from the mideastern US.

  5. The dissolution of carbon doixide in silicate melts

    NASA Astrophysics Data System (ADS)

    Nowak, M.; Spickenbom, K.; Porbatzki, D.

    2003-04-01

    Carbon dioxide and H_2O are the two most abundant volatile components in Earth's crust, mantle, and in magmatic liquids. In contrast to H_2O there is still little information about the dissolution mechanism of CO_2 in silicate melts. First annealing experiments of CO_2-bearing albitic and dacitic glasses near the glass transition temperature at 0.5 GPa demonstrate that in contrast to previous suggestions [1] the equilibrium of the homogeneous CO_2 species reaction CO_2 (melt) + O2- (melt) = CO_32- (melt) shifts towards molecular CO_2 with increasing temperature [2]. This behaviour was recently confirmed for dissolved CO_2 in jadeitic glasses [3]. In order to provide more insights into the thermodynamics and kinetics of CO_2 in silicate melts we performed additional annealing experiments with dacitic and albitic glasses, especially with different run times. Glass cylinders containing 0.15--0.2 wt% CO_2 were synthesized at 1603 K and 0.5 GPa and rapidly quenched to room temperature. Glass slabs 2--3 mm in height were used for time dependent annealing experiments at ambient P, 0.5 GPa, and at 673--973 K. Run durations were 1--1000 min. MIR micro-spectroscopy was used to determine the peak areas of the molecular CO_2 band at 2350 cm-1 and the CO_32- band system at 1800 to 1250 cm-1. In the temperature range 673--973 K the CO_2 speciation shifts significantly towards molecular CO_2 with increasing temperature, which is in agreement with [2,3]. The CO_2 species concentrations and an ideal solution model were used to derive values for the enthalpy Δ H^0 and entropy Δ S^0 of the homogeneous CO_2 species reaction, assuming that the CO_2 speciation reflects those at annealing temperatures (albitic composition: Δ H^0 = -12 ± 2 kJ mol-1 and Δ S^0 = -23 ± 3 J mol-1 K-1; dacitic composition: Δ H^0 = -29 ± 2 kJ mol-1 and Δ S^0 = -32 ± 3 J mol-1 K-1). Within error the thermodynamic values for dacitic composition derived from annealing experiments at ambient P and at 0

  6. Dissolution and carbonation of Portlandite [Ca(OH)2] single crystals.

    PubMed

    Ruiz-Agudo, Encarnación; Kudłacz, Krzysztof; Putnis, Christine V; Putnis, Andrew; Rodriguez-Navarro, Carlos

    2013-10-01

    The dissolution and carbonation of portlandite (Ca(OH)2) single crystals was studied by a combination of in situ Atomic Force Microscopy, Scanning Electron Microscopy, and two-dimensional X-ray diffraction. The dissolution of portlandite {0001} surfaces in water proceeds by the formation and expansion of pseudohexagonal etch pits, with edges parallel to ⟨100⟩ directions. Etch pits on {010} surfaces are elongated along ⟨001⟩, with edges parallel to ⟨101⟩. The interaction between carbonate-bearing solutions and portlandite results in the dissolution of the substrate coupled with the precipitation of thick islands of CaCO3 that appear oriented on the portlandite substrate. Ex situ carbonation of portlandite in contact with air results in the formation of pseudomorphs that fully preserve the external shape of the original portlandite single crystals. Our observations suggest that portlandite carbonation in contact with air and carbonate-bearing solutions occurs by a similar mechanism, i.e. coupled dissolution-precipitation. Calcite grows epitaxially on {0001} portlandite surfaces with the following orientation: ⟨001⟩Cc∥ ⟨001⟩Port. Apparently, no porosity is generated during the reaction, which progresses through the formation of fractures. Our results are of relevance to many processes in which the carbonation of portlandite takes place, such as CO2 capture and storage or the carbonation of cementitious materials. PMID:23915181

  7. Predicting carbonate mineral precipitation/dissolution events during progressive diagenesis of clastic rocks

    SciTech Connect

    Surdam, R.C.; MacGowan, D.B.; Dunn, T.L. ); Moraes, M. )

    1991-03-01

    There is an observable, regular progression of early and late carbonate cements that is separated by carbonate mineral dissolution in many sandstones during progressive burial and diagenesis. The distribution of early cements is a function of incipient hydration of framework grains, sulfate reduction, and bacterial methanogenesis. These early cements typically precipitate from the sediment water interace to burial depths corresponding to about 80C. The distribution of late carbonate cements is a function of the relationship of organic acid anions, aluminosilicate reactions and CO{sub 2} in formation waters. Elevated PCO{sub 2} in a fluid where the pH is buffered by organic acid anions or aluminosilicates results in precipitation of a late carbonate cement (typically ferroan); these late carbonate cements generally form over the temperature interval of 100-130C. The late and early carbonate cement events are separated in time by a period of carbonate mineral dissolution or nonprecipitation. This dissolution is related to the increase in concentration of carboxylic acid anions resulting from the thermocatalytic cracking of oxygen-bearing functional groups from kerogen and/or redox reactions involving kerogen. Examples of the importance of early carbonate cementation/decementation to hydrocarbon reservoirs include the Campos basin of Brazil and the U.S. Gulf Coast. An example of late carbonate cementation/decementation includes the Norphlet Formation. This observed sequence of cementation and decementation can be modeled, and the modeling results can be used to predict enhanced porosity in the subsurface.

  8. Experimental determination of natural carbonate rock dissolution rates with a focus on temperature dependency

    NASA Astrophysics Data System (ADS)

    Kirstein, Jens; Hellevang, Helge; Haile, Beyene G.; Gleixner, Gerd; Gaupp, Reinhard

    2016-05-01

    The denudation of carbonate rocks at landscape scale is controlled by factors like mineral composition, temperature, precipitation, runoff, fracture spacing and vegetation cover. Knowledge on carbonate denudation is important in order to understand landscape development and long-term terrestrial/marine carbon transport, but there are few laboratory studies done on weathering rates of natural carbonate rocks under the low temperatures relevant for glacial-interglacial periods. To enhance the understanding of carbonate dissolution kinetics we studied low-temperature dissolution reactions of various natural Triassic carbonate rocks belonging to the Lower Muschelkalk in Germany. We conducted batch and flow-through experiments investigating the direct correlation of dissolution rates with temperature, and to establish whether the fine-grained carbonate rocks (micrite) are more reactive than the coarser-grained sparitic limestones. By increasing the temperature from 5 to 26 °C far-from-equilibrium dissolution rates of micritic and sparitic limestone samples increased from 2.42 × 10- 07 to 10.88 × 10- 07 and 4.19 × 10- 07 to 7.74 × 10- 07 mol m- 2 s- 1, respectively (Specific Surface Areas (SSA) of about 0.006-0.01 m2/g). The dissolution rates of dolomite rock samples varied only slightly from 1.06 × 10- 07 to 2.02 × 10- 07 mol m- 2 s- 1 (SSA approximately 0.002 m2/g) in the temperature range 5-25 °C at circum-neutral pH. The obtained apparent activation energies are in the range of earlier experiments done at higher temperatures, but there is a distinct difference between the calcite in the micrite (~ 51 kJ/mol) and sparitic (~ 20-22 kJ/mol) lithologies, indicating that the dissolution mechanisms are not the same. Using these activation energies in modelling of natural carbonate denudation we see that there is a clear effect of changing temperature, but this is mostly through the increased solubility at lower temperatures and not through the increasing far

  9. Diurnal variation in rates of calcification and carbonate sediment dissolution in Florida Bay

    USGS Publications Warehouse

    Yates, K.K.; Halley, R.B.

    2006-01-01

    Water quality and circulation in Florida Bay (a shallow, subtropical estuary in south Florida) are highly dependent upon the development and evolution of carbonate mud banks distributed throughout the Bay. Predicting the effect of natural and anthropogenic perturbations on carbonate sedimentation requires an understanding of annual, seasonal, and daily variations in the biogenic and inorganic processes affecting carbonate sediment precipitation and dissolution. In this study, net calcification rates were measured over diurnal cycles on 27 d during summer and winter from 1999 to 2003 on mud banks and four representative substrate types located within basins between mud banks. Substrate types that were measured in basins include seagrass beds of sparse and intermediate density Thalassia sp., mud bottom, and hard bottom communities. Changes in total alkalinity were used as a proxy for calcification and dissolution. On 22 d (81%), diurnal variation in rates of net calcification was observed. The highest rates of net carbonate sediment production (or lowest rates of net dissolution) generally occurred during daylight hours and ranged from 2.900 to -0.410 g CaCO3 m-2 d-1. The lowest rates of carbonate sediment production (or net sediment dissolution) occurred at night and ranged from 0.210 to -1.900 g CaCO3 m -2 night-1. During typical diurnal cycles, dissolution during the night consumed an average of 29% of sediment produced during the day on banks and 68% of sediment produced during the day in basins. Net sediment dissolution also occurred during daylight, but only when there was total cloud cover, high turbidity, or hypersalinity. Diurnal variation in calcification and dissolution in surface waters and surface sediments of Florida Bay is linked to cycling of carbon dioxide through photosynthesis and respiration. Estimation of long-term sediment accumulation rates from diurnal rates of carbonate sediment production measured in this study indicates an overall average

  10. Lithologic controls on morphology of pressure dissolution surfaces in Paleozoic carbonates from the mideastern U. S

    SciTech Connect

    Railsback, L.B. . Dept. of Geology)

    1992-01-01

    Quantitative examination of pressure dissolution surfaces (stylolites and dissolution seams) in carbonate rocks from the mideastern US demonstrates that morphology of these surfaces is dependent on rock fabric. Morphology of these pressure dissolution surfaces can be effectively quantified using just four parameters: thickness (T) of the surface, amplitude of irregularity (I) of the surface, amplitude of vertical offsets (O) of the surface, and frequency (F) of offsets along the surface. I and O vary with T, reflecting the progressive development of stylolites, whereas F varies with 1/T, apparently because the physical strength of a stylolite inhibits formation of offsets. Mean values of F, O and T are greater in grainstones and packstones than in mudstones and wackestones, and mean values of T and O are greater in limestones than in dolostones. The proportion of dissolution seams to stylolites decreases through the lithologic spectrum from mudstones to grainstones. These relationships suggest that elaboration of pressure dissolution surfaces depends on the heterogeneity of the carbonate fabric. Maximum values of T and O in grainstones are correlative with abundance of intergranular cement. Within those grainstones, grains disproportionately occur as leading or penetrating elements of stylolite columns, and by contrast cements are apparently disfavored to survive stylolite development. Dissolution seams occur only in rocks containing fine-grained dolomite, and in those seams T and I decrease with increasing dolomite abundance. This relationship, combined with the observations from grainstones, suggests that development of pressure-dissolution surfaces is inhibited by relative abundance of pressure-resistant components such as carbonate grains and dolomite.

  11. Effects of acid deposition on dissolution of carbonate stone during summer storms in the Adirondack Mountains, New York, 1987-89

    USGS Publications Warehouse

    Schuster, Paul F.; Reddy, Michael M.; Sherwood, S.I.

    1994-01-01

    This study is part of a long-term research program designed to identify and quantify acid rain damage to carbonate stone. Acidic deposition accelerates the dissolution of carbonate-stone monuments and building materials. Sequential sampling of runoff from carbonate-stone (marble) and glass (reference) microcatchments in the Adirondack Mountains in New York State provided a detailed record of the episodic fluctuations in rain rate and runoff chemistry during individual summer storms. Rain rate and chemical concentrations from carbonate-stone and glass runoff fluctuated three to tenfold during storms. Net calcium-ion concentrations from the carbonatestone runoff, a measure of stone dissolution, typically fluctuated twofold during these storms. High net sulfate and net calcium concentrations in the first effective runoff at the start of a storm indicated that atmospheric pollutants deposited on the stone surface during dry periods formed calcium sulfate minerals, an important process in carbonate stone dissolution. Dissolution of the carbonate stone generally increased up to twofold during coincident episodes of low rain rate (less than 5 millimeters per hour) and decreased rainfall (glass runoff) pH (less than 4.0); episodes of high rain rate (cloudbursts) were coincident with a rapid increase in rainfall pH and also a rapid decrease in the dissolution of carbonate-stone. During a storm, it seems the most important factors causing increased dissolution of carbonate stone are coincident periods of low rain rate and decreased rainfall pH. Dissolution of the carbonate stone decreased slightly as the rain rate exceeded about 5 millimeters per hour, probably in response to rapidly increasing rainfall pH during episodes of high rain rate and shorter contact time between the runoff and the stone surface. High runoff rates resulting from cloudbursts remove calcium sulfate minerals formed during dry periods prior to storms and also remove dissolution products formed in large

  12. Comparative Dissolution Kinetics of Biogenic and Chemogenic Uraninite Under Oxidizing Conditions in the Presence of Carbonate

    SciTech Connect

    Ulrich, Kai-Uwe; Ilton, Eugene S.; Veeramani, Harish; Sharp, Jonathan O.; Bernier-Latmani, Rizlan; Schofield, Eleanor J.; Bargar, John; Giammar, Daniel E.

    2009-10-15

    The long-term stability of biogenic uraninite with respect to oxidation is pivotal to the success of in situ bioreduction strategies for the subsurface remediation of uranium legacies. Given the structural homology between biogenic uraninite nanoparticles obtained from Shewanella oneidensis MR-1 and chemogenic UO2.00, similar surface free energy and reactivity is expected. Batch and flow-through dissolution experiments were conducted along with spectroscopic analyses to compare both materials with respect to their equilibrium solubility, dissolution mechanisms, and dissolution kinetics in water of varied oxygen and carbonate concentrations. Both uraninite materials exhibited a similar intrinsic solubility of ~10-8 M under reducing conditions. The observation of comparable dissolution rates under anoxic as well as oxidizing conditions is consistent with the structural bulk homology of biogenic and stoichiometric uraninite. Carbonate, a ubiquitous groundwater component and strong complexant of U(VI), reversibly promoted the uraninite dissolution not only under moderately oxidizing, but also under reducing conditions, where the biogenic material yielded higher dissolution rates than the chemogenic. This difference is in accordance with the higher proportion of U(V) detected on the biogenic uraninite surface by means of x-ray photoelectron spectroscopy. Reasonable sources of the intermediate U(V) are discussed. The observed increase of the dissolution rates can be explained by carbonate complexation of U(V) facilitating the detachment of U(V) from the uraninite surface. The fraction of surface U(VI) increased with increasing oxygen concentration; this result is consistent with x-ray absorption near-edge spectra showing evidence of higher-valent U in the form of UO2+x (0 < x ≤ 0.20). In equilibrium with air, combined spectroscopic results support the formation of a near-surface layer of U4O9 (UO2.25) coated by an outer layer of U(VI) corresponding to a metaschoepite

  13. CO2-induced dissolution of low permeability carbonates. Part II: Numerical modeling of experiments

    NASA Astrophysics Data System (ADS)

    Hao, Yue; Smith, Megan; Sholokhova, Yelena; Carroll, Susan

    2013-12-01

    We used the 3D continuum-scale reactive transport models to simulate eight core flood experiments for two different carbonate rocks. In these experiments the core samples were reacted with brines equilibrated with pCO2 = 3, 2, 1, 0.5 MPa (Smith et al., 2013 [27]). The carbonate rocks were from specific Marly dolostone and Vuggy limestone flow units at the IEAGHG Weyburn-Midale CO2 Monitoring and Storage Project in south-eastern Saskatchewan, Canada. Initial model porosity, permeability, mineral, and surface area distributions were constructed from micro tomography and microscopy characterization data. We constrained model reaction kinetics and porosity-permeability equations with the experimental data. The experimental data included time-dependent solution chemistry and differential pressure measured across the core, and the initial and final pore space and mineral distribution. Calibration of the model with the experimental data allowed investigation of effects of carbonate reactivity, flow velocity, effective permeability, and time on the development and consequences of stable and unstable dissolution fronts. The continuum scale model captured the evolution of distinct dissolution fronts that developed as a consequence of carbonate mineral dissolution and pore scale transport properties. The results show that initial heterogeneity and porosity contrast control the development of the dissolution fronts in these highly reactive systems. This finding is consistent with linear stability analysis and the known positive feedback between mineral dissolution and fluid flow in carbonate formations. Differences in the carbonate kinetic drivers resulting from the range of pCO2 used in the experiments and the different proportions of more reactive calcite and less reactive dolomite contributed to the development of new pore space, but not to the type of dissolution fronts observed for the two different rock types. The development of the dissolution front was much more

  14. Dissolution of Uranium(IV) Oxide in Solutions of Ammonium Carbonate and Hydrogen Peroxide

    SciTech Connect

    Smith, Steven C.; Peper, Shane M.; Douglas, Matthew; Ziegelgruber, Kate L.; Finn, Erin C.

    2009-09-12

    Understanding the dissolution characteristics of uranium oxides is of fundamental scientific interest. Bench scale experiments were conducted to determine the optimal dissolution parameters of uranium(IV) oxide (UO2) powder in solutions of ammonium carbonate [(NH4)2CO3] and hydrogen peroxide (H2O2). Experimental parameters included variable peroxide and carbonate concentrations, and temperature. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M (1:1 to 40:1 mol ratio H2O2:U), with no apparent maximum rate reached under the limited conditions used in our study. Temperature ranging studies show the dissolution rate of UO2 in 1 M (NH4)2CO3 and 0.1 M H2O2 (2:1 mol ratio H2O2:U) increases linearly from 15 °C to 60 °C, again with no apparent maximum rate reached. Dissolution of UO2 in solutions with constant [H2O2] and [(NH4)2CO3] ranging from 0.5 to 2 M showed no difference in rate; however dissolution was significantly reduced in 0.05 M (NH4)2CO3 solution. The results of this study demonstrate the influence of [H2O2], [(NH4)2CO3], and temperature on the dissolution of UO2 in peroxide-containing (NH4)2CO3 solutions. Future studies are planned to elucidate the solution and solid state complexes in these systems.

  15. Experiment and Simulation Study of Hydrodynamic Dispersion and Finger Dynamics for Convective Dissolution of Carbon Dioxide

    NASA Astrophysics Data System (ADS)

    Liang, Y.; DiCarlo, D. A.; Hesse, M. A.

    2015-12-01

    Carbon capture and storage in deep geological formations has the potential to reduce anthropogenic CO2 emissions from industrial point sources. Dissolution of CO2 into the brine, resulting in stable stratification, has been identified as the key to long-term storage security. Here we present new analogue laboratory experiment method, advanced image processing method and optimized simulation method to characterize CO2 convective dissolution trapping process and gravitational finger behaviors, in order to study the effect of hydrodynamic dispersion on the CO2 convective dissolution process, as well as to study the effect of control physical parameters on the gravitational finger dynamics. Figure 1 shows the image processing method to analyze the finger dynamics. Understanding the effect of hydrodynamic dispersion and the finger dynamics are essential to evaluate whether convective dissolution occurs, as well as to predict how fast it occurs at the geological CO2 storage field scale. The effect of hydrodynamics dispersion and the finger dynamics can be applied to estimate the security of geological CO2 storage fields, in turn. Optimiezed simulation work is conducted to predict the CO2 dissolution rate at geological CO2 storage field. The large experimental assembly will allow us to quantify in detail for the first time the relationship between convective dissolution rate and the controlling factors of the system, including permeability and driven force, which could be essential to trapping process at Bravo Dome geological CO2 storage field. We complement the homogeneous experiments with a detailed study of the scaling law of the convective flux with dispersion effect. The advanced image processing method with Fourier's transform method allow us to understand the finger dynamics and corresponding control factors in porous media, for the first time. By applying the dispersion effect and finger dynamics we found from the experimental study, we optimize the simulation

  16. Fracture Dissolution of Carbonate Rock: An Innovative Process for Gas Storage

    SciTech Connect

    James W. Castle; Ronald W. Falta; David Bruce; Larry Murdoch; Scott E. Brame; Donald Brooks

    2006-10-31

    The goal of the project is to develop and assess the feasibility and economic viability of an innovative concept that may lead to commercialization of new gas-storage capacity near major markets. The investigation involves a new approach to developing underground gas storage in carbonate rock, which is present near major markets in many areas of the United States. Because of the lack of conventional gas storage and the projected growth in demand for storage capacity, many of these areas are likely to experience shortfalls in gas deliverability. Since depleted gas reservoirs and salt formations are nearly non-existent in many areas, alternatives to conventional methods of gas storage are required. The need for improved methods of gas storage, particularly for ways to meet peak demand, is increasing. Gas-market conditions are driving the need for higher deliverability and more flexibility in injection/withdrawal cycling. In order to meet these needs, the project involves an innovative approach to developing underground storage capacity by creating caverns in carbonate rock formations by acid dissolution. The basic concept of the acid-dissolution method is to drill to depth, fracture the carbonate rock layer as needed, and then create a cavern using an aqueous acid to dissolve the carbonate rock. Assessing feasibility of the acid-dissolution method included a regional geologic investigation. Data were compiled and analyzed from carbonate formations in six states: Indiana, Ohio, Kentucky, West Virginia, Pennsylvania, and New York. To analyze the requirements for creating storage volume, the following aspects of the dissolution process were examined: weight and volume of rock to be dissolved; gas storage pressure, temperature, and volume at depth; rock solubility; and acid costs. Hydrochloric acid was determined to be the best acid to use because of low cost, high acid solubility, fast reaction rates with carbonate rock, and highly soluble products (calcium chloride

  17. The Effect of Micrite on Velocity, Its Sensitivity to Pressure, and Dissolution of Carbonates

    NASA Astrophysics Data System (ADS)

    El Husseiny, A.; Vanorio, T.

    2014-12-01

    This study investigates the effect of micrite on the acoustic properties of well-controlled microstructures created in the laboratory to closely mimic carbonate rocks. In particular, we examine the effect of micrite content on the elastic stiffness rock, its sensitivity to pressure, and induced dissolution upon saturation with a reactive fluid. We followed Dunham's classification and fabricated the samples by mixing coarse (sand size) and very fine (micrite size) calcite grains in different ratios, with the addition of cement and then cold-compressing the mixture. The acoustic velocities were measured under bench-top conditions and as functions of confining pressure before and after the injection of a CO2aqueous solution. Our bench-top measurements indicated that micrite makes the frame of the carbonate samples stiffer. Since the sensitivity of the elastic stiffness to pressure decreases as the content of micrite increases (see figure 1), we hypothesize a stiffer pore structure (i.e., rounder pores) in micrite-richer fabrics. Furthermore, the presence of micrite makes the carbonate sample more reactive upon dissolution. The concentration of Ca+2 cations in the fluid measured at the outlet after the injection of the CO2 aqueous solution shows larger dissolution in the micrite-rich samples likely due to the higher surface area of the micrite aggregates. The content of micrite also seems to affect the evolution of stiffness as dissolution proceeds. As the content of micrite increases, the enhanced dissolution translates into a marked softening of the rock frame. We conclude that the content of micrite can play an important role in the complex rock-fluid interaction of carbonates as well as when comparing Gassmann's predictions to velocity measurements of saturated carbonates.

  18. Kinetics of carbonate dissolution in CO2-saturated aqueous system at reservoir conditions

    NASA Astrophysics Data System (ADS)

    Peng, Cheng; Crawshaw, John P.; Maitland, Geoffrey; Trusler, J. P. Martin

    2014-05-01

    In recent years, carbon capture and storage (CCS) has emerged as a key technology for limiting anthropogenic CO2 emissions while allowing the continued utilisation of fossil fuels. The most promising geological storage sites are deep saline aquifers because the capacity, integrity and injection economics are most favourable, and the environmental impact can be minimal. Many rock-fluid chemical reactions are known to occur both during and after CO2 injection in saline aquifers. The importance of rock-fluid reactions in the (CO2 + H2O) system can be understood in terms of their impact on the integrity and stability of both the formation rocks and cap rocks. The chemical interactions between CO2-acidified brines and the reservoir minerals can influence the porosity and permeability of the formations, resulting in changes in the transport processes occurring during CO2 storage. Since carbonate minerals are abundant in sedimentary rocks, one of the requirements to safely implement CO2 storage in saline aquifers is to characterise the reactivity of carbonate minerals in aqueous solutions at reservoir conditions. In this work, we reported measurements of the intrinsic rate of carbonate dissolution in CO2-saturated water under high-temperature high-pressure reservoir conditions extending up to 373 K and 14 MPa. The rate of carbonate dissolution in CO2-free HCl(aq) was also measured at ambient pressure at temperatures up to 353 K. Various pure minerals and reservoir rocks were investigated in this study, including single-crystals of calcite and magnesite, and samples of dolomite, chalks and sandstones. A specially-designed batch reactor system, implementing the rotating disc technique, was used to obtain the intrinsic reaction rate at the solid/liquid interface, free of mass transfer effects. The effective area and mineralogy of the exposed surface was determined by a combination of surface characterisation techniques including XRD, SEM, EDX and optical microscopy. The

  19. Macroscopic rates, microscopic observations, and molecular models of the dissolution of carbonate phases.

    SciTech Connect

    Duckworth, Owen W.; Cygan, Randall Timothy; Martin, Scot T.

    2004-05-01

    Bulk and surface energies are calculated for endmembers of the isostructural rhombohedral carbonate mineral family, including Ca, Cd, Co, Fe, Mg, Mn, Ni, and Zn compositions. The calculations for the bulk agree with the densities, bond distances, bond angles, and lattice enthalpies reported in the literature. The calculated energies also correlate with measured dissolution rates: the lattice energies show a log-linear relationship to the macroscopic dissolution rates at circumneutral pH. Moreover, the energies of ion pairs translated along surface steps are calculated and found to predict experimentally observed microscopic step retreat velocities. Finally, pit formation excess energies decrease with increasing pit size, which is consistent with the nonlinear dissolution kinetics hypothesized for the initial stages of pit formation.

  20. Setting accelerated dissolution test for PLGA microspheres containing peptide, investigation of critical parameters affecting drug release rate and mechanism.

    PubMed

    Tomic, I; Vidis-Millward, A; Mueller-Zsigmondy, M; Cardot, J-M

    2016-05-30

    The objective of this study was development of accelerated in vitro release method for peptide loaded PLGA microspheres using flow-through apparatus and assessment of the effect of dissolution parameters (pH, temperature, medium composition) on drug release rate and mechanism. Accelerated release conditions were set as pH 2 and 45°C, in phosphate buffer saline (PBS) 0.02M. When the pH was changed from 2 to 4, diffusion controlled phases (burst and lag) were not affected, while release rate during erosion phase decreased two-fold due to slower ester bonds hydrolyses. Decreasing temperature from 45°C to 40°C, release rate showed three-fold deceleration without significant change in release mechanism. Effect of medium composition on drug release was tested in PBS 0.01M (200 mOsm/kg) and PBS 0.01M with glucose (380 mOsm/kg). Buffer concentration significantly affected drug release rate and mechanism due to the change in osmotic pressure, while ionic strength did not have any effect on peptide release. Furthermore, dialysis sac and sample-and-separate techniques were used, in order to evaluate significance of dissolution technique choice on the release process. After fitting obtained data to different mathematical models, flow-through method was confirmed as the most appropriate for accelerated in vitro dissolution testing for a given formulation. PMID:27025293

  1. A probabilistic assessment of calcium carbonate export and dissolution in the modern ocean

    NASA Astrophysics Data System (ADS)

    Battaglia, Gianna; Steinacher, Marco; Joos, Fortunat

    2016-05-01

    The marine cycle of calcium carbonate (CaCO3) is an important element of the carbon cycle and co-governs the distribution of carbon and alkalinity within the ocean. However, CaCO3 export fluxes and mechanisms governing CaCO3 dissolution are highly uncertain. We present an observationally constrained, probabilistic assessment of the global and regional CaCO3 budgets. Parameters governing pelagic CaCO3 export fluxes and dissolution rates are sampled using a Monte Carlo scheme to construct a 1000-member ensemble with the Bern3D ocean model. Ensemble results are constrained by comparing simulated and observation-based fields of excess dissolved calcium carbonate (TA*). The minerals calcite and aragonite are modelled explicitly and ocean-sediment fluxes are considered. For local dissolution rates, either a strong or a weak dependency on CaCO3 saturation is assumed. In addition, there is the option to have saturation-independent dissolution above the saturation horizon. The median (and 68 % confidence interval) of the constrained model ensemble for global biogenic CaCO3 export is 0.90 (0.72-1.05) Gt C yr-1, that is within the lower half of previously published estimates (0.4-1.8 Gt C yr-1). The spatial pattern of CaCO3 export is broadly consistent with earlier assessments. Export is large in the Southern Ocean, the tropical Indo-Pacific, the northern Pacific and relatively small in the Atlantic. The constrained results are robust across a range of diapycnal mixing coefficients and, thus, ocean circulation strengths. Modelled ocean circulation and transport timescales for the different set-ups were further evaluated with CFC11 and radiocarbon observations. Parameters and mechanisms governing dissolution are hardly constrained by either the TA* data or the current compilation of CaCO3 flux measurements such that model realisations with and without saturation-dependent dissolution achieve skill. We suggest applying saturation-independent dissolution rates in Earth system

  2. A probabilistic assessment of calcium carbonate export and dissolution in the modern ocean

    NASA Astrophysics Data System (ADS)

    Battaglia, G.; Steinacher, M.; Joos, F.

    2015-12-01

    The marine cycle of calcium carbonate (CaCO3) is an important element of the carbon cycle and co-governs the distribution of carbon and alkalinity within the ocean. However, CaCO3 fluxes and mechanisms governing CaCO3 dissolution are highly uncertain. We present an observationally-constrained, probabilistic assessment of the global and regional CaCO3 budgets. Parameters governing pelagic CaCO3 export fluxes and dissolution rates are sampled using a Latin-Hypercube scheme to construct a 1000 member ensemble with the Bern3D ocean model. Ensemble results are constrained by comparing simulated and observation-based fields of excess dissolved calcium carbonate (TA*). The minerals calcite and aragonite are modelled explicitly and ocean-sediment fluxes are considered. For local dissolution rates either a strong, a weak or no dependency on CaCO3 saturation is assumed. Median (68 % confidence interval) global CaCO3 export is 0.82 (0.67-0.98) Gt PIC yr-1, within the lower half of previously published estimates (0.4-1.8 Gt PIC yr-1). The spatial pattern of CaCO3 export is broadly consistent with earlier assessments. Export is large in the Southern Ocean, the tropical Indo-Pacific, the northern Pacific and relatively small in the Atlantic. Dissolution within the 200 to 1500 m depth range (0.33; 0.26-0.40 Gt PIC yr-1) is substantially lower than inferred from the TA*-CFC age method (1 ± 0.5 Gt PIC yr-1). The latter estimate is likely biased high as the TA*-CFC method neglects transport. The constrained results are robust across a range of diapycnal mixing coefficients and, thus, ocean circulation strengths. Modelled ocean circulation and transport time scales for the different setups were further evaluated with CFC11 and radiocarbon observations. Parameters and mechanisms governing dissolution are hardly constrained by either the TA* data or the current compilation of CaCO3 flux measurements such that model realisations with and without saturation-dependent dissolution achieve

  3. Acid dissolution experiments - Carbonates and the 6.8-micrometer bands in interplanetary dust particles

    NASA Astrophysics Data System (ADS)

    Sandford, S. A.

    1986-03-01

    A chemical dissolution experiment on an interplanetary dust particle (IDP) showed that carbonates, not acid-insoluble organic compounds, were responsible for virtually all the absorption at 6.8 micrometers seen in the infrared spectra of this particle. The IDP examined had an infrared spectrum characteristic of layer-lattice silicates and belongs to a class of IDP's whose spectra resemble those of protostellar objects like W33 A, which also exhibit a band at 6.8 micrometers.

  4. Impact of geoengineering with olivine dissolution on the carbon cycle and marine biology

    NASA Astrophysics Data System (ADS)

    Köhler, P.; Abrams, J.; Völker, C.; Wolf-Gladrow, D. A.; Hartmann, J.

    2012-04-01

    We investigate the potential of a specific geoengineering technique: the carbon sequestration by artificially enhanced silicate weathering via the dissolution of olivine. This approach would not only operate against rising temperatures but would also oppose ocean acidification. If details of the marine chemistry are taken into consideration, a new mass ratio of CO2 sequestration per olivine dissolution of about 1 is achieved, 20% smaller than previously assumed. We calculate that this approach has the potential to sequestrate up to 1 Pg of C per year directly, if olivine is distributed as fine powder over land areas of the humid tropics, but this rate is limited by the saturation concentration of silicic acid. These upper limit sequestration rates come at the environmental cost of pH values in the rivers rising to 8.2 in examples for the rivers Amazon and Congo (Köhler et al., 2010). The secondary effects of the input of silicic acid connected with this approach leads in an ecosystem model (ReCOM2.0 in MITgcm) to species shifts aways from the calcifying species towards diatoms, thus altering the biological carbon pumps. Open ocean dissolution of olivine would sequestrate about 1 Pg CO2 per Pg olivine from which about 8% are caused by changes in the biological pumps (increase export of organic matter, decreased export of CaCO3). The chemical impact of open ocean dissolution of olivine (the increased alkalinity input) is therefore less efficient than dissolution on land, but leads due to different chemical impacts to a higher surface ocean pH enhancement to counteract ocean acidification. We finally investigate open ocean dissolution rates of up to 10 Pg olivine per year corresponding to geoengineering rates which might be of interest in the light of expected future emission (e.g. A2 scenario with emissions rising to 30 PgC/yr in 2100 AD). Those rates would still sequestrate only less than 20% of the emission until 2100, but would require that the nowadays available

  5. Tertiary carbonate-dissolution cycles on the Sierra Leone Rise, eastern equatorial Atlantic Ocean

    USGS Publications Warehouse

    Dean, W.E.; Gardner, J.V.; Cepek, P.

    1981-01-01

    Most of the Tertiary section on Sierra Leone Rise off northwest Africa consists of chalk, marl, and limestone that show cyclic alterations of clay-rich and clay-poor beds about 20-60 cm thick. On the basis of biostratigraphic accumulation rates, the cycles in Oligocene and Miocene chalk have periods which average about 44,000 years, and those in Eocene siliceous limestone have periods of 4000-27,000 years. Several sections were sampled in detail to further define the cycles in terms of content of CaCO3, clay minerals, and relative abundances of calcareous nannofossils. Extending information gained by analyses of Pleistocene cores from the continental margin of northwest Africa to the Tertiary cycles on Sierra Leone Rise, both dilution by noncarbonate material and dissolution of CaCO3 could have contributed to the observed relative variations in clay and CaCO3. However, dissolution of CaCO3 as the main cause of the carbonate-clay cycles on the Sierra Leone Rise, rather than dilution by clay, is suggested by the large amount of change (several thousand percent) in terrigenous influx required to produce the observed variations in amount of clay and by the marked increase in abundance of dissolution-resistant discoasters relative to more easily dissolved coccoliths in low-carbonate parts of cycles. The main cause of dissolution of CaCO3 was shoaling of the carbonate compensation depth (CCD) during the early Neogene and climatically induced fluctuations in the thickness of Antarctic Bottom Water. ?? 1981.

  6. Calcite cement generations after sulphate dissolution - Evidence for uplift diagenesis in Capitan and Zechstein carbonates

    SciTech Connect

    Harwood, G. ); Lee, M. ); Darke, G. )

    1991-03-01

    Upper Permian Capitan shelf margin and U.K. Zechstein carbonates contain evidence of former replacive anhydrite, formed early during their diagenetic histories. Both sequences were uplifted during the last 90 Ma with consequent sulfate hydration and dissolution. Resultant open cavities are occluded by calcite cements. Cement generations in the two areas are strikingly similar, although the areas were in contrasting climatic belts during uplift. Earliest uplift cements contain relics/evidence of former sulfates with minor bacteriogenic sulfide and precipitation from sulfate reduction. Two major generations of cavity-lining calcite cements formed after sulfate dissolution. Geochemical and isotopic analyses demonstrate these cements to be aquifer-related. The earlier luminescent cements, precipitated from stagnant anoxic waters, were etched and corroded, before minor iron oxide precipitation. These iron oxides enable paleomagnetic dating of uplift. The corrosion marks an anoxic-oxic transition within the pore fluids, with a later incursion of active oxic fluids, from which were precipitated iron-free nonluminescent columnar cements. Cores through the Zechstein carbonates show that cement phases develop successively as uplift proceeds. Thus cement generations were not precipitated synchronously but are representative of different levels within a downwards-penetrating aquifer. The cements relate to successive stages of aquifer evolution and allow a common history of uplift diagenesis to be determined for both areas, although on different continents and within different climatic zones. A similar cement sequence related to downwards aquifer penetration is thus predicted for other areas where sulfate dissolution has occurred on uplift.

  7. Pore-scale simulation of carbonate dissolution in micro-CT images

    NASA Astrophysics Data System (ADS)

    Pereira Nunes, J. P.; Blunt, M. J.; Bijeljic, B.

    2016-02-01

    We present a particle-based method to simulate carbonate dissolution at the pore scale directly on the voxels of three-dimensional micro-CT images. The flow field is computed on the images by solving the incompressible Navier-Stokes equations. Rock-fluid interaction is modeled using a three-step approach: solute advection, diffusion, and reaction. Advection is simulated with a semianalytical pore-scale streamline tracing algorithm, diffusion by random walk is superimposed, while the reaction rate is defined by the flux of particles through the pore-solid interface. We derive a relationship between the local particle flux and the independently measured batch calcite dissolution rate. We validate our method against a dynamic imaging experiment where a Ketton oolite is imaged during CO2-saturated brine injection at reservoir conditions. The image-calculated increases in porosity and permeability are predicted accurately, and the spatial distribution of the dissolution front is correctly replicated. The experiments and simulations are performed at a high flow rate, in the uniform dissolution regime - Pe ≫ 1 and PeDa ≪ 1—thus extending the reaction throughout the sample. Transport is advection dominated, and dissolution is limited to regions with significant inflow of solute. We show that the sample-averaged reaction rate is 1 order of magnitude lower than that measured in batch reactors. This decrease is the result of restrictions imposed on the flux of solute to the solid surface by the heterogeneous flow field, at the millimeter scale.

  8. Acceleration of convective dissolution by chemical reaction in a Hele-Shaw cell.

    PubMed

    Cherezov, Ilia; Cardoso, Silvana S S

    2016-09-14

    New laboratory experiments quantify the destabilising effect of a second-order chemical reaction on the fingering instability of a diffusive boundary layer in a Hele-Shaw cell. We show that, for a given chemical system, the dynamics of such a reactive boundary layer is fully determined by two dimensionless groups, Da/Ra(2), which measures the timescale for convection compared to those for reaction and diffusion, and CBo', which reflects the excess of the environmental reactant species relative to the diffusing solute. Results of a systematic study varying CBo' in the range 0-0.1 are presented. It is shown that the chemical reaction increases the growth rate of a perturbation and favours small wavelengths compared to the inert system. A higher concentration of CBo' not only accelerates the onset of convection, but crucially also increases the transport of the solute by up to 150% compared to the inert system. This increase in solute transfer has important practical implications, such as in the storage of carbon dioxide in saline aquifers. PMID:27510413

  9. Permeability evolution due to dissolution and precipitation of carbonates using reactive transport modeling in pore networks

    NASA Astrophysics Data System (ADS)

    Nogues, Juan P.; Fitts, Jeffrey P.; Celia, Michael A.; Peters, Catherine A.

    2013-09-01

    A reactive transport model was developed to simulate reaction of carbonates within a pore network for the high-pressure CO2-acidified conditions relevant to geological carbon sequestration. The pore network was based on a synthetic oolithic dolostone. Simulation results produced insights that can inform continuum-scale models regarding reaction-induced changes in permeability and porosity. As expected, permeability increased extensively with dissolution caused by high concentrations of carbonic acid, but neither pH nor calcite saturation state alone was a good predictor of the effects, as may sometimes be the case. Complex temporal evolutions of interstitial brine chemistry and network structure led to the counterintuitive finding that a far-from-equilibrium solution produced less permeability change than a nearer-to-equilibrium solution at the same pH. This was explained by the pH buffering that increased carbonate ion concentration and inhibited further reaction. Simulations of different flow conditions produced a nonunique set of permeability-porosity relationships. Diffusive-dominated systems caused dissolution to be localized near the inlet, leading to substantial porosity change but relatively small permeability change. For the same extent of porosity change caused from advective transport, the domain changed uniformly, leading to a large permeability change. Regarding precipitation, permeability changes happen much slower compared to dissolution-induced changes and small amounts of precipitation, even if located only near the inlet, can lead to large changes in permeability. Exponent values for a power law that relates changes in permeability and porosity ranged from 2 to 10, but a value of 6 held constant when conditions led to uniform changes throughout the domain.

  10. Effect of magnesium carbonate on the solubility, dissolution and oral bioavailability of fenofibric acid powder as an alkalising solubilizer.

    PubMed

    Kim, Kyeong Soo; Kim, Jeong Hyun; Jin, Sung Giu; Kim, Dong Wuk; Kim, Dong Shik; Kim, Jong Oh; Yong, Chul Soon; Cho, Kwan Hyung; Li, Dong Xun; Woo, Jong Soo; Choi, Han-Gon

    2016-04-01

    To investigate the possibility of developing a novel oral pharmaceutical product using fenofibric acid instead of choline fenofibrate, the powder properties, solubility, dissolution and pharmacokinetics in rats of fenofibrate, choline fenofibrate and fenofibric acid were compared. Furthermore, the effect of magnesium carbonate, an alkalising agent on the solubility, dissolution and oral bioavailability of fenofibric acid was assessed, a mixture of fenofibric acid and magnesium carbonate being prepared by simple blending at a weight ratio of 2/1. The three fenofibrate derivatives showed different particle sizes and melting points with similar crystalline shape. Fenofibric acid had a significantly higher aqueous solubility and dissolution than fenofibrate, but significantly lower solubility and dissolution than choline fenofibrate. However, the fenofibric acid/magnesium carbonate mixture greatly improved the solubility and dissolution of fenofibric acid with an enhancement to levels similar with those for choline fenofibrate. Fenofibric acid gave lower plasma concentrations, AUC and Cmax values compared to choline fenofibrate in rats. However, the mixture resulted in plasma concentrations, AUC and Cmax values levels not significantly different from those for choline fenofibrate. Specifically, magnesium carbonate increased the aqueous solubility, dissolution and bioavailability of fenofibric acid by about 7.5-, 4- and 1.6-fold, respectively. Thus, the mixture of fenofibric acid and magnesium carbonate at the weight ratio of 2/1 might be a candidate for an oral pharmaceutical product with improved oral bioavailability. PMID:26992922

  11. CO2-induced dissolution of low permeability carbonates. Part I: Characterization and experiments

    NASA Astrophysics Data System (ADS)

    Smith, Megan M.; Sholokhova, Yelena; Hao, Yue; Carroll, Susan A.

    2013-12-01

    The effect of elevated dissolved CO2 concentrations on compositionally and structurally distinct carbonate sample cores from the Weyburn-Midale CO2-enhanced oil recovery and storage site (Canada) was measured from analysis of 3-D sample characterization and fluid chemistry data from core-flood experiments. Experimental conditions (60 °C; 24.8 MPa confining pressure) and brine composition were chosen to mimic in situ reservoir conditions. Mineralogy and pore space distributions within the eight individual cores were characterized with X-ray computed microtomography and scanning electron microscopy both before and after exposure to brine with 0.5 ⩽ pCO2 ⩽ 3 MPa, while solution chemistry and differential fluid pressures were monitored during experiments. Our experimental study aimed to quantify the relationship between fluid flow, heterogeneity, and reaction specific to carbon storage at the Weyburn-Midale field by integrating characterization imaging, pressure data, and solution chemistry. Through the use of non-invasive microtomographic imaging, a variety of dissolution behaviors were observed, with variable effects on the evolution of solution chemistry and permeability as a result of heterogeneity within these two relatively low permeability carbonate samples. Similar-sized, evenly distributed pores, and steadily advancing dissolution fronts suggested that uniform flow velocities were maintained throughout the duration of the higher permeability “Marly” dolostone core experiments. The development of unstable dissolution fronts and fast pathways occurred in the “Vuggy” sample experiments when fluid velocities varied widely within the sample (as a result of increased pore structure heterogeneity). The overall effect of fast pathway development was to increase bulk permeability values by several orders of magnitude, allowing CO2-acidified fluids to travel through the cores largely unmodified by carbonate mineral reaction, as indicated by a lack of change

  12. Will peak oil accelerate carbon dioxide emissions?

    NASA Astrophysics Data System (ADS)

    Caldeira, K.; Davis, S. J.; Cao, L.

    2008-12-01

    The relative scarcity of oil suggests that oil production is peaking and will decline thereafter. Some have suggested that this represents an opportunity to reduce carbon dioxide emissions. However, in the absence of constraints on carbon dioxide emission, "peak oil" may drive a shift towards increased reliance on coal as a primary energy source. Because coal per unit energy, in the absence of carbon capture and disposal, releases more carbon dioxide to the atmosphere than oil, "peak oil" may lead to an acceleration of carbon dioxide emissions. We will never run out of oil. As oil becomes increasingly scarce, prices will rise and therefore consumption will diminish. As prices rise, other primary energy sources will become increasingly competitive with oil. The developed world uses oil primarily as a source of transportation fuels. The developing world uses oil primarily for heat and power, but the trend is towards increasing reliance on oil for transportation. Liquid fuels, including petroleum derivatives such as gasoline and diesel fuel, are attractive as transportation fuels because of their relative abundance of energy per unit mass and volume. Such considerations are especially important for the air transport industry. Today, there is little that can compete with petroleum-derived transportation fuels. Future CO2 emissions from the transportation sector largely depend on what replaces oil as a source of fuel. Some have suggested that biomass-derived ethanol, hydrogen, or electricity could play this role. Each of these potential substitutes has its own drawbacks (e.g., low power density per unit area in the case of biomass, low power density per unit volume in the case of hydrogen, and low power density per unit mass in the case of battery storage). Thus, it is entirely likely that liquefaction of coal could become the primary means by which transportation fuels are produced. Since the burning of coal produces more CO2 per unit energy than does the burning of

  13. Dissolution of Irradiated Commercial UO2 Fuels in Ammonium Carbonate and Hydrogen Peroxide

    SciTech Connect

    Soderquist, Chuck Z.; Johnsen, Amanda M.; McNamara, Bruce K.; Hanson, Brady D.; Chenault, Jeffrey W.; Carson, Katharine J.; Peper, Shane M.

    2011-01-18

    We propose and test a disposition path for irradiated nuclear fuel using ammonium carbonate and hydrogen peroxide media. We demonstrate on a 13 g scale that >98% of the irradiated fuel dissolves. Subsequent expulsion of carbonate from the dissolver solution precipitates >95% of the plutonium, americium, curium, and substantial amounts of fission products, effectively partitioning the fuel at the dissolution step. Uranium can be easily recovered from solution by any of several means, such as ion exchange, solvent extraction, or direct precipitation. Ammonium carbonate can be evaporated from solution and recovered for re-use, leaving an extremely compact volume of fission products, transactinides, and uranium. Stack emissions are predicted to be less toxic, less radioactive, chemically simpler, and simpler to treat than those from the conventional PUREX process.

  14. Experimental Study of Convective Dissolution of Carbon Dioxide in Heterogeneous Media

    NASA Astrophysics Data System (ADS)

    Liang, Y.; DiCarlo, D. A.; Hesse, M. A.

    2013-12-01

    Carbon capture and storage in deep geological formations has the potential to reduce anthropogenic carbon dioxide (CO2) emissions from industrial point sources. The technology is only viable, if the long-term security of the geological CO2 storage can be demonstrated. Dissolution of CO2 into the brine, resulting in stable stratification, has been identified as the key to long-term storage security. Here we present new analogue laboratory experiments to characterize convective dissolution and to study the effect of porosity and permeability heterogeneity on the CO2 dissolution rate. Understanding the effect of heterogeneity is essential to evaluate if convective dissolution occurs in the field and, in turn, to estimate the security of geological CO2 storage fields. In particular we want to test if the strong heterogeneity observed at the Bravo Dome natural CO2 field can prevent convective currents, which may explain the persistence of free phase CO2 over millennia. Initial laboratory experiments in homogeneous media confirm that the non-classical scaling of the convective flux scales with the 4/5 power of the Rayleigh number that has recently been reported. The large experimental assembly will allow us to quantify for the first time the relationship between wavenumber of the convective motion and the Rayleigh number of the system, which could be essential to trapping process at Bravo Dome. Figure 1 shows the number of fingers that we can observe in our new experimental setup. Figure 2 shows the same photograph that has been processed to enhance the visibility of the dense plumes descending from the interface. Also we plan to complement the homogeneous experiments with a detailed study of the scaling law of the convective flux in heterogeneous, layered media; in particular. Low permeability layers are ubiquitous in geological storage formations and have been observed at Bravo Dome. We plan to measure the reduction in the convective flux due to these barriers compared

  15. Dissolution of CO2 in Brines and Mineral Reactions during Geological Carbon Storage: AN Eor Experiment

    NASA Astrophysics Data System (ADS)

    Bickle, M. J.; Chapman, H.; Galy, A.; Kampman, N.; Dubacq, B.; Ballentine, C. J.; Zhou, Z.

    2015-12-01

    Dissolution of CO2 in formation brines is likely to be a major process which stabilises stored CO2 on longer time scales and mitigates CO2 migrating through storage complexes. However very little is known about the likely rates of CO2 dissolution as CO2 flows through natural heterogeneous brine filled reservoirs. Here we report the results of sampling fluids over 6 months after a phase of CO2 injection commenced for enhanced oil recovery coupled with injection of isotopically enriched 3He and 129Xe. Modelling of the changes in fluid chemistry has previously been interpreted to indicate significant dissolution of silicate minerals where fluids remained close to saturation with calcite. These calculations, which are based on modal decomposition of changes in cation concentrations, are supported by changes in the isotopic compositions of Sr, Li and Mg. Analysis of Sr-isotopic compositions of samples from outcrops of the Frontier Formation, which forms the reservoir sampled by the EOR experiment, reveals substantial heterogeneity. Silicate mineral compositions have 87Sr/86Sr ratios between 0.709 and 0.719 whereas carbonate cements have values around 0.7076. Calculation of CO2 dissolution based on simplified 2-D flow models shows that fluids likely sample reservoir heterogeneities present on a finer scale with CO2 fingers occupying the most permeable horizons and most water flow in the adjacent slightly less permeable zones. Smaller time scale variations in 87Sr/86Sr ratios are interpreted to reflect variations in flow paths on small length scales driven by invading CO2.

  16. The three steps of the carbonate biogenic dissolution process by microborers in coral reefs (New Caledonia).

    PubMed

    Grange, J S; Rybarczyk, H; Tribollet, A

    2015-09-01

    Biogenic dissolution of carbonates by microborers is one of the main destructive forces in coral reefs and is predicted to be enhanced by eutrophication and ocean acidification by 2100. The chlorophyte Ostreobium sp., the main agent of this process, has been reported to be one of the most responsive of all microboring species to those environmental factors. However, very little is known about its recruitment, how it develops over successions of microboring communities, and how that influences rates of biogenic dissolution. Thus, an experiment with dead coral blocks exposed to colonization by microborers was carried out on a reef in New Caledonia over a year period. Each month, a few blocks were collected to study microboring communities and the associated rates of biogenic dissolution. Our results showed a drastic shift in community species composition between the 4th and 5th months of exposure, i.e., pioneer communities dominated by large chlorophytes such as Phaeophila sp. were replaced by mature communities dominated by Ostreobium sp. Prior the 4th month of exposure, large chlorophytes were responsible for low rates of biogenic dissolution while during the community shift, rates increased exponentially (×10). After 6 months of exposure, rates slowed down and reached a "plateau" with a mean of 0.93 kg of CaCO3 dissolved per m(2) of reef after 12 months of exposure. Here, we show that (a) Ostreobium sp. settled down in new dead substrates as soon as the 3rd month of exposure but dominated communities only after 5 months of exposure and (b) microbioerosion dynamics comprise three distinct steps which fully depend on community development stage and grazing pressure. PMID:25592911

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  18. Laboratory experiments on CO2 dissolution in water for carbon sequestration

    NASA Astrophysics Data System (ADS)

    Fernandez de La Reguera, D.; Stute, M.; Matter, J. M.

    2010-12-01

    The standard approach to geologic sequestration is the injection of CO2 as a bulk phase into storage reservoirs at depths >800m where it is buoyant with respect to the host rocks and aqueous fluids, and may migrate upward thereby reducing the storage efficiency. The CarbFix pilot project in Iceland tests the feasibility of an alternative storage approach, which is the mineralization of CO2 into stable carbonate minerals through the reaction with basaltic rocks [1]. The mineralization of CO2 is facilitated by the dissolution of CO2 gas into the aqueous phase. Therefore, CarbFix will inject the CO2 fully dissolved in water. Dissolution will occur within the injection well, where water and CO2 are simultaneously injected. A downscaled version of the CarbFix injection system was designed in the laboratory and used to study the dissolution kinetics of CO2 gas bubbles in a water column while injection took place. The injection system consisted of 100 m long ~1 cm inner diameter inner braided PVC tubing, which was deployed in a staircase of a 60m tall building. The tubing was intersected with a series of 10 cm long sections of clear tubing (windows) every eight meters in order to detect the number of bubbles in the flow with a digital camera equipped with a flash system. As CO2 gas was injected through a sparger into the water stream at a constant rate, gas bubbles were created, with bubble size and density decreasing along the vertical flow path, as the CO2 dissolved. The number and volume of gas bubbles were estimated from the digital images taken at each window. Various devices that were supposed to facilitate the dissolution of CO2 were tested. The pressure change due to elevation change and frictional effects was calculated using the Darcy-Weisbach equation and the amount of CO2 per bubble in each window was approximated using the van der Waals equation of state for real gases. The experimental results reveal that bubble size and density decrease along the flow path

  19. Peridotite dissolution and carbonation rates at fracture surfaces under conditions relevant for in situ mineralization of CO2

    NASA Astrophysics Data System (ADS)

    van Noort, R.; Spiers, C. J.; Drury, M. R.; Kandianis, M. T.

    2013-04-01

    Whereas the dissolution of pure single phases (e.g. olivine and other mafic minerals) has been the focus of many studies, no investigation has been reported on the progress of reactions at and within polymineralic, transgranular fracture surfaces cutting peridotites. We document experiments that address the evolution of dissolving peridotite surfaces, and the rates of dissolution and carbonation reactions that occur at these surfaces, under both open- and closed-system conditions relevant for in situ CO2-sequestration. The results of experiments, conducted under quasi-open system conditions, on solid samples of peridotite whose surfaces were taken as an analogue of free fracture surfaces, demonstrate apparent rates of olivine dissolution at the free surfaces that are equivalent to or upwards of 100 times greater than those determined for pure olivine under similar conditions. This increase in apparent olivine dissolution rate is ascribed to fluid penetration along grain boundaries and veins, which resulted in increased accessibility of reactive olivine surface area. Apparent dissolution rates under closed system conditions, where serial olivine dissolution and magnesite precipitation take place, are ˜1 order of magnitude slower owing to changes in fluid composition and pH. In both of these reaction environments, it is apparent that serpentinized veins and mineral grain boundaries within the peridotite allowed fluids to penetrate the rock and to promote the release of divalent metals and silica from within the sample or simulated fracture walls. These results indicate that the microstructure of free (fracture) surfaces exerts a dominant control on peridotite dissolution and carbonation rates, relative to the proportion of highly reactive minerals that compose such ultramafic rock. The rapid dissolution we observe under open system conditions implies that CO2-mineralization may be viable, in open systems, if the composition of injected fluids can be maintained at or

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

    NASA Technical Reports Server (NTRS)

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

    2006-01-01

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

  1. Relative roles of endolithic algae and carbonate chemistry variability in the skeletal dissolution of crustose coralline algae

    NASA Astrophysics Data System (ADS)

    Reyes-Nivia, C.; Diaz-Pulido, G.; Dove, S.

    2014-09-01

    The susceptibility of crustose coralline algae (CCA) skeletons to dissolution is predicted to increase as oceans warm and acidify. Skeletal dissolution is caused by bioerosion from endolithic microorganisms and by chemical processes associated with undersaturation of carbonate minerals in seawater. Yet, the relative contribution of algal microborers and seawater carbonate chemistry to the dissolution of organisms that cement reefs under projected pCO2 and temperature (pCO2-T) scenarios have not been quantified. We exposed CCA skeletons (Porolithon onkodes) to four pCO2-T treatments (pre-industrial, present-day, SRES-B1 "reduced" pCO2, and SRES-A1FI "business-as-usual" pCO2 emission scenarios) under natural light cycles vs. constant dark conditions for 8 weeks. Dissolution rates of skeletons without photo-endoliths were dramatically higher (200%) than those colonized by endolithic algae across all pCO2-T scenarios. This suggests that daytime photosynthesis by microborers counteract dissolution by reduced saturation states resulting in lower net erosion rates over day-night cycles. Regardless of the presence or absence of phototrophic microborers, skeletal dissolution increased significantly under the spring A1FI "business-as-usual" scenario, confirming the CCA sensitivity to future oceans. Projected ocean acidity and temperature may significantly disturb the stability of reef frameworks cemented by CCA, but surficial substrates harbouring photosynthetic microborers will be less impacted than those without algal endoliths.

  2. Relative roles of endolithic algae and carbonate chemistry variability in the skeletal dissolution of crustose coralline algae

    NASA Astrophysics Data System (ADS)

    Reyes-Nivia, C.; Diaz-Pulido, G.; Dove, S.

    2014-02-01

    The susceptibility of crustose coralline algae (CCA) skeletons to dissolution is predicted to increase as oceans warm and acidify. Skeletal dissolution is caused by bioerosion from endolithic microorganisms and by chemical processes associated with undersaturation of carbonate minerals in seawater. Yet, the relative contribution of algal microborers and seawater carbonate chemistry to the dissolution of organisms that cement reefs under projected CO2 and temperature (CO2-T) scenarios have not been quantified. We exposed CCA skeletons (Porolithon onkodes) to four CO2-T treatments (pre-industrial, present-day, SRES-B1 reduced CO2 emission scenario, SRES-A1FI business-as-usual CO2 emission scenario) under natural light cycles vs. constant dark conditions for 8 weeks. Dissolution rates of skeletons without photo-endoliths were dramatically higher (200%) than those colonized by endolithic algae across all CO2-T scenarios. This suggests that daytime photosynthesis by microborers counteract dissolution by reduced saturation states resulting in lower net erosion rates over day-night cycles. Regardless of the presence or absence of phototrophic microborers, skeletal dissolution increased significantly under the spring A1FI "business-as-usual" scenario, confirming the CCA sensitivity to future oceans. Projected ocean acidity and temperature may significantly disturb the stability of reef frameworks cemented by CCA, but surficial substrates harboring photosynthetic microborers will be less impacted than those without algal endoliths.

  3. Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling

    USGS Publications Warehouse

    Brown, J.G.; Glynn, P.D.

    2003-01-01

    The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

  4. Modeling and simulation of NiO dissolution and Ni deposition in molten carbonate fuel cells

    SciTech Connect

    Nam, Suk Woo; Choi, Hyung-Joon; Lim, Tae Hoon

    1996-12-31

    Dissolution of NiO cathode into the electrolyte matrix is an important phenomena limiting the lifetime of molten carbonate fuel cell (MCFC). The dissolved nickel diffuses into the matrix and is reduced by dissolved hydrogen leading to the formation of metallic nickel films in the pores of the matrix. The growth of Ni films in the electrolyte matrix during the continuous cell operation results eventually in shorting between cathode and anode. Various mathematical and empirical models have been developed to describe the NiO dissolution and Ni deposition processes, and these models have some success in estimating the lifetime of MCFC by correlating the amount of Ni deposited in the matrix with shorting time. Since the exact mechanism of Ni deposition was not well understood, deposition reaction was assumed to be very fast in most of the models and the Ni deposition region was limited around a point in the matrix. In fact, formation of Ni films takes place in a rather broad region in the matrix, the location and thickness of the film depending on operating conditions as well as matrix properties. In this study, we assumed simple reaction kinetics for Ni deposition and developed a mathematical model to get the distribution of nickel in the matrix.

  5. Dissolution along faults-fractures and hypogenic karst in carbonates: examples from Brazil

    NASA Astrophysics Data System (ADS)

    Ennes-Silva, Renata; Cazarin, Caroline; Bezerra, Francisco; Auler, Augusto; Klimchouk, Alexander

    2015-04-01

    Dissolution along faults-fractures and hypogenic karst in carbonates: examples from Brazil Ennes-Silva, R.A; Cazarin, C.L.; Bezerra, F.H.; Auler, A.S.; Klimchouk, A.B. Dissolution along zones of preferential flow enhances anisotropy in geological media and increases its complexity. Changes in parameters such as porosity and permeability due to diagenesis and presence of ascendant fluids along fractures and faults can be responsible for hypogenic karstic system. The present study investigates the relationship between lithofacies, tectonics and karstification in the Neoproterozoic Salitre Formation, located in the central-eastern Brazil. This unit comprises several systems of caves including the Toca da Boa Vista and da Barriguda hypogenic caves, the largests in South America, and focus of this study. We focused on cave mapping and morphogenetic analysis, determination of petrophysical properties, thin-section description, micro-tomography, and isotopic analysis. The Salitre Formation, deposited in an epicontinental sea, comprises mud/wakestones, grainstones, microbial facies, and fine siliciclastic rocks. Passages occur in several levels within ca. 60 m thick cave-forming section, limited at the top by lithofacies with low permeability and fractures. Cave development occurred in phreatic sluggish-flow environment with overall upwelling flow. Fluids rise via cross-formational fractures and were distributed laterally within the cave-forming section using geological heterogeneities to eventually discharge up through outlets breaching across the upper confining beds. Maps of conduits show preferred directions for development of conduits: NNE-SSW and E-W. These two directions represents a relation between structures and hypogenic morphology. Joints, axis fold and fractures allowed pathways to the fluid rises, and then development of channels of entrance (feeders), outputs (outlets) and some cupolas, which are clearly aligned to fractures. Our data indicate several events

  6. The acceleration and dissolution of stars moving through the blackbody radiation of a collapsing universe

    NASA Astrophysics Data System (ADS)

    Argon, Alice L.

    This dissertation deals with the motion and ablation of stars in the collapse phase of a closed Friedmann universe. Stars are initially accelerated due to the collapse of space. Radiation drag becomes increasingly important, however, and in most of the cases considered leads to maximum speeds and rapid deceleration. The external blackbody radiation also leads to mass loss, which acts as an additional accelerating mechanism. Three species of degenerate stars are considered: black dwarfs (BD), white dwarfs (WD), and neutron stars (NS). Each is assumed to have a non-degenerate, ionized atmosphere. In the star's rest frame the external blackbody radiation appears highly anisotropic, with most of the radiation entering the atmosphere through a narrow cone centered on the forward direction (opposite to the direction of motion). This radiation is Compton scattered. Atmospheric electrons (and hence ions) are accelerated azimuthally. After having travelled about one quarter of a circumference, they detach themselves from the star and stream away. The atmosphere is constantly replenished by upwelling from the interior. Mass loss then is a result of mechanical forces and is not due to thermal boiling. Four optical depths are considered for each species: 0, 1, 2, and 3. Maximum speeds and related temperatures are given for BD0, BD1, WD0, WD1, WD2, NS0, NS1, NS2 and NS3.

  7. The effect of the carbon dissolution on the crystal structure of a-quartz

    NASA Astrophysics Data System (ADS)

    Mitani, S.; Kyono, A.

    2015-12-01

    Silicon is one of the major and important element that constitutes the Earth's crust and mantle. An enormous amount of carbon is also contained in the Earth's interior, which suggests that silicate could be closely interacted with carbon under high-pressure and high-temperature (Sen et al. 2013, PNAS). It is suggested that carbon dioxide is dissolved in cristobalite and the average composition of CO2-SiO2 solid solution is C0.6(1)Si0.4(1)O2 High-pressure experiment (Santoro et al. 2014, Nat. Commun.). Furthermore, the first-principles calculations suggested the possibility of successive CO2 dissolution in cristobalite at ambient pressure (Aravindh et al. 2007, Solid State Commun.). However, CO2-SiO2 solid solution at ambient pressure has not confirmed in laboratory experiment. In this study, we mixed amorphous silica and amorphous carbon and synthesized CO2-SiO2 solid solution at high-temperature under ambient pressure. Powder amorphous silica and graphite was mixed together in the agate mill in order to be homogenized mixture. They were heated for 1300 ˚C, 3 days under ambient pressure. Then, the samples were quenched at room temperature. The samples of CO2-SiO2 solid solution were carefully examined by powder XRD, EPMA measurement, and so on. From the result of the powder XRD, the products were a-quartz. In this lecture, we report the quantity of carbon dissolved in a-quartz and its effect for the crystal structure of a-quartz in detail.

  8. Noble gas and carbon isotopic evidence for CO2-driven silicate dissolution in a recent natural CO2 field

    NASA Astrophysics Data System (ADS)

    Dubacq, Benoît; Bickle, Mike J.; Wigley, Max; Kampman, Niko; Ballentine, Chris J.; Sherwood Lollar, Barbara

    2012-08-01

    Secure storage of anthropogenic carbon dioxide (CO2) in geological reservoirs requires predicting gas-water-rock interactions over millennial timescales. Noble gases and carbon isotope measurements can be used to shed light on the nature of competing dissolution-precipitation processes over different timescales, from the fast dissolution of gaseous CO2 in groundwater to more sluggish reactions involving dissolution and precipitation of newly formed minerals in the reservoir. Here we study a compilation of gas analyses including noble gases and δ13C of CO2 from nine different natural CO2 reservoirs. Amongst these reservoirs, the Bravo Dome CO2 field (New Mexico, USA) shows distinct geochemical trends which are explained by degassing of noble gases from groundwater altering the composition of the gas phase. This groundwater degassing is synchronous with the dissolution of CO2 in groundwater. Progressive creation of alkalinity via CO2-promoted mineral dissolution is required to explain the observed positive correlation between CO2/3He and δ13C of the gas phase, a unique feature of Bravo Dome. The differences between Bravo Dome and other natural CO2 reservoirs are likely explained by the more recent filling of Bravo Dome, reflecting CO2-water-rock interactions over thousands of years rather than over millions of years in older reservoirs.

  9. Carbon Dissolution in Reduced Silicate and Alloy Melts - a Frontier for Understanding Evolution of Terrestrial Planets

    NASA Astrophysics Data System (ADS)

    Dasgupta, R.; Chi, H.; Li, Y.; Duncan, M. S.; Tsuno, K.

    2014-12-01

    C-O-H-S-N volatile elements sequestration in and release from silicate and metallic melts are key in controlling the planet scale distribution of these elements and thus are critical for thermo-chemical and dynamic evolution of terrestrial planets. To understand the distribution of carbon during accretion, core formation, magma ocean crystallization, and ongoing evolution of reduced mantles domains such as those of Mars, the Moon, and deep Earth, carbon chemistry in reduced silicates and alloys must be constrained, but currently are poorly known. Here we summarize recent experimental efforts to (1) constrain the speciation and solubility of carbon in graphite-saturated natural mafic melts at fO2 below IW buffer and (2) C solubility in Fe-Ni-rich alloy melts. Quenched glasses and alloys generated to 8 GPa and 2200 °C are analyzed using a combination of electron and ion microprobe, FTIR, and Raman spectroscopy. Dissolved carbonates and bulk C solubility (<200 ppm) of graphite-saturated silicate glasses are observed to increase with decreasing pressure and increasing temperature, melt depolymerization index (e.g., NBO/T), and fO2 from ~IW-1.5 to IW [1,2]. Over the range in fO2, melt H2O content also mildly enhances carbonate dissolution, likely in part owing to the depolymerizing effect of H2O in the melt. At fO2>IW-1.5, dissolved C is a mixture of carbonates and other species, but below ~IW-1.5 the carbonate doublet is undetectable in IR spectra, with Raman spectra indicating the dominant species being methane or other methyl groups. In addition, with diminishing fO2 from IW-2 to IW-5, C solubility trend reverses, i.e., it increases with decreasing fO2 and also shows a much stronger dependence on melt H content [3], consistent with the enhanced solubility of methane in silicate melt with decreasing fO2 and increasing with square of fH2. However, Fe-Ni-rich alloy melts have high C solubility (~0.7-7 wt.%) that diminishes mostly with increasing Ni, Si, and S contents

  10. Experimental approaches to marine and meteoric dissolution-to-repreciptiation cycles of fine-grained marine carbonate sediments

    NASA Astrophysics Data System (ADS)

    Immenhauser, Adrian; Buhl, Dieter; Riechelmann, Sylvia; Kwiecien, Ola; Lokier, Stephen; Neuser, Rolf

    2016-04-01

    Fine-grained carbonate (carbonate ooze), or microcrystalline carbonate (micrite), its lithified counterpart, forms a main constituent of limestones throughout much of Earth's history. Fine-grained carbonates are deposited below the permanent fair-weather wave base in neritic lagoonal environments or below the storm-wave base in basinal settings. The origin of components forming these fine-grained carbonates often remains poorly understood and represents a major challenge in carbonate sedimentology, particularly when these materials are used as carbonate archives (bulk micrite geochemistry). Here we present a novel experimental approach exposing natural, fine-grained carbonate sediments to dissolution-reprecipitation cycles under non-sterile conditions that mimick earth-surface conditions. In a first stage, the experiment simulated subaerial exposure of an ooid (aragonite) shoal and leaching and carbonate dissolution under meteoric phreatic conditions. In a second stage, CO2 was added to the experimental fluid (natural rainwater) representing soil-zone activity. In a third stage, partly dissolved (micro-karstified) sediments were exposed to marine phreatic conditions simulating renewed flooding of the shoal carbonates. During the third stage, precipitation was induced by degassing the CO2 in the fluid with N2. Degassing induced nucleation and growth of a diagenetic inorganic aragonite (and subordinate calcite) phase upon the surface of carbonate particles. The outcome of these first experiments is promising. The CO2 concentration of the fluid and the air are low under atmospheric conditions and increase as expected due to adding CO2 to the experiment resulting in a lower pH. Carbonate dissolution increases conductivity, alkalinity, and calcium concentration reaching a plateau at the end of the first experimental phase. Small surficial damages to ooids represent zones of weakness and form the preferred sites of dissolution leading to a deepening and widening of these

  11. Loading amorphous Asarone in mesoporous silica SBA-15 through supercritical carbon dioxide technology to enhance dissolution and bioavailability.

    PubMed

    Zhang, Zhengzan; Quan, Guilan; Wu, Qiaoli; Zhou, Chan; Li, Feng; Bai, Xuequn; Li, Ge; Pan, Xin; Wu, Chuanbin

    2015-05-01

    The aim of this study was to load amorphous hydrophobic drug into ordered mesoporous silica (SBA-15) by supercritical carbon dioxide technology in order to improve the dissolution and bioavailability of the drug. Asarone was selected as a model drug due to its lipophilic character and poor bioavailability. In vitro dissolution and in vivo bioavailability of the obtained Asarone-SBA-15 were significantly improved as compared to the micronized crystalline drug. This study offers an effective, safe, and environmentally benign means of solving the problems relating to the solubility and bioavailability of hydrophobic molecules. PMID:25720818

  12. Dynamic Pore-Scale Imaging of Reactive Transport in Heterogeneous Carbonates at Reservoir Conditions Across Multiple Dissolution Regimes

    NASA Astrophysics Data System (ADS)

    Menke, H. P.; Bijeljic, B.; Andrew, M. G.; Blunt, M. J.

    2014-12-01

    Sequestering carbon in deep geologic formations is one way of reducing anthropogenic CO2 emissions. When supercritical CO2 mixes with brine in a reservoir, the acid generated has the potential to dissolve the surrounding pore structure. However, the magnitude and type of dissolution are condition dependent. Understanding how small changes in the pore structure, chemistry, and flow properties affect dissolution is paramount for successful predictive modelling. Both 'Pink Beam' synchrotron radiation and a Micro-CT lab source are used in dynamic X-ray microtomography to investigate the pore structure changes during supercritical CO2 injection in carbonate rocks of varying heterogeneity at high temperatures and pressures and various flow-rates. Three carbonate rock types were studied, one with a homogeneous pore structure and two heterogeneous carbonates. All samples are practically pure calcium carbonate, but have widely varying rock structures. Flow-rate was varied in three successive experiments by over an order of magnitude whlie keeping all other experimental conditions constant. A 4-mm carbonate core was injected with CO2-saturated brine at 10 MPa and 50oC. Tomographic images were taken at 30-second to 20-minute time-resolutions during a 2 to 4-hour injection period. A pore network was extracted using a topological analysis of the pore space and pore-scale flow modelling was performed directly on the binarized images with connected pathways and used to track the altering velocity distributions. Significant differences in dissolution type and magnitude were found for each rock type and flowrate. At the highest flow-rates, the homogeneous carbonate was seen to have predominately uniform dissolution with minor dissolution rate differences between the pores and pore throats. Alternatively, the heterogeneous carbonates which formed wormholes at high flow rates. At low flow rates the homogeneous rock developed wormholes, while the heterogeneous samples showed evidence

  13. Modeling of dissolution patterns for carbonate acidizing in the porous media

    NASA Astrophysics Data System (ADS)

    Samadi, Fereshteh; Esmaeilzadeh, Feridun; Mowla, Dariush

    2012-05-01

    Matrix acidizing is a common technique to stimulate wells for improving well inflow performance. In this treatment that is widely used in the oil industry, acid solution is injected into the formation to dissolve some minerals to increase permeability of carbonate near the wellbore. The aim of the treatment is to create empty channels called wormholes. Wormholing in carbonate rocks is a complex 3-D phenomenon. Matrix acidizing generally should be applied when a well has a high skin factor that cannot be attributed to partial penetration, perforation efficiency or other mechanical aspects of the completion. Obviously, it is of extreme importance to quantify the skin factor to evaluate the effectiveness of stimulation treatments. When wormholes extend beyond the damaged zone or connect with natural fissures in the formation, a negative skin effect is obtained. An ideal matrix treatment restores the permeability in the near wellbore region to a value at least as high as the original undamaged permeability; it accomplishes this over the entire completed interval and it leaves the formation in the treated region with high relative permeability to the oil and/or gas phase. Designing a treatment should strive to achieve this ideal at the lowest possible cost, which requires consideration of the many physical and chemical interactions taking place between the injected fluids and the reservoir minerals and fluids. In this work, a threescale continuum model is used to model reactive dissolution of carbonate rocks in radial flow. Both the Darcy and pore scale physics such as mass transfer of acid molecules to the mineral surface and subsequent reaction at the surface, changing pore structure and variations in reservoir permeability are included in this model. Partial differential equations obtained from the model, have been solved by numerical method. The influence of reservoir temperature on optimum injection rate is investigated. Results show that optimum injection rate

  14. Processes at the magnesium-bearing carbonates/solution interface. II. kinetics and mechanism of magnesite dissolution.

    NASA Astrophysics Data System (ADS)

    Pokrovsky, Oleg S.; Schott, Jacques

    1999-07-01

    Steady-state dissolution rates of magnesite (MgCO 3) were measured at 25°C as a function of pH (from 0.2 to 12), total dissolved carbonate concentration (10 -5 < ΣCO 2 < 0.1 M), and ionic strength (0.002 < I < 0.5 M) using a mixed-flow reactor. Dissolution rates were found to be pH-independent at 0 < pH < 3, proportional to a H+ at 3 < pH < 5, pH-independent at 5 < pH < 8, and decreasing with increasing pH at pH > 8 and ΣCO 2 > 10 -3 M. In the acid pH region (3 ≤ pH ≤ 5), the rates increase significantly with ionic strength. In the alkaline pH region, carbonate and bicarbonate ions and ionic strength inhibit significantly the dissolution rate even at far from equilibrium conditions. The surface complexation model developed by Pokrovsky et al. (1999a) was used to correlate magnesite dissolution kinetics with its surface speciation. Dissolution rates in the acid pH region are controlled by the protonation of >CO 3- surface complexes. In neutral and carbonate-rich alkaline solutions, >MgOH 2+ controls the dissolution kinetics. The following rate equation, consistent with transition state theory was used to describe magnesite dissolution kinetics over the full range of solution composition: R (mol/cm 2/s)=[10 7.198·{>CO 3H°} 3.97+10 5.38·{>MgOH 2+} 3.94]·(1-exp(-4 A/ RT)) where {> i} stands for surface species concentration (mol/m 2), and A refers to the chemical affinity of the overall reaction. This equation reflects the formation of two different precursor-activated complexes which contain four protonated >CO 3H° species in acid solutions and four protonated (hydrated) >MgOH 2+ groups in neutral and alkaline solutions. The very low magnesite dissolution/precipitation rates predicted by this equation, especially at close to equilibrium conditions, are consistent with those deduced from field measurements.

  15. Observations, Measurements, and Simulations of Convectively Enhanced Carbon Dioxide Dissolution (Invited)

    NASA Astrophysics Data System (ADS)

    Kneafsey, T. J.; Pruess, K.

    2010-12-01

    Carbon dioxide injected into a porous, permeable rock stratum overlain by low-permeability caprock will flow in response to applied pressures and buoyant, viscous, and capillary forces. Four modes of CO2 storage will occur upon injection, which are (in order of increased security and permanence): 1) free-phase supercritical CO2, 2) capillary-trapped CO2, 3) CO2 dissolved into the brine, and 4) CO2 that has chemically reacted with aqueous species and host rock resulting in precipitation. In the target formation, the injected supercritical CO2 will tend to rise due to buoyancy, and accumulate beneath the caprock. At some distance from the injection well, the CO2/brine interface will be roughly horizontal. In the absence of fluid motion, CO2 dissolution into the brine will be dominated by the slow process of molecular diffusion of the CO2 away from the CO2-brine interface, and the rate of dissolution will decrease with time. As CO2 dissolves into the brine, the density of the brine increases by a small amount, on the order of 0.1 to 1%. This results in a fluid dynamics instability because denser fluid overlies less dense fluid, which induces convective flow of the denser fluid downward. The downward convection of the CO2-bearing denser fluid causes less dense brine to flow upwards and contact the CO2. This is a desirable process because it significantly increases the dissolution of CO2 into the brine. We have performed laboratory visualization tests, quantitative measurements at elevated pressures, and numerical simulations to examine this phenomenon. In our visualization tests, we introduce CO2 into the headspace above water containing a pH sensitive indicator contained in a transparent Hele-Shaw cell. When CO2 dissolves into the water, the pH is lowered and the indicator changes color. Upon introduction of CO2 into the cell, a fairly uniform layer of low pH fluid containing dissolved CO2 slowly enlarges downward from the gas-water interface. At some point, many

  16. EVALUATION OF ARG-1 SAMPLES PREPARED BY CESIUM CARBONATE DISSOLUTION DURING THE ISOLOK SME ACCEPTABILITY TESTING

    SciTech Connect

    Edwards, T.; Hera, K.; Coleman, C.

    2011-12-05

    Evaluation of Defense Waste Processing Facility (DWPF) Chemical Process Cell (CPC) cycle time identified several opportunities to improve the CPC processing time. The Mechanical Systems & Custom Equipment Development (MS&CED) Section of the Savannah River National Laboratory (SRNL) recently completed the evaluation of one of these opportunities - the possibility of using an Isolok sampling valve as an alternative to the Hydragard valve for taking DWPF process samples at the Slurry Mix Evaporator (SME). The use of an Isolok for SME sampling has the potential to improve operability, reduce maintenance time, and decrease CPC cycle time. The SME acceptability testing for the Isolok was requested in Task Technical Request (TTR) HLW-DWPF-TTR-2010-0036 and was conducted as outlined in Task Technical and Quality Assurance Plan (TTQAP) SRNLRP-2011-00145. RW-0333P QA requirements applied to the task, and the results from the investigation were documented in SRNL-STI-2011-00693. Measurement of the chemical composition of study samples was a critical component of the SME acceptability testing of the Isolok. A sampling and analytical plan supported the investigation with the analytical plan directing that the study samples be prepared by a cesium carbonate (Cs{sub 2}CO{sub 3}) fusion dissolution method and analyzed by Inductively Coupled Plasma - Optical Emission Spectroscopy (ICP-OES). The use of the cesium carbonate preparation method for the Isolok testing provided an opportunity for an additional assessment of this dissolution method, which is being investigated as a potential replacement for the two methods (i.e., sodium peroxide fusion and mixed acid dissolution) that have been used at the DWPF for the analysis of SME samples. Earlier testing of the Cs{sub 2}CO{sub 3} method yielded promising results which led to a TTR from Savannah River Remediation, LLC (SRR) to SRNL for additional support and an associated TTQAP to direct the SRNL efforts. A technical report resulting

  17. The Dissolution of Synthetic Na-Boltwoodite in Sodium Carbonate Solutions

    SciTech Connect

    Ilton, Eugene S.; Liu, Chongxuan; Yantasee, Wassana; Wang, Zheming; Moore, Dean A.; Felmy, Andrew R.; Zachara, John M.

    2006-09-01

    Uranyl silicates such as uranophane and Na-boltwoodite appear to control the solubility of uranium in the contaminated sediments at the US Department of Energy Hanford site (Liu et al., 2004). Consequently, the solubility of synthetic Na-boltwoodite was determined over a wide range of bicarbonate concentrations, from circumneutral to alkaline pH, that are representative of porewater and groundwater compositions at the Hanford site. Results show that Na-boltwoodite dissolution was nearly congruent and its solubility increased with increasing bicarbonate concentration. Calculated solubility constants varied by nearly 2 log units from low bicarbonate (no added NaCO3) to 50 mmol/L bicarbonate. However, the solubility constants only vary by 0.5 log units from 0 added bicarbonate to 1.2 mmol/L bicarbonate, where logKsp = 5.39-5.92 and the average logKsp = 5.63. No systematic trend in logKsp was apparent over this range in bicarbonate concentrations. LogKsp values trended down with increasing bicarbonate concentration, where logKsp = 4.06 at 50 mmol/L bicarbonate. We conclude that the calculated solubility constants at high bicarbonate are compromised by an incomplete or inaccurate uranyl-carbonate speciation model.

  18. Reactive Transport at the Pore Scale with Applications to the Dissolution of Carbonate Rocks for CO2 Sequestration Operations

    NASA Astrophysics Data System (ADS)

    Boek, E.; Gray, F.; Welch, N.; Shah, S.; Crawshaw, J.

    2014-12-01

    In CO2 sequestration operations, CO2 injected into a brine aquifer dissolves in the liquid to create an acidic solution. This may result in dissolution of the mineral grains in the porous medium. Experimentally, it is hard to investigate this process at the pore scale. Therefore we develop a new hybrid particle simulation algorithm to study the dissolution of solid objects in a laminar flow field, as encountered in porous media flow situations. First, we calculate the flow field using a multi-relaxation-time lattice Boltzmann (LB) algorithm implemented on GPUs, which demonstrates a very efficient use of the GPU device and a considerable performance increase over CPU calculations. Second, using a stochastic particle approach, we solve the advection-diffusion equation for a single reactive species and dissolve solid voxels according to our reaction model. To validate our simulation, we first calculate the dissolution of a solid sphere as a function of time under quiescent conditions. We compare with the analytical solution for this problem [1] and find good agreement. Then we consider the dissolution of a solid sphere in a laminar flow field and observe a significant change in the sphericity with time due to the coupled dissolution - flow process. Second, we calculate the dissolution of a cylinder in channel flow in direct comparison with corresponding dissolution experiments. We discuss the evolution of the shape and dissolution rate. Finally, we calculate the dissolution of carbonate rock samples at the pore scale in direct comparison with micro-CT experiments. This work builds on our recent research on calculation of multi-phase flow [2], [3] and hydrodynamic dispersion and molecular propagator distributions for solute transport in homogeneous and heterogeneous porous media using LB simulations [4]. It turns out that the hybrid simulation model is a suitable tool to study reactive flow processes at the pore scale. This is of great importance for CO2 storage and

  19. Application of Foraminiferal Calcium Carbonate Chemistry to Proxy Past Ocean Conditions: key roles of Biomineral Formation and Dissolution

    NASA Astrophysics Data System (ADS)

    Elderfield, H.

    2001-12-01

    The use of the shell chemistry of foraminiferal calcite and aragonite for seawater paleothermometry and paleochemistry rests on confidence in the calibrations established to link metal uptake or isotope fractionation by the marine biogenic calcium carbonate to modern seawater composition. The early pioneering work in this field led to a period of application, principally of the establishment and expansion of stable oxygen and carbon isotope studies. But new work on trace metals in foraminifera has led to an upsurge of interest in, and reappraisal of, what controls metal uptake and the extent to which foraminifera do a good a job in recording and revealing the ocean's secrets. Two issues are considered: (i) understanding how secretion by the organism takes place and the chemical consequences; (ii) how dissolution changes the initial chemistry. The early work on ultrastructure shows that different, often progressive, layers are formed ranging from anhedral microgranules to euhedral crystallites; and that there is sequential and preferential dissolution of the different textural forms. This forms some basis for understanding, for example, the heterogeneity in foraminiferal Mg/Ca and how this is affected by dissolution. In general, warmer species (higher Mg/Ca) show greatest 104 line broadening and depth (or carbonate ion) related dissolution is accompanied by a decrease both in Mg/Ca and line broadening. Variation in calcification rate has been linked to changes in carbon isotope and Sr/Ca, perhaps through a carbonate ion effect. This is also seen from size fraction data. There is also variability in shell mass both from initial calcification history and from dissolution, and both affect shell chemistry. Shell mass is also associated with changes in normalised size and accompanied by chemical changes. One clear effect of Mg heterogeneity is in its effect on calibrations for thermometry and the extent to which phase differences between temperature (dissolution

  20. Isotopic tracer evidence for the amorphous calcium carbonate to calcite transformation by dissolution-reprecipitation

    NASA Astrophysics Data System (ADS)

    Giuffre, Anthony J.; Gagnon, Alexander C.; De Yoreo, James J.; Dove, Patricia M.

    2015-09-01

    Observations that some biogenic and sedimentary calcites grow from amorphous calcium carbonate (ACC) raise the question of how this mineralization process influences composition. However, the detailed pathway and geochemical consequences of the ACC to calcite transformation are not well constrained. This experimental study investigated the formation of calcite from ACC by using magnesium and calcium stable isotope labeling to directly probe the transformation pathway and controls on composition. Four processes were considered: dissolution-reprecipitation, solid state transformation, and combinations of these end-members. To distinguish between these scenarios, ACC was synthesized from natural isotope abundance solutions and subsequently transferred to spiked solutions that were enriched in 43Ca and 25Mg for the transformation to calcite. Isotope measurements by NanoSIMS determined the 43Ca/40Ca, and 25Mg/24Mg ratios of the resulting calcite crystals. Analysis of the data shows the transformation is best explained by a dissolution-reprecipitation process. We find that when a small amount of ACC is transferred, the isotopic signals in the resulting calcite are largely replaced by the composition of the surrounding spiked solution. When larger amounts of ACC are transferred, calcite compositions reflect a mixture between the ACC and initial solution end-member. Comparisons of the measurements to the predictions of a simple mixing model indicate that calcite compositions (1) are sensitive to relative amounts of ACC and the surrounding solution reservoir and (2) are primarily governed by the conditions at the time of ACC transformation rather than the initial ACC formation. Shifts in calcite composition over the duration of the transformation period reflect the progressive evolution of the local solution conditions. This dependence indicates the extent to which there is water available would change the end point composition on the mixing line. While these findings have

  1. Biotechnology for the acceleration of carbon dioxide capture and sequestration.

    PubMed

    Savile, Christopher K; Lalonde, James J

    2011-12-01

    The potential for enzymatic acceleration of carbon dioxide capture from combustion products of fossil fuels has been demonstrated. Carbonic anhydrase (CA) accelerates post combustion CO(2) capture, but available CAs are woefully inadequate for the harsh conditions employed in most of these processes. In this review, we summarize recent approaches to improve CA, and processes employing this enzyme, to maximize the benefit from this extremely fast biocatalyst. Approaches to overcoming limitations include sourcing CAs from thermophilic organisms, using protein engineering to evolve thermo-tolerant enzymes, immobilizing the enzyme for stabilization and confinement to cooler regions and process modifications that minimize the (thermo-, solvent) stress on the enzyme. PMID:21737251

  2. Dissolution rates of pure methane hydrate and carbon-dioxide hydrate in undersaturated seawater at 1000-m depth

    USGS Publications Warehouse

    Rehder, G.; Kirby, S.H.; Durham, W.B.; Stern, L.A.; Peltzer, E.T.; Pinkston, J.; Brewer, P.G.

    2004-01-01

    To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH4 and CO2 hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 ??m/s and between 9.0 and 10.6 ?? 10-2 ??m/s for the CO2 and CH4 hydrates, respectively, corresponding to dissolution rates of 4.15 ?? 0.5 mmol CO2/m2s and 0.37 ?? 0.03 mmol CH4/m2s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH4) or tens of mm (CO2) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO2 hydrates in marine carbon sequestration strategies. ?? 2003 Elsevier Ltd.

  3. Isotopic evidence of enhanced carbonate dissolution at a coal mine drainage site in Allegheny County, Pennsylvania, USA

    SciTech Connect

    Sharma, Shikha; Sack, Andrea; Adams, James P.; Vesper, Dorothy; J Capo, Rosemary C.; Hartsock, Angela; Edenborn, Harry M.

    2013-01-01

    Stable isotopes were used to determine the sources and fate of dissolved inorganic C (DIC) in the circumneutral pH drainage from an abandoned bituminous coal mine in western Pennsylvania. The C isotope signatures of DIC (δ{sup 13}C{sub DIC}) were intermediate between local carbonate and organic C sources, but were higher than those of contemporaneous Pennsylvanian age groundwaters in the region. This suggests a significant contribution of C enriched in {sup 13}C due to enhanced carbonate dissolution associated with the release of H{sub 2}SO{sub 4} from pyrite oxidation. The Sr isotopic signature of the drainage was similar to other regional mine waters associated with the same coal seam and reflected contributions from limestone dissolution and cation exchange with clay minerals. The relatively high δ{sup 34}S{sub SO4} and δ{sup 18}O{sub SO4} isotopic signatures of the mine drainage and the presence of presumptive SO{sub 4}-reducing bacteria suggest that SO{sub 4} reduction activity also contributes C depleted in {sup 13}C isotope to the total DIC pool. With distance downstream from the mine portal, C isotope signatures in the drainage increased, accompanied by decreased total DIC concentrations and increased pH. These data are consistent with H{sub 2}SO{sub 4} dissolution of carbonate rocks, enhanced by cation exchange, and C release to the atmosphere via CO{sub 2} outgassing.

  4. Deep-sea benthic foraminifera, carbonate dissolution and species diversity in Hardangerfjord, Norway: An initial assessment

    NASA Astrophysics Data System (ADS)

    Alve, Elisabeth; Murray, John W.; Skei, Jens

    2011-03-01

    This is the first record of live (stained) deep-sea benthic foraminifera in the 850 m deep silled Hardangerfjord, the second deepest fjord in Western Norway. Estimates of organic carbon flux (˜2.5 g Cm -2 y -1) show that the fjord-values are comparable to similar depths on the continental slope. Accordingly, although these first samples only provide relative abundance data, the low proportion of live to dead individuals in the top cm of the sediment suggests a low foraminifera biomass. Another similarity with the deep sea is that the abiotic environment of the deep basins is stable even though the deepest basins are isolated from the open deep sea by the continental shelf and sills in the outer parts of the fjord suggesting that the deep-sea species are introduced as propagules during deep-water renewals. There is evidence of an increase in dissolution of fragile calcareous tests (e.g., Nonionella iridea) especially in the innermost part of Hardangerfjord since the 1960s and this has led to a relative increase in dead agglutinated assemblages. The presence of larger forms with tests >1 mm provides substrata for the attachment of smaller forms and therefore an increase in species diversity. Indeed, the diversity is comparable both to that of the open deep sea and that of reported macrofauna from the same sites, reflecting similar ecological status. Holtedahl (1965) suggested that there may be some down-slope transport of sediment into the deep basins with the deposition of turbidites. Despite some evidence of transport, no major recent disturbance due to turbidite deposition seems to have occurred and hence Hardangerfjord presents a unique environment with elements of deep-sea faunas in a land-locked setting.

  5. On the Spheroidized Carbide Dissolution and Elemental Partitioning in High Carbon Bearing Steel 100Cr6

    NASA Astrophysics Data System (ADS)

    Song, Wenwen; Choi, Pyuck-Pa; Inden, Gerhard; Prahl, Ulrich; Raabe, Dierk; Bleck, Wolfgang

    2014-02-01

    We report on the characterization of high carbon bearing steel 100Cr6 using electron microscopy and atom probe tomography in combination with multi-component diffusion simulations. Scanning electron micrographs show that around 14 vol pct spheroidized carbides are formed during soft annealing and only 3 vol pct remain after dissolution into the austenitic matrix through austenitization at 1123 K (850 °C) for 300 seconds. The spheroidized particles are identified as (Fe, Cr)3C by transmission electron microscopy. Atom probe analysis reveals the redistribution and partitioning of the elements involved, i.e., C, Si, Mn, Cr, Fe, in both, the spheroidized carbides and the bainitic matrix in the sample isothermally heat-treated at 773 K (500 °C) after austenitization. Homogeneous distribution of C and a Cr gradient were detected within the spheroidized carbides. Due to its limited diffusivity in (Fe, Cr)3C, Cr exhibits a maximum concentration at the surface of spheroidized carbides (16 at. pct) and decreases gradually from the surface towards the core down to about 2 at. pct. The atom probe results also indicate that the partially dissolved spheroidized carbides during austenitization may serve as nucleation sites for intermediate temperature cementite within bainite, which results in a relatively softer surface and harder core in spheroidized particles. This microstructure may contribute to the good wear resistance and fatigue properties of the steel. Good agreement between DICTRA simulations and experimental composition profiles is obtained by an increase of mobility of the substitutional elements in cementite by a factor of five, compared to the mobility in the database MOBFE2.

  6. Transformation, morphology, and dissolution of silicon and carbon in rice straw-derived biochars under different pyrolytic temperatures.

    PubMed

    Xiao, Xin; Chen, Baoliang; Zhu, Lizhong

    2014-03-18

    Biochars are increasingly recognized as environmentally friendly and cheap remediation agents for soil pollution. The roles of silicon in biochars and interactions between silicon and carbon have been neglected in the literature to date, while the transformation, morphology, and dissolution of silicon in Si-rich biochars remain largely unaddressed. In this study, Si-rich biochars derived from rice straw were prepared under 150-700 °C (named RS150-RS700). The transformation and morphology of carbon and silicon in biochar particles were monitored by FTIR, XRD, and SEM-EDX. With increasing pyrolytic temperature, silicon accumulated, and its speciation changed from amorphous to crystalline matter, while the organic matter evolved from aliphatic to aromatic. For rice straw biomass containing amorphous carbon and amorphous silicon, dehydration (<250 °C) made silicic acid polymerize, resulting in a closer integration of carbon and silicon. At medium pyrolysis temperatures (250-350 °C), an intense cracking of carbon components occurred, and, thus, the silicon located in the inside tissue was exposed. At high pyrolysis temperatures (500-700 °C), the biochar became condensed due to the aromatization of carbon and crystallization of silicon. Correspondingly, the carbon release in water significantly decreased, while the silicon release somewhat decreased and then sharply increased with pyrolytic temperature. Along with SEM-EDX images of biochars before and after water washing, we proposed a structural relationship between carbon and silicon in biochars to explain the mutual protection between carbon and silicon under different pyrolysis temperatures, which contribute to the broader understanding of biochar chemistry and structure. The silicon dissolution kinetics suggests that high Si biochars could serve as a novel slow release source of biologically available Si in low Si agricultural soils. PMID:24601595

  7. Dissolution kinetics of granular calcium carbonate in concentrated aqueous sodium dichromate solution at pH 6.0-7.0 and 110-130 degrees C.

    PubMed

    Wang, Tiangui; Li, Zuohu

    2005-01-01

    An understanding of the factors controlling calcite dissolution is important for modeling geochemical cycles and impacts of greenhouse gases on climate, diagenesis of sediments, and sedimentary rocks. It also has practical significance in the investigation of behavior of carbonates in petroleum and natural gas reservoirs and in the preservation of buildings and monuments constructed from limestone and marble. A large number of papers have been published on dissolution kinetics of calcium carbonate in aqueous solutions. But few involved the near-equilibrium region, especially at elevated temperatures and in concentrated solutions. In this paper, the dissolution kinetics of calcium carbonate in concentrated aqueous sodium dichromate solutions at pH 6.0-7.0 and 110-130 degrees C were studied in a 2-L autoclave. The results indicate that the dissolution reaction is mix-controlled, with surface reaction as the prevailing factor. The concentration of calcium ions in solution hardly affects the dissolution rate, but carbon dioxide in the vapor phase inhibits the dissolution reaction. The dissolution rate can be expressed by R = k(1)a(2)(H+) + k(2), and the apparent activation energy is 55-84 kJ mol(-1). PMID:15567388

  8. Cellulose Dissolution and In Situ Grafting in a Reversible System using an Organocatalyst and Carbon Dioxide.

    PubMed

    Song, Longchu; Yang, Yunlong; Xie, Haibo; Liu, Enhui

    2015-10-12

    Cellulose is a promising renewable material, but cannot easily be processed homogeneously owing to the stiffness of the molecules and the dense packing of its chains, due to intermolecular hydrogen bonds. Cellulose processability can be improved by chemical modification. The reversible reaction of cellulose with carbon dioxide in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) allows dissolution of cellulose in dimethyl sulfoxide (DMSO). This DMSO solution is an effective medium for grafting L-lactide (LLA) from cellulose by ring-opening polymerization (ROP) under mild conditions, allowing to prepare cellulose-graft-poly(L-lactide) co-polymers with a molar substitution (MSPLLA ) of poly(L-lactide) in the range of 0.37-5.32, at 80 °C. This makes DBU not only an important reagent to achieve cellulose dissolution, but it also acts as organocatalyst for the subsequent ring-opening polymerization process. Characterization of the structure and thermal properties of the co-polymers by a variety of techniques reveals that they have a single glass-transition temperature (Tg ), which decreases with increasing MSPLLA . Thus, the modification results in a transformation of the originally semirigid cellulose into a thermoplastic material with tunable Tg . The carbon dioxide dissolution strategy is an efficient platform for cellulose derivatization by homogeneous organocatalysis. PMID:26220825

  9. Recovery of uranium from (U,Gd)O 2 nuclear fuel scrap using dissolution and precipitation in carbonate media

    NASA Astrophysics Data System (ADS)

    Kim, Kwang-Wook; Hyun, Jun-Taek; Lee, Eil-Hee; Park, Geun-Il; Lee, Kune-Woo; Yoo, Myung-June; Song, Kee-Chan; Moon, Jei-Kwon

    2011-11-01

    This work studied a process to recover uranium from contaminated (U,Gd)O 2 scraps generated from nuclear fuel fabrication processes by using the dissolution of (U,Gd)O 2 scraps in a carbonate with H 2O 2 and the precipitation of the dissolved uranium as UO 4. The dissolution characteristics of uranium, Gd, and impurity metal oxides were tested, and the behaviors of UO 4 precipitation and Gd solubility were evaluated with changes of the pH of the solution. A little Gd was entrained in the UO 4 precipitate to contaminate the uranium precipitate. Below a pH of 3, the uranium dissolved in the form of uranyl peroxo-carbonato complex ions in the carbonate solution was precipitated as UO 4 with a high precipitation yield, and the Gd had a very high solubility. Using these characteristics, the Gd-contaminated UO 4 could be purified using dissolution in a 1-M HNO 3 solution with heating and re-precipitation upon addition of H 2O 2 to the solution. Finally, an environmentally friendly and economical process to recover pure uranium from contaminated (U,Gd)O 2 scraps was suggested.

  10. Carbonate mineral dissolution and the impacts of flood water exchange between conduit and matrix

    NASA Astrophysics Data System (ADS)

    Spellman, P.; Screaton, E.; Gulley, J. D.; Martin, J. B.

    2012-12-01

    Studies of flow and dissolution in karst aquifers have traditionally focused on conduits, and contributions from matrix sources have been generally ignored. This conceptual model works for limestone that has been deeply buried and had its matrix permeability obliterated by cementation (telogenetic) so that most aquifer recharge occurs by conduits. In limestone that has not been deeply buried (eogenetic), however, high matrix permeability is preserved, resulting in greater degrees of interaction between conduit and matrix porosity than occurs in telogenetic limestone. Interactions between conduit and matrix porosity, and how these interactions affect flow and dissolution within aquifers, is particularly important in karst aquifers subject to dynamic changes in head gradients between conduits and aquifers. These exchanges are particularly prevalent in transitional areas between confined and unconfined aquifer conditions. In such transitional areas, allogenic runoff from confining units can increase river stages on adjacent unconfined aquifers faster than infiltration of local rainfall can increase groundwater heads. As a result, normal hydraulic gradients between the aquifer and rivers are reversed, causing river water to flow into springs. Simultaneously, rapid increases in conduit hydraulic head will also reverse gradients between the conduit and the aquifer, driving exchange from the conduit to the matrix. Because allogenic runoff is highly undersaturated with respect to calcite after storm events, dissolution resulting from this exchange can be extensive. The magnitude of dissolution that occurs is a function of the calcite saturation state of the allogenic runoff, the surface area of the limestone in contact with the water, and the time that water remains in contact with the limestone. In eogenetic aquifers, the magnitude of dissolution that occurs during spring reversals should be higher than in telogenetic aquifers because of their elevated matrix

  11. Storm-generated bedforms and relict dissolution pits and channels on the Yucatan carbonate platform

    NASA Astrophysics Data System (ADS)

    Gulick, S. P.; Goff, J. A.; Stewart, H. A.; Perez-Cruz, L. L.; Davis, M. B.; Duncan, D.; Saustrup, S.; Sanford, J. C.; Fucugauchi, J. U.

    2013-12-01

    The Yucatan 2013 (cruise number 2013/4_ECORD) geophysical and geotechnical hazard site survey took place aboard the R/V Justo Sierra in April 2013. Our study was conducted within the Chicxulub impact crater, encompassing three potential IODP drilling sites. The survey was located ~32 km northwest of Progreso, Mexico; data acquired included ~15.6 km2 of complete multibeam bathymetry coverage, ~435 line km of side scan sonar and CHIRP data, 204 line kilometers of magnetometer data, and 194 line kilometers of surface tow boomer profiles. Based on these data, this portion of the Yucatan Shelf consists of flat-lying, hard limestone rock overlain by isolated ribbons of carbonate sand <1.0 m thick. These ribbons are oriented along NE-SW trends and have smaller scale orthogonal sand-waves (~20-100 m wavelengths and relief of ~0.2-0.6 m) on them. The sand waves are anisotropic with steeper slopes facing the NE. The larger scale morphology can be classified as longitudinal bedforms (ribbons), and the smaller scale transverse bedforms formed in response to a NE-directed flow. This flow direction is inconsistent with the ambient west-directed current conditions, and may therefore be indicative of storm-driven currents. Numerous dissolution pits, ~5-50m in diameter, ~0.2-0.5 m deep with steep (0.1-0.5 gradient) walls, are present in the bare rock regions of most of the study area. These occasionally are floored by rippled, highly reflective (coarse) sediments. We interpret these pits as representing karstic morphology formed during the last sub-aerial exposure of the study area interpreted to have occurred during Holocene times given the present day ~17 m average water depth. A sub-surface reflector imaged on the surface tow boomer data lies 1-3 m below the hard seafloor reflection (sand ribbons are below the vertical resolution of the surface tow boomer), which we interpret as a layer within the limestone bedrock. This reflector is flat-lying and undisturbed throughout the

  12. Dissolution-precipitation processes governing the carbonation and silicification of the serpentinite sole of the New Caledonia ophiolite

    NASA Astrophysics Data System (ADS)

    Ulrich, Marc; Muñoz, Manuel; Guillot, Stéphane; Cathelineau, Michel; Picard, Christian; Quesnel, Benoit; Boulvais, Philippe; Couteau, Clément

    2014-01-01

    The weathering of mantle peridotite tectonically exposed to the atmosphere leads commonly to natural carbonation processes. Extensive cryptocrystalline magnesite veins and stock-work are widespread in the serpentinite sole of the New Caledonia ophiolite. Silica is systematically associated with magnesite. It is commonly admitted that Mg and Si are released during the laterization of overlying peridotites. Thus, the occurrence of these veins is generally attributed to a per descensum mechanism that involves the infiltration of meteoric waters enriched in dissolved atmospheric CO2. In this study, we investigate serpentinite carbonation processes, and related silicification, based on a detailed petrographic and crystal chemical study of serpentinites. The relationships between serpentine and alteration products are described using an original method for the analysis of micro-X-ray fluorescence images performed at the centimeter scale. Our investigations highlight a carbonation mechanism, together with precipitation of amorphous silica and sepiolite, based on a dissolution-precipitation process. In contrast with the per descensum Mg/Si-enrichment model that is mainly concentrated in rock fractures, dissolution-precipitation process is much more pervasive. Thus, although the texture of rocks remains relatively preserved, this process extends more widely into the rock and may represent a major part of total carbonation of the ophiolite.

  13. Dissolution-precipitation processes governing the carbonation and silicification of the serpentinite sole of the New Caledonia ophiolite

    NASA Astrophysics Data System (ADS)

    Ulrich, M.; Munoz, M.; Guillot, S.; Cathelineau, M.; Picard, C.; Quesnel, B.; Boulvais, P.; Couteau, C.

    2014-12-01

    The weathering of mantle peridotite tectonically exposed to the atmosphere leads commonly to natural carbonation processes. Extensive cryptocrystalline magnesite veins and stock-work are widespread in the serpentinite sole of the New Caledonia ophiolite. Silica is systematically associated with magnesite. It is commonly admitted that Mg and Si are released during the laterization of overlying peridotites. Thus, the occurrence of these veins is generally attributed to a per descensum mechanism that involves the infiltration of meteoric waters enriched in dissolved atmospheric CO2. In this study, we investigate serpentinite carbonation processes, and related silicification, based on a detailed petrographic and crystal chemical study of serpentinites. The relationships between serpentine and alteration products are described using an original method for the analysis of micro-X-ray fluorescence images performed at the centimeter scale. Our investigations highlight a carbonation mechanism, together with precipitation of amorphous silica and sepiolite, based on a dissolution-precipitation process. In contrast with the per descensum Mg/Si-enrichment model that is mainly concentrated in rock fractures, dissolution-precipitation process is much more pervasive. Thus, although the texture of rocks remains relatively preserved, this process extends more widely into the rock and may represent a major part of total carbonation of the ophiolite.

  14. Electrolytic recycling of a carbonate salt in a process with a dissolution of spent nuclear fuel in a strong alkaline carbonate media

    SciTech Connect

    Kwang-Wook Kim; In-Tae Kim; Seong-Min Kim; Yeon-Hwa Kim; Eil-Hee Lee; Kwang-Yong Jee

    2007-07-01

    A removal of only uranium from spent nuclear fuel with the concepts of a high proliferation-resistance and a minimal generation of waste is helpful for a spent fuel management in view of a volume reduction of the high level radioactive waste generated from the spent fuel treatment. That can be accomplished by a process using a selective oxidative dissolution of the spent fuel in a carbonate solution of high alkalinity. In this work, an electrolytic method for a de-carbonation and a recovery of CO{sub 2} for recycling the used carbonate solution contaminated with some impurity metal ions generated in such a process with a concept of zero-release of waste solution was studied. A carbonate solution generated from such a system was confirmed to be completely recycled within the system, while the impurity ions being separated from the carbonate solution. (authors)

  15. Measuring the Influence of Pearlite Dissolution on the Transient Dynamic Strength of Rapidly Heated Plain Carbon Steels

    NASA Astrophysics Data System (ADS)

    Mates, Steven; Stoudt, Mark; Gangireddy, Sindhura

    2016-05-01

    Carbon steels containing ferrite-pearlite microstructures weaken dramatically when pearlite dissolves into austenite on heating. The kinetics of this phase transformation, while fast, can play a role during dynamic, high-temperature manufacturing processes, including high-speed machining, when the time scale of this transformation is on the order of the manufacturing process itself. In such a regime, the mechanical strength of carbon steel can become time dependent. The present work uses a rapidly heated, high-strain-rate mechanical test to study the effect of temperature and time on the amount of pearlite dissolved and on the resulting transient effect on dynamic strength of a low and a high carbon (eutectoid) steel. Measurements indicate that the transient effect occurs for heating times less than about 3 s. The 1075 steel loses about twice the strength compared to the 1018 steel (85 MPa to 45 MPa) owing to its higher initial pearlite volume fraction. Pearlite dissolution is confirmed by metallographic examination of tested samples. Despite the different starting pearlite fractions, the kinetics of dissolution are comparable for the two steels, owing to the similarity in their initial pearlite morphology.

  16. Measuring the Influence of Pearlite Dissolution on the Transient Dynamic Strength of Rapidly Heated Plain Carbon Steels

    NASA Astrophysics Data System (ADS)

    Mates, Steven; Stoudt, Mark; Gangireddy, Sindhura

    2016-07-01

    Carbon steels containing ferrite-pearlite microstructures weaken dramatically when pearlite dissolves into austenite on heating. The kinetics of this phase transformation, while fast, can play a role during dynamic, high-temperature manufacturing processes, including high-speed machining, when the time scale of this transformation is on the order of the manufacturing process itself. In such a regime, the mechanical strength of carbon steel can become time dependent. The present work uses a rapidly heated, high-strain-rate mechanical test to study the effect of temperature and time on the amount of pearlite dissolved and on the resulting transient effect on dynamic strength of a low and a high carbon (eutectoid) steel. Measurements indicate that the transient effect occurs for heating times less than about 3 s. The 1075 steel loses about twice the strength compared to the 1018 steel (85 MPa to 45 MPa) owing to its higher initial pearlite volume fraction. Pearlite dissolution is confirmed by metallographic examination of tested samples. Despite the different starting pearlite fractions, the kinetics of dissolution are comparable for the two steels, owing to the similarity in their initial pearlite morphology.

  17. HLW glass dissolution in the presence of magnesium carbonate: Diffusion cell experiment and coupled modeling of diffusion and geochemical interactions

    NASA Astrophysics Data System (ADS)

    Debure, Mathieu; De Windt, Laurent; Frugier, Pierre; Gin, Stéphane

    2013-11-01

    The influence of diffusion of reactive species in aqueous solutions on the alteration rate of borosilicate glass of nuclear interest in the presence of magnesium carbonate (hydromagnesite: 4MgCO3·Mg(OH)2·4H2O) is investigated together with the ability of coupled chemistry/transport models to simulate the processes involved. Diffusion cells in which the solids are separated by an inert stainless steel sintered filter were used to establish parameters for direct comparison with batch experiments in which solids are intimately mixed. The chemistry of the solution and solid phases was monitored over time by various analytical techniques including ICP-AES, XRD, and SEM. The primary mechanism controlling the geochemical evolution of the system remains the consumption of silicon from the glass by precipitation of magnesium silicates. The solution chemistry and the dissolution and precipitation of solid phases are correctly described by 2D modeling with the GRAAL model implemented in the HYTEC reactive transport code. The spatial symmetry of the boron concentrations in both compartments of the cells results from dissolution coupled with simple diffusion, whereas the spatial asymmetry of the silicon and magnesium concentrations is due to strong coupling between dissolution, diffusion, and precipitation of secondary phases. A sensitivity analysis on the modeling of glass alteration shows that the choice of these phases and their thermodynamic constants have only a moderate impact whereas the thickness of the filter has a greater barrier effect.

  18. Precipitation and dissolution of calcium carbonate: key processes bridging the bio- and geosciences (Vladimir Ivanovich Vernadsky Medal Lecture)

    NASA Astrophysics Data System (ADS)

    Gattuso, J.-P.

    2012-04-01

    In this Vladimir Ivanovich Vernadsky medal lecture, I will focus on the biogeochemical cycle of calcium carbonate (CaCO3) which is arguably one of the best example of a set processes that bridge the bio- and geosciences. The main reactions involved are calcification and dissolution that, respectively, manufacture and destroy calcium carbonate. Biology is intimately involved in these two processes which are key controls of the Earth's climate and leave remains that are of great use to human societies (as building materials) and geoscientists. I will illustrate the bridge between the bio- and geosciences by providing brief examples for each of the following four issues. (1) The marine cycle of CaCO3 and its relationship with climate. The release of CO2 by the precipitation of calcium carbonate and the uptake of CO2 by its dissolution are important controls of atmospheric CO2 and climate. The vertical distribution of Ψ, the ratio of CO2 released/used per CaCO3 precipitated/dissolved in the ocean will be shown to be consistent with the Högbom-Urey reactions. (2) The use of CaCO3 in paleooceanography. The remains of calcium carbonate shells and skeletons are wonderful archives of past environmental changes. Their isotopic composition and the concen-tration of trace elements are invaluable in the reconstruction of past climate. I will address the challenge of calibrating one of the proxies used to reconstruct past ocean pH. (3) The challenge of understanding calcification. Despite having been investigated for decades, many aspects of the physiological and molecular processes involved in calcification by marine organisms remain obscure. Recent breakthroughs, mostly on reef-building corals, will be briefly reviewed. (4) The response of calcification and dissolution to environmental change. The critical importance of CaCO3 precipitation and dissolution as climate controls makes it vital to understand their response to global environmental changes such as ocean warming and

  19. Karst Lands: The dissolution of carbonate rock produces unique landscapes and poses significant hydrological and environmental concerns

    SciTech Connect

    White, W.B.; Culver, D.C.; Herman, J.S.

    1995-09-01

    Karst lands are produced by the action of water on soluble rocks, a process among the most dynamic of all erosive forces that counterbalance the uplifting forces of tectonics. The dissolution of carbonate rock, primarily limestone and dolomite, produces unique landscapes and poses significant hydrological and environmental concerns. The major topic areas discussed in this article include the following: processes that form karst; karst drainage basins; discharge from karst aquifers; caves as paleoclimatic recorders; caves as ecosystems; water issues in karst regions; and sinkholes, soil piping and subsidence. 20 refs., 9 figs.

  20. Single-walled carbon nanotube transparent conductive films fabricated by reductive dissolution and spray coating for organic photovoltaics

    SciTech Connect

    Ostfeld, Aminy E.; Arias, Ana Claudia; Catheline, Amélie; Ligsay, Kathleen; Kim, Kee-Chan; Fogden, Siân; Chen, Zhihua; Facchetti, Antonio

    2014-12-22

    Solutions of unbundled and unbroken single-walled carbon nanotubes have been prepared using a reductive dissolution process. Transparent conductive films spray-coated from these solutions show a nearly twofold improvement in the ratio of electrical conductivity to optical absorptivity versus those deposited from conventional aqueous dispersions, due to substantial de-aggregation and sizable nanotube lengths. These transparent electrodes have been utilized to fabricate P3HT-PCBM organic solar cells achieving power conversion efficiencies up to 2.3%, comparable to those of solar cells using indium tin oxide transparent electrodes.

  1. A silica-supported solid dispersion of bifendate using supercritical carbon dioxide method with enhanced dissolution rate and oral bioavailability.

    PubMed

    Cai, Cuifang; Liu, Muhua; Li, Yun; Guo, Bei; Chang, Hui; Zhang, Xiangrong; Yang, Xiaoxu; Zhang, Tianhong

    2016-01-01

    In this study, to enhance the dissolution rate and oral bioavailability of bifendate, a silica-supported solid dispersion (SD) of bifendate was prepared using supercritical carbon dioxide (ScCO2) technology. The properties of bifendate-silica SD were characterized by differential scanning calorimetry (DSC), X-ray diffraction (X-RD) and scanning electron microscopy. The pharmacokinetic study was carried out in beagle dogs using commercial bifendate dropping pills as a reference which is a conventional SD formulation of bifendate and PEG6000. A novel method of Ultra Performance Convergence Chromatography-tandem mass spectrometry (UPC(2)™-MS/MS) method was applied to determine bifendate concentration in plasma. The amorphous state of bifendate in bifendate-silica SD was revealed in X-RD and DSC when the ratios of bifendate and silica were 1:15 and 1:19, respectively. In vitro dissolution rate was significantly improved with cumulative release of 67% within 20 min relative to 8% for the physical mixture of bifendate and silica, and which was also higher than the commercial dropping pill of 52%. After storage at 75% relative humidity (RH) for 10 d, no recrystallization was found and reduced dissolution rate was obtained due to the absorption of moisture. In pharmacokinetic study, Cmax and AUC0-t for bifendate-silica SD were 153.1 ng/ml and 979.8 ng h/ml, respectively. AUC0-t of bifendate-silica SDs was ∼1.6-fold higher than that of the commercial dropping pills. These results suggest that adsorbing bifendate onto porous silica via ScCO2 technique could be a feasible method to enhance oral bioavailability together with a higher dissolution rate. PMID:26219343

  2. Dynamics of carbonate chemistry, production, and calcification of the Florida Reef Tract (2009-2010): Evidence for seasonal dissolution

    NASA Astrophysics Data System (ADS)

    Muehllehner, Nancy; Langdon, Chris; Venti, Alyson; Kadko, David

    2016-05-01

    Ocean acidification is projected to lower the Ωar of reefal waters by 0.3-0.4 units by the end of century, making it more difficult for calcifying organisms to secrete calcium carbonate while at the same time making the environment more favorable for abiotic and biotic dissolution of the reefal framework. There is great interest in being able to project the point in time when coral reefs will cross the tipping point between being net depositional to net erosional in terms of their carbonate budgets. Periodic in situ assessments of the balance between carbonate production and dissolution that spans seasonal time scales may prove useful in monitoring and formulating projections of the impact of ocean acidification on reefal carbonate production. This study represents the first broad-scale geochemical survey of the rates of net community production (NCP) and net community calcification (NCC) across the Florida Reef Tract (FRT). Surveys were performed at approximately quarterly intervals in 2009-2010 across seven onshore-offshore transects spanning the upper, middle, and lower Florida Keys. Averaged across the FRT, the rates of NCP and NCC were positive during the spring/summer at 62 ± 7 and 17 ± 2 mmol m-2 d-1, respectively, and negative during the fall/winter at -33 ± 6 and -7 ± 2 mmol m-2 d-1. The most significant finding of the study was that the northernmost reef is already net erosional (-1.1 ± 0.4 kg CaCO3 m-2 yr-1) and midreefs to the south were net depositional on an annual basis (0.4 ± 0.1 kg CaCO3 m-2 yr-1) but erosional during the fall and winter. Only the two southernmost reefs were net depositional year-round. These results indicate that parts of the FRT have already crossed the tipping point for carbonate production and other parts are getting close.

  3. Characterization of carbonate reservoir property changes due to dissolution for far-field conditions of CO2 storage

    NASA Astrophysics Data System (ADS)

    Mangane, P. O.; Gouze, P.; Luquot, L.

    2012-12-01

    Geological storage of CO2 in reservoir pore fluid (e.g. deep saline aquifers), is one of the diverse technologies being explored for deacreasing atmospheric CO2 concentration. After injecting the CO2 as a supercritical fluid at depth, it will slowly dissolve into the pore water producing low pH fluids with a high capacity for dissolving carbonates and consequently changing irreversibly the hydrodynamical properties of the reservoir. Characterizing these changes is essential for modelling flow and CO2 transport during and after the CO2 injection. Here we report experimental results from the injection of the CO2-saturated brine into two distinct limestone cores (a bioclastic carbonate and an oolitic carbonate) of 9 mm diameter, 18 mm length. 3D high-resolution X-ray microtomography (XRMT) of the rock sample have been performed before and after the experiments. The experiments were performed using in-situ sequestration conditions (P = 12MPa and T = 100°C), and notably, under chemical conditions given at the position far away from the well injection site (i.e area where the volume of dissolved CO2 into the brine is low, due to CO2 consumption by the dissolution processes occured during its transport from the well injection site). Permeability k is calculated from the pressure drop across the sample and porosity Φ is deduced from chemical concentration of the outlet fluid. The change of the pore structure is analysed in terms of connectivity, tortuosity and fluid-rock interface from processing the XRMT images. These experiments show that far from the well injection site, dissolution processes are characterized by slow mass tranfer including, in the case of carbonate rock, transport of fine particles, which locally clog the porous space. Then, that leads to the damage of the carbonate reservoir both in terms of connectivity of the porous space and CO2 hydrodynamical storage capacity. In fact, the results of the two experiments show that the porosity decreased locally

  4. Acid neutralisation capacity of accelerated carbonated stainless steel slag.

    PubMed

    Johnson, D C; MacLeod, C L; Hills, C D

    2003-05-01

    The acid neutralisation capacity test is widely used to assess the long-term performance of waste materials prior to disposal. Samples of fixed mass are exposed to increasing additions of nitric add in sealed containers and the resultant pH is plotted as a titration curve. In this work, the add neutralisation capacity test was used in the assessment of an accelerated carbonated stainless steel slag. Difficulties arose in applying the test procedure to this material. This was largely because of the raised pressure from significant volumes of released carbon dioxide trapped in the sealed sample containers, causing an alteration to leachate pH values. Consequently, the add neutralisation capacity test was modified to enable testing of samples in equilibrium with the atmosphere. No adverse effects on the results from testing of a carbonate free material were recorded. PMID:12803247

  5. Carbonate dissolution and transport in H2O fluids during subduction revealed by diamond-bearing rocks from the Alps

    NASA Astrophysics Data System (ADS)

    Frezzotti, M.; Selverstone, J.; Sharp, Z. D.; Compagnoni, R.

    2011-12-01

    Here we discuss the fate of subducted carbonates and its implications for recycling of crustal carbon. Thermodynamic models predict little decarbonation along most subduction geotherms, and the mechanisms by which carbon is transferred from the subducting slab to the overlying mantle remain poorly constrained. Diamond-bearing fluid inclusions in garnet in oceanic metasedimentary rocks from Lago di Cignana (western Alps) represent the first occurrence of diamond from a low-temperature subduction complex of clearly oceanic origin (T ≤600°C; P ≥3.5 GPa). The presence of diamonds in and associated with fluid inclusions provides clear evidence of carbon transport by fluids at depths that are directly relevant to slab-mantle fluid transfer during subduction. At room temperature, the fluid inclusions contain aqueous fluid, a vapor bubble, and multiple solid daughter crystals. Daughter crystals identified by Raman spectroscopy and microprobe analysis include ubiquitous Mg-calcite/calcite and rutile, and less common diamond, quartz, paragonite, dawsonite, rhodochrosite, dypingite, and pentahydrite. Molecular CO2 is absent or in trace amounts. The aqueous liquid phase contains ≥0.2 wt%, HCO3-, CO32-, and SO42- ions. In Raman spectra, broad peaks at 773 and 1017 cm-1 point to the presence of both Si(OH)4(aq) and deprotonated monomers (e.g., SiO(OH)3-(aq), and SiO2(OH)22-(aq)), indicative of alkaline solutions. The absence of CO2 in the vapor, and the presence of carbonate daughter minerals, CO32-(aq), and HCO3-(aq) also show that the trapped fluids are alkaline at ambient conditions. High activities of aqueous carbon species reveal that carbonate dissolution is an important mechanism for mobilizing slab carbon at sub-arc depths (100-200 km) during oceanic subduction. Our results imply that the magnitude of carbon release and transport from the slab at sub-arc depths is greater than experimentally predicted on the basis of decarbonation reactions alone.

  6. Prediction and inhibition of molten carbonate fuel cell shorting by NiO cathode dissolution

    SciTech Connect

    Ogawa, Takashi; Nirasawa, Hitoshi; Murata, Kenji

    1995-12-31

    A model of time until shorting begins due to NiO dissolution/precipitation in MCFC was developed on the assumption that electronic conduction in the cell would happen when the concentration of dispersed nickel particles exceeded a critical value at the anode/electrolyte interface. The equation for the estimation of time-to-short-beginning (TTS) was derived as: TTS{sup 0.5}/t = A + B/K{sub Ni} pCO{sub 2} (t: matrix thickness, K{sub Ni}: NiO solubility at pCO{sub 2} = 1 atm., and A, B: constant). Life tests under different conditions on several single cells proved the usability of this equation. For the purpose of retarding MCFC shorting, a cell with a low rate of NiO dissolution, with a LiFeO{sub 2} layer, an out-of-cell oxidized NiO cathode, and a Li{sub 2}CO{sub 3}-Na{sub 2}CO{sub 3} eutectic electrolyte was made. The life test results showed that the nickel dissolution rate in the cell was less than 1/5 slower than that in the ordinary cells with an in situ oxidized NiO cathode and high Li{sub 2}CO{sub 3}-K{sub 2}CO{sub 3} eutectic electrolyte.

  7. Carbon stripper foils for heavy-ion accelerators

    SciTech Connect

    Thomas, G.E.

    1980-01-01

    Carbon stripper foils have for many years been successfully used with accelerators because they yield higher average charge states than gas strippers. However, with the development of heavy ion accelerators and the resulting use of heavier ions, the carbon stripper foil lifetimes are greatly reduced. Even when using the new foils changer systems, which typically contain two hundred foils or more, it becomes necessary to have frequent accelerator shutdowns for foil reloading. The rate of experiment interruption makes it clear a new approach is necessary to increase foil lifetimes. Several techniques have been tried with varying degrees of success to strengthen these foils so that they will last longer; the most successful one reported a lifetime increase of the order of a factor of 30 over foils produced in the conventional manner. Methods of producing various types of foils will be presented, a discussion will be given on theories for foil breakage, and some new ideas will be introduced for further increasing foil lifetimes.

  8. A porous silica rock ("tripoli") in the footwall of the Jurassic Úrkút manganese deposit, Hungary: composition, and origin through carbonate dissolution

    USGS Publications Warehouse

    Polgari, Marta; Szabo, Zoltan; Szabo-Drubina, Magda; Hein, James R.; Yeh, Hsueh-Wen

    2005-01-01

    The mineralogical, chemical, and isotopic compositions were determined for a white tripoli from the footwall of the Jurassic Úrkút Mn-oxide ore deposit in the Bakony Mountains, Hungary. The tripoli consists of quartz and chalcedony, with SiO2 contents up to 100 wt.%; consequently, trace-element contents are very low. Oxygen isotopes and quartz crystallinity indicate a low-temperature diagenetic origin for this deposit. The tripoli was formed by dissolution of the carbonate portion of the siliceous (sponge spicules) Isztimér Limestone. Dissolution of the carbonate was promoted by inorganic and organic acids generated during diagensis and left a framework composed of diagenetic silica that preserved the original volume of the limestone layer. The relative enrichment of silica and high porosity is the result of that carbonate dissolution. The silty texture of this highly friable rock is due to the structurally weak silica framework.

  9. Carbon nanotube foils for electron stripping in tandem accelerators

    NASA Astrophysics Data System (ADS)

    von Reden, Karl; Zhang, Mei; Meigs, Martha; Sichel, Enid; Fang, Shaoli; Baughman, Ray H.

    2007-08-01

    Carbon nanotube technology has rapidly advanced in recent years, making it possible to create meter-long, ∼4 cm wide films of multi-walled tubes of less than 3 μg/cm2 areal density in a bench top open-air procedure. The physical properties of individual carbon nanotubes have been well established, equaling or surpassing electrical and thermal conductivity and mechanical strength of most other materials, graphite in particular. The handling and transport of such nanotube films, dry-mounted self-supporting on metal frames with several cm2 of open area, is problem-free: the aerogel films having a volumetric density of about 1.5 mg/cm3 survived the trip by car and air from Dallas to Oak Ridge without blemish. In this paper we will present the results of first tests of these nanotube films as electron stripper media in a tandem accelerator. The tests were performed in the Model 25 URC tandem accelerator of the Holifield radioactive ion beam facility (HRIBF) at Oak Ridge National Laboratory. We will discuss the performance of nanotube films in comparison with chemical vapor deposition and laser-ablated carbon foils.

  10. The dissolution of synthetic Na-boltwoodite in sodium carbonate solutions

    NASA Astrophysics Data System (ADS)

    Ilton, Eugene S.; Liu, Chongxuan; Yantasee, Wassana; Wang, Zheming; Moore, Dean A.; Felmy, Andrew R.; Zachara, John M.

    2006-10-01

    Uranyl silicates such as uranophane and Na-boltwoodite appear to control the solubility of uranium in certain contaminated sediments at the US Department of Energy Hanford site [Liu, C., Zachara, J.M., Qafoku, O., McKinley, J.P., Heald, S.M., Wang, Z. 2004. Dissolution of uranyl microprecipitates in subsurface sediments at Hanford Site, USA. Geochim. Cosmochim. Acta68, 4519-4537.]. Consequently, the solubility of synthetic Na-boltwoodite, Na(UO 2)(SiO 3OH) · 1.5H 2O, was determined over a wide range of bicarbonate concentrations, from circumneutral to alkaline pH, that are representative of porewater and groundwater compositions at the Hanford site and calcareous environments generally. Experiments were open to air. Results show that Na-boltwoodite dissolution was nearly congruent and its solubility and dissolution kinetics increased with increasing bicarbonate concentration and pH. A consistent set of solubility constants were determined from circumneutral pH (0 added bicarbonate) to alkaline pH (50 mM added bicarbonate). Average logKspo=5.86±0.24 or 5.85 ± 0.0.26; using the Pitzer ion-interaction model or Davies equation, respectively. These values are close to the one determined by [Nguyen, S.N., Silva, R.J., Weed, H.C., Andrews, Jr., J.E., 1992. Standard Gibbs free energies of formation at the temperature 303.15 K of four uranyl silicates: soddyite, uranophane, sodium boltwoodite, and sodium weeksite. J. Chem. Thermodynamics24, 359-376.] under very different conditions (pH 4.5, Ar atmosphere).

  11. Carbide Formation and Dissolution in Biomedical Co-Cr-Mo Alloys with Different Carbon Contents during Solution Treatment

    NASA Astrophysics Data System (ADS)

    Mineta, Shingo; Namba, Shigenobu; Yoneda, Takashi; Ueda, Kyosuke; Narushima, Takayuki

    2010-08-01

    The microstructures of as-cast and heat-treated biomedical Co-Cr-Mo (ASTM F75) alloys with four different carbon contents were investigated. The as-cast alloys were solution treated at 1473 to 1548 K for 0 to 43.2 ks. The precipitates in the matrix were electrolytically extracted from the as-cast and heat-treated alloys. An M23C6 type carbide and an intermetallic σ phase (Co(Cr,Mo)) were detected as precipitates in the as-cast Co-28Cr-6Mo-0.12C alloy; an M23C6 type carbide, a σ phase, an η phase (M6C-M12C type carbide), and a π phase (M2T3X type carbide with a β-manganese structure) were detected in the as-cast Co-28Cr-6Mo-0.15C alloy; and an M23C6 type carbide and an η phase were detected in the as-cast Co-28Cr-6Mo-0.25C and Co-28Cr-6Mo-0.35C alloys. After solution treatment, complete precipitate dissolution occurred in all four alloys. Under incomplete precipitate dissolution conditions, the phase and shape of precipitates depended on the heat-treatment conditions and the carbon content in the alloys. The π phase was detected in the alloys with carbon contents of 0.15, 0.25, and 0.35 mass pct after heat treatment at high temperature such as 1548 K for a short holding time of less than 1.8 ks. The presence of the π phase in the Co-Cr-Mo alloys has been revealed in this study for the first time.

  12. Oxidative dissolution of unirradiated Mimas MOX fuel (U/Pu oxides) in carbonated water under oxic and anoxic conditions

    NASA Astrophysics Data System (ADS)

    Odorowski, Mélina; Jégou, Christophe; De Windt, Laurent; Broudic, Véronique; Peuget, Sylvain; Magnin, Magali; Tribet, Magaly; Martin, Christelle

    2016-01-01

    Few studies exist concerning the alteration of Mimas Mixed-OXide (MOX) fuel, a mixed plutonium and uranium oxide, and data is needed to better understand its behavior under leaching, especially for radioactive waste disposal. In this study, two leaching experiments were conducted on unirradiated MOX fuel with a strong alpha activity (1.3 × 109 Bq.gMOX-1 reproducing the alpha activity of spent MOX fuel with a burnup of 47 GWd·tHM-1 after 60 years of decay), one under air (oxic conditions) for 5 months and the other under argon (anoxic conditions with [O2] < 1 ppm) for one year in carbonated water (10-2 mol L-1). For each experiment, solution samples were taken over time and Eh and pH were monitored. The uranium in solution was assayed using a kinetic phosphorescence analyzer (KPA), plutonium and americium were analyzed by a radiochemical route, and H2O2 generated by the water radiolysis was quantified by chemiluminescence. Surface characterizations were performed before and after leaching using Scanning Electron Microscopy (SEM), Electron Probe Microanalyzer (EPMA) and Raman spectroscopy. Solubility diagrams were calculated to support data discussion. The uranium releases from MOX pellets under both oxic and anoxic conditions were similar, demonstrating the predominant effect of alpha radiolysis on the oxidative dissolution of the pellets. The uranium released was found to be mostly in solution as carbonate species according to modeling, whereas the Am and Pu released were significantly sorbed or precipitated onto the TiO2 reactor. An intermediate fraction of Am (12%) was also present as colloids. SEM and EPMA results indicated a preferential dissolution of the UO2 matrix compared to the Pu-enriched agglomerates, and Raman spectroscopy showed the Pu-enriched agglomerates were slightly oxidized during leaching. Unlike Pu-enriched zones, the UO2 grains were much more sensitive to oxidative dissolution, but the presence of carbonates did not enable observation of an

  13. Dissolved inorganic carbon (DIC) and its δ13C in the Ganga (Hooghly) River estuary, India: Evidence of DIC generation via organic carbon degradation and carbonate dissolution

    NASA Astrophysics Data System (ADS)

    Samanta, Saumik; Dalai, Tarun K.; Pattanaik, Jitendra K.; Rai, Santosh K.; Mazumdar, Aninda

    2015-09-01

    In this study, we present comprehensive data on dissolved Ca, dissolved inorganic carbon (DIC) and its carbon isotope composition (δ13CDIC) of (i) the Ganga (Hooghly) River estuary water sampled during six seasons of contrasting water discharge over 2 years (2012 and 2013), (ii) shallow groundwater from areas adjacent to the estuary and (iii) industrial effluent water and urban wastewater draining into the estuary. Mass balance calculations indicate that processes other than the conservative mixing of seawater and river water are needed to explain the measured DIC and δ13CDIC. Results of mixing calculations in conjunction with the estimated undersaturated levels of dissolved O2 suggest that biological respiration and organic carbon degradation dominate over biological production in the estuary. An important outcome of this study is that a significant amount of DIC and dissolved Ca is produced within the estuary at salinity ⩾10, particularly during the monsoon period. Based on consideration of mass balance and a strong positive correlation observed between the "excess" DIC and "excess" Ca, we contend that the dominant source of DIC generated within the estuary is carbonate dissolution that is inferred to be operating in conjunction with degradation of organic carbon. Calculations show that groundwater cannot account for the observed "excess" Ca in the high salinity zone. Estimated DIC contributions from anthropogenic activity are minor, and they constitute ca. 2-3% of the river water DIC concentrations. The estimated annual DIC flux from the estuary to the Bay of Bengal is ca. (3-4) × 1012 g, of which ca. 40-50% is generated within the estuary. The monsoon periods account for the majority (ca. 70%) of the annual DIC generation in the estuary. The annual DIC flux from the Hooghly estuary accounts for ca. 1% of the global river DIC flux to the oceans. This is disproportionately higher than the water contribution from the Hooghly River to the oceans, which

  14. Enhancement of accelerated carbonation of alkaline waste residues by ultrasound.

    PubMed

    Araizi, Paris K; Hills, Colin D; Maries, Alan; Gunning, Peter J; Wray, David S

    2016-04-01

    The continuous growth of anthropogenic CO2 emissions into the atmosphere and the disposal of hazardous wastes into landfills present serious economic and environmental issues. Reaction of CO2 with alkaline residues or cementitius materials, known as accelerated carbonation, occurs rapidly under ambient temperature and pressure and is a proven and effective process of sequestering the gas. Moreover, further improvement of the reaction efficiency would increase the amount of CO2 that could be permanently sequestered into solid products. This paper examines the potential of enhancing the accelerated carbonation of air pollution control residues, cement bypass dust and ladle slag by applying ultrasound at various water-to-solid (w/s) ratios. Experimental results showed that application of ultrasound increased the CO2 uptake by up to four times at high w/s ratios, whereas the reactivity at low water content showed little change compared with controls. Upon sonication, the particle size of the waste residues decreased and the amount of calcite precipitates increased. Finally, the sonicated particles exhibited a rounded morphology when observed by scanning electron microscopy. PMID:26905698

  15. Constraints on the magnitude and rate of carbon dioxide dissolution at Bravo Dome natural gas field

    NASA Astrophysics Data System (ADS)

    Sathaye, K.; Hesse, M. A.

    2013-12-01

    The Bravo Dome field in northeastern New Mexico contains at least 10 trillion cubic feet (tcf) of magmatic CO2. The CO2 has been emplaced in the reservoir for at least 10,000 years, providing a useful analog for geologic CO2 storage. The reservoir is comprised of a CO2 gas layer overlying brine water in a sandstone reservoir. Previous estimates have used differences in the CO2/3He ratio in the gas to infer that locally, half of the CO2 originally emplaced has dissolved into the underlying brine. This study presents the first estimate of the total amount of CO2 dissolved. We incorporate gas pressure, reservoir geometry, and gas layer thickness to show that over 80% of the CO2 originally emplaced is still present in the gas layer. It is generally assumed that the dissolution of CO2 is driven by convective currents in the brine. We present an alternative hypothesis for the spatial differences of the CO2/3He ratio seen in this reservoir. Gas injection theory predicts that as gas displaces a liquid, relatively insoluble gas components will become enriched at the front of the displacement. If the emplacement occurred from west to east this would cause 3He enrichment in the eastern portion of the Bravo Dome field overlying the brine. This effect could be responsible for the spatial differences in the CO2/3He ratio. Mass per area in the gas layer of the reservoir is seen in the 2 right panes. The measured bottom hole pressure data from 1981 is used in combination with CO2/3He measurements to estimate the mass of CO2 originally in place. The water thickness is inversely correlated with the CO2/3He ratio, suggesting that there may be convective dissolution occurring in the eastern part of the reservoir. Present day mass of CO2 is roughly 83% of the original total.

  16. Facilitating Conceptual Understanding of Gas-Liquid Mass Transfer Coefficient through a Simple Experiment Involving Dissolution of Carbon Dioxide in Water in a Surface Aeration Reactor

    ERIC Educational Resources Information Center

    Utgikar, Vivek P.; MacPherson, David

    2016-01-01

    Students in the undergraduate "transport phenomena" courses typically have a greater difficulty in understanding the theoretical concepts underlying the mass transport phenomena as compared to the concepts of momentum and energy transport. An experiment based on dissolution of carbon dioxide in water was added to the course syllabus to…

  17. Dissolution of single-walled carbon nanotubes in alkanol-cholic acid mixtures

    NASA Astrophysics Data System (ADS)

    Dyshin, A. A.; Eliseeva, O. V.; Bondarenko, G. V.; Kiselev, M. G.

    2015-09-01

    A procedure for dispersing the single-walled carbon nanotubes (SWCNTs) for preparing stable suspensions with high concentrations of individual nanotubes in various alcohols was described. The obtained suspensions were studied by Raman spectroscopy. The solubility of the single-walled carbon nanotubes in alcohols was found to depend on the concentration of cholic acid. The ethanol-surfactant mixture was shown to be the best solvent for all alkanol-cholic acid mixtures (0.018 mol/kg) under study used for preparing time-stable suspensions of single-walled carbon nanotubes. The dissolving ability of aliphatic alcohols was found to decrease in the series: ethanol-isopropanol- tert-butanol-butanol-propanol.

  18. An ecological mechanism to create regular patterns of surface dissolution in a low-relief carbonate landscape

    NASA Astrophysics Data System (ADS)

    Cohen, M. J.; Martin, J. B.; Mclaughlin, D. L.; Osborne, T.; Murray, A.; Watts, A. C.; Watts, D.; Heffernan, J. B.

    2012-12-01

    Development of karst landscapes is controlled by focused delivery of water undersaturated with respect to the soluble rock minerals. As that water comes to equilibrium with the rock, secondary porosity is incrementally reinforced creating a positive feedback that acts to augment the drainage network and subsequent water delivery. In most self-organizing systems, spatial positive feedbacks create features (in landscapes: patches; in karst aquifers: conduits) whose size-frequency relationship follows a power function, indicating a higher probability of large features than would occur with a random or Gaussian genesis process. Power functions describe several aspects of secondary porosity in the Upper Floridan Aquifer in north Florida. In contrast, a different pattern arises in the karst landscape in southwest Florida (Big Cypress National Preserve; BICY), where low-relief and a shallow aquiclude govern regional hydrology. There, the landscape pattern is highly regular (Fig. 1), with circular cypress-dominated wetlands occupying depressions that are hydrologically isolated and distributed evenly in a matrix of pine uplands. Regular landscape patterning results from spatially coupled feedbacks, one positive operating locally that expands patches coupled to another negative that operates at distance, eventually inhibiting patch expansion. The positive feedback in BICY is thought to derive from the presence of surface depressions, which sustain prolonged inundation in this low-relief setting, and facilitate wetland development that greatly augments dissolution potential of infiltrating water in response to ecosystem metabolic processes. In short, wetlands "drill" into the carbonate leading to both vertical and lateral basin expansion. Wetland expansion occurs at the expense of surrounding upland area, which is the local catchment that subsidizes water availability. A distal inhibitory feedback on basin expansion thus occurs as the water necessary to sustain prolonged

  19. Submarine Dissolution During the Late-Miocene Carbonate Crash and Subsequent Mega-Pockmark Formation on the Cocos Ridge

    NASA Astrophysics Data System (ADS)

    Kluesner, J.; Silver, E. A.; Bangs, N. L.; McIntosh, K. D.

    2014-12-01

    A large field (245km2) seabed mega-pockmarks (~1 km to 4 km in diameter) was recently imaged on the western edge of the Cocos Ridge near the Middle American Trench. The pockmarks are part of a vast mega-pockmark field (~10x150 km) and were imaged using high-resolution multibeam bathymetry and backscatter and 3D seismic reflection data. On the seafloor, multiple pockmarks exhibit a two-tiered geomorphology, some of which contain small high-backscatter mounds, possibly indicating recent seafloor seepage. 3D seismic data reveal that the two-tiered morphology is caused by collapse structures at depth with large pockmarks above the walls of the former. Observed collapse structures are characterized by steep walls that truncate surrounding strata, apparent normal "ring" faults, chaotic internal reflections interpreted as infill, and circular morphologies. Younger pockmarks located above the walls of the collapse structures are larger in diameter, have gently dipping walls that do not truncate surrounding strata, and typically show elliptical morphologies. Physical properties results at IODP Site U1414 that intersects the 3D seismic volume suggest that observed reverse polarity lens-shaped zones, which are truncated by the deeper collapse structures, represent anomalous regions of high porosity and low density. In addition, a rapid drop in Ca concentrations observed within this interval at Site U1414 suggests a relationship with possible carbonate dissolution. Correlation of the collapse structures stratigraphic timing with nanno-fossil data at Site U1414 suggests formation occurred ~8-10 Ma, approximately during the Late Miocene eastern Pacific carbonate crash. Based on 3D seismic analysis and recent drilling results, we propose a two-stage formation process that consists of initial collapse caused by carbonate dissolution during the late Miocene, followed by sustained fluid-flow along the walls of established collapse features, resulting in pockmark formation. This

  20. Global change accelerates carbon assimilation by a wetland ecosystem engineer

    NASA Astrophysics Data System (ADS)

    Caplan, Joshua S.; Hager, Rachel N.; Megonigal, J. Patrick; Mozdzer, Thomas J.

    2015-11-01

    The primary productivity of coastal wetlands is changing dramatically in response to rising atmospheric carbon dioxide (CO2) concentrations, nitrogen (N) enrichment, and invasions by novel species, potentially altering their ecosystem services and resilience to sea level rise. In order to determine how these interacting global change factors will affect coastal wetland productivity, we quantified growing-season carbon assimilation (≈gross primary productivity, or GPP) and carbon retained in living plant biomass (≈net primary productivity, or NPP) of North American mid-Atlantic saltmarshes invaded by Phragmites australis (common reed) under four treatment conditions: two levels of CO2 (ambient and +300 ppm) crossed with two levels of N (0 and 25 g N added m-2 yr-1). For GPP, we combined descriptions of canopy structure and leaf-level photosynthesis in a simulation model, using empirical data from an open-top chamber field study. Under ambient CO2 and low N loading (i.e., the Control), we determined GPP to be 1.66 ± 0.05 kg C m-2 yr-1 at a typical Phragmites stand density. Individually, elevated CO2 and N enrichment increased GPP by 44 and 60%, respectively. Changes under N enrichment came largely from stimulation to carbon assimilation early and late in the growing season, while changes from CO2 came from stimulation during the early and mid-growing season. In combination, elevated CO2 and N enrichment increased GPP by 95% over the Control, yielding 3.24 ± 0.08 kg C m-2 yr-1. We used biomass data to calculate NPP, and determined that it represented 44%-60% of GPP, with global change conditions decreasing carbon retention compared to the Control. Our results indicate that Phragmites invasions in eutrophied saltmarshes are driven, in part, by extended phenology yielding 3.1× greater NPP than native marsh. Further, we can expect elevated CO2 to amplify Phragmites productivity throughout the growing season, with potential implications including accelerated spread

  1. Is there a component of Pleistocene CO2 change associated with carbonate dissolution cycles?

    NASA Astrophysics Data System (ADS)

    Keir, Robin S.

    1995-10-01

    The only processes which could have decreased atmospheric CO2 during glacial climates without appreciably changing the carbon isotope distribution in the sea appear to be (1) dissolved calcium carbonate input to the ocean, e.g., coral reef buildup and erosion, (2) the ocean solubility pump, due to changes in surface temperature or air-sea exchange, or (3) decreased biological production of calcium carbonate. It is assumed here that one of these mechanisms caused part of the atmospheric CO2 changes recorded in the 200-kyr-long Vostok ice core. Two residual CO2 records are generated by scaling the δ13C difference between planktonic and benthic foraminifera in marine sediment cores to -82 ppm CO2 per 1‰ increase in Δδ13C and subtracting from this the measured CO2 concentration in the ice core. Both residual CO2 records exhibit two broad maximums between about 20-50 ka and 140-200 ka, indicating that during these times, about 40 ppm of the CO2 decrease from interglacial levels cannot be explained by the interaction of the ocean's biological and vertical mixing cycles. The shape of the residual CO2 curve is similar qualitatively to the variation of calcium carbonate in central equatorial Pacific sediments during this time period, which would imply that changes in dissolved carbonate input to the ocean contributed the added component of CO2 change. However, recent models of atmospheric CO2 change in response to changing alkaline input to the ocean exhibit about a 25 to 35 ppm decrease per 1013 mol yr-1 increase in dissolved CaCO3 input. If compensation for the changing input is occurring mostly within an area of about 40 × 106 km² below the lysocline in the Indo-Pacific, the change in carbonate accumulation rate corresponding to a -40 ppm CO2 change would be a minimum of 3 mg cm-2 yr-1. This can be compared to glacial increases of 0.5 to 1.0 mg cm-2 yr-1 during the last 200 kyr in central equatorial Pacific sediments. Thus, the added glacial accumulation of

  2. Effects of suspension pH and mineral dissolution on carbon dioxide hydrate formation

    NASA Astrophysics Data System (ADS)

    Lee, W.; Lamorena, R. B.

    2008-12-01

    CO2 sequestration as a form of hydrate into geological formations could be significantly affected by soil mineral heterogeneity potentially contributing to the stochastic behavior of hydrate formation. In this study, we controlled the pH of soil mineral suspensions (Na-montmorillonite, kaolinite mixture, and pyrite) by the addition of 2M/10M NaOH and 2M/10M HCl before the dissolution of CO2. The soil mineral suspensions were prepared in deionized water (DIW) and NaCl (3.5 %) solutions. The formation of mass of CO2 hydrates was observed in most of the soil mineral suspensions at 30 bar and 0.3°C. In montmorillonite and kaolinite mixture suspensions with and without NaCl near neutral (pH 6~8) suspension pHs can provide the fastest hydrate formation kinetics followed by basic (~pH 12.0) and acidic (pH 2.0) suspension pHs. Acidic suspension pH gives the fastest kinetics in pyrite suspensions without NaCl followed by neutral and basic pHs, while no hydrate formations were observed in basic and near neutral pyrite suspensions with NaCl. The experimental results suggest that different types of soil mineral structures and chemical species can form under different suspension pHs, significantly affecting the hydrate formation time. Chemical species (e.g. Al+3) that could potentially affect hydrate formation times were identified by a chemical equilibrium modeling software, PHREEQC. The results obtained from this research could provide promising avenues for hydrate formation mechanism studies.

  3. Elevated pCO2 effects on the geochemistry of carbonate aquifers: calcite dissolution as a driver of elevated metal concentrations

    NASA Astrophysics Data System (ADS)

    Wunsch, A.; Navarre-Sitchler, A. K.; Moore, J.; McCray, J. E.

    2012-12-01

    Geological carbon capture, utilization and storage has gained momentum in the last decade as a viable option of reducing anthropogenic emissions of CO2, with several demonstration projects completed, in progress or planned for upcoming years. However, large-scale CO2-injection operations are accompanied by concerns of CO2 leakage from deep geological repositories and subsequent contact with shallower aquifers, such as underground sources of drinking water. Direct toxicity of CO2 is of lesser concern; rather, it is the acidification of aquifers from increased CO2 partial-pressures (pCO2), which may lead to release of metals into groundwater through mineral dissolution and metal desorption. Previous geochemical studies have suggested that the presence of calcite in aquifer material would reduce the hazard of metal release by effectively buffering acidity via calcite dissolution at elevated pCO2, thus placing carbonate aquifers at lesser risk in case of CO2 leakage. Yet calcite is rarely found in pure form, and often contains a wide range of impurities, including metals such as As, Cr, and Pb, in solid-solution. Dissolution of calcite during acidity buffering is accompanied by release of these impurities from the calcite lattice. We show through experimental work that dissolution of calcite is the primary mechanism responsible for elevated concentrations of metals in carbonate aquifers at high pCO2. It is also evident that the mechanism responsible for metal release, i.e. dissolution or desorption, is metal-specific and pCO2-specific. Modeling work based on our experimental results suggests that in reducing aquifers calcite can contribute more to release of metals than sulfides, which are generally viewed as likely sources of metals in aquifers, during a hypothetical 30-year CO2 leak. In addition, modeling work suggests that when sulfide minerals are present in a carbonate aquifer, metals release would be more sensitive to pO2 than to pCO2.

  4. Carbonation acceleration of calcium hydroxide nanoparticles: induced by yeast fermentation

    NASA Astrophysics Data System (ADS)

    Lopez-Arce, Paula; Zornoza-Indart, Ainara

    2015-09-01

    Carbonation of Ca(OH)2 nanoparticles and consolidation of limestone are accelerated by high humidity and a yeast fermentation system that supplies a saturated atmosphere on CO2, H2O vapor and ethanol during 28 days. Nanoparticles were analyzed by X-ray diffraction and differential thermal analyses with thermogravimetry. Spectrophotometry, scanning electron microscopy analyses, and hydric and mechanical tests were also performed in stones specimens. Samples exposed to the yeast environment achieve 100 % relative CaCO3 yield, whereas at high humidity but without the yeast and under laboratory environment, relative yields of 95 % CaCO3 and 15 % CaCO3 are, respectively, reached, with white crusts and glazing left on the stone surfaces when the nanoparticles are applied at a concentration of 25 g/l. The largest increase in the drilling resistance and surface hardness values with slight increase in the capillarity absorption and desorption coefficients and with lesser stone color changes are produced at a concentration of 5 g/l, in the yeast system environment. This especially happens in stone specimens initially with bimodal pore size distributions, more amounts of pores with diameters between 0.1 and 1 µm, higher open porosity values and faster capillary coefficients. An inexpensive and reliable method based on water and yeast-sugar solution is presented to speed up carbonation of Ca(OH)2 nanoparticles used as a consolidating product to improve the mechanical properties of decayed limestone from archaeological and architectural heritage.

  5. Glacial magnetite dissolution in abyssal NW Pacific sediments - evidence for carbon trapping?

    NASA Astrophysics Data System (ADS)

    Korff, Lucia; von Dobeneck, Tilo; Frederichs, Thomas; Kasten, Sabine; Kuhn, Gerhard; Gersonde, Rainer; Diekmann, Bernhard

    2016-04-01

    The abyssal North Pacific Ocean's large volume, depth, and terminal position on the deep oceanic conveyor make it a candidate site for deep carbon trapping as postulated by climate theory to explain the massive glacial drawdown of atmospheric CO2. As the major basins of the North Pacific have depths of 5500-6500m, far below the modern and glacial Calcite Compensation Depths (CCD), these abyssal sediments are carbonate-free and therefore not suitable for carbonate-based paleoceanographic proxy reconstructions. Instead, paleo-, rock and environmental magnetic methods are generally well applicable to hololytic abyssal muds and clays. In 2009, the international paleoceanographic research cruise SO 202 INOPEX ('Innovative North Pacific Experiment') of the German RV SONNE collected two ocean-spanning EW sediment core transects of the North Pacific and Bering Sea recovering a total of 50 piston and gravity cores from 45 sites. Out of seven here considered abyssal Northwest Pacific piston cores collected at water depths of 5100 to 5700m with mostly coherent shipboard susceptibility logs, the 20.23m long SO202-39-3, retrieved from 5102 m water depth east of northern Shatsky Rise (38°00.70'N, 164°26.78'E), was rated as the stratigraphically most promising record of the entire core transect and selected for detailed paleo- and environmental magnetic, geochemical and sedimentological investigations. This core was dated by correlating its RPI and Ba/Ti records to well-dated reference records and obviously provides a continuous sequence of the past 940 kyrs. The most striking orck magnetic features are coherent magnetite-depleted zones corresponding to glacial periods. In the interglacial sections, detrital, volcanic and even submicron bacterial magnetite fractions are excellently preserved. These alternating magnetite preservation states seem to reflect dramatic oxygenation changes in the deep North Pacific Ocean and hint at large-scale benthic glacial carbon trapping

  6. Direct electrolytic dissolution of silicate minerals for air CO2 mitigation and carbon-negative H2 production

    PubMed Central

    Rau, Greg H.; Carroll, Susan A.; Bourcier, William L.; Singleton, Michael J.; Smith, Megan M.; Aines, Roger D.

    2013-01-01

    We experimentally demonstrate the direct coupling of silicate mineral dissolution with saline water electrolysis and H2 production to effect significant air CO2 absorption, chemical conversion, and storage in solution. In particular, we observed as much as a 105-fold increase in OH− concentration (pH increase of up to 5.3 units) relative to experimental controls following the electrolysis of 0.25 M Na2SO4 solutions when the anode was encased in powdered silicate mineral, either wollastonite or an ultramafic mineral. After electrolysis, full equilibration of the alkalized solution with air led to a significant pH reduction and as much as a 45-fold increase in dissolved inorganic carbon concentration. This demonstrated significant spontaneous air CO2 capture, chemical conversion, and storage as a bicarbonate, predominantly as NaHCO3. The excess OH− initially formed in these experiments apparently resulted via neutralization of the anolyte acid, H2SO4, by reaction with the base mineral silicate at the anode, producing mineral sulfate and silica. This allowed the NaOH, normally generated at the cathode, to go unneutralized and to accumulate in the bulk electrolyte, ultimately reacting with atmospheric CO2 to form dissolved bicarbonate. Using nongrid or nonpeak renewable electricity, optimized systems at large scale might allow relatively high-capacity, energy-efficient (<300 kJ/mol of CO2 captured), and inexpensive (<$100 per tonne of CO2 mitigated) removal of excess air CO2 with production of carbon-negative H2. Furthermore, when added to the ocean, the produced hydroxide and/or (bi)carbonate could be useful in reducing sea-to-air CO2 emissions and in neutralizing or offsetting the effects of ongoing ocean acidification. PMID:23729814

  7. Direct electrolytic dissolution of silicate minerals for air CO2 mitigation and carbon-negative H2 production.

    PubMed

    Rau, Greg H; Carroll, Susan A; Bourcier, William L; Singleton, Michael J; Smith, Megan M; Aines, Roger D

    2013-06-18

    We experimentally demonstrate the direct coupling of silicate mineral dissolution with saline water electrolysis and H2 production to effect significant air CO2 absorption, chemical conversion, and storage in solution. In particular, we observed as much as a 10(5)-fold increase in OH(-) concentration (pH increase of up to 5.3 units) relative to experimental controls following the electrolysis of 0.25 M Na2SO4 solutions when the anode was encased in powdered silicate mineral, either wollastonite or an ultramafic mineral. After electrolysis, full equilibration of the alkalized solution with air led to a significant pH reduction and as much as a 45-fold increase in dissolved inorganic carbon concentration. This demonstrated significant spontaneous air CO2 capture, chemical conversion, and storage as a bicarbonate, predominantly as NaHCO3. The excess OH(-) initially formed in these experiments apparently resulted via neutralization of the anolyte acid, H2SO4, by reaction with the base mineral silicate at the anode, producing mineral sulfate and silica. This allowed the NaOH, normally generated at the cathode, to go unneutralized and to accumulate in the bulk electrolyte, ultimately reacting with atmospheric CO2 to form dissolved bicarbonate. Using nongrid or nonpeak renewable electricity, optimized systems at large scale might allow relatively high-capacity, energy-efficient (<300 kJ/mol of CO2 captured), and inexpensive (<$100 per tonne of CO2 mitigated) removal of excess air CO2 with production of carbon-negative H2. Furthermore, when added to the ocean, the produced hydroxide and/or (bi)carbonate could be useful in reducing sea-to-air CO2 emissions and in neutralizing or offsetting the effects of ongoing ocean acidification. PMID:23729814

  8. Carbide Dissolution/Carbon Loss as a Function of Spray Distance in Unshrouded/Shrouded Plasma Sprayed Cr3C2-NiCr Coatings

    NASA Astrophysics Data System (ADS)

    Matthews, S.

    2015-02-01

    Thermal spraying of Cr3C2-NiCr composites generates varying degrees of carbide dissolution into the Ni binder. During high-temperature exposure, the carbide dissolution zones precipitate high concentrations of small carbides which develop into finely structured networks. This raises the possibility of producing unique tailored carbide composite structures through the generation of controlled carbide dissolution and appropriate heat treatment. The first step in this process is to produce a supersaturated Ni-Cr-C solid solution from which the carbide phase could be precipitated. In a previous work, a broad range of plasma parameters were trialed to assess their effect on the degree of carbide dissolution at a fixed spray distance of 100 mm. The current two-part work builds on the most promising plasma parameters from those trials. In Part 1 of this two-part article series, the effect of spray distance on the extent of carbide dissolution and carbon loss during high energy plasma spraying was investigated. The effectiveness of solid shield and gas shrouding is contrasted, and the mechanisms by which they influence the degree of decarburization discussed.

  9. The Role of Sulfur Oxidation in Carbonate Precipitation and Dissolution Within Sulfidic Hot Springs

    NASA Astrophysics Data System (ADS)

    Alford, S. E.; Kapitulčinová, D.; Kotrc, B.; Langerhuus, A. T.; Berelson, W.; Dawson, S.; Corsetti, F.; Hanselmann, K.; Johnson, H.; Spear, J.; Stevenson, B. S.; de La Torre, J.; 2008, G.

    2008-12-01

    Geothermal waters that have interacted with subsurface limestones often precipitate aragonite and calcite (travertine) upon cooling and degassing of CO2, forming terraced travertine deposits like those at Mammoth Hot Springs (MHS) in Yellowstone National Park. It has been shown that surfaces of filamentous microbial "Aquificales-dominated streamer communities" comprising the Apron and Channel Facies in these systems can act as nucleation sites for carbonate precipitation leading to the fine-scale tubular micro-structures consistently observed in travertine terraces, modern and ancient. The expected carbonate precipitates were found on streamer communities on the proximal Slope facies, however, ESEM imaging and EDX analysis revealed sulfur crystals, rather than carbonate precipitates, in association with Aquificales-dominated communities collected near the mouth of Narrow Gauge (pH 6.43, T 73.5°C), a sulfidic bicarbonate spring within the MHS system. Thermodynamic analysis of geochemical spring water datasets (data from Angel Terrace Spring applied to the Narrow Gauge site) demonstrates that lowering of the acid-neutralizing capacity (ANC) of spring waters can be achieved by sulfur oxidation. Although the first step of oxidation from H2S to S° cannot account for the lack of aragonite on the streamer biofilms, oxidation of even small amounts of S° to S2O32- and further to SO42- markedly decreases ANC. This microbially mediated reaction may lead to a shift in the local pH and a shift in the ion activity product (IAP) for Ca2+ x CO32- to below the solubility product (Ksp) of CaCO3. Our calculations suggest that this reaction, sulfur oxidation with oxygen to sulfate, can liberate sufficient protons to drive aragonite to undersaturation, if the initial sulfur concentration is 5 mM, and the [Ca] and [CO3] concentrations are initially 0.01 M and 1-10 uM, respectively. The potential importance of sulfur oxidation in hot springs, the molecular signatures of this process

  10. Coupled alkai fieldspar dissolution and secondary mineral precipatation in batch systems-2: New experiments with supercritical CO2 and implications for carbon sequestration

    SciTech Connect

    Lu, Peng; Fu, Qi; Seyfried, William E. Jr.; Hedges, Sheila W.; Soong, Yee; Jones, Kyle; Zhua, Chen

    2013-01-01

    In order to evaluate the extent of CO{sub 2}–water–rock interactions in geological formations for C sequestration, three batch experiments were conducted on alkali feldspars–CO{sub 2}–brine interactions at 150–200 °C and 300 bars. The elevated temperatures were necessary to accelerate the reactions to facilitate attainable laboratory measurements. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. SEM, TEM and XRD analysis of reaction products showed extensive dissolution features (etch pits, channels, kinks and steps) on feldspars and precipitation of secondary minerals (boehmite, kaolinite, muscovite and paragonite) on feldspar surfaces. Therefore, these experiments have generated both solution chemistry and secondary mineral identity. The experimental results show that partial equilibrium was not attained between secondary minerals and aqueous solutions for the feldspar hydrolysis batch systems. Evidence came from both solution chemistry (supersaturation of the secondary minerals during the entire experimental duration) and metastable co-existence of secondary minerals. The slow precipitation of secondary minerals results in a negative feedback in the dissolution–precipitation loop, reducing the overall feldspar dissolution rates by orders of magnitude. Furthermore, the experimental data indicate the form of rate laws greatly influence the steady state rates under which feldspar dissolution took place. Negligence of both the mitigating effects of secondary mineral precipitation and the sigmoidal shape of rate–ΔG{sub r} relationship can overestimate the extent of feldspar dissolution during CO{sub 2} storage. Finally, the literature on feldspar dissolution in CO{sub 2}-charged systems has been reviewed. The data available are insufficient and new experiments are urgently needed to establish a database on feldspar dissolution mechanism, rates and rate laws, as well as secondary mineral

  11. Carbon nanohorns allow acceleration of osteoblast differentiation via macrophage activation

    NASA Astrophysics Data System (ADS)

    Hirata, Eri; Miyako, Eijiro; Hanagata, Nobutaka; Ushijima, Natsumi; Sakaguchi, Norihito; Russier, Julie; Yudasaka, Masako; Iijima, Sumio; Bianco, Alberto; Yokoyama, Atsuro

    2016-07-01

    Carbon nanohorns (CNHs), formed by a rolled graphene structure and terminating in a cone, are promising nanomaterials for the development of a variety of biological applications. Here we demonstrate that alkaline phosphatase activity is dramatically increased by coculture of human monocyte derived macrophages (hMDMs) and human mesenchymal stem cells (hMSCs) in the presence of CNHs. CNHs were mainly localized in the lysosome of macrophages more than in hMSCs during coculturing. At the same time, the amount of Oncostatin M (OSM) in the supernatant was also increased during incubation with CNHs. Oncostatin M (OSM) from activated macrophage has been reported to induce osteoblast differentiation and matrix mineralization through STAT3. These results suggest that the macrophages engulfed CNHs and accelerated the differentiation of mesenchymal stem cells into the osteoblast via OSM release. We expect that the proof-of-concept on the osteoblast differentiation capacity by CNHs will allow future studies focused on CNHs as ideal therapeutic materials for bone regeneration.Carbon nanohorns (CNHs), formed by a rolled graphene structure and terminating in a cone, are promising nanomaterials for the development of a variety of biological applications. Here we demonstrate that alkaline phosphatase activity is dramatically increased by coculture of human monocyte derived macrophages (hMDMs) and human mesenchymal stem cells (hMSCs) in the presence of CNHs. CNHs were mainly localized in the lysosome of macrophages more than in hMSCs during coculturing. At the same time, the amount of Oncostatin M (OSM) in the supernatant was also increased during incubation with CNHs. Oncostatin M (OSM) from activated macrophage has been reported to induce osteoblast differentiation and matrix mineralization through STAT3. These results suggest that the macrophages engulfed CNHs and accelerated the differentiation of mesenchymal stem cells into the osteoblast via OSM release. We expect that the

  12. DISSOLUTION OF METAL OXIDES AND SEPARATION OF URANIUM FROM LANTHANIDES AND ACTINIDES IN SUPERCRITICAL CARBON DIOXIDE

    SciTech Connect

    Donna L. Quach; Bruce J. Mincher; Chien M. Wai

    2013-10-01

    This paper investigates the feasibility of extracting and separating uranium from lanthanides and other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of a counter current stripping technique, which would be a more efficient and environmentally benign technology for spent nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U, Pu, and Np) and europium were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, uranium/europium and uranium/plutonium extraction and separation in sc-CO2 modified with TBP is successful at nitric acid concentrations of less than 6 M and at nitric acid concentrations of less than 3 M with acetohydroxamic acid or oxalic acid, respectively. A scheme for recycling uranium from spent nuclear fuel by using sc-CO2 and counter current stripping columns is presented.

  13. Dissolution of metal oxides and separation of uranium from lanthanides and actinides in supercritical carbon dioxide

    SciTech Connect

    Quach, D.L.; Wai, C.M.; Mincher, B.J.

    2013-07-01

    This paper investigates the feasibility of extracting and separating uranium from lanthanides and other actinides by using supercritical fluid carbon dioxide (sc-CO{sub 2}) as a solvent modified with tri-n-butylphosphate (TBP) for the development of a counter current stripping technique, which would be a more efficient and environmentally benign technology for spent nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U, Pu, and Np) and europium were extracted in sc-CO{sub 2} modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, uranium/europium and uranium/plutonium extraction and separation in sc-CO{sub 2} modified with TBP is successful at nitric acid concentrations of less than 6 M and at nitric acid concentrations of less than 3 M with acetohydroxamic acid or oxalic acid, respectively. A scheme for recycling uranium from spent nuclear fuel by using sc-CO{sub 2} and counter current stripping columns is presented. (authors)

  14. Accelerating Gas Adsorption on 3D Percolating Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Li, Hui; Wen, Chenyu; Zhang, Youwei; Wu, Dongping; Zhang, Shi-Li; Qiu, Zhi-Jun

    2016-02-01

    In the field of electronic gas sensing, low-dimensional semiconductors such as single-walled carbon nanotubes (SWCNTs) can offer high detection sensitivity owing to their unprecedentedly large surface-to-volume ratio. The sensitivity and responsivity can further improve by increasing their areal density. Here, an accelerated gas adsorption is demonstrated by exploiting volumetric effects via dispersion of SWCNTs into a percolating three-dimensional (3D) network in a semiconducting polymer. The resultant semiconducting composite film is evaluated as a sensing membrane in field effect transistor (FET) sensors. In order to attain reproducible characteristics of the FET sensors, a pulsed-gate-bias measurement technique is adopted to eliminate current hysteresis and drift of sensing baseline. The rate of gas adsorption follows the Langmuir-type isotherm as a function of gas concentration and scales with film thickness. This rate is up to 5 times higher in the composite than only with an SWCNT network in the transistor channel, which in turn results in a 7-fold shorter time constant of adsorption with the composite. The description of gas adsorption developed in the present work is generic for all semiconductors and the demonstrated composite with 3D percolating SWCNTs dispersed in functional polymer represents a promising new type of material for advanced gas sensors.

  15. Accelerating Gas Adsorption on 3D Percolating Carbon Nanotubes

    PubMed Central

    Li, Hui; Wen, Chenyu; Zhang, Youwei; Wu, Dongping; Zhang, Shi-Li; Qiu, Zhi-Jun

    2016-01-01

    In the field of electronic gas sensing, low-dimensional semiconductors such as single-walled carbon nanotubes (SWCNTs) can offer high detection sensitivity owing to their unprecedentedly large surface-to-volume ratio. The sensitivity and responsivity can further improve by increasing their areal density. Here, an accelerated gas adsorption is demonstrated by exploiting volumetric effects via dispersion of SWCNTs into a percolating three-dimensional (3D) network in a semiconducting polymer. The resultant semiconducting composite film is evaluated as a sensing membrane in field effect transistor (FET) sensors. In order to attain reproducible characteristics of the FET sensors, a pulsed-gate-bias measurement technique is adopted to eliminate current hysteresis and drift of sensing baseline. The rate of gas adsorption follows the Langmuir-type isotherm as a function of gas concentration and scales with film thickness. This rate is up to 5 times higher in the composite than only with an SWCNT network in the transistor channel, which in turn results in a 7-fold shorter time constant of adsorption with the composite. The description of gas adsorption developed in the present work is generic for all semiconductors and the demonstrated composite with 3D percolating SWCNTs dispersed in functional polymer represents a promising new type of material for advanced gas sensors. PMID:26888337

  16. Carbon nanohorns allow acceleration of osteoblast differentiation via macrophage activation.

    PubMed

    Hirata, Eri; Miyako, Eijiro; Hanagata, Nobutaka; Ushijima, Natsumi; Sakaguchi, Norihito; Russier, Julie; Yudasaka, Masako; Iijima, Sumio; Bianco, Alberto; Yokoyama, Atsuro

    2016-08-14

    Carbon nanohorns (CNHs), formed by a rolled graphene structure and terminating in a cone, are promising nanomaterials for the development of a variety of biological applications. Here we demonstrate that alkaline phosphatase activity is dramatically increased by coculture of human monocyte derived macrophages (hMDMs) and human mesenchymal stem cells (hMSCs) in the presence of CNHs. CNHs were mainly localized in the lysosome of macrophages more than in hMSCs during coculturing. At the same time, the amount of Oncostatin M (OSM) in the supernatant was also increased during incubation with CNHs. Oncostatin M (OSM) from activated macrophage has been reported to induce osteoblast differentiation and matrix mineralization through STAT3. These results suggest that the macrophages engulfed CNHs and accelerated the differentiation of mesenchymal stem cells into the osteoblast via OSM release. We expect that the proof-of-concept on the osteoblast differentiation capacity by CNHs will allow future studies focused on CNHs as ideal therapeutic materials for bone regeneration. PMID:27412794

  17. Accelerating Gas Adsorption on 3D Percolating Carbon Nanotubes.

    PubMed

    Li, Hui; Wen, Chenyu; Zhang, Youwei; Wu, Dongping; Zhang, Shi-Li; Qiu, Zhi-Jun

    2016-01-01

    In the field of electronic gas sensing, low-dimensional semiconductors such as single-walled carbon nanotubes (SWCNTs) can offer high detection sensitivity owing to their unprecedentedly large surface-to-volume ratio. The sensitivity and responsivity can further improve by increasing their areal density. Here, an accelerated gas adsorption is demonstrated by exploiting volumetric effects via dispersion of SWCNTs into a percolating three-dimensional (3D) network in a semiconducting polymer. The resultant semiconducting composite film is evaluated as a sensing membrane in field effect transistor (FET) sensors. In order to attain reproducible characteristics of the FET sensors, a pulsed-gate-bias measurement technique is adopted to eliminate current hysteresis and drift of sensing baseline. The rate of gas adsorption follows the Langmuir-type isotherm as a function of gas concentration and scales with film thickness. This rate is up to 5 times higher in the composite than only with an SWCNT network in the transistor channel, which in turn results in a 7-fold shorter time constant of adsorption with the composite. The description of gas adsorption developed in the present work is generic for all semiconductors and the demonstrated composite with 3D percolating SWCNTs dispersed in functional polymer represents a promising new type of material for advanced gas sensors. PMID:26888337

  18. Dissolution effect and cytotoxicity of diamond-like carbon coatings on orthodontic archwires.

    PubMed

    Kobayashi, Shinya; Ohgoe, Yasuharu; Ozeki, Kazuhide; Hirakuri, Kenji; Aoki, Hideki

    2007-12-01

    Nickel-titanium (NiTi) has been used for implants in orthodontics due to the unique properties such as shape memory effect and superelasticity. However, NiTi alloys are eroded in the oral cavity because they are immersed by saliva with enzymolysis. Their reactions lead corrosion and nickel release into the body. The higher concentrations of Ni release may generate harmful reactions. Ni release causes allergenic, toxic and carcinogenic reactions. It is well known that diamond-like carbon (DLC) films have excellent properties, such as extreme hardness, low friction coefficients, high wear resistance. In addition, DLC film has many other superior properties as a protective coating for biomedical applications such as biocompatibility and chemical inertness. Therefore, DLC film has received enormous attention as a biocompatible coating. In this study, DLC film coated NiTi orthodontic archwires to protect Ni release into the oral cavity. Each wire was immersed in physiological saline at the temperature 37 degrees C for 6 months. The release concentration of Ni ions was detected using microwave induced plasma mass spectrometry (MIP-MS) with the resolution of ppb level. The toxic effect of Ni release was studied the cell growth using squamous carcinoma cells. These cells were seeded in 24 well culture plates and materials were immersed in each well directly. The concentration of Ni ions in the solutions had been reduced one-sixth by DLC films when compared with non-coated wire. This study indicated that DLC films have the protective effect of the diffusion and the non-cytotoxicity in corrosive environment. PMID:17562139

  19. Dissolution of Columbia River Basalt Under Mildly Acidic Conditions as a Function of Temperature: Experimental Results Relevant to the Geological Sequestration of Carbon Dioxide

    SciTech Connect

    Schaef, Herbert T.; McGrail, B. Peter

    2009-05-01

    Increasing attention is being focused on the rapid rise of carbon dioxide levels in the atmosphere, which many believe to be the major contributing factor to global climate change. Sequestering CO2 in deep geological formations has been proposed as a long-term solution to help stabilize CO2 levels. However, before such technology can be developed and implemented, a basic understanding of H2O-CO2 systems and the chemical interactions of these fluids with the host formation must be obtained. Important issues concerning mineral stability, reaction rates, and carbonate formation are all controlled or at least significantly impacted by the kinetics of rock-water reactions in mildly acidic, CO2-saturated solutions. Basalt has recently been identified as a potentially important host formation for geological sequestration. Dissolution kinetics of the Columbia River Basalt (CRB) were measured for a range of temperatures (25° to 90°C) under mildly acidic to neutral pH conditions using the single-pass flow-through test method. Under anaerobic conditions, the normalized dissolution rates for CRB decrease with increasing pH (3≤pH≤7) with a slope, η, of -0.12 ± 0.02. An activation energy, Ea, has been estimated at 30.3 ± 2.4 kJ mol-1. Dissolution kinetics measurements like these are essential for modeling the rate at which the CO2 reacts with basalt and ultimately converted to carbonate minerals in situ.

  20. Enhanced olivine carbonation within a basalt as compared to single-phase experiments: the impact of redox and bulk composition on the dissolution kinetics of olivine

    NASA Astrophysics Data System (ADS)

    Sissmann, O.; Brunet, F.; Martinez, I.; Guyot, F. J.; Verlaguet, A.; Pinquier, Y.; Garcia, B.; Chardin, M.; Kohler, E.; Daval, D.

    2014-12-01

    Olivine (Mg,Fe)2SiO4, which is one of the major mineral constituents of mafic and ultramafic rocks, has an attractive potential for CO2 mineral sequestration, as it possesses a high content of carbonate-forming divalent cations and exhibits one of the highest dissolution rate amongst rock-forming minerals. This study reports drastic differences in carbonation yields between experiments performed on olivine-rich basalt samples and on olivine separates (a more restricted chemical system). Batch experiments were conducted in water at 150°C and pCO2 = 280 bars on a Mg-rich tholeiitic basalt (9.3 wt.% MgO and 12.2 wt.% CaO), composed of olivine, Ti-magnetite, plagioclase and clinopyroxene. After 45 days of reaction, 56 wt.% of the initial MgO has reacted with CO2 to form Fe-bearing magnesite (Mg0.8Fe0.2)CO3 along with minor calcium carbonates. The substantial decrease of olivine content upon carbonation supports the idea that ferroan magnesite formation mainly follows from olivine dissolution. In contrast, in experiments performed under similar run durations and P/T conditions with a San Carlos olivine separate (47.8 wt.% MgO) of similar grain size, only 5 wt.% of the initial MgO content reacted to form Fe-bearing magnesite. The overall carbonation kinetics of the basalt is enhanced by a factor of 40. It could be accounted for by differences in chemical and textural properties of the secondary-silica layer which covers reacted olivine grains in both types of sample. A TEM inspection of mineral surfaces shows that the thin amorphous silica layer (~100 nm) is porous in the case of the basalt sample and that it contains significant amounts of iron and aluminum. Thus, we propose that the composition of the olivine environment itself can strongly influence the olivine dissolution-carbonation process. Consequently, laboratory data obtained on olivine separates might yield a conservative estimate of the true carbonation potential of olivine-bearing basaltic rocks. More

  1. The difference between surface ocean carbonate chemistry and calcite dissolution in deep sea sediments as observed in tests of Globorotalia menardii

    NASA Astrophysics Data System (ADS)

    Russo, M.; Mekik, F.

    2010-12-01

    The Globorotalia menardii Fragmentation Index (MFI) was developed to trace deep sea calcite dissolution within sediments. While this proxy has a multi-basin core top calibration ranging the tropical and subtropical world ocean, the effect of the surface ocean [CO32-] on thickness of whole G. menardii shells has not been previously tested. If the size-normalized shell weight (SNSW) of G. menardii tests were affected by the [CO32-] of ambient habitat waters, this would put constraints on the applicability of MFI as a reliable bulk sediment calcite dissolution proxy. We present new SNSW data from G. menardii shells within core tops in the eastern equatorial Pacific where there is both a strong gradient to surface ocean [CO32-] and calcite dissolution in the sediments. We compare our G.menardii SNSW data with that of other species in the region, such as Neogloboquadrina dutertrei and Pulleniatina obliquiloculata. While SNSW of both N. dutertrei and P. obliquiloculata have clear relationships with surface ocean [CO32-], we do not find a similar relationship between G. menardii SNSW and surface ocean parameters, particularly [CO32-]. This bolsters our confidence in the reliability of MFI as a deep sea carbonate dissolution tracer.

  2. Accelerated soil carbon turnover under tree plantations limits soil carbon storage

    NASA Astrophysics Data System (ADS)

    Chen, Guangshui; Yang, Yusheng; Yang, Zhijie; Xie, Jinsheng; Guo, Jianfen; Gao, Ren; Yin, Yunfeng; Robinson, David

    2016-01-01

    The replacement of native forests by tree plantations is increasingly common globally, especially in tropical and subtropical areas. Improving our understanding of the long-term effects of this replacement on soil organic carbon (SOC) remains paramount for effectively managing ecosystems to mitigate anthropogenic carbon emissions. Meta-analyses imply that native forest replacement usually reduces SOC stocks and may switch the forest from a net sink to a net source of atmospheric carbon. Using a long-term chronosequence during which areas of subtropical native forest were replaced by Chinese fir, we show by direct measurement that plantations have significantly accelerated SOC turnover compared with native forest, an effect that has persisted for almost a century. The immediate stimulation of SOC decomposition was caused by warmer soil before the closure of the plantation’s canopy. Long-term reductions in SOC mean residence times were coupled to litter inputs. Faster SOC decomposition was associated with lower soil microbial carbon use efficiency, which was due to smaller litter inputs and reduced nutrient availabilities. Our results indicate a previously unelucidated control on long-term SOC dynamics in native forests and demonstrate a potential constraint on climate mitigation when such forests are replaced by plantations.

  3. Accelerated soil carbon turnover under tree plantations limits soil carbon storage.

    PubMed

    Chen, Guangshui; Yang, Yusheng; Yang, Zhijie; Xie, Jinsheng; Guo, Jianfen; Gao, Ren; Yin, Yunfeng; Robinson, David

    2016-01-01

    The replacement of native forests by tree plantations is increasingly common globally, especially in tropical and subtropical areas. Improving our understanding of the long-term effects of this replacement on soil organic carbon (SOC) remains paramount for effectively managing ecosystems to mitigate anthropogenic carbon emissions. Meta-analyses imply that native forest replacement usually reduces SOC stocks and may switch the forest from a net sink to a net source of atmospheric carbon. Using a long-term chronosequence during which areas of subtropical native forest were replaced by Chinese fir, we show by direct measurement that plantations have significantly accelerated SOC turnover compared with native forest, an effect that has persisted for almost a century. The immediate stimulation of SOC decomposition was caused by warmer soil before the closure of the plantation's canopy. Long-term reductions in SOC mean residence times were coupled to litter inputs. Faster SOC decomposition was associated with lower soil microbial carbon use efficiency, which was due to smaller litter inputs and reduced nutrient availabilities. Our results indicate a previously unelucidated control on long-term SOC dynamics in native forests and demonstrate a potential constraint on climate mitigation when such forests are replaced by plantations. PMID:26805949

  4. Accelerated soil carbon turnover under tree plantations limits soil carbon storage

    PubMed Central

    Chen, Guangshui; Yang, Yusheng; Yang, Zhijie; Xie, Jinsheng; Guo, Jianfen; Gao, Ren; Yin, Yunfeng; Robinson, David

    2016-01-01

    The replacement of native forests by tree plantations is increasingly common globally, especially in tropical and subtropical areas. Improving our understanding of the long-term effects of this replacement on soil organic carbon (SOC) remains paramount for effectively managing ecosystems to mitigate anthropogenic carbon emissions. Meta-analyses imply that native forest replacement usually reduces SOC stocks and may switch the forest from a net sink to a net source of atmospheric carbon. Using a long-term chronosequence during which areas of subtropical native forest were replaced by Chinese fir, we show by direct measurement that plantations have significantly accelerated SOC turnover compared with native forest, an effect that has persisted for almost a century. The immediate stimulation of SOC decomposition was caused by warmer soil before the closure of the plantation’s canopy. Long-term reductions in SOC mean residence times were coupled to litter inputs. Faster SOC decomposition was associated with lower soil microbial carbon use efficiency, which was due to smaller litter inputs and reduced nutrient availabilities. Our results indicate a previously unelucidated control on long-term SOC dynamics in native forests and demonstrate a potential constraint on climate mitigation when such forests are replaced by plantations. PMID:26805949

  5. Chemical acceleration of a neutral granulated blast-furnace slag activated by sodium carbonate

    SciTech Connect

    Kovtun, Maxim Kearsley, Elsabe P. Shekhovtsova, Julia

    2015-06-15

    This paper presents results of a study on chemical acceleration of a neutral granulated blast-furnace slag activated using sodium carbonate. As strength development of alkali-activated slag cements containing neutral GBFS and sodium carbonate as activator at room temperature is known to be slow, three accelerators were investigated: sodium hydroxide, ordinary Portland cement and a combination of silica fume and slaked lime. In all cements, the main hydration product is C–(A)–S–H, but its structure varies between tobermorite and riversideite depending on the accelerator used. Calcite and gaylussite are present in all systems and they were formed due to either cation exchange reaction between the slag and the activator, or carbonation. With accelerators, compressive strength up to 15 MPa can be achieved within 24 h in comparison to 2.5 MPa after 48 h for a mix without an accelerator.

  6. Environmental remediation and conversion of carbon dioxide (CO(2)) into useful green products by accelerated carbonation technology.

    PubMed

    Lim, Mihee; Han, Gi-Chun; Ahn, Ji-Whan; You, Kwang-Suk

    2010-01-01

    This paper reviews the application of carbonation technology to the environmental industry as a way of reducing carbon dioxide (CO(2)), a green house gas, including the presentation of related projects of our research group. An alternative technology to very slow natural carbonation is the co-called 'accelerated carbonation', which completes its fast reaction within few hours by using pure CO(2). Carbonation technology is widely applied to solidify or stabilize solid combustion residues from municipal solid wastes, paper mill wastes, etc. and contaminated soils, and to manufacture precipitated calcium carbonate (PCC). Carbonated products can be utilized as aggregates in the concrete industry and as alkaline fillers in the paper (or recycled paper) making industry. The quantity of captured CO(2) in carbonated products can be evaluated by measuring mass loss of heated samples by thermo-gravimetric (TG) analysis. The industrial carbonation technology could contribute to both reduction of CO(2) emissions and environmental remediation. PMID:20195442

  7. Desorption and dissolution of heavy metals from contaminated soil using Shewanella sp. (HN-41) amended with various carbon sources and synthetic soil organic matters.

    PubMed

    Ayyasamy, Pudukadu Munusamy; Chun, Saho; Lee, Sanghoon

    2009-01-30

    Heavy metals in soil are considered a major environmental problem facing many countries around the world. Contamination of heavy metals occurs in soil due to both anthropogenic and natural causes. During the last two decades, extensive attention has been paid to the management and control of soil contamination. Decontamination of heavy metals in the soil has been a challenge for a long time. Microbial solubilization is one of promising process for remediation of heavy metals from contaminated sites. In this study, we attempted to treat soil contaminated with heavy metals using a facultative anaerobic bacterium Shewanella sp. (HN-41). The effect of carbon sources on the dissolution and conversion of heavy metals was first investigated using a defined medium containing 1 g of highly contaminated soil to select the most effective carbon source. Among three carbon sources, namely glucose, acetic acid and lactic acid, glucose at 10 mM was found to be the most effective. Therefore, glucose was used as a representative carbon source for the second part of the biological treatment in the defined medium, amended with humic acid (HA) and anthraquinone-2,6-disulfonate (ADQS), respectively. Among the heavy metals, iron and manganese exhibited the highest dissolution efficiency in the medium supplemented with glucose at 10mM. The rates of dissolution and removal of heavy metals were little bit higher in the medium amended with humic acid and ADQS. Per these results outlined above, a combined system of humic acid and ADQS incorporated with glucose was found to be effective for the removal of heavy metals from soil. PMID:18541365

  8. Environmental Remediation and Conversion of Carbon Dioxide (CO2) into Useful Green Products by Accelerated Carbonation Technology

    PubMed Central

    Lim, Mihee; Han, Gi-Chun; Ahn, Ji-Whan; You, Kwang-Suk

    2010-01-01

    This paper reviews the application of carbonation technology to the environmental industry as a way of reducing carbon dioxide (CO2), a green house gas, including the presentation of related projects of our research group. An alternative technology to very slow natural carbonation is the co-called ‘accelerated carbonation’, which completes its fast reaction within few hours by using pure CO2. Carbonation technology is widely applied to solidify or stabilize solid combustion residues from municipal solid wastes, paper mill wastes, etc. and contaminated soils, and to manufacture precipitated calcium carbonate (PCC). Carbonated products can be utilized as aggregates in the concrete industry and as alkaline fillers in the paper (or recycled paper) making industry. The quantity of captured CO2 in carbonated products can be evaluated by measuring mass loss of heated samples by thermo-gravimetric (TG) analysis. The industrial carbonation technology could contribute to both reduction of CO2 emissions and environmental remediation. PMID:20195442

  9. Generation of quasi-monoenergetic carbon ions accelerated parallel to the plane of a sandwich target

    SciTech Connect

    Wang, J. W.; Murakami, M.; Weng, S. M.; Xu, H.; Ju, J. J.; Luan, S. X.; Yu, W.

    2014-12-15

    A new ion acceleration scheme, namely, target parallel Coulomb acceleration, is proposed in which a carbon plate sandwiched between gold layers is irradiated with intense linearly polarized laser pulses. The high electrostatic field generated by the gold ions efficiently accelerates the embedded carbon ions parallel to the plane of the target. The ion beam is found to be collimated by the concave-shaped Coulomb potential. As a result, a quasi-monoenergetic and collimated C{sup 6+}-ion beam with an energy exceeding 10 MeV/nucleon is produced at a laser intensity of 5 × 10{sup 19} W/cm{sup 2}.

  10. Chemically Accelerated Carbon Mineralization: Chemical and Biological Catalytic Enhancement of Weathering of Silicate Minerals as Novel Carbon Capture and Storage

    SciTech Connect

    2010-07-01

    IMPACCT Project: Columbia University is developing a process to pull CO2 out of the exhaust gas of coal-fired power plants and turn it into a solid that can be easily and safely transported, stored above ground, or integrated into value-added products (e.g. paper filler, plastic filler, construction materials, etc.). In nature, the reaction of CO2 with various minerals over long periods of time will yield a solid carbonate—this process is known as carbon mineralization. The use of carbon mineralization as a CO2 capture and storage method is limited by the speeds at which these minerals can be dissolved and CO2 can be hydrated. To facilitate this, Columbia University is using a unique process and a combination of chemical catalysts which increase the mineral dissolution rate, and the enzymatic catalyst carbonic anhydrase which speeds up the hydration of CO2.

  11. Electrochemical in-situ dissolution study of structurally ordered, disordered and gold doped PtCu3 nanoparticles on carbon composites

    NASA Astrophysics Data System (ADS)

    Jovanovič, Primož; Šelih, Vid Simon; Šala, Martin; Hočevar, Samo B.; Pavlišič, Andraž; Gatalo, Matija; Bele, Marjan; Ruiz-Zepeda, Francisco; Čekada, Miha; Hodnik, Nejc; Gaberšček, Miran

    2016-09-01

    Commercial deployment of low-temperature-fuel cells is still hugely restricted by platinum alloy catalysts corrosion. Extensive research of the last years is focused on increasing stability of the catalyst composite, however a comprehensive understanding is still lacking. In pursuing this fundamentally and practically very important objective we present a comparative corrosion study of a PtCu3 nano-alloy system by investigating the effects of structural ordering and gold doping. For that purpose a recently developed electrochemical flow cell (EFC) coupled to inductively coupled plasma mass spectrometer (ICP-MS) is employed. This approach provides potential- and time-resolved insight into dissolution process at extremely low concentrations (ppb level). Our results show a structure-dependent copper corrosion, where ordering and gold-doping significantly improve copper retention in the native alloy. Two assumptions can be drawn from the measured Pt dissolution profiles: (i) a better Pt re-deposition efficiency in catalysts with higher porosity and (ii) the beneficial effect of Au surface doping that lowers the amount of dissolved Pt amount and shifts the Pt cathodic dissolution to lower potentials. A 2.6 nm Pt/C standard catalyst with the same carbon loading shows a much lower stability which is due to the well-known particle size effect.

  12. Thermodynamic characterization of metal dissolution and inhibitor adsorption processes in the low carbon steel/mimosa tannin/sulfuric acid system

    NASA Astrophysics Data System (ADS)

    Martinez, Sanja; Stern, Ivica

    2002-10-01

    The corrosion rates in the presence of mimosa tannin as a low carbon steel corrosion inhibitor in sulfuric acid media, were measured by the weight loss method, in the range of temperatures from 20 to 60 °C. The Temkin, Frumkin and Freundlich isotherms were tested for their fit to the experimental data. The free energies and enthalpies for the adsorption process and the apparent activation energies, enthalpies and entropies of the dissolution process were determined. The fundamental thermodynamic functions were used to glean important information about the mimosa tannin inhibitory behavior. The results were explained in terms of chemical thermodynamics.

  13. Preferential enhancement of laser-driven carbon ion acceleration from optimized nanostructured surfaces

    NASA Astrophysics Data System (ADS)

    Dalui, Malay; Wang, W.-M.; Trivikram, T. Madhu; Sarkar, Subhrangshu; Tata, Sheroy; Jha, J.; Ayyub, P.; Sheng, Z. M.; Krishnamurthy, M.

    2015-07-01

    High-intensity ultrashort laser pulses focused on metal targets readily generate hot dense plasmas which accelerate ions efficiently and can pave way to compact table-top accelerators. Laser-driven ion acceleration studies predominantly focus on protons, which experience the maximum acceleration owing to their highest charge-to-mass ratio. The possibility of tailoring such schemes for the preferential acceleration of a particular ion species is very much desired but has hardly been explored. Here, we present an experimental demonstration of how the nanostructuring of a copper target can be optimized for enhanced carbon ion acceleration over protons or Cu-ions. Specifically, a thin (≈0.25 μm) layer of 25-30 nm diameter Cu nanoparticles, sputter-deposited on a polished Cu-substrate, enhances the carbon ion energy by about 10-fold at a laser intensity of 1.2×1018  W/cm2. However, particles smaller than 20 nm have an adverse effect on the ion acceleration. Particle-in-cell simulations provide definite pointers regarding the size of nanoparticles necessary for maximizing the ion acceleration. The inherent contrast of the laser pulse is found to play an important role in the species selective ion acceleration.

  14. Preferential enhancement of laser-driven carbon ion acceleration from optimized nanostructured surfaces.

    PubMed

    Dalui, Malay; Wang, W-M; Trivikram, T Madhu; Sarkar, Subhrangsu; Sarkar, Subhrangshu; Tata, Sheroy; Jha, J; Ayyub, P; Sheng, Z M; Krishnamurthy, M

    2015-01-01

    High-intensity ultrashort laser pulses focused on metal targets readily generate hot dense plasmas which accelerate ions efficiently and can pave way to compact table-top accelerators. Laser-driven ion acceleration studies predominantly focus on protons, which experience the maximum acceleration owing to their highest charge-to-mass ratio. The possibility of tailoring such schemes for the preferential acceleration of a particular ion species is very much desired but has hardly been explored. Here, we present an experimental demonstration of how the nanostructuring of a copper target can be optimized for enhanced carbon ion acceleration over protons or Cu-ions. Specifically, a thin (≈ 0.25 μm) layer of 25-30 nm diameter Cu nanoparticles, sputter-deposited on a polished Cu-substrate, enhances the carbon ion energy by about 10-fold at a laser intensity of 1.2 × 10(18)  W/cm(2). However, particles smaller than 20 nm have an adverse effect on the ion acceleration. Particle-in-cell simulations provide definite pointers regarding the size of nanoparticles necessary for maximizing the ion acceleration. The inherent contrast of the laser pulse is found to play an important role in the species selective ion acceleration. PMID:26153048

  15. Preferential enhancement of laser-driven carbon ion acceleration from optimized nanostructured surfaces

    PubMed Central

    Dalui, Malay; Wang, W.-M.; Trivikram, T. Madhu; Sarkar, Subhrangshu; Tata, Sheroy; Jha, J.; Ayyub, P.; Sheng, Z. M.; Krishnamurthy, M.

    2015-01-01

    High-intensity ultrashort laser pulses focused on metal targets readily generate hot dense plasmas which accelerate ions efficiently and can pave way to compact table-top accelerators. Laser-driven ion acceleration studies predominantly focus on protons, which experience the maximum acceleration owing to their highest charge-to-mass ratio. The possibility of tailoring such schemes for the preferential acceleration of a particular ion species is very much desired but has hardly been explored. Here, we present an experimental demonstration of how the nanostructuring of a copper target can be optimized for enhanced carbon ion acceleration over protons or Cu-ions. Specifically, a thin (≈0.25 μm) layer of 25–30 nm diameter Cu nanoparticles, sputter-deposited on a polished Cu-substrate, enhances the carbon ion energy by about 10-fold at a laser intensity of 1.2×1018  W/cm2. However, particles smaller than 20 nm have an adverse effect on the ion acceleration. Particle-in-cell simulations provide definite pointers regarding the size of nanoparticles necessary for maximizing the ion acceleration. The inherent contrast of the laser pulse is found to play an important role in the species selective ion acceleration. PMID:26153048

  16. Mass exchange during simultaneous grinding and dissolution

    SciTech Connect

    Aksel'rud, G.A.; Semenishin, E.M.; Kopyt, S.Ya.; Trotskii, V.I.

    1988-03-20

    Extraction of ore components of interest has a number of disadvantages, one of which being low efficiency. Combining the grinding and dissolution steps in one apparatus makes the process more efficient. Adoption of this technology, however, requires theoretical and mathematical studies. This paper reports the kinetics of simultaneous grinding and dissolution of copper-containing minerals. Simultaneous grinding and dissolution accelerated several fold the mass transfer of components of interest in the interaction of malachite and azurite with sulfuric acid solutions. The complete dissolution time was determined by adding the experimental rates of dissolution and abrasion.

  17. Changes in mineralogical and leaching properties of converter steel slag resulting from accelerated carbonation at low CO2 pressure.

    PubMed

    van Zomeren, André; van der Laan, Sieger R; Kobesen, Hans B A; Huijgen, Wouter J J; Comans, Rob N J

    2011-11-01

    below these limit values at the relatively high pH that remained after carbonation. The V-bearing di-Ca silicate (C2S) phase has been identified as the major source of the V-leaching. It is shown that the dissolution of this mineral is limited in fresh steel slag, but strongly enhanced by carbonation, which causes the observed enhanced release of V from the K3 slag. The obtained insights in the mineral transformation reactions and their effect on pH and V-leaching provide guidance for further improvement of an accelerated carbonation technology. PMID:21741816

  18. Computational Tools for Accelerating Carbon Capture Process Development

    SciTech Connect

    Miller, David; Sahinidis, N V; Cozad, A; Lee, A; Kim, H; Morinelly, J; Eslick, J; Yuan, Z

    2013-06-04

    This presentation reports development of advanced computational tools to accelerate next generation technology development. These tools are to develop an optimized process using rigorous models. They include: Process Models; Simulation-Based Optimization; Optimized Process; Uncertainty Quantification; Algebraic Surrogate Models; and Superstructure Optimization (Determine Configuration).

  19. Characterization of reactive flow-induced evolution of carbonate rocks using digital core analysis- part 1: Assessment of pore-scale mineral dissolution and deposition

    NASA Astrophysics Data System (ADS)

    Qajar, Jafar; Arns, Christoph H.

    2016-09-01

    The application of X-ray micro-computed tomography (μ-CT) for quantitatively characterizing reactive-flow induced pore structure evolution including local particle detachment, displacement and deposition in carbonate rocks is investigated. In the studies conducted in this field of research, the experimental procedure has involved alternating steps of imaging and ex-situ core sample alteration. Practically, it is impossible to return the sample, with micron precision, to the same position and orientation. Furthermore, successive images of a sample in pre- and post-alteration states are usually taken at different conditions such as different scales, resolutions and signal-to-noise ratios. These conditions accompanying with subresolution features in the images make voxel-by-voxel comparisons of successive images problematic. In this paper, we first address the respective challenges in voxel-wise interpretation of successive images of carbonate rocks subject to reactive flow. Reactive coreflood in two carbonate cores with different rock types are considered. For the first rock, we used the experimental and imaging results published by Qajar et al. (2013) which showed a quasi-uniform dissolution regime. A similar reactive core flood was conducted in the second rock which resulted in wormhole-like dissolution regime. We particularly examine the major image processing operations such as transformation of images to the same grey-scale, noise filtering and segmentation thresholding and propose quantitative methods to evaluate the effectiveness of these operations in voxel-wise analysis of successive images of a sample. In the second part, we generalize the methodology based on the three-phase segmentation of normalized images, microporosity assignment and 2D histogram of image intensities to estimate grey-scale changes of individual image voxels for a general case where the greyscale images are segmented into arbitrary number of phases. The results show that local (voxel

  20. Characterization of reactive flow-induced evolution of carbonate rocks using digital core analysis- part 1: Assessment of pore-scale mineral dissolution and deposition.

    PubMed

    Qajar, Jafar; Arns, Christoph H

    2016-09-01

    The application of X-ray micro-computed tomography (μ-CT) for quantitatively characterizing reactive-flow induced pore structure evolution including local particle detachment, displacement and deposition in carbonate rocks is investigated. In the studies conducted in this field of research, the experimental procedure has involved alternating steps of imaging and ex-situ core sample alteration. Practically, it is impossible to return the sample, with micron precision, to the same position and orientation. Furthermore, successive images of a sample in pre- and post-alteration states are usually taken at different conditions such as different scales, resolutions and signal-to-noise ratios. These conditions accompanying with subresolution features in the images make voxel-by-voxel comparisons of successive images problematic. In this paper, we first address the respective challenges in voxel-wise interpretation of successive images of carbonate rocks subject to reactive flow. Reactive coreflood in two carbonate cores with different rock types are considered. For the first rock, we used the experimental and imaging results published by Qajar et al. (2013) which showed a quasi-uniform dissolution regime. A similar reactive core flood was conducted in the second rock which resulted in wormhole-like dissolution regime. We particularly examine the major image processing operations such as transformation of images to the same grey-scale, noise filtering and segmentation thresholding and propose quantitative methods to evaluate the effectiveness of these operations in voxel-wise analysis of successive images of a sample. In the second part, we generalize the methodology based on the three-phase segmentation of normalized images, microporosity assignment and 2D histogram of image intensities to estimate grey-scale changes of individual image voxels for a general case where the greyscale images are segmented into arbitrary number of phases. The results show that local (voxel

  1. Accelerated carbonation of different size fractions of bottom ash from RDF incineration.

    PubMed

    Baciocchi, R; Costa, G; Lategano, E; Marini, C; Polettini, A; Pomi, R; Postorino, P; Rocca, S

    2010-07-01

    This paper investigates the effects of accelerated carbonation on the characteristics of bottom ash from refuse derived fuel (RDF) incineration, in terms of CO(2) uptake, heavy metal leaching and mineralogy of different particle size fractions. Accelerated aqueous carbonation batch experiments were performed to assess the influence of operating parameters (temperature, CO(2) pressure and L/S ratio) on reaction kinetics. Pressure was found to be the most relevant parameter affecting the carbonation yield. This was also found to be largely dependent on the specific BA fraction treated, with CO(2) uptakes ranging from approximately 4% for the coarse fractions to approximately 14% for the finest one. Carbonation affected both the mineralogical characteristics of bottom ash, with the appearance of neo-formation minerals, and the leaching behaviour of the material, which was found to be mainly related to the change upon carbonation in the natural pH of the ash. PMID:20045306

  2. Effects of acid rain and sulfur dioxide on marble dissolution

    SciTech Connect

    Schuster, P.F.; Reddy, M.M. ); Sherwood, S.I. )

    1994-01-01

    Acid precipitation and the dry deposition of sulfur dioxide (SO[sub 2]) accelerate damage to carbonate-stone monuments and building materials. This study identified and quantified environmental damage to a sample of Vermont marble during storms and their preceding dry periods. Results from field experiments indicated the deposition of SO[sub 2] gas to the stone surface during dry periods and a twofold increase in marble dissolution during coincident episodes of low rain rate and decreased rainfall pH. The study is widely applicable to the analysis of carbonate-stone damage at locations affected by acid rain and air pollution.

  3. Effects of acid rain and sulfur dioxide on marble dissolution

    USGS Publications Warehouse

    Schuster, Paul F.; Reddy, Michael M.; Sherwood, Susan I.

    1994-01-01

    Acid precipitation and the dry deposition of sulfur dioxide (SO2) accelerate damage to carbonate-stone monuments and building materials. This study identified and quantified environmental damage to a sample of Vermont marble during storms and their preceding dry periods. Results from field experiments indicated the deposition of SO2 gas to the stone surface during dry periods and a twofold increase in marble dissolution during coincident episodes of low rain rate and decreased rainfall pH. The study is widely applicable to the analysis of carbonate-stone damage at locations affected by acid rain and air pollution.

  4. Permafrost carbon-climate feedbacks accelerate global warming

    PubMed Central

    Koven, Charles D.; Ringeval, Bruno; Friedlingstein, Pierre; Ciais, Philippe; Cadule, Patricia; Khvorostyanov, Dmitry; Krinner, Gerhard; Tarnocai, Charles

    2011-01-01

    Permafrost soils contain enormous amounts of organic carbon, which could act as a positive feedback to global climate change due to enhanced respiration rates with warming. We have used a terrestrial ecosystem model that includes permafrost carbon dynamics, inhibition of respiration in frozen soil layers, vertical mixing of soil carbon from surface to permafrost layers, and CH4 emissions from flooded areas, and which better matches new circumpolar inventories of soil carbon stocks, to explore the potential for carbon-climate feedbacks at high latitudes. Contrary to model results for the Intergovernmental Panel on Climate Change Fourth Assessment Report (IPCC AR4), when permafrost processes are included, terrestrial ecosystems north of 60°N could shift from being a sink to a source of CO2 by the end of the 21st century when forced by a Special Report on Emissions Scenarios (SRES) A2 climate change scenario. Between 1860 and 2100, the model response to combined CO2 fertilization and climate change changes from a sink of 68 Pg to a 27 + -7 Pg sink to 4 + -18 Pg source, depending on the processes and parameter values used. The integrated change in carbon due to climate change shifts from near zero, which is within the range of previous model estimates, to a climate-induced loss of carbon by ecosystems in the range of 25 + -3 to 85 + -16 Pg C, depending on processes included in the model, with a best estimate of a 62 + -7 Pg C loss. Methane emissions from high-latitude regions are calculated to increase from 34 Tg CH4/y to 41–70 Tg CH4/y, with increases due to CO2 fertilization, permafrost thaw, and warming-induced increased CH4 flux densities partially offset by a reduction in wetland extent. PMID:21852573

  5. Solidification of stainless steel slag by accelerated carbonation.

    PubMed

    Johnson, D C; MacLeod, C L; Carey, P J; Hills, C D

    2003-06-01

    On exposure to carbon dioxide (CO2) at a pressure of 3 bars, compacts formed from pressed ground slag, and 12.5 weight percent water, were found to react with approximately 18% of their own weight of CO2. The reaction product formed was calcium carbonate causing the slag to self-cement. Unconfined compressive strengths of 9MPa were recorded in carbonated compacts whereas strengths of < 1 MPa were recorded in non-carbonated slag compacts. As molten stainless steel slag containing dicalcium silicate (C2S) cools it can undergo several phase transitions. The final transformation from the beta-polymorph to gamma-C2S is accompanied by a volume change that causes the slag to self-pulverise or 'dust'. As a consequence of this the fine grained portion of the slag contains more of this phase whilst the coarser particles of the slag contain more of the calcium magnesium silicates that contribute the bulk of the waste. The fine fraction (< 125 microm) of the slag when ground is found to react to the same extent as the ground bulk slag and produces compacts with equivalent strength. A coarser fraction (4-8 mm) when ground to a similar grading does not react as extensively and produces a weaker product. Additions of ordinary Portland cement (OPC) at 5 and 10 percent by weight did not alter the degree of reaction during carbonation of the bulk slag or ground fine fraction, however the strength of the 4-8 mm fraction was increased by this change. PMID:12868521

  6. The abundances of solar accelerated nuclei from carbon to iron.

    NASA Technical Reports Server (NTRS)

    Mogro-Campero, A.; Simpson, J. A.

    1972-01-01

    Revised observation periods and new data are found to confirm previous evidence that the overabundance of solar-flare nuclei with respect to solar photospheric and coronal abundances increases with increasing atomic number. It is also verified that enhancements can vary from flare to flare and that this variability is large enough to explain the differences observed by various investigators regarding the magnitude of solar-flare high-Z particle enhancements. Additional evidence for a two-stage solar acceleration mechanism is obtained. It is shown that the galactic cosmic-ray source composition displays a similar overabundance as a function of atomic number.

  7. Electron string ion sources for carbon ion cancer therapy accelerators.

    PubMed

    Boytsov, A Yu; Donets, D E; Donets, E D; Donets, E E; Katagiri, K; Noda, K; Ponkin, D O; Ramzdorf, A Yu; Salnikov, V V; Shutov, V B

    2015-08-01

    The type of the Electron String Ion Sources (ESIS) is considered to be the appropriate one to produce pulsed C(4+) and C(6+) ion beams for cancer therapy accelerators. In fact, the new test ESIS Krion-6T already now provides more than 10(10) C(4+) ions per pulse and about 5 × 10(9) C(6+) ions per pulse. Such ion sources could be suitable to apply at synchrotrons. It has also been found that Krion-6T can provide more than 10(11) C(6+) ions per second at the 100 Hz repetition rate, and the repetition rate can be increased at the same or larger ion output per second. This makes ESIS applicable at cyclotrons as well. ESIS can be also a suitable type of ion source to produce the (11)C radioactive ion beams. A specialized cryogenic cell was experimentally tested at the Krion-2M ESIS for pulse injection of gaseous species into the electron string. It has been shown in experiments with stable methane that the total conversion efficiency of methane molecules to C(4+) ions reached 5%÷10%. For cancer therapy with simultaneous irradiation and precise dose control (positron emission tomography) by means of (11)C, transporting to the tumor with the primary accelerated (11)C(4+) beam, this efficiency is preliminarily considered to be large enough to produce the (11)C(4+) beam from radioactive methane and to inject this beam into synchrotrons. PMID:26329182

  8. Electron string ion sources for carbon ion cancer therapy accelerators

    NASA Astrophysics Data System (ADS)

    Boytsov, A. Yu.; Donets, D. E.; Donets, E. D.; Donets, E. E.; Katagiri, K.; Noda, K.; Ponkin, D. O.; Ramzdorf, A. Yu.; Salnikov, V. V.; Shutov, V. B.

    2015-08-01

    The type of the Electron String Ion Sources (ESIS) is considered to be the appropriate one to produce pulsed C4+ and C6+ ion beams for cancer therapy accelerators. In fact, the new test ESIS Krion-6T already now provides more than 1010 C4+ ions per pulse and about 5 × 109 C6+ ions per pulse. Such ion sources could be suitable to apply at synchrotrons. It has also been found that Krion-6T can provide more than 1011 C6+ ions per second at the 100 Hz repetition rate, and the repetition rate can be increased at the same or larger ion output per second. This makes ESIS applicable at cyclotrons as well. ESIS can be also a suitable type of ion source to produce the 11C radioactive ion beams. A specialized cryogenic cell was experimentally tested at the Krion-2M ESIS for pulse injection of gaseous species into the electron string. It has been shown in experiments with stable methane that the total conversion efficiency of methane molecules to C4+ ions reached 5%÷10%. For cancer therapy with simultaneous irradiation and precise dose control (positron emission tomography) by means of 11C, transporting to the tumor with the primary accelerated 11C4+ beam, this efficiency is preliminarily considered to be large enough to produce the 11C4+ beam from radioactive methane and to inject this beam into synchrotrons.

  9. Monitoring accelerated carbonation on standard Portland cement mortar by nonlinear resonance acoustic test

    NASA Astrophysics Data System (ADS)

    Eiras, J. N.; Kundu, T.; Popovics, J. S.; Monzó, J.; Borrachero, M. V.; Payá, J.

    2015-03-01

    Carbonation is an important deleterious process for concrete structures. Carbonation begins when carbon dioxide (CO2) present in the atmosphere reacts with portlandite producing calcium carbonate (CaCO3). In severe carbonation conditions, C-S-H gel is decomposed into silica gel (SiO2.nH2O) and CaCO3. As a result, concrete pore water pH decreases (usually below 10) and eventually steel reinforcing bars become unprotected from corrosion agents. Usually, the carbonation of the cementing matrix reduces the porosity, because CaCO3 crystals (calcite and vaterite) occupy more volume than portlandite. In this study, an accelerated carbonation-ageing process is conducted on Portland cement mortar samples with water to cement ratio of 0.5. The evolution of the carbonation process on mortar is monitored at different levels of ageing until the mortar is almost fully carbonated. A nondestructive technique based on nonlinear acoustic resonance is used to monitor the variation of the constitutive properties upon carbonation. At selected levels of ageing, the compressive strength is obtained. From fractured surfaces the depth of carbonation is determined with phenolphthalein solution. An image analysis of the fractured surfaces is used to quantify the depth of carbonation. The results from resonant acoustic tests revealed a progressive increase of stiffness and a decrease of material nonlinearity.

  10. Changes in mineralogical and leaching properties of converter steel slag resulting from accelerated carbonation at low CO{sub 2} pressure

    SciTech Connect

    Zomeren, Andre van; Laan, Sieger R. van der; Kobesen, Hans B.A.; Huijgen, Wouter J.J.; Comans, Rob N.J.

    2011-11-15

    Highlights: > Accelerated carbonation studied to improve environmental properties of steel slag. > Carbonation found to occur predominantly at surface of the steel slag grains. > Combined geochemical modelling and mineral analysis revealed controlling processes. > Enhanced V-leaching with di-Ca silicate (C2S) dissolution identified as major source. > Identified mineral transformations provide guidance for further quality improvement. - Abstract: Steel slag can be applied as substitute for natural aggregates in construction applications. The material imposes a high pH (typically 12.5) and low redox potential (Eh), which may lead to environmental problems in specific application scenarios. The aim of this study is to investigate the potential of accelerated steel slag carbonation, at relatively low pCO{sub 2} pressure (0.2 bar), to improve the environmental pH and the leaching properties of steel slag, with specific focus on the leaching of vanadium. Carbonation experiments are performed in laboratory columns with steel slag under water-saturated and -unsaturated conditions and temperatures between 5 and 90 {sup o}C. Two types of steel slag are tested; free lime containing (K3) slag and K1 slag with a very low free lime content. The fresh and carbonated slag samples are investigated using a combination of leaching experiments, geochemical modelling of leaching mechanisms and microscopic/mineralogical analysis, in order to identify the major processes that control the slag pH and resulting V leaching. The major changes in the amount of sequestered CO{sub 2} and the resulting pH reduction occurred within 24 h, the free lime containing slag (K3-slag) being more prone to carbonation than the slag with lower free lime content (K1-slag). While carbonation at these conditions was found to occur predominantly at the surface of the slag grains, the formation of cracks was observed in carbonated K3 slag, suggesting that free lime in the interior of slag grains had also reacted

  11. Pore-scale simulation of calcium carbonate precipitation and dissolution under highly supersaturated conditions in a microfludic pore network

    NASA Astrophysics Data System (ADS)

    Yoon, H.; Dewers, T. A.; Valocchi, A. J.; Werth, C. J.

    2011-12-01

    Dissolved CO2 during geological CO2 storage may react with minerals in fractured rocks or confined aquifers and cause mineral precipitation. The overall rate of reaction can be affected by coupled processes among hydrodynamics, transport, and reactions at pore-scale. Pore-scale models of coupled fluid flow, reactive transport, and CaCO3 precipitation and dissolution are applied to account for transient experimental results of CaCO3 precipitation and dissolution under highly supersaturated conditions in a microfluidic pore network (i.e., micromodel). Pore-scale experiments in the micromodel are used as a basis for understanding coupled physics of systems perturbed by geological CO2 injection. In the micromodel, precipitation is induced by transverse mixing along the centerline in pore bodies. Overall, the pore-scale model qualitatively captured the governing physics of reactions such as precipitate morphology, precipitation rate, and maximum precipitation area in first few pore spaces. In particular, we found that proper estimation of the effective diffusion coefficient and the reactive surface area is necessary to adequately simulate precipitation and dissolution rates. As the model domain increases, the effect of flow patterns affected by precipitation on the overall reaction rate also increases. The model is also applied to account for the effect of different reaction rate laws on mineral precipitation and dissolution at pore-scale. Reaction rate laws tested include the linear rate law, nonlinear power law, and newly-developed rate law based on in-situ measurements at nano scale in the literature. Progress on novel methods for upscaling pore-scale models for reactive transport are discussed, and are being applied to mineral precipitation patterns observed in natural analogues. H.Y. and T. D. were supported as part of the Center for Frontiers of Subsurface Energy Security, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of

  12. Microstructural record of cataclastic and dissolution-precipitation processes from shallow crustal carbonate strike-slip faults, Northern Calcareous Alps (Austria)

    NASA Astrophysics Data System (ADS)

    Bauer, Helene; Grasemann, Bernhard; Decker, Kurt

    2015-04-01

    The concept of coseismic slip and aseismic creep deformation along faults is supported by the variability of natural fault rocks and their microstructures. Faults in carbonate rocks are characterized by very narrow principal slip zones (cm to mm wide) containing (ultra)cataclastic fault rocks that accommodate most of the fault displacement. Fluidization of ultracataclastic sub layers and thermal decomposition of calcite due to frictional heating have been proposed as possible indicators for seismic slip. Dissolution-precipitation (DP) processes are possible mechanism of aseismic sliding, resulting in spaced cleavage solution planes and associated veins, indicating diffusive mass transfer and precipitation in pervasive vein networks. We investigated exhumed, sinistral strike-slip faults in carbonates of the Northern Calcareous Alps. The study presents microstructural investigations of natural carbonate fault rocks that formed by cataclastic and dissolution-precipitation related deformation processes. Faults belong to the eastern segment of the Salzachtal-Ennstal-Mariazell-Puchberg (SEMP) fault system that was formed during eastward lateral extrusion of the Eastern Alps in Oligocene to Lower Miocene. The investigated faults accommodated sinistral slip between several tens and few hundreds of meters. Microstructural analysis of fault rocks was done with scanning electron microscopy and optical microscopy. Deformation experiments of natural fault rocks are planned to be conducted at the Sapienza University of Roma and should be available at the meeting. The investigated fault rocks give record of alternating cataclastic deformation and DP creep. DP fault rocks reveal various stages of evolution including early stylolites, pervasive pressure solution seams and cleavage, localized shear zones with syn-kinematic calcite fibre growth and mixed DP/cataclastic microstructures, involving pseudo sc- and scc'-fabrics. Pressure solution seams host fine grained kaolinit, chlorite

  13. Electron string ion sources for carbon ion cancer therapy accelerators

    SciTech Connect

    Boytsov, A. Yu.; Donets, D. E.; Donets, E. D.; Donets, E. E.; Ponkin, D. O.; Ramzdorf, A. Yu.; Salnikov, V. V.; Shutov, V. B.; Katagiri, K.; Noda, K.

    2015-08-15

    The type of the Electron String Ion Sources (ESIS) is considered to be the appropriate one to produce pulsed C{sup 4+} and C{sup 6+} ion beams for cancer therapy accelerators. In fact, the new test ESIS Krion-6T already now provides more than 10{sup 10} C{sup 4+} ions per pulse and about 5 × 10{sup 9} C{sup 6+} ions per pulse. Such ion sources could be suitable to apply at synchrotrons. It has also been found that Krion-6T can provide more than 10{sup 11} C{sup 6+} ions per second at the 100 Hz repetition rate, and the repetition rate can be increased at the same or larger ion output per second. This makes ESIS applicable at cyclotrons as well. ESIS can be also a suitable type of ion source to produce the {sup 11}C radioactive ion beams. A specialized cryogenic cell was experimentally tested at the Krion-2M ESIS for pulse injection of gaseous species into the electron string. It has been shown in experiments with stable methane that the total conversion efficiency of methane molecules to C{sup 4+} ions reached 5%÷10%. For cancer therapy with simultaneous irradiation and precise dose control (positron emission tomography) by means of {sup 11}C, transporting to the tumor with the primary accelerated {sup 11}C{sup 4+} beam, this efficiency is preliminarily considered to be large enough to produce the {sup 11}C{sup 4+} beam from radioactive methane and to inject this beam into synchrotrons.

  14. The effects of accelerated carbonation on CO(2) uptake and metal release from incineration APC residues.

    PubMed

    Baciocchi, Renato; Costa, Giulia; Di Bartolomeo, Elisabetta; Polettini, Alessandra; Pomi, Raffaella

    2009-12-01

    This work presents the results of a study on accelerated carbonation of incinerator air pollution control residues, with a particular focus on the modifications in the leaching behaviour of the ash. Aqueous carbonation experiments were carried out using 100% CO(2) at different temperatures, pressures and liquid-to-solid ratios, in order to assess their influence on process kinetics, CO(2) uptake and the leaching behaviour of major and trace elements. The ash showed a particularly high reactivity towards CO(2), owing to the abundance of calcium hydroxides phases, with a maximum CO(2) uptake of approximately 250g/kg. The main effects of carbonation on trace metal leaching involved a significant decrease in mobility for Pb, Zn and Cu at high pH values, a slight change or mobilization for Cr and Sb, and no major effects on the release of As and soluble salts. Geochemical modelling of leachates indicated solubility control by different minerals after carbonation. In particular, in the stability pH range of carbonates, solubility control by a number of metal carbonates was clearly suggested by modelling results. These findings indicate that accelerated carbonation of incinerator ashes has the potential to convert trace contaminants into sparingly soluble carbonate forms, with an overall positive effect on their leaching behaviour. PMID:19700299

  15. An accelerated carbonation procedure for studies of corrosion in reinforced concrete

    SciTech Connect

    Al-Kadhimi, T.K.H.; Banfill, P.F.G.; Millard, S.G.; Bungey, J.H.

    1995-10-01

    Carbonation of the concrete leading to reduced alkalinity around the steel is one of the main reasons for the corrosion of reinforced concrete. Studies of carbonation induced corrosion and of rehabilitation methods, such as electrochemical realkalization, require the convenient preparation of realistically large specimens of carbonated concrete in a sufficiently short time. This paper describes a rapid method of preparing carbonated concrete by exposing concrete, which has been dried to an internal relative humidity of 60%, to a pure atmosphere of carbon dioxide gas at 15 bar pressure (1,500 kPa). The pressure chamber used can accommodate specimens up to 150mm diameter or 100 x 100 mm section and such specimens can be fully carbonated in 2 weeks, much more quickly than by other methods. Carbonation increases the electrical resistivity and strength of the concrete and reduces the water absorption. Optical and electron microscopical investigations on the carbonated concrete confirm that the microstructure is no different from that produced in concrete by carbonation under natural exposure. The accelerated carbonation method can be used for development work on materials and repair methods and has been used by the authors in preparing carbonated concrete specimens for re-alkalization tests.

  16. Accelerated carbonation of steel slags in a landfill cover construction

    SciTech Connect

    Diener, S.; Andreas, L.; Herrmann, I.; Ecke, H.; Lagerkvist, A.

    2010-01-15

    Steel slags from high-alloyed tool steel production were used in a full scale cover construction of a municipal solid waste (MSW) landfill. In order to study the long-term stability of the steel slags within the final cover, a laboratory experiment was performed. The effect on the ageing process, due to i.e. carbonation, exerted by five different factors resembling both the material characteristics and the environmental conditions is investigated. Leaching behaviour, acid neutralization capacity and mineralogy (evaluated by means of X-ray diffraction, XRD, and thermogravimetry/differential thermal analysis, TG/DTA) are tested after different periods of ageing under different conditions. Samples aged for 3 and 10 months were evaluated in this paper. Multivariate data analysis was used for data evaluation. The results indicate that among the investigated factors, ageing time and carbon dioxide content of the atmosphere were able to exert the most relevant effect. However, further investigations are required in order to clarify the role of the temperature.

  17. Frost Induces Respiration and Accelerates Carbon Depletion in Trees.

    PubMed

    Sperling, Or; Earles, J Mason; Secchi, Francesca; Godfrey, Jessie; Zwieniecki, Maciej A

    2015-01-01

    Cellular respiration depletes stored carbohydrates during extended periods of limited photosynthesis, e.g. winter dormancy or drought. As respiration rate is largely a function of temperature, the thermal conditions during such periods may affect non-structural carbohydrate (NSC) availability and, ultimately, recovery. Here, we surveyed stem responses to temperature changes in 15 woody species. For two species with divergent respirational response to frost, P. integerrima and P. trichocarpa, we also examined corresponding changes in NSC levels. Finally, we simulated respiration-induced NSC depletion using historical temperature data for the western US. We report a novel finding that tree stems significantly increase respiration in response to near freezing temperatures. We observed this excess respiration in 13 of 15 species, deviating 10% to 170% over values predicted by the Arrhenius equation. Excess respiration persisted at temperatures above 0 °C during warming and reoccurred over multiple frost-warming cycles. A large adjustment of NSCs accompanied excess respiration in P. integerrima, whereas P. trichocarpa neither excessively respired nor adjusted NSCs. Over the course of the years included in our model, frost-induced respiration accelerated stem NSC consumption by 8.4 mg (glucose eq.) cm(-3) yr(-1) on average in the western US, a level of depletion that may continue to significantly affect spring NSC availability. This novel finding revises the current paradigm of low temperature respiration kinetics. PMID:26629819

  18. Frost Induces Respiration and Accelerates Carbon Depletion in Trees

    PubMed Central

    Sperling, Or; Earles, J. Mason; Secchi, Francesca; Godfrey, Jessie; Zwieniecki, Maciej A.

    2015-01-01

    Cellular respiration depletes stored carbohydrates during extended periods of limited photosynthesis, e.g. winter dormancy or drought. As respiration rate is largely a function of temperature, the thermal conditions during such periods may affect non-structural carbohydrate (NSC) availability and, ultimately, recovery. Here, we surveyed stem responses to temperature changes in 15 woody species. For two species with divergent respirational response to frost, P. integerrima and P. trichocarpa, we also examined corresponding changes in NSC levels. Finally, we simulated respiration-induced NSC depletion using historical temperature data for the western US. We report a novel finding that tree stems significantly increase respiration in response to near freezing temperatures. We observed this excess respiration in 13 of 15 species, deviating 10% to 170% over values predicted by the Arrhenius equation. Excess respiration persisted at temperatures above 0°C during warming and reoccurred over multiple frost-warming cycles. A large adjustment of NSCs accompanied excess respiration in P. integerrima, whereas P. trichocarpa neither excessively respired nor adjusted NSCs. Over the course of the years included in our model, frost-induced respiration accelerated stem NSC consumption by 8.4 mg (glucose eq.) cm-3 yr-1 on average in the western US, a level of depletion that may continue to significantly affect spring NSC availability. This novel finding revises the current paradigm of low temperature respiration kinetics. PMID:26629819

  19. Computational Tools for Accelerating Carbon Capture Process Development

    SciTech Connect

    Miller, David

    2013-01-01

    The goals of the work reported are: to develop new computational tools and models to enable industry to more rapidly develop and deploy new advanced energy technologies; to demonstrate the capabilities of the CCSI Toolset on non-proprietary case studies; and to deploy the CCSI Toolset to industry. Challenges of simulating carbon capture (and other) processes include: dealing with multiple scales (particle, device, and whole process scales); integration across scales; verification, validation, and uncertainty; and decision support. The tools cover: risk analysis and decision making; validated, high-fidelity CFD; high-resolution filtered sub-models; process design and optimization tools; advanced process control and dynamics; process models; basic data sub-models; and cross-cutting integration tools.

  20. Effects of thin-film accelerated carbonation on steel slag leaching.

    PubMed

    Baciocchi, R; Costa, G; Polettini, A; Pomi, R

    2015-04-01

    This paper discusses the effects of accelerated carbonation on the leaching behaviour of two types of stainless steel slags (electric arc furnace and argon oxygen decarburisation slag). The release of major elements and toxic metals both at the natural pH and at varying pH conditions was addressed. Geochemical modelling of the eluates was used to theoretically describe leaching and derive information about mineralogical changes induced by carbonation. Among the investigated elements, Ca and Si were most appreciably affected by carbonation. A very clear effect of carbonation on leaching was observed for silicate phases; geochemical modelling indicated that the Ca/Si ratio of Ca-controlling minerals shifted from ∼ 1 for the untreated slag to 0.5-0.67 for the carbonated samples, thus showing that the carbonation process left some residual Ca-depleted silicate phases while the extracted Ca precipitated in the form of carbonate minerals. For toxic metals the changes in leaching induced by carbonation appeared to be mainly related to the resulting pH changes, which were as high as ∼ 2 orders of magnitude upon carbonation. Depending on the specific shape of the respective solubility curves, the extent of leaching of toxic metals from the slag was differently affected by carbonation. PMID:25596552

  1. Homonuclear decoupling for spectral simplification of carbon-13 enriched molecules in solution-state NMR enhanced by dissolution DNP.

    PubMed

    Chinthalapalli, Srinivas; Bornet, Aurélien; Carnevale, Diego; Jannin, Sami; Bodenhausen, Geoffrey

    2016-04-20

    Complex overlapping multiplets due to scalar couplings (n)J((13)C, (13)C) in fully (13)C-enriched molecules can be simplified by polychromatic irradiation of selected spins. The signal intensities of the remaining non-irradiated signals are proportional to the concentrations, as shown in this work for the anomeric (13)C signals of the α- and β-conformers of glucose. Homonuclear decoupling can therefore be useful for quantitative NMR studies. The resulting decoupled lineshapes show residual fine structures that have been investigated by means of numerical simulations. Simulations also show that homonuclear decoupling schemes remain effective despite inhomogeneous static fields that tend to hamper in cellulo and in vivo studies. Homonuclear decoupling schemes can be combined with dissolution DNP to obtain signal enhancements of more than four orders of magnitude. Polychromatic irradiation of selected spins does not cause significant losses of hyperpolarization of the remaining non-irradiated spins. PMID:27058951

  2. Accelerated carbonation of different size fractions of MSW IBA and the effect on leaching.

    PubMed

    Lin, Wenlin Yvonne; Heng, Kim Soon; Sun, Xiaolong; Wang, Jing-Yuan

    2015-07-01

    Accelerated carbonation has been studied as a treatment method for MSW IBA, and the main advantage is that it can shorten the treatment duration from months to days, compared to natural weathering. This study investigated the effect of accelerated carbonation on different size fractions of IBA collected from two incineration plants in Singapore. The different size fractions were ground to <425μm to minimise the influence of morphological difference on carbonation efficiency from that of chemical and mineralogical differences. Total element content was carried out for IBA collected from both incineration plants and the different size fractions. XRD was also used to analyse the mineralogical composition of IBA. Results showed that the degree of carbonation decreased as the size increased, which in turn corresponded to decreasing total Ca content and portlandite phase. The leaching behaviour of Pb, Zn, Cu, Cr and soluble constituents like DOC, Cl(-), and SO4(2-) were evaluated. It was found that carbonation resulted in the reduction of leaching of most constituents, except Cl(-) and SO4(2-). The reduction in leaching after carbonation can be attributed to the decrease in pH and formation of secondary minerals, rather than the precipitation of calcite. The research also suggested that since the leaching of soluble constituents from untreated IBA is mainly from the fine fractions and the fine fractions are more reactive to accelerated carbonation, size separation is beneficial in improving the carbonation efficiency and reducing the volume of IBA that needs to be treated, which can potentially reduce the treatment cost of IBA. PMID:25892439

  3. Investigating Eastern Equatorial Pacific Export Production and Carbonate Dissolution with XRF Core Scanning at ODP Site 846 Over the Last 5 Million Years

    NASA Astrophysics Data System (ADS)

    Jones, C.; Robinson, R. S.

    2015-12-01

    Coastal and equatorial upwelling in the Eastern Equatorial Pacific (EEP) are responsible for about 10% of the ocean's total production. The deep, cold, nutrient-rich waters supplied by upwelling originate in high latitudes, linking changes at high latitudes to the tropics. The Pliocene/Pleistocene transition which started around 2.7-3 million years ago (Ma) marked a period of higher variability in biological production and sea surface temperatures dominated by glacial/interglacial cycles. In addition, secular changes in the development of both Walker and Hadley cells appear to have impacted the strength of equatorial upwelling. However, the large positive production excursions, such as those found from 1.6 to 2.2 Ma, remain only moderately well characterized and both changes in high latitude nutrient supply and regional upwelling strength are implicated. ODP Site 846 is located in the heart of the EEP upwelling cold tongue and has ideal characteristics for examining these links and excursions. We present high-resolution (~0.5 ky) X-Ray Fluorescence (XRF) chemical profiles of Ca, Si, Ba, Mn, Fe, Al, and Ti, as well as a total nitrogen (TN%) record for the last 5 million years from ODP Site 846. We use these high resolution profiles in conjunction with other regional data to assess biogeochemical processes in the EEP over the last 5 million years. CaCO3 and SiO2 are the two dominant biogenic components and account for more than 95% of the sediment. BaSO4 and the discrete TN% measurements record total productivity. MnO and Fe2O3 are redox-sensitive species and are particularly suited to tracing dissolution related to excess bottom-water metabolic processes driven by high export production at the high-alkalinity Site 846. Al2O3 and TiO2 are tracers of terrigenous input. A transition between low amplitude and high amplitude carbonate cycles occurs at 2.8 Ma, coinciding with the Pliocene/Pleistocene transition to higher amplitude glacial cycles. Notable excursions from

  4. Microbially Accelerated Carbonate Mineral Precipitation as a Strategy for in Situ Carbon Sequestration and Rehabilitation of Asbestos Mine Sites.

    PubMed

    McCutcheon, Jenine; Wilson, Siobhan A; Southam, Gordon

    2016-02-01

    A microbially accelerated process for the precipitation of carbonate minerals was implemented in a sample of serpentinite mine tailings collected from the abandoned Woodsreef Asbestos Mine in New South Wales, Australia as a strategy to sequester atmospheric CO2 while also stabilizing the tailings. Tailings were leached using sulfuric acid in reaction columns and subsequently inoculated with an alkalinity-generating cyanobacteria-dominated microbial consortium that was enriched from pit waters at the Woodsreef Mine. Leaching conditions that dissolved 14% of the magnesium from the serpentinite tailings while maintaining circumneutral pH (1800 ppm, pH 6.3) were employed in the experiment. The mineralogy, water chemistry, and microbial colonization of the columns were characterized following the experiment. Micro-X-ray diffraction was used to identify carbonate precipitates as dypingite [Mg5(CO3)4(OH)2·5H2O] and hydromagnesite [Mg5(CO3)4(OH)2·4H2O] with minor nesquehonite (MgCO3·3H2O). Scanning electron microscopy revealed that carbonate mineral precipitates form directly on the filamentous cyanobacteria. These findings demonstrate the ability of these organisms to generate localized supersaturating microenvironments of high concentrations of adsorbed magnesium and photosynthetically generated carbonate ions while also acting as nucleation sites for carbonate precipitation. This study is the first step toward implementing in situ carbon sequestration in serpentinite mine tailings via microbial carbonate precipitation reactions. PMID:26720600

  5. Dissolution of barite for the analysis of strontium isotopes and other chemical and isotopic variations using aqueous sodium carbonate

    USGS Publications Warehouse

    Breit, G.N.; Simmons, E.C.; Goldhaber, M.B.

    1985-01-01

    A simple procedure for preparing barite samples for chemical and isotopic analysis is described. Sulfate ion, in barite, in the presence of high concentrations of aqueous sodium carbonate, is replaced by carbonate. This replacement forms insoluble carbonates with the cations commonly in barite: Ba, Sr, Ca and Pb. Sulfate is released into the solution by the carbonate replacement and is separated by filtration. The aqueous sulfate can then be reprecipitated for analysis of the sulfur and oxygen isotopes. The cations in the carbonate phase can be dissolved by acidifying the solid residue. Sr can be separated from the solution for Sr isotope analysis by ion-exchange chromatography. The sodium carbonate used contains amounts of Sr which will affect almost all barite 87Sr 86Sr ratios by less than 0.00001 at 1.95?? of the mean. The procedure is preferred over other techniques used for preparing barite samples for the determination of 87Sr 86Sr ratios because it is simple, rapid and enables simultaneous determination of many compositional parameters on the same material. ?? 1985.

  6. Corrosion behavior of modified nano carbon black/epoxy coating in accelerated conditions

    NASA Astrophysics Data System (ADS)

    Ghasemi-Kahrizsangi, Ahmad; Shariatpanahi, Homeira; Neshati, Jaber; Akbarinezhad, Esmaeil

    2015-03-01

    The electrochemical behavior and anticorrosion properties of modified carbon black (CB) nanoparticles in epoxy coatings were investigated in accelerated conditions. Nanoparticles of CB were modified by sodium dodecyl sulfate (SDS) as surfactant. Dispersion of nanoparticles into epoxy was confirmed by Transmission Electron Microscopy (TEM). The accelerated condition was prepared at 65 °C. CB nanoparticles improved corrosion resistance of the epoxy coating. The optimum concentration of CB in the epoxy coating was 0.75 wt%. Results showed that the CB hinder the corrosion due to its barrier properties. CB can decrease the diffusion coefficient of water in the coating with filling the micropores.

  7. Thorium-230 profiling in deep-sea sediments: High-resolution records of flux and dissolution of carbonate in the equatorial Atlantic during the last 24,000 years

    NASA Astrophysics Data System (ADS)

    Francois, Roger; Bacon, Michael P.; Suman, Daniel O.

    1990-10-01

    Variations in carbonate flux and dissolution, which occurred in the equatorial Atlantic during the last 24,000 years, have been estimated by a new approach that allows the point-by-point determination of paleofluxes to the seafloor. An unprecedented time resolution can thus be obtained which allows sequencing of the relatively rapid events occurring during deglaciation. The method is based on observations that the flux of unsupported 230Th into deep-sea sediments is nearly independent of the total mass flux and is close to the production rate. Thus excess 230Th activity in sediments can be used as a reference against which fluxes of other sedimentary components can be estimated. The study was conducted at two sites (Ceará Rise; western equatorial Atlantic, and Sierra Leone Rise; eastern equatorial Atlantic) in cores raised from three different depths at each site. From measurements of 230Th and CaCO3, changes in carbonate flux with time and depth were obtained. A rapid increase in carbonate production, starting at the onset of deglaciation, was found in both areas. This event may have important implications for the postglacial increase in atmospheric CO2 by increasing the global carbonate carbon to organic carbon rain ratio and decreasing the alkalinity of surface waters (and possibly the North Atlantic Deep Water). Increased carbonate dissolution occurred in the two regions during deglaciation, followed by a minimum during mid-Holocene and renewed intensification of dissolution in late Holocene. During the last 16,000 years, carbonate dissolution was consistently more pronounced in the western than in the eastern basin, reflecting the influence of Antarctic Bottom Water in the west. This trend was reversed during stage 2, possibly due to the accumulation of metabolic CO2 below the level of the Romanche Fracture Zone in the eastern basin.

  8. Impact of nitrogenous fertilizers on carbonate dissolution in small agricultural catchments: Implications for weathering CO 2 uptake at regional and global scales

    NASA Astrophysics Data System (ADS)

    Perrin, Anne-Sophie; Probst, Anne; Probst, Jean-Luc

    2008-07-01

    The goal of this study was to highlight the occurrence of an additional proton-promoted weathering pathway of carbonate rocks in agricultural areas where N-fertilizers are extensively spread, and to estimate its consequences on riverine alkalinity and uptake of CO 2 by weathering. We surveyed 25 small streams in the calcareous molassic Gascogne area located in the Garonne river basin (south-western France) that drain cultivated or forested catchments for their major element compositions during different hydrologic periods. Among these catchments, the Hay and the Montoussé, two experimental catchments, were monitored on a weekly basis. Studies in the literature from other small carbonate catchments in Europe were dissected in the same way. In areas of intensive agriculture, the molar ratio (Ca + Mg)/HCO 3 in surface waters is significantly higher (0.7 on average) than in areas of low anthropogenic pressure (0.5). This corresponds to a decrease in riverine alkalinity, which can reach 80% during storm events. This relative loss of alkalinity correlates well with the NO3- content in surface waters. In cultivated areas, the contribution of atmospheric/soil CO 2 to the total riverine alkalinity (CO 2 ATM-SOIL/HCO 3) is less than 50% (expected value for carbonate basins), and it decreases when the nitrate concentration increases. This loss of alkalinity can be attributed to the substitution of carbonic acid (natural weathering pathway) by protons produced by nitrification of N-fertilizers (anthropogenic weathering pathway) occurring in soils during carbonate dissolution. As a consequence of these processes, the alkalinity over the last 30 years shows a decreasing trend in the Save river (one of the main Garonne river tributaries, draining an agricultural catchment), while the nitrate and calcium plus magnesium contents are increasing. We estimated that the contribution of atmospheric/soil CO 2 to riverine alkalinity decreased by about 7-17% on average for all the studied

  9. Effects of CO2 (aq), pH, and Salinity on Biotite Dissolution Kinetics under Hydrothermal Conditions

    NASA Astrophysics Data System (ADS)

    Hu, Y.; Jun, Y.

    2010-12-01

    A holistic understanding of dissolution and precipitation rates of Fe-bearing clay minerals under hydrothermal conditions is crucial for sustainable geological CO2 sequestration, underground nuclear waste disposal, and reclaimed reuse at aquifer recharge. In this study, batch dissolution experiments under high temperature (35-95 °C) and high pressure (PCO2 or PN2 = 1100 psi-1500 psi) were conducted to study the effect of CO2 (aq), pH, salinity, and temperature on the dissolution kinetics of biotite, which serves as a representative Fe-bearing clay mineral. To investigate the effect of dissolved CO2, dissolution rates of biotite under high CO2 pressure and HCl-pH-adjusted high N2 pressure condition were compared. Biotite intrinsic dissolution rates under PCO2 = 1100 psi-1500 psi (pH = 2.94-3.00) and 35 °C were conducted and they were similar within experimental error ranges. Thus, the effect of dissolved CO2 mostly results from the pH effect, the dissolved total inorganic carbon (CO2) concentration (2.18-3 M) and the pressure of CO2 does not alter the biotite dissolution rates significantly. The effect of pH during the range of 2.94-4.47 was also studied by conducting dissolution experiments in NaHCO3 solution (0-50 mM) under 35 °C and PCO2 = 1500 psi. The effect of ionic strength was studied using 0.1 and 1 M NaCl solutions. Higher Na+ concentration in solution accelerated K+ dissolution through Na+-K+ ion exchange. The ion exchange exfoliated the biotite layers, exposing more surfaces into acidic solution and accelerating the dissolution. Arrhenius equation was used to describe the temperature effect and to extract activation energy of dissolution. The results will provide important information for a more accurate reactive-transport modeling of Fe-bearing clay mineral behavior under hydrothermal conditions.

  10. Accelerated carbonation of cement pastes in situ monitored by neutron diffraction

    SciTech Connect

    Castellote, M. Andrade, C.; Turrillas, X.; Campo, J.; Cuello, G.J.

    2008-12-15

    In-situ monitoring of the changes that take place in the phase composition of cement pastes during accelerated carbonation (100% CO{sub 2}) for different binders, has been carried out, by taking Neutron Diffraction patterns in parallel with the carbonation experiments. The variation of the intensity of chosen reflections for each phase along the experiment has been used to monitor concentration changes and has supplied data, in real time, for fractional conversion of different phases (Portlandite, Ettringite and CSH gel) of the hydrated cement pastes. Fitting of these results has allowed to make a qualitative approach to the kinetics of the carbonation of the different phases and extracting conclusions on the microstructural changes that takes place during the carbonation of cement pastes.

  11. Dissolution of Biogenic and Synthetic UO2 under Varied Reducing Conditions

    PubMed Central

    ULRICH, KAI – UWE; SINGH, ABHAS; SCHOFIELD, ELEANOR J.; BARGAR, JOHN R.; VEERAMANI, HARISH; SHARP, JONATHAN O.; LATMANI, RIZLAN BERNIER -; GIAMMAR, DANIEL E.

    2008-01-01

    The chemical stability of biogenic UO2, a nanoparticulate product of environmental bioremediation, may be impacted by the particles’ surface free energy, structural defects, and compositional variability in analogy to abiotic UO2+x (0 ≤ x ≤ 0.25). This study quantifies and compares intrinsic solubility and dissolution rate constants of biogenic nano-UO2 and synthetic bulk UO2.00, taking molecular-scale structure into account. Rates were determined under anoxic conditions as a function of pH and dissolved inorganic carbon in continuous-flow experiments. The dissolution rates of biogenic and synthetic UO2 solids were lowest at near neutral pH and increased with decreasing pH. Similar surface area-normalized rates of biogenic and synthetic UO2 suggest comparable reactive surface site densities. This finding is consistent with the identified structural homology of biogenic UO2 and stoichiometric UO2.00. Compared to carbonate-free anoxic conditions, dissolved inorganic carbon accelerated the dissolution rate of biogenic UO2 by 3 orders of magnitude. This phenomenon suggests continuous surface oxidation of U(IV) to U(VI), with detachment of U(VI) as the rate-determining step in dissolution. Although reducing conditions were maintained throughout the experiments, the UO2 surface can be oxidized by water and radiogenic oxidants. Even in anoxic aquifers, UO2 dissolution may be controlled by surface U(VI) rather than U(IV) phases. PMID:18754482

  12. Preparation of a novel starch-derived three-dimensional ordered macroporous carbon for improving the dissolution rate and oral bioavailability of water-insoluble drugs.

    PubMed

    Liu, Ying; Wu, Chao; Hao, Yanna; Xu, Jie; Zhao, Ying; Qiu, Yang; Jiang, Jie; Yu, Tong; Ji, Peng

    2016-01-25

    In our study, soluble starch was applied as a novel carbon source for preparing three-dimensional ordered macroporous carbon (3DOMC) using monodisperse silica nanospheres as the hard template. The 3DOMC was used as an insoluble drug carrier when it was found that it could markedly improve the water solubility of felodipine (FDP). The structural features of 3DOMC were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The 3DOMC structure was found to have a higher drug loading than microporous and mesoporous structures, and the interconnected nanostructure effectively inhibited the formation of drug crystals. FDP, belonging to the Biopharmaceutics Classification System II (BCSII), was chosen as the model drug and was loaded into the 3DOMC structure by solvent evaporation. The state of FDP in the 3DOMC structure was characterized by powder X-ray diffractometry (PXRD), differential scanning calorimetry (DSC) and Fourier-transform infrared spectroscopy (FTIR). The results obtained showed that FDP was present in the pores in an amorphous or microcrystalline state. In vivo and in vitro experiments indicated that 3DOMC could significantly improve the drug dissolution rate, but the FDP-3DOMC self-made common tablets had the disadvantage of a burst effect. For this reason, osmotic pump technology was used to control the drug release rate. We developed a potentially useful insoluble drug carrier for pharmaceutical applications. PMID:26580824

  13. DISSOLUTION OF PLUTONIUM CONTAINING CARRIER PRECIPITATE BY CARBONATE METATHESIS AND SEPARATION OF SULFIDE IMPURITIES THEREFROM BY SULFIDE PRECIPITATION

    DOEpatents

    Duffield, R.B.

    1959-07-14

    A process is described for recovering plutonium from foreign products wherein a carrier precipitate of lanthanum fluoride containing plutonium is obtained and includes the steps of dissolving the carrier precipitate in an alkali metal carbonate solution, adding a soluble sulfide, separating the sulfide precipitate, adding an alkali metal hydroxide, separating the resulting precipitate, washing, and dissolving in a strong acid.

  14. Possible incorporation of petroleum-based carbons in biochemicals produced by bioprocess--biomass carbon ratio measured by accelerator mass spectrometry.

    PubMed

    Kunioka, Masao

    2010-06-01

    The biomass carbon ratios of biochemicals related to biomass have been reviewed. Commercial products from biomass were explained. The biomass carbon ratios of biochemical compounds were measured by accelerator mass spectrometry (AMS) based on the (14)C concentration of carbons in the compounds. This measuring method uses the mechanism that biomass carbons include a very low level of (14)C and petroleum carbons do not include (14)C similar to the carbon dating measuring method. It was confirmed that there were some biochemicals synthesized from petroleum-based carbons. This AMS method has a high accuracy with a small standard deviation and can be applied to plastic products. PMID:20454790

  15. Sample distillation/graphitization system for carbon pool analysis by accelerator mass spectrometry (AMS)

    NASA Astrophysics Data System (ADS)

    Pohlman, J. W.; Knies, D. L.; Grabowski, K. S.; DeTurck, T. M.; Treacy, D. J.; Coffin, R. B.

    2000-10-01

    A facility at the Naval Research Laboratory (NRL), Washington, DC, has been developed to extract, trap, cryogenically distill and graphitize carbon from a suite of organic and inorganic carbon pools for analysis by accelerator mass spectrometry (AMS). The system was developed to investigate carbon pools associated with the formation and stability of methane hydrates. However, since the carbon compounds found in hydrate fields are ubiquitous in aquatic ecosystems, this apparatus is applicable to a number of oceanographic and environmental sample types. Targeted pools are dissolved methane, dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), solid organic matrices (e.g., seston, tissue and sediments), biomarkers and short chained (C 1-C 5) hydrocarbons from methane hydrates. In most instances, the extraction, distillation and graphitization events are continuous within the system, thus, minimizing the possibility of fractionation or contamination during sample processing. A variety of methods are employed to extract carbon compounds and convert them to CO 2 for graphitization. Dissolved methane and DIC from the same sample are sparged and cryogenically separated before the methane is oxidized in a high temperature oxygen stream. DOC is oxidized to CO 2 by 1200 W ultraviolet photo-oxidation lamp, and solids oxidized in sealed, evacuated tubes. Hydrocarbons liberated from the disassociation of gas hydrates are cryogenically separated with a cryogenic temperature control unit, and biomarkers separated and concentrated by preparative capillary gas chromatography (PCGC). With this system, up to 20 samples, standards or blanks can be processed per day.

  16. Multiple model approach to evaluation of accelerated carbonation for steelmaking slag in a slurry reactor.

    PubMed

    Pan, Shu-Yuan; Liu, Hsing-Lu; Chang, E-E; Kim, Hyunook; Chen, Yi-Hung; Chiang, Pen-Chi

    2016-07-01

    Basic oxygen furnace slag (BOFS) exhibits highly alkaline properties due to its high calcium content, which is beneficial to carbonation reaction. In this study, accelerated carbonation of BOFS was evaluated under different reaction times, temperatures, and liquid-to-solid (L/S) ratios in a slurry reactor. CO2 mass balance within the slurry reactor was carried out to validate the technical feasibility of fixing gaseous CO2 into solid precipitates. After that, a multiple model approach, i.e., theoretical kinetics and empirical surface model, for carbonation reaction was presented to determine the maximal carbonation conversion of BOFS in a slurry reactor. On one hand, the reaction kinetics of BOFS carbonation was evaluated by the shrinking core model (SCM). Calcite (CaCO3) was identified as a reaction product through the scanning electronic microscopy and X-ray diffraction analyses, which provided the rationale of applying the SCM in this study. The rate-limiting step of carbonation was found to be ash-diffusion controlled, and the effective diffusivity for carbonation of BOFS in a slurry reactor were determined accordingly. On the other hand, the carbonation conversion of BOFS was predicted by the response surface methodology (RSM) via a nonlinear mathematical programming. According to the experimental data, the highest carbonation conversion of BOFS achieved was 57% under an L/S ratio of 20 mL g(-1), a CO2 flow rate of 0.1 L min(-1), and a pressure of 101.3 kPa at 50 °C for 120 min. Furthermore, the applications and limitations of SCM and RSM were examined and exemplified by the carbonation of steelmaking slags. PMID:27038901

  17. Electrochemical Acceleration of Carbonate and Silicate Weathering for CO2 Mitigation

    NASA Astrophysics Data System (ADS)

    Rau, G. H.; Carroll, S.

    2011-12-01

    Carbonate and many silicate minerals dissolve in strong acids, and such acids are commonly generated at the anode of a conventional saline water electrolysis cell. It was therefore reasoned that encasing such an anode with base minerals would lead to enhanced mineral dissolution and hence increased hydroxide (base) generation at the cathode, formed in course of splitting water, generating H2 and OH-. Subsequent exposue of the alkalized solution to CO2 (e.g., as in air) would lead to absorption of the CO2 and formation of stable dissolved or solid (bi)carbonates for carbon sequestration. Previously, it has been demonstrated that mineral carbonate encasement of a seawater electrolysis cell anode indeed generated basic solutions in excess of pH 9 that were subsequently neutralized via contact with air CO2, increasing the carbon content of the initial seawater by 30% (Rau, G.H. 2008. Environ Sci. Techol. 42, 8935-). To test such a weathering/CO2 capture scheme using silicate minerals, either powdered wollastonite or ultramafic rock standard (UM-4) was encased around the anode of an electrolysis cell composed of graphite electrodes and a 0.25M Na2SO4 electrolyte solution. After 0.5 to 1.5 hrs of electricity application (3.5Vdc, 5-10mA), the electrolyte pH rose to as much as 11.1 (initial and blank solution pH's <6.6). Subequent bubbling of these basic solutions with air lowered pH by at least 2 units and increased dissolve carbon content (primarily bicarbonate) by as much as 50X that of the blanks. While Ca2+ and Mg2+ concentrations were elevated, these were insufficient to balance the majority of the bicarbonate anions formed in solution. This suggests that in these experiments the silicate minerals acted as a neutralizer of the anolyte acid, H2SO4, forming mostly insoluble CaSO4 and MgSO4 at the anode. This then allowed NaOH normally produced at the cathode to accumulate in solution, in turn reacting with air CO2 to form NaHCO3. Longer electrolysis times and

  18. Cyclic magnetite dissolution in Pleistocene sediments of the abyssal northwest Pacific Ocean: Evidence for glacial oxygen depletion and carbon trapping

    NASA Astrophysics Data System (ADS)

    Korff, Lucia; Dobeneck, Tilo; Frederichs, Thomas; Kasten, Sabine; Kuhn, Gerhard; Gersonde, Rainer; Diekmann, Bernhard

    2016-05-01

    The carbonate-free abyss of the North Pacific defies most paleoceanographic proxy methods and hence remains a "blank spot" in ocean and climate history. Paleomagnetic and rock magnetic, geochemical, and sedimentological methods were combined to date and analyze seven middle to late Pleistocene northwest Pacific sediment cores from water depths of 5100 to 5700 m. Besides largely coherent tephra layers, the most striking features of these records are nearly magnetite-free zones corresponding to glacial marine isotope stages (MISs) 22, 12, 10, 8, 6, and 2. Magnetite depletion is correlated with organic carbon and quartz content and anticorrelated with biogenic barite and opal content. Within interglacial sections and mid-Pleistocene transition glacial stages MIS 20, 18, 16, and 14, magnetite fractions of detrital, volcanic, and bacterial origin are all well preserved. Such alternating successions of magnetic iron mineral preservation and depletion are known from sapropel-marl cycles, which accumulated under periodically changing bottom water oxygen and redox conditions. In the open central northwest Pacific Ocean, the only conceivable mechanism to cause such abrupt change is a modified glacial bottom water circulation. During all major glaciations since MIS 12, oxygen-depleted Antarctic Bottom Water (AABW)-sourced bottom water seems to have crept into the abyssal northwest Pacific below ~5000 m depth, thereby changing redox conditions in the sediment, trapping and preserving dissolved and particulate organic matter and, in consequence, reducing and dissolving both, biogenic and detrital magnetite. At deglaciation, a downward progressing oxidation front apparently remineralized and released these sedimentary carbon reservoirs without replenishing the magnetite losses.

  19. Recent acceleration of biomass burning and carbon losses in Alaskan forests and peatlands

    USGS Publications Warehouse

    Turetsky, M.R.; Kane, E.S.; Harden, J.W.; Ottmar, R.D.; Manies, K.L.; Hoy, E.; Kasischke, E.S.

    2011-01-01

    Climate change has increased the area affected by forest fires each year in boreal North America. Increases in burned area and fire frequency are expected to stimulate boreal carbon losses. However, the impact of wildfires on carbon emissions is also affected by the severity of burning. How climate change influences the severity of biomass burning has proved difficult to assess. Here, we examined the depth of ground-layer combustion in 178 sites dominated by black spruce in Alaska, using data collected from 31 fire events between 1983 and 2005. We show that the depth of burning increased as the fire season progressed when the annual area burned was small. However, deep burning occurred throughout the fire season when the annual area burned was large. Depth of burning increased late in the fire season in upland forests, but not in peatland and permafrost sites. Simulations of wildfire-induced carbon losses from Alaskan black spruce stands over the past 60 years suggest that ground-layer combustion has accelerated regional carbon losses over the past decade, owing to increases in burn area and late-season burning. As a result, soils in these black spruce stands have become a net source of carbon to the atmosphere, with carbon emissions far exceeding decadal uptake.

  20. Effect of accelerated carbonation and zero valent iron on metal leaching from bottom ash.

    PubMed

    Nilsson, M; Andreas, L; Lagerkvist, A

    2016-05-01

    About 85% of the ashes produced in Sweden originated from the incineration of municipal solid waste and biofuel. The rest comes from the thermal treatment of recycled wood, peat, charcoal and others. About 68% of all ashes annually produced in Sweden are used for constructions on landfills, mainly slopes, roads and embankments, and only 3% for construction of roads and working surfaces outside the landfills (SCB, 2013). Since waste bottom ash (BA) often has similar properties to crushed bedrock or gravel, it could be used for road constructions to a larger extent. However, the leaching of e.g. Cr, Cu, Mo, Pb and Zn can cause a threat to the surrounding environment if the material is used as it is. Carbonation is a commonly used pre-treatment method, yet it is not always sufficient. As leaching from aged ash is often controlled by adsorption to iron oxides, increasing the number of Fe oxide sorption sites can be a way to control the leaching of several critical elements. The importance of iron oxides as sorption sites for metals is known from both mineralogical studies of bottom ash and from the remediation of contaminated soil, where iron is used as an amendment. In this study, zero valent iron (Fe(0)) was added prior to accelerated carbonation in order to increase the number of adsorption sites for metals and thereby reduce leaching. Batch, column and pHstat leaching tests were performed and the leaching behaviour was evaluated with multivariate data analysis. It showed that leaching changed distinctly after the tested treatments, in particular after the combined treatment. Especially, the leaching of Cr and Cu clearly decreased as a result of accelerated carbonation. The combination of accelerated carbonation with Fe(0) addition reduced the leaching of Cr and Cu even further and reduced also the leaching of Mo, Zn, Pb and Cd compared to untreated BA. Compared with only accelerated carbonation, the Fe(0) addition significantly reduced the leaching of Cr, Cu and Mo

  1. Diamond dissolution and the production of methane and other carbon-bearing species in hydrothermal diamond-anvil cells

    USGS Publications Warehouse

    Chou, I.-Ming; Anderson, Alan J.

    2009-01-01

    Raman analysis of the vapor phase formed after heating pure water to near critical (355-374 ??C) temperatures in a hydrothermal diamond-anvil cell (HDAC) reveals the synthesis of abiogenic methane. This unexpected result demonstrates the chemical reactivity of diamond at relatively low temperatures. The rate of methane production from the reaction between water and diamond increases with increasing temperature and is enhanced by the presence of a metal gasket (Re, Ir, or Inconel) which is compressed between the diamond anvils to seal the aqueous sample. The minimum detection limit for methane using Raman spectroscopy was determined to be ca. 0.047 MPa, indicating that more than 1.4 nanograms (or 8.6 ?? 10-11 mol) of methane were produced in the HDAC at 355 ??C and 30 MPa over a period of ten minutes. At temperatures of 650 ??C and greater, hydrogen and carbon dioxide were detected in addition to methane. The production of abiogenic methane, observed in all HDAC experiments where a gasket was used, necessitates a reexamination of the assumed chemical systems and intensive parameters reported in previous hydrothermal investigations employing diamonds. The results also demonstrate the need to minimize or eliminate the production of methane and other carbonic species in experiments by containing the sample within a HDAC without using a metal gasket.

  2. Studies of second phase particles in different zirconium alloys using extractive carbon replica and an electrolytic anodic dissolution procedure [rapid communication

    NASA Astrophysics Data System (ADS)

    Toffolon-Masclet, Caroline; Brachet, Jean-Christophe; Jago, Gilles

    2002-10-01

    Zirconium alloys are widely studied for applications as cladding tubes and structural components of PWR fuel assemblies. Due to their influence on some of the alloys properties (corrosion resistance, irradiation growth, …), the crystallographic structure and the chemical stoichiometry of the second phase particles (SPP) precipitated in these alloys have to be well established. The aim of this paper is to present the results obtained using two methods of SPP extractions. The first one, the extractive carbon replica method, allowed us to determine the chemical composition of SPP in different zirconium alloys: Zr-Sn-Fe-Cr (Zircaloy-4 ®), Zr-Sn-Fe-Cr-(V,Mo), Zr-Nb and Zr-Nb-Fe alloys. The second one, an anodic dissolution procedure of the matrix, is an interesting way of isolating SPP from the surrounding α-Zr matrix, giving access to a precise determination of the crystallographic structure and lattice parameters of the SPP by X-ray diffraction. This procedure was validated for Zy-4 by comparing the SPP size distribution obtained by extraction with that directly measured on a massive Zy-4 alloy (i.e. the SPP size distributions were the same for both measurements).

  3. Gel nanostructure in alkali-activated binders based on slag and fly ash, and effects of accelerated carbonation

    SciTech Connect

    Bernal, Susan A.; Provis, John L.; Walkley, Brant; San Nicolas, Rackel; Gehman, John D.; Brice, David G.; Kilcullen, Adam R.; Duxson, Peter; Deventer, Jannie S.J. van

    2013-11-15

    Binders formed through alkali-activation of slags and fly ashes, including ‘fly ash geopolymers’, provide appealing properties as binders for low-emissions concrete production. However, the changes in pH and pore solution chemistry induced during accelerated carbonation testing provide unrealistically low predictions of in-service carbonation resistance. The aluminosilicate gel remaining in an alkali-activated slag system after accelerated carbonation is highly polymerised, consistent with a decalcification mechanism, while fly ash-based binders mainly carbonate through precipitation of alkali salts (bicarbonates at elevated CO{sub 2} concentrations, or carbonates under natural exposure) from the pore solution, with little change in the binder gel identifiable by nuclear magnetic resonance spectroscopy. In activated fly ash/slag blends, two distinct gels (C–A–S–H and N–A–S–H) are formed; under accelerated carbonation, the N–A–S–H gel behaves comparably to fly ash-based systems, while the C–A–S–H gel is decalcified similarly to alkali-activated slag. This provides new scope for durability optimisation, and for developing appropriate testing methodologies. -- Highlights: •C-A-S-H gel in alkali-activated slag decalcifies during accelerated carbonation. •Alkali-activated fly ash gel changes much less under CO{sub 2} exposure. •Blended slag-fly ash binder contains two coexisting gel types. •These two gels respond differently to carbonation. •Understanding of carbonation mechanisms is essential in developing test methods.

  4. Enzyme-accelerated and structure-guided crystallization of calcium carbonate: role of the carbonic anhydrase in the homologous system.

    PubMed

    Müller, Werner E G; Schlossmacher, Ute; Schröder, Heinz C; Lieberwirth, Ingo; Glasser, Gunnar; Korzhev, Michael; Neufurth, Meik; Wang, Xiaohong

    2014-01-01

    The calcareous spicules from sponges, e.g. from Sycon raphanus, are composed of almost pure calcium carbonate. In order to elucidate the formation of those structural skeletal elements, the function of the enzyme carbonic anhydrase (CA), isolated from this species, during the in vitro calcium carbonate-based spicule formation, was investigated. It is shown that the recombinant sponge CA substantially accelerates calcium carbonate formation in the in vitro diffusion assay. A stoichiometric calculation revealed that the turnover rate of the sponge CA during the calcification process amounts to 25 CO2s(-1) × molecule CA(-1). During this enzymatically driven process, initially pat-like particles are formed that are subsequently transformed to rhomboid/rhombohedroid crystals with a dimension of ~50 μm. The CA-catalyzed particles are smaller than those which are formed in the absence of the enzyme. The Martens hardness of the particles formed is ~4 GPa, a value which had been determined for other biogenic calcites. This conclusion is corroborated by energy-dispersive X-ray spectroscopy, which revealed that the particles synthesized are composed predominantly of the elements calcium, oxygen and carbon. Surprising was the finding, obtained by light and scanning electron microscopy, that the newly formed calcitic crystals associate with the calcareous spicules from S. raphanus in a highly ordered manner; the calcitic crystals almost perfectly arrange in an array orientation along the two opposing planes of the spicules, leaving the other two plane arrays uncovered. It is concluded that the CA is a key enzyme controlling the calcium carbonate biomineralization process, which directs the newly formed particles to existing calcareous spicular structures. It is expected that with the given tools new bioinspired materials can be fabricated. PMID:23978410

  5. Characterization and preliminary assessment of a sorbent produced by accelerated mineral carbonation.

    PubMed

    Shtepenko, Olga L; Hills, Colin D; Coleman, Nichola J; Brough, Adrian

    2005-01-01

    This study shows that calcium silicate/aluminate-based materials can be carbonated to produce sorbents for metal removal. The material chosen for investigation, cement clinker, was accelerated carbonated, and its structural properties were investigated using X-ray diffraction (XRD), scanning electron microscopy, thermal gravimetric and differential thermal analysis, nuclear magnetic resonance spectroscopy, and nitrogen gas adsorption techniques. The principal carbonation reactions involved the transformation of dicalcium silicate, tricalcium silicate, and tricalcium aluminate into a Ca/Al-modified amorphous silica and calcium carbonate. It was found that carbonated cement had high acid buffering capacity, and maintained its structural integrity within a wide pH range. The uptake of Pb(II), Cd(II), Zn(II), Ni(II), Cr(II), Sr(II), Mo(VI), Cs(II), Co(II), and Cu(II) from concentrated (1000 mg L(-1)) single-metal solutions varied from 35 to 170 mg g(-1) of the carbonate cement. The removal of metals was hardly effected by the initial solution pH due to the buffering capability of the carbonated material. The kinetics of Pb, Cd, Cr, Sr, Cs, and Co removal followed a pseudo-second-order kinetic model, whereas the equilibrium batch data for Cu fitted the pseudo-first-order rate equation. PHREEQC simulation supported by XRD analysis suggested the formation of metal carbonates and silicates, calcium molybdate, and chromium (hydro)oxide. Cesium was likely to be adsorbed by Ca/Al-modified amorphous silica. PMID:15667116

  6. Accelerated carbonation of steelmaking slags in a high-gravity rotating packed bed.

    PubMed

    Chang, E-E; Pan, Shu-Yuan; Chen, Yi-Hung; Tan, Chung-Sung; Chiang, Pen-Chi

    2012-08-15

    Carbon dioxide (CO(2)) sequestration using the accelerated carbonation of basic oxygen furnace (BOF) slag in a high-gravity rotating packed bed (RPB) under various operational conditions was investigated. The effects of reaction time, reaction temperature, rotation speed and slurry flow rate on the CO(2) sequestration process were evaluated. The samples of reacted slurry were analyzed quantitatively using thermogravimetric analysis (TGA) and atomic absorption spectrometry (AAS) and qualitatively using X-ray diffraction (XRD), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDX), and transmission electron microscopy (TEM). The sequestration experiments were performed at a liquid-to-solid ratio of 20:1 with a flow rate of 2.5 L min(-1) of a pure CO(2) stream under atmospheric temperature and pressure. The results show that a maximum conversion of BOF slag was 93.5% at a reaction time of 30 min and a rotation speed of 750 rpm at 65°C. The experimental data were utilized to determine the rate-limiting mechanism based on the shrinking core model (SCM), which was validated by the observations of SEM and TEM. Accelerated carbonation in a RPB was confirmed to be a viable method due to its higher mass-transfer rate. PMID:22633879

  7. Deep water dissolution in Marine Isotope Stage 3 from the northern South China Sea

    NASA Astrophysics Data System (ADS)

    Huang, B.

    2015-12-01

    The production, transport, deposition, and dissolution of carbonate profoundly implicate the global carbon cycle affect the inventory and distribution of dissolved organic carbon (DIC) and alkalinity (ALK), which drive atmospheric CO2 change on glacial-interglacial timescale. the process may provide significant clues for improved understanding of the mechanisms that control the global climate system. In this study, we calculate and analyze the foraminiferal dissolution index (FDX) and the fragmentation ratios of planktonic foraminifera over 60-25 ka based on samples from 17924 and ODP 1144 in the northeastern South China Sea (SCS) to reconstruct the deep water carbonate dissolution during Marine Isotope Stage 3 (MIS 3). Result shows that the dissolution of carbonate increases gradually at 17924 but keeps stable at ODP 1144. The changes of FDX coincidence with that of fragmentation ratios at 17924 and ODP 1144 suggest both indexes can be used as reliable dissolving proxies of planktonic foraminifera. Comparing FDX and fragmentation ratios at both sites, we find the FDX and fragmentation ratios at 17924 are higher than those at 1144, indicating that carbonate dissolution is intenser in 17924 core during MIS 3. The increasing total percentage of both N. dutertrei and G. bulloides during MIS 3 reveals the rising primary productivity that may lead to deep water [CO32-] decrease. The slow down of thermohaline circulation may increase deep water residence time and accelerate carbonate dissolution. In addition, the covering of ice caps, iron supply and increased surface-water stratification also contribute to atmosphere CO2 depletion and [CO32-] decrease in deep water. In the meanwhile, regression result from colder temperature increases the input of ALK and DIC to the deep ocean and deepens the carbonate saturation depth, which makes the deep water [CO32-] rise. In ODP Site 1144, the decrease in [CO32-] caused by more CO2 restored in deep water is equal to the increase in

  8. Application of accelerated carbonation on MSW combustion APC residues for metal immobilization and CO2 sequestration.

    PubMed

    Cappai, G; Cara, S; Muntoni, A; Piredda, M

    2012-03-15

    The present study focuses on the application of an aqueous phase accelerated carbonation treatment on air pollution control (APC) residues from municipal solid waste combustion, aimed at assessing its influence on the environmental behaviour of the residue under concern, as well as the potential of the process in terms of sequestration of the CO2. APC residues are considered hazardous waste and must be treated before final disposal in order to achieve the immobilization/mobilization of critical contaminants such as heavy metals as well as mobilization of soluble salts. The treatment applied proved to be effective in reducing the mobility of Pb, Zn, Cr, Cu and Mo, the optimum final pH for the carbonated APC residues being in a range of 10-10.5, whilst a mobilization effect was noticed for Sb and no effect was assessed for chlorides. The effect of carbonation treatment on the contaminant release was further evaluated by means of a sequential extraction procedure, indicating that the distribution of contaminants on water soluble, exchangeable and carbonate fraction was modified after treatment. The CO2 sequestration potential assessed for the APC residues showed that the carbonation technology could be a technically viable option in order to reduce emissions from WtE plants. PMID:21601357

  9. Accelerated export of sediment and carbon from a landscape under intensive agriculture.

    PubMed

    Glendell, M; Brazier, R E

    2014-04-01

    The export of total organic carbon (particulate and dissolved) from terrestrial to aquatic ecosystems has important implications for water quality and the global carbon cycle. However, most research to date has focused on DOC losses from either forested or peaty catchments, with only limited studies examining the controls and rates of total fluvial carbon losses from agricultural catchments, particularly during storm events. This study examined the controls and fluxes of total suspended sediment (SS), total particulate (TPC) and dissolved organic carbon (DOC) from two adjacent catchments with contrasting intensive agricultural and semi-natural land-use. Data from 35 individual storm events showed that the agricultural catchment exported significantly higher SS concentrations on a storm-by-storm basis than the semi-natural catchment, with peak discharge exerting a greater control over SS, TPC and DOC concentrations. Baseflow DOC concentrations in the agricultural catchment were significantly higher. DOC quality monitored during one simultaneous rainfall event differed between the two study catchments, with more humic, higher molecular weight compounds prevailing in the agricultural catchment and lower molecular weight compounds prevailing in the semi-natural catchment. During an eight month period for which a comparable continuous turbidity record was available, the estimated SS yields from the agricultural catchment were higher than from the semi-natural catchment. Further, the agricultural catchment exported proportionally more TPC and a comparable amount of DOC, despite a lower total soil carbon pool. These results suggest that altered hydrological and biogeochemical processes within the agricultural catchment, including accelerated soil erosion and soil organic matter turnover, contributed to an enhanced fluvial SS and carbon export. Thus, we argue that enhancing semi-natural vegetation within intensively farmed catchments could reduce sediment and carbon losses

  10. An experimental study of magnesite dissolution rates at neutral to alkaline conditions and 150 and 200 °C as a function of pH, total dissolved carbonate concentration, and chemical affinity

    NASA Astrophysics Data System (ADS)

    Saldi, Giuseppe D.; Schott, Jacques; Pokrovsky, Oleg S.; Oelkers, Eric H.

    2010-11-01

    Steady-state magnesite dissolution rates were measured in mixed-flow reactors at 150 and 200 °C and 4.6 < pH < 8.4, as a function of ionic strength (0.001 M ⩽ I ⩽ 1 M), total dissolved carbonate concentration (10 -4 M < ΣCO 2 < 0.1 M), and distance from equilibrium. Rates were found to increase with increasing ionic strength, but decrease with increasing temperature from 150 to 200 °C, pH, and aqueous CO 32- activity. Measured rates were interpreted using the surface complexation model developed by Pokrovsky et al. (1999a) in conjunction with transition state theory ( Eyring, 1935). Within this formalism, magnesite dissolution rates are found to be consistent with r=k{>MgOH2+}41-exp (-4ART), where rd represents the BET surface area normalized dissolution rate, {>MgOH2+} stands for the concentration of hydrated magnesium centers on the magnesite surface, kMg designates a rate constant, A refers to the chemical affinity of the overall reaction, R denotes the gas constant, and T symbolizes absolute temperature. Within this model decreasing rates at far-from-equilibrium conditions (1) at constant pH with increasing temperature and (2) at constant temperature with increasing pH and ΣCO 2 stem from a corresponding decrease in {>MgOH2+}. This decrease in {>MgOH2+} results from the increasing stability of the >MgCO3- and >MgOH° surface species with increasing temperature, pH and CO 32- activity. The decrease in constant pH dissolution rates yields negative apparent activation energies. This behavior makes magnesite resistant to re-dissolution if formed as part of mineral carbon sequestration efforts in deep geologic formations.

  11. Accelerated ageing of an EAF black slag by carbonation and percolation for long-term behaviour assessment.

    PubMed

    Gurtubay, L; Gallastegui, G; Elias, A; Rojo, N; Barona, A

    2014-07-01

    The efficient reuse of industrial by-products, such as the electric arc furnace (EAF) black slag, is still hindered by concern over their long-term behaviour in outdoor environments. The aim of this study was to develop an accelerated ageing method to simulate the long-term natural carbonation of EAF slag exposed to the elements. The degree of carbonation achieved in a freshly produced slag after accelerated ageing and in a slag used on a fifteen-year-old unpaved road was very similar. The influence of particle size on accelerated carbonation was assessed, with it being concluded that the slag sample with a particle size bigger than 5-6 mm underwent slight carbonation over time when it was exposed to CO2. The accelerated ageing procedure based on percolating a previously carbonated water solution through the slag column allowed gradual leaching with simulated acid rain, as well as providing information about the gradual and total chemical release from the slag. Three classification groups were established according to the release rate of the determined elements. The joint use of the accelerated carbonation method and the percolation test is proposed as a useful tool for environmental risk assessment concerning the long-term air exposure of EAF black slag. PMID:24726964

  12. GPU-accelerated automatic identification of robust beam setups for proton and carbon-ion radiotherapy

    NASA Astrophysics Data System (ADS)

    Ammazzalorso, F.; Bednarz, T.; Jelen, U.

    2014-03-01

    We demonstrate acceleration on graphic processing units (GPU) of automatic identification of robust particle therapy beam setups, minimizing negative dosimetric effects of Bragg peak displacement caused by treatment-time patient positioning errors. Our particle therapy research toolkit, RobuR, was extended with OpenCL support and used to implement calculation on GPU of the Port Homogeneity Index, a metric scoring irradiation port robustness through analysis of tissue density patterns prior to dose optimization and computation. Results were benchmarked against an independent native CPU implementation. Numerical results were in agreement between the GPU implementation and native CPU implementation. For 10 skull base cases, the GPU-accelerated implementation was employed to select beam setups for proton and carbon ion treatment plans, which proved to be dosimetrically robust, when recomputed in presence of various simulated positioning errors. From the point of view of performance, average running time on the GPU decreased by at least one order of magnitude compared to the CPU, rendering the GPU-accelerated analysis a feasible step in a clinical treatment planning interactive session. In conclusion, selection of robust particle therapy beam setups can be effectively accelerated on a GPU and become an unintrusive part of the particle therapy treatment planning workflow. Additionally, the speed gain opens new usage scenarios, like interactive analysis manipulation (e.g. constraining of some setup) and re-execution. Finally, through OpenCL portable parallelism, the new implementation is suitable also for CPU-only use, taking advantage of multiple cores, and can potentially exploit types of accelerators other than GPUs.

  13. Evaluation of Decomposition Treatment for Halogenized Compounds by Acceleration of Electrons from Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Yamaura, Michiteru; Uchida, Shigeaki; Fujita, Masayuki; Nakatsuka, Masahiro; Yamanaka, Chiyoe

    2007-10-01

    A novel decomposition treatment for halogenized compounds using a carbon nanotube (CNT) electron source is proposed [1]. It is observed that high concentrations of chlorophenols can be significantly decreased by using a CNT electron source. The concentration is reduced to a maximum level of less than 1/1000 after only a few minutes of treatment. The input energy required for 1 g of chlorophenol is 46 J when the injection power is 0.5 W. The input energy is only 1/161 times lesser than that required for the treatment using barrier discharge. The proposed treatment using CNTs has a high efficiency because the input energy is provided only by the accelerated electrons. A harmless and high-efficiency decomposition treatment for halogenized compounds using an electron source with carbon nanotubes is discussed. [1] M.Yamaura, et al. Chem. Phys. Lett 435, 148 (2007).

  14. Dolomite Dissolution in Alkaline Cementious Media

    NASA Astrophysics Data System (ADS)

    Mittermayr, Florian; Klammer, Dietmar; Köhler, Stephan; Dietzel, Martin

    2010-05-01

    Chemical alteration of concrete has gained much attention over the past years as many cases of deterioration due to sulphate attack, thaumasite formation (TSA) or alkali silica reactions (ASR) have been reported in various constructions (Schmidt et al, 2009). Much less is known about the so called alkali carbonate reaction (ACR). It is believed that dolomite aggregates can react with the alkalis from the cement, dissolve and form calcite and brucite (Katayama, 2004). Due to very low solubility of dolomite in alkaline solutions this reaction seems doubtful. In this study we are trying to gain new insides about the conditions that can lead to the dissolution of dolomite in concrete. Therefore we investigated concrete samples from Austrian tunnels that show partially dissolved dolomite aggregates. Petrological analysis such as microprobe, SEM and Raman spectroscopy as well as a hydrochemical analysis of interstitial solutions and ground water and modelling with PhreeqC (Parkhurst and Appelo, 1999) are carried out. In addition a series of batch experiments is set up. Modelling approaches by PhreeqC show a thermodynamically possibility in the alkaline range when additional Ca2+ in solution causes dolomite to become more and more undersaturated as calcite gets supersaturated. Interacting ground water is enriched in Ca2+and saturated with respect to gypsum as marine evaporites are found in situ rocks. Furthermore it is more likely that Portlandite (Ca(OH)2) plays a more important role than Na and K in the cement. Portlandite acts as an additional Ca2+ source and is much more abundant than the alkalies. Some interstitial solutions are dominated mainly by Na+ and SO42- and reach concentrations up to 30 g/l TDS. It is believed that solutions can even reach thenardite saturation as efflorescences are found on the tunnel walls. In consequence dolomite solubility increases with increasing ionic strength. pH > 11 further accelerate the process of dedolomitization by the removal

  15. Dissolution of Uranium Oxides Under Alkaline Oxidizing Conditions

    SciTech Connect

    Smith, Steven C.; Peper, Shane M.; Douglas, Matthew; Ziegelgruber, Kate L.; Finn, Erin C.

    2009-11-01

    Bench scale experiments were conducted to determine the dissolution characteristics of uranium oxide powders (UO2, U3O8, and UO3) in aqueous peroxide-carbonate solutions. Experimental parameters included H2O2 concentration, carbonate counter cation (NH4+, Na+, K+, and Rb+), and pH. Results indicate the dissolution rate of UO2 in 1 M (NH4)2CO3 increases linearly with peroxide concentration ranging from 0.05 – 2 M. The three uranium oxide powders exhibited different dissolution patterns however, UO3 exhibited prompt complete dissolution. Carbonate counter cation affected the dissolution kinetics. There is minimal impact of solution pH, over the range 8.8 to 10.6, on initial dissolution rate.

  16. Field ionization model implemented in Particle In Cell code and applied to laser-accelerated carbon ions

    SciTech Connect

    Nuter, R.; Gremillet, L.; Lefebvre, E.; Levy, A.; Ceccotti, T.; Martin, P.

    2011-03-15

    A novel numerical modeling of field ionization in PIC (Particle In Cell) codes is presented. Based on the quasistatic approximation of the ADK (Ammosov Delone Krainov) theory and implemented through a Monte Carlo scheme, this model allows for multiple ionization processes. Two-dimensional PIC simulations are performed to analyze the cut-off energies of the laser-accelerated carbon ions measured on the UHI 10 Saclay facility. The influence of the target and the hydrocarbon pollutant composition on laser-accelerated carbon ion energies is demonstrated.

  17. CATALYZED OXIDATION OF URANIUM IN CARBONATE SOLUTIONS

    DOEpatents

    Clifford, W.E.

    1962-05-29

    A process is given wherein carbonate solutions are employed to leach uranium from ores and the like containing lower valent uranium species by utilizing catalytic amounts of copper in the presence of ammonia therein and simultaneously supplying an oxidizing agent thereto. The catalysis accelerates rate of dissolution and increases recovery of uranium from the ore. (AEC)

  18. Climate-change effects on soils: Accelerated weathering, soil carbon and elemental cycling

    SciTech Connect

    Qafoku, Nikolla

    2015-04-01

    Climate change [i.e., high atmospheric carbon dioxide (CO2) concentrations (≥400 ppm); increasing air temperatures (2-4°C or greater); significant and/or abrupt changes in daily, seasonal, and inter-annual temperature; changes in the wet/dry cycles; intensive rainfall and/or heavy storms; extended periods of drought; extreme frost; heat waves and increased fire frequency] is and will significantly affect soil properties and fertility, water resources, food quantity and quality, and environmental quality. Biotic processes that consume atmospheric CO2, and create organic carbon (C) that is either reprocessed to CO2 or stored in soils are the subject of active current investigations, with great concern over the influence of climate change. In addition, abiotic C cycling and its influence on the inorganic C pool in soils is a fundamental global process in which acidic atmospheric CO2 participates in the weathering of carbonate and silicate minerals, ultimately delivering bicarbonate and Ca2+ or other cations that precipitate in the form of carbonates in soils or are transported to the rivers, lakes, and oceans. Soil responses to climate change will be complex, and there are many uncertainties and unresolved issues. The objective of the review is to initiate and further stimulate a discussion about some important and challenging aspects of climate-change effects on soils, such as accelerated weathering of soil minerals and resulting C and elemental fluxes in and out of soils, soil/geo-engineering methods used to increase C sequestration in soils, soil organic matter (SOM) protection, transformation and mineralization, and SOM temperature sensitivity. This review reports recent discoveries, identifies key research needs, and highlights opportunities offered by the climate-change effects on soils.

  19. Analytical Validation of Accelerator Mass Spectrometry for Pharmaceutical Development: the Measurement of Carbon-14 Isotope Ratio.

    SciTech Connect

    Keck, B D; Ognibene, T; Vogel, J S

    2010-02-05

    Accelerator mass spectrometry (AMS) is an isotope based measurement technology that utilizes carbon-14 labeled compounds in the pharmaceutical development process to measure compounds at very low concentrations, empowers microdosing as an investigational tool, and extends the utility of {sup 14}C labeled compounds to dramatically lower levels. It is a form of isotope ratio mass spectrometry that can provide either measurements of total compound equivalents or, when coupled to separation technology such as chromatography, quantitation of specific compounds. The properties of AMS as a measurement technique are investigated here, and the parameters of method validation are shown. AMS, independent of any separation technique to which it may be coupled, is shown to be accurate, linear, precise, and robust. As the sensitivity and universality of AMS is constantly being explored and expanded, this work underpins many areas of pharmaceutical development including drug metabolism as well as absorption, distribution and excretion of pharmaceutical compounds as a fundamental step in drug development. The validation parameters for pharmaceutical analyses were examined for the accelerator mass spectrometry measurement of {sup 14}C/C ratio, independent of chemical separation procedures. The isotope ratio measurement was specific (owing to the {sup 14}C label), stable across samples storage conditions for at least one year, linear over 4 orders of magnitude with an analytical range from one tenth Modern to at least 2000 Modern (instrument specific). Further, accuracy was excellent between 1 and 3 percent while precision expressed as coefficient of variation is between 1 and 6% determined primarily by radiocarbon content and the time spent analyzing a sample. Sensitivity, expressed as LOD and LLOQ was 1 and 10 attomoles of carbon-14 (which can be expressed as compound equivalents) and for a typical small molecule labeled at 10% incorporated with {sup 14}C corresponds to 30 fg

  20. Buoyant currents arrested by convective dissolution

    NASA Astrophysics Data System (ADS)

    MacMinn, Christopher W.; Juanes, Ruben

    2013-05-01

    When carbon dioxide (CO2) dissolves into water, the density of water increases. This seemingly insubstantial phenomenon has profound implications for geologic carbon sequestration. Here we show, by means of laboratory experiments with analog fluids, that the up-slope migration of a buoyant current of CO2 is arrested by the convective dissolution that ensues from a fingering instability at the moving CO2-groundwater interface. We consider the effectiveness of convective dissolution as a large-scale trapping mechanism in sloping aquifers, and we show that a small amount of slope is beneficial compared to the horizontal case. We study the development and coarsening of the fingering instability along the migrating current and predict the maximum migration distance of the current with a simple sharp-interface model. We show that convective dissolution exerts a powerful control on CO2 plume dynamics and, as a result, on the potential of geologic carbon sequestration.

  1. Woody plant encroachment into grasslands leads to accelerated erosion of previously stable organic carbon from dryland soils

    NASA Astrophysics Data System (ADS)

    Puttock, Alan; Dungait, Jennifer A. J.; Macleod, Christopher J. A.; Bol, Roland; Brazier, Richard E.

    2014-12-01

    Drylands worldwide are experiencing rapid and extensive environmental change, concomitant with the encroachment of woody vegetation into grasslands. Woody encroachment leads to changes in both the structure and function of dryland ecosystems and has been shown to result in accelerated soil erosion and loss of soil nutrients. Covering 40% of the terrestrial land surface, dryland environments are of global importance, both as a habitat and a soil carbon store. Relationships between environmental change, soil erosion, and the carbon cycle are uncertain. There is a clear need to further our understanding of dryland vegetation change and impacts on carbon dynamics. Here two grass-to-woody ecotones that occur across large areas of the southwestern United States are investigated. This study takes a multidisciplinary approach, combining ecohydrological monitoring of structure and function and a dual-proxy biogeochemical tracing approach using the unique natural biochemical signatures of the vegetation. Results show that following woody encroachment, not only do these drylands lose significantly more soil and organic carbon via erosion but that this includes significant amounts of legacy organic carbon which would previously have been stable under grass cover. Results suggest that these dryland soils may not act as a stable organic carbon pool, following encroachment and that accelerated erosion of carbon, driven by vegetation change, has important implications for carbon dynamics.

  2. Accelerated adsorption by activated carbon powders in the presence of an acoustic field

    NASA Astrophysics Data System (ADS)

    Hawkins, Timothy W.; Meegan, G. Douglas; Peterson, Chris E.

    2003-10-01

    Vaporous contaminants can be removed from a gas stream by adsorption into powdered activated carbon (PAC). For example, the injection of PAC upstream of particle collectors is the leading approach for the removal of mercury vapor from the exhaust streams of incinerators and coal fired power plants. The removal of dilute vapors, though, can require significant time and significant quantities of PAC. A numerical model will be described that suggests that the adsorption process can be accelerated by applying an intense sound field to the gas after the PAC is injected. It is theorized that a sound field improves diffusion limited adsorption reactions by creating an oscillatory motion of the gas relative to the activated carbon particles. The translation effectively mixes the particles and gas on a microscopic scale and improves the concentration gradient at the surface of the PAC. Results from the numerical model suggest that adsorption rates can be increased by over 50% with the application of an appropriate sound field. Simple laboratory experiments have been performed studying the adsorption of dilute vaporous ethanol in air, and the results support the model. Data has also been collected at a coal fired power plant that demonstrates the improved adsorption of mercury vapor.

  3. The Alkaline Dissolution Rate of Calcite.

    PubMed

    Colombani, Jean

    2016-07-01

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

  4. In situ X-ray pair distribution function analysis of accelerated carbonation of a synthetic calcium-silicate-hydrate gel

    SciTech Connect

    Morandeau, Antoine E.; White, Claire E.

    2015-04-21

    Calcium–silicate–hydrate (C–S–H) gel is the main binder component in hydrated ordinary Portland cement (OPC) paste, and is known to play a crucial role in the carbonation of cementitious materials, especially for more sustainable alternatives containing supplementary cementitious materials. However, the exact atomic structural changes that occur during carbonation of C–S–H gel remain unknown. Here, we investigate the local atomic structural changes that occur during carbonation of a synthetic calcium–silicate–hydrate gel exposed to pure CO₂ vapour, using in situ X-ray total scattering measurements and subsequent pair distribution function (PDF) analysis. By analysing both the reciprocal and real-space scattering data as the C–S–H carbonation reaction progresses, all phases present during the reaction (crystalline and non-crystalline) have been identified and quantified, with the results revealing the emergence of several polymorphs of crystalline calcium carbonate (vaterite and calcite) in addition to the decalcified C–S–H gel. Furthermore, the results point toward residual calcium being present in the amorphous decalcified gel, potentially in the form of an amorphous calcium carbonate phase. As a result of the quantification process, the reaction kinetics for the evolution of the individual phases have been obtained, revealing new information on the rate of growth/dissolution for each phase associated with C–S–H gel carbonation. Moreover, the investigation reveals that the use of real space diffraction data in the form of PDFs enables more accurate determination of the phases that develop during complex reaction processes such as C–S–H gel carbonation in comparison to the conventional reciprocal space Rietveld analysis approach.

  5. Polarization Losses under Accelerated Stress Test Using Multiwalled Carbon Nanotube Supported Pt Catalyst in PEM Fuel Cells

    SciTech Connect

    Park, Seh K.; Shao, Yuyan; Kou, Rong; Viswanathan, Vilayanur V.; Towne, Silas A.; Rieke, Peter C.; Liu, Jun; Lin, Yuehe; Wang, Yong

    2011-03-01

    The electrochemical behavior for Pt catalysts supported on multiwalled carbon nanotubes and Vulcan XC-72 in proton exchange membrane fuel cells under accelerated stress test was examined by cyclic voltammetry, electrochemical impedance spectroscopy, and polarization technique. Pt catalyst supported on multiwalled carbon nanotubes exhibited highly stable electrochemical surface area, oxygen reduction kinetics, and fuel cell performance at a highly oxidizing condition, indicating multiwalled carbon nanotubes show high corrosion resistance and strong interaction with Pt nanoparticles. The Tafel slope, ohmic resistances, and limiting current density determined were used to differentiate kinetic, ohmic, mass-transfer polarization losses from the actual polarization curve. Kinetic contribution to the total overpotential was larger throughout the stress test. However, the fraction of kinetic overpotential decreased and mass-transfer overpotential portion remained quite constant during accelerated stress test, whereas the fraction of ohmic overpotential primarily originating from severe proton transport limitation in the catalyst layer increased under the anodic potential hold.

  6. Microbially mediated carbon mineralization: Geoengineering a carbon-neutral mine

    NASA Astrophysics Data System (ADS)

    Power, I. M.; McCutcheon, J.; Harrison, A. L.; Wilson, S. A.; Dipple, G. M.; Southam, G.

    2013-12-01

    Ultramafic and mafic mine tailings are a potentially valuable feedstock for carbon mineralization, affording the mining industry an opportunity to completely offset their carbon emissions. Passive carbon mineralization has previously been documented at the abandoned Clinton Creek asbestos mine, and the active Diavik diamond mine and Mount Keith nickel mine, yet the majority of tailings remain unreacted. Examples of microbe-carbonate interactions at each mine suggest that biological pathways could be harnessed to promote carbon mineralization. In suitable environmental conditions, microbes can mediate geochemical processes to accelerate mineral dissolution, increase the supply of carbon dioxide (CO2), and induce carbonate precipitation, all of which may accelerate carbon mineralization. Tailings mineralogy and the availability of a CO2 point source are key considerations in designing tailings storage facilities (TSF) for optimizing carbon mineralization. We evaluate the efficacy of acceleration strategies including bioleaching, biologically induced carbonate precipitation, and heterotrophic oxidation of waste organics, as well as abiotic strategies including enhancing passive carbonation through modifying tailings management practices and use of CO2 point sources (Fig. 1). With the aim of developing carbon-neutral mines, implementation of carbon mineralization strategies into TSF design will be driven by economic incentives and public pressure for environmental sustainability in the mining industry. Figure 1. Schematic illustrating geoengineered scenarios for carbon mineralization of ultramafic mine tailings. Scenarios A and B are based on non-point and point sources of CO2, respectively.

  7. Economic innovation and efficiency gains as the driving force for accelerating carbon dioxide emissions

    NASA Astrophysics Data System (ADS)

    Garrett, T. J.

    2012-12-01

    It is normally assumed that gains in energy efficiency are one of the best routes that society has available to it for stabilizing future carbon dioxide emissions. For a given degree of economic productivity less energy is consumed and a smaller quantity of fossil fuels is required. While certainly this observation is true in the instant, it ignores feedbacks in the economic system such that efficiency gains ultimately lead to greater energy consumption: taken as a global whole, they permit civilization to accelerate its expansion into the energy reserves that sustain it. Here this argument is formalized from a general thermodynamic perspective. The core result is that there exists a fixed, time-independent link between a very general representation of global inflation-adjusted economic wealth (units currency) and civilization's total capacity to consume power (units energy per time). Based on 40 years of available statistics covering more than a tripling of global GDP and a doubling of wealth, this constant has a value of 7.1 +/- 0.01 Watts per one thousand 2005 US dollars. Essentially, wealth is power. Civilization grows by dissipating power in order to sustain all its current activities and to incorporate more raw material into its existing structure. Growth of its structure is related to economic production, so more energy efficient economic production facilitates growth. Growth is into the reserves that sustain civilization, in which case there is a positive feedback in the economic system whereby energy efficiency gains ultimately "backfire" if their intended purpose is to reduce energy consumption and carbon dioxide emissions. The analogy that can be made is to a growing child: a healthy child who efficiently incorporates food into her structure grows quickly and is able to consume more in following years. Economically, an argument is made that, for a range of reasons, there are good reasons to refer to efficiency gains as economic "innovation", both for

  8. The Impact of Back-Sputtered Carbon on the Accelerator Grid Wear Rates of the NEXT and NSTAR Ion Thrusters

    NASA Technical Reports Server (NTRS)

    Soulas, George C.

    2013-01-01

    A study was conducted to quantify the impact of back-sputtered carbon on the downstream accelerator grid erosion rates of the NASA's Evolutionary Xenon Thruster (NEXT) Long Duration Test (LDT1). A similar analysis that was conducted for the NASA's Solar Electric Propulsion Technology Applications Readiness Program (NSTAR) Life Demonstration Test (LDT2) was used as a foundation for the analysis developed herein. A new carbon surface coverage model was developed that accounted for multiple carbon adlayers before complete surface coverage is achieved. The resulting model requires knowledge of more model inputs, so they were conservatively estimated using the results of past thin film sputtering studies and particle reflection predictions. In addition, accelerator current densities across the grid were rigorously determined using an ion optics code to determine accelerator current distributions and an algorithm to determine beam current densities along a grid using downstream measurements. The improved analysis was applied to the NSTAR test results for evaluation. The improved analysis demonstrated that the impact of back-sputtered carbon on pit and groove wear rate for the NSTAR LDT2 was negligible throughout most of eroded grid radius. The improved analysis also predicted the accelerator current density for transition from net erosion to net deposition considerably more accurately than the original analysis. The improved analysis was used to estimate the impact of back-sputtered carbon on the accelerator grid pit and groove wear rate of the NEXT Long Duration Test (LDT1). Unlike the NSTAR analysis, the NEXT analysis was more challenging because the thruster was operated for extended durations at various operating conditions and was unavailable for measurements because the test is ongoing. As a result, the NEXT LDT1 estimates presented herein are considered preliminary until the results of future post-test analyses are incorporated. The worst-case impact of carbon

  9. The Impact of Back-Sputtered Carbon on the Accelerator Grid Wear Rates of the NEXT and NSTAR Ion Thrusters

    NASA Technical Reports Server (NTRS)

    Soulas, George C.

    2013-01-01

    A study was conducted to quantify the impact of back-sputtered carbon on the downstream accelerator grid erosion rates of the NEXT (NASA's Evolutionary Xenon Thruster) Long Duration Test (LDT1). A similar analysis that was conducted for the NSTAR (NASA's Solar Electric Propulsion Technology Applications Readiness Program) Life Demonstration Test (LDT2) was used as a foundation for the analysis developed herein. A new carbon surface coverage model was developed that accounted for multiple carbon adlayers before complete surface coverage is achieved. The resulting model requires knowledge of more model inputs, so they were conservatively estimated using the results of past thin film sputtering studies and particle reflection predictions. In addition, accelerator current densities across the grid were rigorously determined using an ion optics code to determine accelerator current distributions and an algorithm to determine beam current densities along a grid using downstream measurements. The improved analysis was applied to the NSTAR test results for evaluation. The improved analysis demonstrated that the impact of back-sputtered carbon on pit and groove wear rate for the NSTAR LDT2 was negligible throughout most of eroded grid radius. The improved analysis also predicted the accelerator current density for transition from net erosion to net deposition considerably more accurately than the original analysis. The improved analysis was used to estimate the impact of back-sputtered carbon on the accelerator grid pit and groove wear rate of the NEXT Long Duration Test (LDT1). Unlike the NSTAR analysis, the NEXT analysis was more challenging because the thruster was operated for extended durations at various operating conditions and was unavailable for measurements because the test is ongoing. As a result, the NEXT LDT1 estimates presented herein are considered preliminary until the results of future posttest analyses are incorporated. The worst-case impact of carbon back

  10. Continuous plutonium dissolution apparatus

    DOEpatents

    Meyer, F.G.; Tesitor, C.N.

    1974-02-26

    This invention is concerned with continuous dissolution of metals such as plutonium. A high normality acid mixture is fed into a boiler vessel, vaporized, and subsequently condensed as a low normality acid mixture. The mixture is then conveyed to a dissolution vessel and contacted with the plutonium metal to dissolve the plutonium in the dissolution vessel, reacting therewith forming plutonium nitrate. The reaction products are then conveyed to the mixing vessel and maintained soluble by the high normality acid, with separation and removal of the desired constituent. (Official Gazette)

  11. A new direction in effective accounting for the atmospheric CO 2 budget: Considering the combined action of carbonate dissolution, the global water cycle and photosynthetic uptake of DIC by aquatic organisms

    NASA Astrophysics Data System (ADS)

    Liu, Zaihua; Dreybrodt, Wolfgang; Wang, Haijing

    2010-05-01

    The magnitudes, variations, locations and mechanisms responsible for the global atmospheric CO 2 sink are uncertain and under continuing debate. Previous studies have focused mainly on the sinks in the oceans, and soil and vegetation on the continents. Here, we show, based on theoretical calculations and field monitoring evidence, that there is an important but previously underestimated sink for atmospheric CO 2 as DIC-dissolved inorganic carbon that results from the combined action of carbonate dissolution, the global water cycle and the photosynthetic uptake of DIC by aquatic organisms in ocean and land. The sink constitutes up to 0.8242 Pg C/a, amounting to 29.4% of the terrestrial CO 2 sink, or 10.4% of the total anthropogenic CO 2 emission. 0.244 Pg C/a are transferred to the sea via continental rivers and 0.2278 Pg C/a by meteoric precipitation over the seas. 0.119 Pg C/a is released back to the atmosphere again, and 0.2334 Pg C/a is stored in the continental aquatic ecosystem. Therefore, the net sink is estimated as 0.7052 Pg C/a. This sink may increase with an intensification of the global water cycle as a consequence of global warming, rising anthropogenic emissions of CO 2 and carbonate dust in atmosphere, and afforestation, which increases the soil pCO 2 and thus the carbonate dissolution. Fertilization with the elements N, P, C, Fe, Zn, and Si increases the organic matter storage/burial by aquatic organisms and thus decreases the CO 2 return to the atmosphere. Based on the ensemble mean projection of global warming for the year 2100 by IPCC, it is estimated that the atmospheric CO 2 sink will increase by 21%, or about 0.18 Pg C/a. However, the uncertainty in the estimation of this sink needs further exploration.

  12. X-ray Thomson scattering of shocked carbon foam on the Z accelerator

    NASA Astrophysics Data System (ADS)

    Ao, Tommy; Harding, Eric; Bailey, James; Lemke, Raymond; Desjarlais, Michael; Hansen, Stephanie; Smith, Ian; Reneker, Joseph; Romero, Dustin; Sinars, Daniel; Rochau, Gregory; Benage, John

    2015-06-01

    Experiments on the Sandia Z pulsed-power accelerator have demonstrated the ability to produce warm dense matter (WDM) states with unprecedented uniformity, duration, and size, which are ideal for investigations of fundamental WDM properties. For the first time, a space-resolved x-ray Thomson scattering (XRTS) spectra from shocked carbon foam was recorded on Z. The large electrical current produced by Z was used to launch Al flyer plates up to 25 km/s. The impact of the flyer plate on a CH2 foam target produced a shocked state with an estimated pressure of 0.75 Mbar, density of 0.52 g/cc, and temperature of 4.3 eV. Both unshocked and shocked portions of the foam target were probed with 6.2 keV x-rays produced by focusing the Z-Beamlet laser onto a nearby Mn foil. The data is comprised of three spatially distinct spectra that were simultaneously captured with a single spectrometer. These three spectra provide detailed information on the following target locations: the laser spot, the unshocked foam, and the shocked foam. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's NNSA under Contract DE-AC04-94AL85000.

  13. Increases in dissolved organic carbon accelerate loss of toxic Al in Adirondack lakes recovering from acidification.

    PubMed

    Lawrence, Gregory B; Dukett, James E; Houck, Nathan; Snyder, Phil; Capone, Sue

    2013-07-01

    Increasing pH and decreasing Al in surface waters recovering from acidification have been accompanied by increasing concentrations of dissolved organic carbon (DOC) and associated organic acids that partially offset pH increases and complicate assessments of recovery from acidification. To better understand the processes of recovery, monthly chemistry from 42 lakes in the Adirondack region, NY, collected from 1994 to 2011, were used to (1) evaluate long-term changes in DOC and associated strongly acidic organic acids and (2) use the base-cation surplus (BCS) as a chemical index to assess the effects of increasing DOC concentrations on the Al chemistry of these lakes. Over the study period, the BCS increased (p < 0.01) and concentrations of toxic inorganic monomeric Al (IMAl) decreased (p < 0.01). The decreases in IMAl were greater than expected from the increases in the BCS. Higher DOC concentrations that increased organic complexation of Al resulted in a decrease in the IMAl fraction of total monomeric Al from 57% in 1994 to 23% in 2011. Increasing DOC concentrations have accelerated recovery in terms of decreasing toxic Al beyond that directly accomplished by reducing atmospheric deposition of strong mineral acids. PMID:23751119

  14. Increases in dissolved organic carbon accelerate loss of toxic Al in Adirondack lakes recovering from acidification

    USGS Publications Warehouse

    Lawrence, Gregory B.; Dukett, James E; Houck, Nathan; Snyder, Phillip; Capone, Susan B.

    2013-01-01

    Increasing pH and decreasing Al in surface waters recovering from acidification have been accompanied by increasing concentrations of dissolved organic carbon (DOC) and associated organic acids that partially offset pH increases and complicate assessments of recovery from acidification. To better understand the processes of recovery, monthly chemistry from 42 lakes in the Adirondack region, NY, collected from 1994 to 2011, were used to (1) evaluate long-term changes in DOC and associated strongly acidic organic acids and (2) use the base-cation surplus (BCS) as a chemical index to assess the effects of increasing DOC concentrations on the Al chemistry of these lakes. Over the study period, the BCS increased (p < 0.01) and concentrations of toxic inorganic monomeric Al (IMAl) decreased (p < 0.01). The decreases in IMAl were greater than expected from the increases in the BCS. Higher DOC concentrations that increased organic complexation of Al resulted in a decrease in the IMAl fraction of total monomeric Al from 57% in 1994 to 23% in 2011. Increasing DOC concentrations have accelerated recovery in terms of decreasing toxic Al beyond that directly accomplished by reducing atmospheric deposition of strong mineral acids.

  15. DISSOLUTION OF LANTHANUM FLUORIDE PRECIPITATES

    DOEpatents

    Fries, B.A.

    1959-11-10

    A plutonium separatory ore concentration procedure involving the use of a fluoride type of carrier is presented. An improvement is given in the derivation step in the process for plutonium recovery by carrier precipitation of plutonium values from solution with a lanthanum fluoride carrier precipitate and subsequent derivation from the resulting plutonium bearing carrier precipitate of an aqueous acidic plutonium-containing solution. The carrier precipitate is contacted with a concentrated aqueous solution of potassium carbonate to effect dissolution therein of at least a part of the precipitate, including the plutonium values. Any remaining precipitate is separated from the resulting solution and dissolves in an aqueous solution containing at least 20% by weight of potassium carbonate. The reacting solutions are combined, and an alkali metal hydroxide added to a concentration of at least 2N to precipitate lanthanum hydroxide concomitantly carrying plutonium values.

  16. Accelerated carbonation using municipal solid waste incinerator bottom ash and cold-rolling wastewater: Performance evaluation and reaction kinetics.

    PubMed

    Chang, E-E; Pan, Shu-Yuan; Yang, Liuhanzi; Chen, Yi-Hung; Kim, Hyunook; Chiang, Pen-Chi

    2015-09-01

    Accelerated carbonation of alkaline wastes including municipal solid waste incinerator bottom ash (MSWI-BA) and the cold-rolling wastewater (CRW) was investigated for carbon dioxide (CO2) fixation under different operating conditions, i.e., reaction time, CO2 concentration, liquid-to-solid ratio, particle size, and CO2 flow rate. The MSWI-BA before and after carbonation process were analyzed by the thermogravimetry and differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. The MSWI-BA exhibits a high carbonation conversion of 90.7%, corresponding to a CO2 fixation capacity of 102g perkg of ash. Meanwhile, the carbonation kinetics was evaluated by the shrinking core model. In addition, the effect of different operating parameters on carbonation conversion of MSWI-BA was statistically evaluated by response surface methodology (RSM) using experimental data to predict the maximum carbonation conversion. Furthermore, the amount of CO2 reduction and energy consumption for operating the proposed process in refuse incinerator were estimated. Capsule abstract: CO2 fixation process by alkaline wastes including bottom ash and cold-rolling wastewater was developed, which should be a viable method due to high conversion. PMID:26025583

  17. The Role of Black Carbon from Wildfires in Accelerating Snow and Glacier Melt in Washington State

    NASA Astrophysics Data System (ADS)

    Kaspari, S.; Delaney, I.; Pittenger, D.; Skiles, M.

    2014-12-01

    In Washington, snow and glacier melt provide an important source of water resources, however spring snowpack levels are declining and glaciers are retreating. While warming temperatures are a well-recognized factor contributing to snowpack decline and glacier retreat, another cause may be the deposition of black carbon (BC) onto snow and glacier surfaces. Since 2010 we have collected snow and ice core samples to characterize the spatial and temporal variability of BC deposited in Washington snow and glacier ice. BC concentrations in the winter snowpack are relatively low, with BC concentrations increasing in spring and summer due to melt induced enrichment and increased dry deposition. BC induced melt may accelerate the timing of spring snowmelt at lower elevations, however BC induced melt is likely largest at relatively high elevations where the snowpack persists into the summer months when BC concentrations were observed to be highest. Based on our research to date, the highest BC concentrations in Washington snow and ice are linked to forest fires. A shallow ice core retrieved from Mt. Olympus demonstrated that BC deposition was a magnitude higher during the 2011 Big Hump forest fire, resulting in a threefold increase in the rate of change of river discharge due to glacier melt. An ice core from South Cascade Glacier spanning the 20th century also suggests that the highest BC concentrations are associated with forest fires. Furthermore, burned areas can continue to provide a source of BC to the snowpack post-fire. We measured BC concentrations in snow at a study site from 2010-2013 in Washington State. The surrounding forest burned in 2012, after which BC deposited on the snowpack post-fire was at least four-fold higher than pre-fire. This research has implications for projected climate change, as forest fires are projected to increase and the seasonal snowpack is projected to decrease, both of which contribute to higher BC concentrations in the snowpack.

  18. The dissolution behavior of scorodite in acidic environments

    NASA Astrophysics Data System (ADS)

    Pande, Preeti

    2001-11-01

    The safe disposal of arsenic-containing waste has been a difficult problem for the mining and metallurgical industry. One of the solutions to the arsenic problem is the precipitation of scorodite, an arsenic-containing mineral. Scorodite is reported to be relatively stable over a wide range of pH, and therefore may be a preferred disposal option. The effect of organic complexing agents on scorodite stability, however, is largely unknown. The present study is a phenomenological investigation into the dissolution kinetics of scorodite in the presence of oxalic acid under varying conditions of pH, oxalic acid concentration and temperature. The effect of scorodite particle size was also investigated. The morphological changes accompanying the dissolution process were examined by SEM and TEM analyses. Dissolution curves were divided into a linear induction period and a post-induction period. Activation energies were determined. Complete dissolution data were fit to the Prout-Tompkins/Austin-Rickett model. Dissolution data are indicative of auto-accelerated processes. The rapid increase in dissolution rate following the induction period is believed to be associated with an increase in the effective surface area. Pitting was observed on the surface of scorodite in the early stages of dissolution. In the later stages of dissolution, these pits were observed to grow and coalesce, in many cases resulting in the formation of dissolution holes.

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

    SciTech Connect

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

    1981-05-08

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

  20. Solubility and dissolution kinetics of gypsum as a function of CO2 partial pressure: Implications for geological carbon sequestration William Wolfe, Philip Bennett The University of Texas at Austin, Jackson School of Geosciences

    NASA Astrophysics Data System (ADS)

    Wolfe, W. W.; Bennett, P.

    2011-12-01

    The storage of carbon dioxide in deep saline (non-potable) aquifers has received increasing attention as a possible near term solution to the emission of carbon dioxide into the atmosphere. As a result of CO2 introduction, a wide array of geochemical reactions will occur involving both the aqueous phase and the solid mineral phase. Potential CO2 storage formations are typically saline Na:Cl or NaCa:ClSO4 type water. To gain insight into the dynamics of this system under the conditions of carbon sequestration we examined the solubility and dissolution/precipitation rates of gypsum in aqueous solutions as a function of CO2 partial pressure. Experimental variables ranged from 30-60 degrees C, 0.1-5 molar NaCl, and 1-130 atmospheres of CO2. Most standard geochemical models predict that gypsum solubility will increase with increasing dissolved CO2 due to the increased acidity driving the protonation of sulfate to form bisulfate: H+ + SO4= <=> HSO4- Thus decreasing sulfate concentration and driving further dissolution of gypsum. However, our findings show that increasing dissolved CO2 results in the precipitation of gypsum, with gypsum solubility decreasing by up to 30-50% at all temperatures examined. Solutions initially at equilibrium with gypsum will nucleate and precipitate gypsum as pCO2 increases. This behavior was predicted by Li and Duan, (2011) based on model results but no experimental evidence was found by the authors. Potential factors for this behavior include a decrease in the activity of water due to hydration of dissolved CO2, or possibly the destabilization of the CaSO4 neutral complex increasing the activity of free Ca++ and SO4= in solution, driving the precipitation of gypsum. We are exploring both of these possible scenarios. The saline aquifers of the Texas gulf coast are a potential target for carbon dioxide sequestration, and many of these aquifers have high Ca and SO4 concentrations due to reaction with gypsum. Precipitation of gypsum under high

  1. Accelerated carbonation using municipal solid waste incinerator bottom ash and cold-rolling wastewater: Performance evaluation and reaction kinetics

    SciTech Connect

    Chang, E-E; Pan, Shu-Yuan; Yang, Liuhanzi; Chen, Yi-Hung; Kim, Hyunook; Chiang, Pen-Chi

    2015-09-15

    Highlights: • Carbonation was performed using CO{sub 2}, wastewater and bottom ash in a slurry reactor. • A maximum capture capacity of 102 g CO{sub 2} per kg BA was achieved at mild conditions. • A maximum carbonation conversion of MSWI-BA was predicted to be 95% by RSM. • The CO{sub 2} emission from Bali incinerator could be expected to reduce by 6480 ton/y. • The process energy consumption per ton CO{sub 2} captured was estimated to be 180 kW h. - Abstract: Accelerated carbonation of alkaline wastes including municipal solid waste incinerator bottom ash (MSWI-BA) and the cold-rolling wastewater (CRW) was investigated for carbon dioxide (CO{sub 2}) fixation under different operating conditions, i.e., reaction time, CO{sub 2} concentration, liquid-to-solid ratio, particle size, and CO{sub 2} flow rate. The MSWI-BA before and after carbonation process were analyzed by the thermogravimetry and differential scanning calorimetry, X-ray diffraction, and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. The MSWI-BA exhibits a high carbonation conversion of 90.7%, corresponding to a CO{sub 2} fixation capacity of 102 g per kg of ash. Meanwhile, the carbonation kinetics was evaluated by the shrinking core model. In addition, the effect of different operating parameters on carbonation conversion of MSWI-BA was statistically evaluated by response surface methodology (RSM) using experimental data to predict the maximum carbonation conversion. Furthermore, the amount of CO{sub 2} reduction and energy consumption for operating the proposed process in refuse incinerator were estimated. Capsule abstract: CO{sub 2} fixation process by alkaline wastes including bottom ash and cold-rolling wastewater was developed, which should be a viable method due to high conversion.

  2. Evaluation of an accelerated mineral carbonation process using Class F fly ash to sequester flue gas CO2

    NASA Astrophysics Data System (ADS)

    Erikson, Lisa N.

    Accelerated mineral carbonation (AMC) processes have been recommended as a mitigation technique to reduce coal-fired flue gas carbon dioxide (CO 2) emissions. This research concerns an AMC process which reacts humid flue gas with fly ash in a fluidized bed reactor (FBR). In theory the alkaline products in the fly ash will react with the CO2 in the flue gas, producing stable mineral carbonates. Although the original goal of the current testing was to optimize an AMC process, recent testing revealed no significant mineralization taking place over the duration of the tests. Further evaluation of the AMC process indicated that small amounts of available alkalinity in the fly ash and limited amounts of water in the flue gas compromised the mineralization reactions. The use of a FBR coupled with an elemental analyzer for carbon measurement may have resulted in quantifying movement of unburned carbon as opposed to changes in carbonation. A subsequent review of previous testing regarding this AMC process indicated less than 1% CO2 uptake by the fly ash with past claims of mineralization based on incorrect data reduction. In general, AMC processes prove to be impractical for the reduction of large quantities of CO2 emissions produced by coal-fired power plants.

  3. Phycocyanobilin accelerates liver regeneration and reduces mortality rate in carbon tetrachloride-induced liver injury mice

    PubMed Central

    Liu, Jie; Zhang, Qing-Yu; Yu, Li-Ming; Liu, Bin; Li, Ming-Yi; Zhu, Run-Zhi

    2015-01-01

    AIM: To investigate the hepatoprotective effects of phycocyanobilin (PCB) in reducing hepatic injury and accelerating hepatocyte proliferation following carbon tetrachloride (CCl4) treatment. METHODS: C57BL/6 mice were orally administered PCB 100 mg/kg for 4 d after CCl4 injection, and then the serum and liver tissue of the mice were collected at days 1, 2, 3, 5 and 7 after CCl4 treatment. A series of evaluations were performed to identify the curative effects on liver injury and recovery. Aspartate aminotransferase (AST), alanine aminotransferase (ALT), albumin and superoxide dismutase (SOD) were detected to indirectly assess the anti-inflammatory effects of PCB. Meanwhile, we detected the expressions of hepatocyte growth factor, transforming growth factor alpha (TGF-α), TGF-β, tumor necrosis factor-alpha (TNF-α) and interleukin-6 (IL-6), the factors which are associated with inflammation and liver regeneration. The protein expressions of proliferating cell nuclear antigen (PCNA), TNF-α and cytochrome C were detected by western blot. Furthermore, the survival rates were analyzed of mice which were administered a lethal dose of CCl4 (2.6 mg/kg) with or without PCB. RESULTS: In our research, PCB showed a strongly anti-inflammatory effect on CCl4-induced liver injury in mice. The ALT was significantly decreased after CCl4 treatment from day 1 (P < 0.01) and the AST was significantly decreased from day 2 (P < 0.001). Both albumin and liver SOD were increased from day 2 (P < 0.001 and P < 0.01), but serum SOD levels did not show a significant increase (P > 0.05). PCB protected the structure of liver from the injury by CCl4. TUNEL assay showed that PCB dramatically reduced the number of apoptotic cells after CCl4 treatment compared to the control (101.0 ± 25.4 vs 25.7 ± 6.4, P < 0.01). The result of western blotting showed that PCB could increase PCNA expression, decrease TNF-α and cytochrome C expression. Furthermore, data shows that PCB could improve the

  4. HEPA filter dissolution process

    SciTech Connect

    Brewer, K.N.; Murphy, J.A.

    1992-12-31

    This invention is comprised of a process for dissolution of spent high efficiency particulate air (HEPA) filters and then combining the complexed filter solution with other radioactive wastes prior to calcining the mixed and blended waste feed. The process is an alternate to a prior method of acid leaching the spent filters which is an inefficient method of treating spent HEPA filters for disposal.

  5. Mergers, Annexations, Dissolutions

    ERIC Educational Resources Information Center

    Russo, Alexander

    2006-01-01

    Consolidations come in all shapes and sizes, including mergers, annexations and dissolutions. They do not all take place under state mandate, however. A handful of districts consolidate every year in some states like Illinois that have large numbers of small districts, many of them dual districts that serve K-8 or 9-12 in the same geographic area.…

  6. Hepa filter dissolution process

    DOEpatents

    Brewer, Ken N.; Murphy, James A.

    1994-01-01

    A process for dissolution of spent high efficiency particulate air (HEPA) filters and then combining the complexed filter solution with other radioactive wastes prior to calcining the mixed and blended waste feed. The process is an alternate to a prior method of acid leaching the spent filters which is an inefficient method of treating spent HEPA filters for disposal.

  7. HEPA filter dissolution process

    DOEpatents

    Brewer, K.N.; Murphy, J.A.

    1994-02-22

    A process is described for dissolution of spent high efficiency particulate air (HEPA) filters and then combining the complexed filter solution with other radioactive wastes prior to calcining the mixed and blended waste feed. The process is an alternate to a prior method of acid leaching the spent filters which is an inefficient method of treating spent HEPA filters for disposal. 4 figures.

  8. Plutonium oxide dissolution

    SciTech Connect

    Gray, J.H.

    1992-09-30

    Several processing options for dissolving plutonium oxide (PuO[sub 2]) from high-fired materials have been studied. The scoping studies performed on these options were focused on PuO[sub 2] typically generated by burning plutonium metal and PuO[sub 2] produced during incineration of alpha contaminated waste. At least two processing options remain applicable for dissolving high-fired PuO[sub 2] in canyon dissolvers. The options involve solid solution formation of PuO[sub 2] With uranium oxide (UO[sub 2]) and alloying incinerator ash with aluminum. An oxidative dissolution process involving nitric acid solutions containing a strong oxidizing agent, such as cerium (IV), was neither proven nor rejected. This uncertainty was due to difficulty in regenerating cerium (IV) ions during dissolution. However, recent work on silver-catalyzed dissolution of PuO[sub 2] with persulfate has demonstrated that persulfate ions regenerate silver (II). Use of persulfate to regenerate cerium (IV) or bismuth (V) ions during dissolution of PuO[sub 2] materials may warrant further study.

  9. Plutonium oxide dissolution

    SciTech Connect

    Gray, J.H.

    1992-09-30

    Several processing options for dissolving plutonium oxide (PuO{sub 2}) from high-fired materials have been studied. The scoping studies performed on these options were focused on PuO{sub 2} typically generated by burning plutonium metal and PuO{sub 2} produced during incineration of alpha contaminated waste. At least two processing options remain applicable for dissolving high-fired PuO{sub 2} in canyon dissolvers. The options involve solid solution formation of PuO{sub 2} With uranium oxide (UO{sub 2}) and alloying incinerator ash with aluminum. An oxidative dissolution process involving nitric acid solutions containing a strong oxidizing agent, such as cerium (IV), was neither proven nor rejected. This uncertainty was due to difficulty in regenerating cerium (IV) ions during dissolution. However, recent work on silver-catalyzed dissolution of PuO{sub 2} with persulfate has demonstrated that persulfate ions regenerate silver (II). Use of persulfate to regenerate cerium (IV) or bismuth (V) ions during dissolution of PuO{sub 2} materials may warrant further study.

  10. 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

  11. Formation of CO2, H2 and condensed carbon from siderite dissolution in the 200-300 °C range and at 50 MPa

    NASA Astrophysics Data System (ADS)

    Milesi, Vincent; Guyot, François; Brunet, Fabrice; Richard, Laurent; Recham, Nadir; Benedetti, Marc; Dairou, Julien; Prinzhofer, Alain

    2015-04-01

    Laboratory experiments were conducted to investigate the chemical processes governing the carbon speciation associated to hydrothermal decomposition of siderite. Experiments were carried out in sealed gold capsules using synthetic siderite and deionised water. The samples were reacted at 200 and 300 °C, under a pressure of 50 MPa. Siderite dissolved to reach the 3FeCO3 + H2O = Fe3O4 + 3CO2 + H2 equilibrium and magnetite, Fe3O4, was produced accordingly. The gas phase was dominated by CO2, H2 and CH4, the latter being in strong thermodynamic disequilibrium with CO2. Contrary to the other gas products, H2 concentration was found to decrease with run duration. TEM observations showed the occurrence of condensed carbon phases at the surfaces of magnetite and residual siderite grains. Thermodynamic calculations predict the formation of condensed carbon in the experiments according to the reaction: CO2 + 2H2 ⇒ C + 2H2O, which accounted for the observed H2 concentration decrease up to the point where H2 and CO2 activities were buffered by the graphite-siderite-magnetite assemblage. The well-organized structure of the carbon coating around magnetite emphasizes the high catalytic potential of magnetite surface for carbon reduction and polymerization. The formation of such C-rich phases may represent a potential source of CH4 by hydrogenation. On the other hand, the catalysis of Fischer-Tropsch type reactions may be poisoned by the presence of carbon coating on mineral surfaces. In any case, this study also demonstrates that abiotic H2 generation by water reduction, widely studied in recent years in ultrabasic contexts, can also occur in sedimentary contexts where siderite is present. We show that, in the latter case, natural H2 concentration will be buffered by a condensed carbon phase associated with magnetite.

  12. Modelling of time resolved and long contact time dissolution studies of spent nuclear fuel in 10 mM carbonate solution A comparison between two different models and experimental data

    NASA Astrophysics Data System (ADS)

    Eriksen, Trygve E.; Jonsson, Mats; Merino, Juan

    2008-04-01

    Using two different models, radiation induced dissolution of spent UO 2 fuel has been simulated. One of the models is conventional homogeneous radiolysis simulations where two different geometrical constraints were used and the second model is the recently developed steady-state model. The results of the simulations are compared to each other and to experimental results from spent fuel leaching experiments performed in carbonate containing aqueous solution under Ar-atmosphere. The influence of radiolytically produced H 2 is incorporated (on the basis of a recently suggested mechanism) in both models and this reproduces the experimentally observed inhibition of spent fuel dissolution fairly well. The conventional radiolysis model reproduces the experimental concentrations of the radiolysis products H 2 and O 2 very well while it fails to reproduce the experimental H 2O 2 concentration. The reasons for this are discussed. The general trend in uranium concentration as a function of time is reproduced by both the conventional radiolysis model and the steady-state model. The conventional radiolysis model (in which the radiation dose is homogeneously distributed in the whole liquid volume) underestimates the uranium concentration while the steady-state model, which represents the worst case scenario, overestimates the concentrations to some extent. When applying the conventional radiolysis model, assuming that all the radiation energy is deposited within 40 μm from the fuel surface, the uranium concentrations during the initial part of the experiments are reproduced quantitatively. The differences between the models and the applicability of the models are discussed in some detail.

  13. Determinants of marriage dissolution

    NASA Astrophysics Data System (ADS)

    Rahim, Mohd Amirul Rafiq Abu; Shafie, Siti Aishah Mohd; Hadi, Az'lina Abdul; Razali, Nornadiah Mohd; Azid @ Maarof, Nur Niswah Naslina

    2015-10-01

    Nowadays, the number of divorce cases among Muslim couples is very worrisome whereby the total cases reported in 2013 increased by half of the total cases reported in the previous year. The questions on the true key factors of dissolution of marriage continue to arise. Thus, the objective of this study is to reveal the factors that contribute to the dissolution of marriage. A total of 181 cases and ten potential determinants were included in this study. The potential determinants considered were age at marriage of husband and wife, educational level of husband and wife, employment status of husband and wife, income of husband and wife, the number of children and the presence at a counseling session. Logistic regression analysis was used to analyze the data. The findings revealed that four determinants, namely the income of husband and wife, number of children and the presence at a counselling session were significant in predicting the likelihood of divorce among Muslim couples.

  14. Dissolution Kinetics of Biogenic Magnesian Calcites

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

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

  15. Advanced modeling to accelerate the scale up of carbon capture technologies

    SciTech Connect

    Miller, David C.; Sun, XIN; Storlie, Curtis B.; Bhattacharyya, Debangsu

    2015-06-01

    In order to help meet the goals of the DOE carbon capture program, the Carbon Capture Simulation Initiative (CCSI) was launched in early 2011 to develop, demonstrate, and deploy advanced computational tools and validated multi-scale models to reduce the time required to develop and scale-up new carbon capture technologies. This article focuses on essential elements related to the development and validation of multi-scale models in order to help minimize risk and maximize learning as new technologies progress from pilot to demonstration scale.

  16. Uranium carbide dissolution in nitric solution: Sonication vs. silent conditions

    NASA Astrophysics Data System (ADS)

    Virot, Matthieu; Szenknect, Stéphanie; Chave, Tony; Dacheux, Nicolas; Moisy, Philippe; Nikitenko, Sergey I.

    2013-10-01

    The dissolution of uranium carbide (UC) in nitric acid media is considered by means of power ultrasound (sonication) or magnetic stirring. The induction period required to initiate UC dissolution was found to be dramatically shortened when sonicating a 3 M nitric solution (Ar, 20 kHz, 18 W cm-2, 20 °C). At higher acidity, magnetic stirring offers faster dissolution kinetics compared to sonication. Ultrasound-assisted UC dissolution is found to be passivated after ∼60% dissolution and remains incomplete whatever the acidity which is confirmed by ICP-AES, LECO and SEM-EDX analyses. In general, the kinetics of UC dissolution is linked to the in situ generation of nitrous acid in agreement with the general mechanism of UC dissolution; the nitrous acid formation is reported to be faster under ultrasound at low acidity due to the nitric acid sonolysis. The carbon balance shared between the gaseous, liquid, and solid phases is strongly influenced by the applied dissolution procedure and HNO3 concentration.

  17. Factors influencing dissolution of carbonaceous materials in liquid iron

    SciTech Connect

    Sun, H.P.

    2005-12-01

    Carbon dissolution into liquid iron was investigated by a kinetic model assuming the rate is limited by interfacial carbon dissociation and mass transfer in the liquid iron. The rate influencing factors and the inter-relations among them were discussed with the aid of the kinetic model.

  18. Interface dissolution control of the [sup 14]C profile in marine sediment

    SciTech Connect

    Keir, R.S. ); Michel, R.L. )

    1993-08-01

    The process of carbonate dissolution at the sediment-water interface has two possible end-member boundary conditions. Either the carbonate particles dissolve mostly before they are incorporated into the sediment by bioturbation (interface dissolution), or the vertical mixing is rapid relative to their extermination rate (homogeneous dissolution). In this study, a detailed radiocarbon profile was determined in deep equatorial Pacific sediment that receives a high rate of carbonate supply. In addition, a box model of sediment mixing was used to simulate radiocarbon, carbonate content, and excess thorium profiles that result from either boundary process following a dissolution increase. Results from homogeneous dissolution imply a strong, very recent erosional event, while interface dissolution suggests that moderately increased dissolution began about 10,000 years ago. In order to achieve the observed mixed layer radiocarbon age, increased homogeneous dissolution would concentrate a greater amount of clay and [sup 230]Th than is observed, while for interface dissolution the predicted concentrations are too small. These results together with small discontinuities beneath the mixed layer in [sup 230]Th profiles suggest a two-stage increase in interface dissolution in the deep Pacific, the first occurring near the beginning of the Holocene and the second more recently, roughly 5,000 years ago. 30 refs., 8 figs., 3 tabs.

  19. Interface dissolution control of the 14C profile in marine sediment

    USGS Publications Warehouse

    Keir, R.S.; Michel, R.L.

    1993-01-01

    The process of carbonate dissolution at the sediment-water interface has two possible endmember boundary conditions. Either the carbonate particles dissolve mostly before they are incorporated into the sediment by bioturbation (interface dissolution), or the vertical mixing is rapid relative to their extermination rate (homogeneous dissolution). In this study, a detailed radiocarbon profile was determined in deep equatorial Pacific sediment that receives a high rate of carbonate supply. In addition, a box model of sediment mixing was used to simulate radiocarbon, carbonate content and excess thorium profiles that result from either boundary process following a dissolution increase. Results from homogeneous dissolution imply a strong, very recent erosional event, while interface dissolution suggests that moderately increased dissolution began about 10,000 years ago. In order to achieve the observed mixed layer radiocarbon age, increased homogeneous dissolution would concentrate a greater amount of clay and 230Th than is observed, while for interface dissolution the predicted concentrations are too small. These results together with small discontinuities beneath the mixed layer in 230Th profiles suggest a two-stage increase in interface dissolution in the deep Pacific, the first occurring near the beginning of the Holocene and the second more recently, roughly 5000 years ago. ?? 1993.

  20. Solubility limits on radionuclide dissolution

    SciTech Connect

    Kerrisk, J.F.

    1984-12-31

    This paper examines the effects of solubility in limiting dissolution rates of a number of important radionuclides from spent fuel and high-level waste. Two simple dissolution models were used for calculations that would be characteristics of a Yucca Mountain repository. A saturation-limited dissolution model, in which the water flowing through the repository is assumed to be saturated with each waste element, is very conservative in that it overestimates dissolution rates. A diffusion-limited dissolution model, in which element-dissolution rates are limited by diffusion of waste elements into water flowing past the waste, is more realistic, but it is subject to some uncertainty at this time. Dissolution rates of some elements (Pu, Am, Sn, Th, Zr, Sm) are always limited by solubility. Dissolution rates of other elements (Cs, Tc, Np, Sr, C, I) are never solubility limited; their release would be limited by dissolution of the bulk waste form. Still other elements (U, Cm, Ni, Ra) show solubility-limited dissolution under some conditions. 9 references, 3 tables.

  1. Use of accelerated helium-3 ions for determining oxygen and carbon impurities in some pure materials

    NASA Technical Reports Server (NTRS)

    Aleksandrova, G. I.; Borisov, G. I.; Demidov, A. M.; Zakharov, Y. A.; Sukhov, G. V.; Shmanenkova, G. I.; Shchelkova, V. P.

    1978-01-01

    Methods are developed for the determination of O impurity in Be and Si carbide and concurrent determination of C and O impurities in Si and W by irradiation with accelerated He-3 ions and subsequent activity measurements of C-11 and F-18 formed from C and O with the aid of a gamma-gamma coincidence spectrometer. Techniques for determining O in Ge and Ga arsenide with radiochemical separation of F-18 are also described.

  2. Microarthropods accelerate litter decomposition and alter the fate of litter carbon and nitrogen in the soil

    NASA Astrophysics Data System (ADS)

    Soong, Jennifer; Horton, Andrew; Wall, Diana; Cotrufo, Francesca

    2015-04-01

    Soil fauna have been found to accelerate litter decomposition in some ecosystems, with calls for the need to include them in global models of C and N cycling. However, their influence on the fate of decomposing litter C and N is not clear. Does the acceleration of mass loss affect how much litter C and N end up stored as soil organic matter (SOM), or how much C and N are lost to the atmosphere during decomposition? We will present the results from our three-year, 100% mass loss, tracking of 13C and 15N labeled Andropogon gerardii leaf litter decomposing at a tallgrass prairie site, where we used a naphthalene treatment to suppress microarthropods and examine their effects on the fate of decomposing litter C and N. Initially, leaching was the main pathway of litter inputs to the mineral associated SOM. We found that microarthropods accelerated the first 18 months of litter mass loss, but after 24 months mass loss rates converged. This early acceleration of mass loss was associated with an increase of litter fragment inputs to the soil. This increase in litter inputs to the soil caused by microarthropods resulted in an increase in microbial uptake of litter C (measured by tracing 13C into phospholipid fatty acids), and a shift in the microbial community. The C:N ratio of litter inputs to the soil was significantly increased by the presence of microarthropods. Together these results demonstrate how microarthropods accelerate shredding, mass loss, and litter fragment inputs to the soil during the early stages of decomposition but they do not affect the total amount of litter contribution to SOM over the entire course of decomposition. However, microarthropods do alter the C:N composition of litter inputs to the soil through their top-down influence on the microbial community responsible for decomposing and transforming litter inputs to the soil. Our results reveal the complex interactions between microarthropods, litter mass loss, soil microbes and C:N dynamics, and

  3. Field studies on the formation of sinking CO2 particles for ocean carbon sequestration: effects of injector geometry on particle density and dissolution rate and model simulation of plume behavior.

    PubMed

    Riestenberg, David E; Tsouris, Costas; Brewer, Peter G; Peltzer, Edward T; Walz, Peter; Chow, Aaron C; Adams, E Eric

    2005-09-15

    We have carried out the second phase of field studies to determine the effectiveness of a coflow injector which mixes liquid CO2 and ambient seawater to produce a hydrate slurry as a possible CO2 delivery method for ocean carbon sequestration. The experiments were carried out at ocean depths of 1000-1300 m in Monterey Bay, CA, using a larger injector than that initially employed under remotely operated vehicle control and imaging of the product. Solidlike composite particles comprised of water, solid CO2 hydrate, and liquid CO2 were produced in both studies. In the recent injections, the particles consistently sank at rates of approximately 5 cm s(-1). The density of the sinking particles suggested that approximately 40% of the injected CO2 was converted to hydrate, while image analysis of the particle shrinking rate indicated a CO2 dissolution rate of 0.76-1.29 micromol cm(-2) s(-1). Plume modeling of the hydrate composite particles suggests that while discrete particles may sink 10-70 m, injections with CO2 mass fluxes of 1-1000 kg s(-1) would result in sinking plumes 120-1000 m belowthe injection point. PMID:16201660

  4. Carbon dioxide enrichment alters plant community structure and accelerates shrub growth in the shortgrass steppe

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Doubling atmospheric carbon dioxide concentrations [CO2] over native Colorado shortgrass steppe progressively increased plant cover over a five year period in Artemisia frigida Willd, fringed sage, a common shrub of North American and Asian native grasslands. Plant community species composition in ...

  5. Phase II of a Six sigma Initiative to Study DWPF SME Analytical Turnaround Times: SRNL's Evaluation of Carbonate-Based Dissolution Methods

    SciTech Connect

    Edwards, Thomas

    2005-09-01

    The Analytical Development Section (ADS) and the Statistical Consulting Section (SCS) of the Savannah River National Laboratory (SRNL) are participating in a Six Sigma initiative to improve the Defense Waste Processing Facility (DWPF) Laboratory. The Six Sigma initiative has focused on reducing the analytical turnaround time of samples from the Slurry Mix Evaporator (SME) by developing streamlined sampling and analytical methods [1]. The objective of Phase I was to evaluate the sub-sampling of a larger sample bottle and the performance of a cesium carbonate (Cs{sub 2}CO{sub 3}) digestion method. Successful implementation of the Cs{sub 2}CO{sub 3} fusion method in the DWPF would have important time savings and convenience benefits because this single digestion would replace the dual digestion scheme now used. A single digestion scheme would result in more efficient operations in both the DWPF shielded cells and the inductively coupled plasma--atomic emission spectroscopy (ICP-AES) laboratory. By taking a small aliquot of SME slurry from a large sample bottle and dissolving the vitrified SME sample with carbonate fusion methods, an analytical turnaround time reduction from 27 hours to 9 hours could be realized in the DWPF. This analytical scheme has the potential for not only dramatically reducing turnaround times, but also streamlining operations to minimize wear and tear on critical shielded cell components that are prone to fail, including the Hydragard{trademark} sampling valves and manipulators. Favorable results from the Phase I tests [2] led to the recommendation for a Phase II effort as outlined in the DWPF Technical Task Request (TTR) [3]. There were three major tasks outlined in the TTR, and SRNL issued a Task Technical and QA Plan [4] with a corresponding set of three major task activities: (1) Compare weight percent (wt%) total solids measurements of large volume samples versus peanut vial samples. (2) Evaluate Cs{sub 2}CO{sub 3} and K{sub 2}CO{sub 3

  6. Accelerating the spin-up of the coupled carbon and nitrogen cycle model in CLM4

    DOE PAGESBeta

    Fang, Yilin; Liu, Chongxuan; Leung, Lai-Yung R.

    2015-03-24

    The commonly adopted biogeochemistry spin-up process in an Earth system model (ESM) is to run the model for hundreds to thousands of years subject to periodic atmospheric forcing to reach dynamic steady state of the carbon–nitrogen (CN) models. A variety of approaches have been proposed to reduce the computation time of the spin-up process. Significant improvement in computational efficiency has been made recently. However, a long simulation time is still required to reach the common convergence criteria of the coupled carbon–nitrogen model. A gradient projection method was proposed and used to further reduce the computation time after examining the trendmore » of the dominant carbon pools. The Community Land Model version 4 (CLM4) with a carbon and nitrogen component was used in this study. From point-scale simulations, we found that the method can reduce the computation time by 20–69% compared to one of the fastest approaches in the literature. We also found that the cyclic stability of total carbon for some cases differs from that of the periodic atmospheric forcing, and some cases even showed instability. Close examination showed that one case has a carbon periodicity much longer than that of the atmospheric forcing due to the annual fire disturbance that is longer than half a year. The rest was caused by the instability of water table calculation in the hydrology model of CLM4. The instability issue is resolved after we replaced the hydrology scheme in CLM4 with a flow model for variably saturated porous media.« less

  7. Accelerating the spin-up of the coupled carbon and nitrogen cycle model in CLM4

    SciTech Connect

    Fang, Yilin; Liu, Chongxuan; Leung, Lai-Yung R.

    2015-03-24

    The commonly adopted biogeochemistry spin-up process in an Earth system model (ESM) is to run the model for hundreds to thousands of years subject to periodic atmospheric forcing to reach dynamic steady state of the carbon–nitrogen (CN) models. A variety of approaches have been proposed to reduce the computation time of the spin-up process. Significant improvement in computational efficiency has been made recently. However, a long simulation time is still required to reach the common convergence criteria of the coupled carbon–nitrogen model. A gradient projection method was proposed and used to further reduce the computation time after examining the trend of the dominant carbon pools. The Community Land Model version 4 (CLM4) with a carbon and nitrogen component was used in this study. From point-scale simulations, we found that the method can reduce the computation time by 20–69% compared to one of the fastest approaches in the literature. We also found that the cyclic stability of total carbon for some cases differs from that of the periodic atmospheric forcing, and some cases even showed instability. Close examination showed that one case has a carbon periodicity much longer than that of the atmospheric forcing due to the annual fire disturbance that is longer than half a year. The rest was caused by the instability of water table calculation in the hydrology model of CLM4. The instability issue is resolved after we replaced the hydrology scheme in CLM4 with a flow model for variably saturated porous media.

  8. Using Advanced Modeling to Accelerate the Scale-Up of Carbon Capture Technologies

    SciTech Connect

    Miller, David; Sun, Xin; Storlie, Curtis; Bhattacharyya, Debangsu

    2015-06-18

    Carbon capture and storage (CCS) is one of many approaches that are critical for significantly reducing domestic and global CO2 emissions. The U.S. Department of Energy’s Clean Coal Technology Program Plan envisions 2nd generation CO2 capture technologies ready for demonstration-scale testing around 2020 with the goal of enabling commercial deployment by 2025 [1]. Third generation technologies have a similarly aggressive timeline. A major challenge is that the development and scale-up of new technologies in the energy sector historically takes up to 15 years to move from the laboratory to pre-deployment and another 20 to 30 years for widespread industrial scale deployment. In order to help meet the goals of the DOE carbon capture program, the Carbon Capture Simulation Initiative (CCSI) was launched in early 2011 to develop, demonstrate, and deploy advanced computational tools and validated multi-scale models to reduce the time required to develop and scale up new carbon capture technologies. The CCSI Toolset (1) enables promising concepts to be more quickly identified through rapid computational screening of processes and devices, (2) reduces the time to design and troubleshoot new devices and processes by using optimization techniques to focus development on the best overall process conditions and by using detailed device-scale models to better understand and improve the internal behavior of complex equipment, and (3) provides quantitative predictions of device and process performance during scale up based on rigorously validated smaller scale simulations that take into account model and parameter uncertainty[2]. This article focuses on essential elements related to the development and validation of multi-scale models in order to help minimize risk and maximize learning as new technologies progress from pilot to demonstration scale.

  9. Numerical Modeling Studies of The Dissolution-Diffusion-Convection ProcessDuring CO2 Storage in Saline Aquifers

    SciTech Connect

    Pruess, Karsten; Zhang, Keni

    2008-11-17

    For purposes of geologic storage, CO2 would be injected into saline formations at supercritical temperature and pressure conditions, and would form a separate phase that is immiscible with the aqueous phase (brine). At typical subsurface temperature and pressure conditions, supercritical CO2 (scCO2) has lower density than the aqueous phase and would experience an upward buoyancy force. Accordingly, the CO2 is expected to accumulate beneath the caprock at the top of the permeable interval, and could escape from the storage formation wherever (sub-)vertical pathways are available, such as fractures or faults through the caprock, or improperly abandoned wells. Over time, an increasing fraction of CO2 may dissolve in the aqueous phase, and eventually some of the aqueous CO2 may react with rock minerals to form poorly soluble carbonates. Dissolution into the aqueous phase and eventual sequestration as carbonates are highly desirable processes as they would increase permanence and security of storage. Dissolution of CO2 will establish phase equilibrium locally between the overlying CO2 plume and the aqueous phase beneath. If the aqueous phase were immobile, CO2 dissolution would be limited by the rate at which molecular diffusion can remove dissolved CO2 from the interface between CO2-rich and aqueous phases. This is a slow process. However, dissolution of CO2 is accompanied by a small increase in the density of the aqueous phase, creating a negative buoyancy force that can give rise to downward convection of CO2-rich brine, which in turn can greatly accelerate CO2 dissolution. This study explores the process of dissolution-diffusion-convection (DDC), using high-resolution numerical simulation. We find that geometric features of convection patterns are very sensitive to small changes in problem specifications, reflecting self-enhancing feedbacks and the chaotic nature of the process. Total CO2 dissolution rates on the other hand are found to be quite robust against

  10. Plutonium dissolution process

    DOEpatents

    Vest, Michael A.; Fink, Samuel D.; Karraker, David G.; Moore, Edwin N.; Holcomb, H. Perry

    1996-01-01

    A two-step process for dissolving plutonium metal, which two steps can be carried out sequentially or simultaneously. Plutonium metal is exposed to a first mixture containing approximately 1.0M-1.67M sulfamic acid and 0.0025M-0.1M fluoride, the mixture having been heated to a temperature between 45.degree. C. and 70.degree. C. The mixture will dissolve a first portion of the plutonium metal but leave a portion of the plutonium in an oxide residue. Then, a mineral acid and additional fluoride are added to dissolve the residue. Alteratively, nitric acid in a concentration between approximately 0.05M and 0.067M is added to the first mixture to dissolve the residue as it is produced. Hydrogen released during the dissolution process is diluted with nitrogen.

  11. Plutonium dissolution process

    DOEpatents

    Vest, M.A.; Fink, S.D.; Karraker, D.G.; Moore, E.N.; Holcomb, H.P.

    1994-01-01

    A two-step process for dissolving Pu metal is disclosed in which two steps can be carried out sequentially or simultaneously. Pu metal is exposed to a first mixture of 1.0-1.67 M sulfamic acid and 0.0025-0.1 M fluoride, the mixture having been heated to 45-70 C. The mixture will dissolve a first portion of the Pu metal but leave a portion of the Pu in an oxide residue. Then, a mineral acid and additional fluoride are added to dissolve the residue. Alternatively, nitric acid between 0.05 and 0.067 M is added to the first mixture to dissolve the residue as it is produced. Hydrogen released during the dissolution is diluted with nitrogen.

  12. Comparative study of ageing, heat treatment and accelerated carbonation for stabilization of municipal solid waste incineration bottom ash in view of reducing regulated heavy metal/metalloid leaching.

    PubMed

    Santos, Rafael M; Mertens, Gilles; Salman, Muhammad; Cizer, Özlem; Van Gerven, Tom

    2013-10-15

    This study compared the performance of four different approaches for stabilization of regulated heavy metal and metalloid leaching from municipal solid waste incineration bottom ash (MSWI-BA): (i) short term (three months) heap ageing, (ii) heat treatment, (iii) accelerated moist carbonation, and (iv) accelerated pressurized slurry carbonation. Two distinct types of MSWI-BA were tested in this study: one originating from a moving-grate furnace incineration operation treating exclusively household refuse (sample B), and another originating from a fluid-bed furnace incineration operation that treats a mixture of household and light industrial wastes (sample F). The most abundant elements in the ashes were Si (20-27 wt.%) and Ca (16-19 wt.%), followed by significant quantities of Fe, Al, Na, S, K, Mg, Ti, and Cl. The main crystalline substances present in the fresh ashes were Quartz, Calcite, Apatite, Anhydrite and Gehlenite, while the amorphous fraction ranged from 56 to 73 wt.%. The leaching values of all samples were compared to the Flemish (NEN 7343) and the Walloon (DIN 38414) regulations from Belgium. Batch leaching of the fresh ashes at natural pH showed that seven elements exceeded at least one regulatory limit (Ba, Cr, Cu, Mo, Pb, Se and Zn), and that both ashes had excess basicity (pH > 12). Accelerated carbonation achieved significant reduction in ash basicity (9.3-9.9); lower than ageing (10.5-12.2) and heat treatment (11.1-12.1). For sample B, there was little distinction between the leaching results of ageing and accelerated carbonation with respect to regulatory limits; however carbonation achieved comparatively lower leaching levels. Heat treatment was especially detrimental to the leaching of Cr. For sample F, ageing was ineffective and heat treatment had marginally better results, while accelerated carbonation delivered the most effective performance, with slurry carbonation meeting all DIN limits. Slurry carbonation was deemed the most

  13. Laser Ablation - Accelerator Mass Spectrometry: An Approach for Rapid Radiocarbon Analyses of Carbonate Archives at High Spatial Resolution.

    PubMed

    Welte, Caroline; Wacker, Lukas; Hattendorf, Bodo; Christl, Marcus; Fohlmeister, Jens; Breitenbach, Sebastian F M; Robinson, Laura F; Andrews, Allen H; Freiwald, André; Farmer, Jesse R; Yeman, Christiane; Synal, Hans-Arno; Günther, Detlef

    2016-09-01

    A new instrumental setup, combining laser ablation (LA) with accelerator mass spectrometry (AMS), has been investigated for the online radiocarbon ((14)C) analysis of carbonate records. Samples were placed in an in-house designed LA-cell, and CO2 gas was produced by ablation using a 193 nm ArF excimer laser. The (14)C/(12)C abundance ratio of the gas was then analyzed by gas ion source AMS. This configuration allows flexible and time-resolved acquisition of (14)C profiles in contrast to conventional measurements, where only the bulk composition of discrete samples can be obtained. Three different measurement modes, i.e. discrete layer analysis, survey scans, and precision scans, were investigated and compared using a stalagmite sample and, subsequently, applied to terrestrial and marine carbonates. Depending on the measurement mode, a precision of typically 1-5% combined with a spatial resolution of 100 μm can be obtained. Prominent (14)C features, such as the atomic bomb (14)C peak, can be resolved by scanning several cm of a sample within 1 h. Stalagmite, deep-sea coral, and mollusk shell samples yielded comparable signal intensities, which again were comparable to those of conventional gas measurements. The novel LA-AMS setup allowed rapid scans on a variety of sample materials with high spatial resolution. PMID:27396439

  14. Accelerating the developing of carbon sequestration technologies. Electricity technology roadmap: limiting challenge No. 11. Final report

    SciTech Connect

    S. Dalton

    2003-12-15

    The report describes the R & D work needed to develop integrated carbon capture, transport, and storage technologies essential to reducing emissions associated with fossil fuel power generation. It incorporates extensive input from: representatives of the electric power industry, oil and gas companies, international research institutions, national laboratories, government agencies, environmental nonprofit organisations and academia. EPRI staff then worked intensively to interpret the inputs from this broad spectrum of contributors, and expand them into a systematic set of needs and recommendations. The document supports the 2003 Electricity Technology Roadmap. 10 figs., 2 tabs.

  15. The measurement results of carbon ion beam structure extracted by bent crystal from U-70 accelerator

    NASA Astrophysics Data System (ADS)

    Afonin, A. G.; Barnov, E. V.; Britvich, G. I.; Chesnokov, Yu A.; Chirkov, P. N.; Durum, A. A.; Kostin, M. Yu; Maisheev, V. A.; Pitalev, V. I.; Reshetnikov, S. F.; Yanovich, A. A.; Nazhmudinov, R. M.; Kubankin, A. S.; Shchagin, A. V.

    2016-07-01

    The carbon ion +6C beam with energy 25 GeV/nucleon was extracted by bent crystal from the U-70 ring. The bent angle of silicon crystal was 85 mrad. About 2×105 particles for 109 circulated ions in the ring were observed in beam line 4a after bent crystal. Geometrical parameters, time structure and ion beam structure were measured. The ability of the bent monocrystal to extract and generate ion beam with necessary parameters for regular usage in physical experiments is shown in the first time.

  16. Application of accelerated carbonation with a combination of Na2CO3 and CO2 in cement-based solidification/stabilization of heavy metal-bearing sediment.

    PubMed

    Chen, Quanyuan; Ke, Yujuan; Zhang, Lina; Tyrer, Mark; Hills, Colin D; Xue, Gang

    2009-07-15

    The efficient remediation of heavy metal-bearing sediment has been one of top priorities of ecosystem protection. Cement-based solidification/stabilization (s/s) is an option for reducing the mobility of heavy metals in the sediment and the subsequent hazard for human beings and animals. This work uses sodium carbonate as an internal carbon source of accelerated carbonation and gaseous CO(2) as an external carbon source to overcome deleterious effects of heavy metals on strength development and improve the effectiveness of s/s of heavy metal-bearing sediment. In addition to the compressive strength and porosity measurements, leaching tests followed the Chinese solid waste extraction procedure for leaching toxicity - sulfuric acid and nitric acid method (HJ/T299-2007), German leaching procedure (DIN38414-S4) and US toxicity characteristic leaching procedures (TCLP) have been conducted. The experimental results indicated that the solidified sediment by accelerated carbonation was capable of reaching all performance criteria for the disposal at a Portland cement dosage of 10 wt.% and a solid/water ratio of 1:1. The concentrations of mercury and other heavy metals in the leachates were below 0.10mg/L and 5mg/L, respectively, complying with Chinese regulatory level (GB5085-2007). Compared to the hydration, accelerated carbonation improved the compressive strength of the solidified sediment by more than 100% and reduced leaching concentrations of heavy metals significantly. It is considered that accelerated carbonation technology with a combination of Na(2)CO(3) and CO(2) may practically apply to cement-based s/s of heavy metal-bearing sediment. PMID:19128876

  17. Accelerated weathering of carbonate rocks following the 2010 forest wildfire on Mt. Carmel, Israel

    NASA Astrophysics Data System (ADS)

    Shtober-Zisu, Nurit; Tessler, Naama; Tsatskin, Alexander; Greenbaum, Noam

    2015-04-01

    Massive destruction of carbonate rocks occurred on the slopes of Mt. Carmel, during the severe forest fire in 2010. The bedrock surfaces exhibited extensive exfoliation into flakes and spalls covering up to 80%-100% of the exposed rocks; detached boulders were totally fractured or disintegrated. The fire affected six carbonate units -- various types of chalk, limestone, and dolomite. The burned flakes show a consistent tendency towards flatness, in all lithologies, as 85%-95% of the flakes were detached in the form of blades, plates, and slabs. The effects of the fire depend to a large extent on the rocks' physical properties and vary with lithology: the most severe response was found in the chalk formations which are covered by calcrete (Nari crusts). These rocks reacted by extreme exfoliation, at an average depth of 7.7 to 9.6 cm and a maximum depth of 20 cm. The flakes formed in chalk were thicker, longer, and wider than those of limestone or dolomite formations. Moreover, the chalk outcrops were exfoliated in a laminar structure, one above the other, to a depth of 10 cm and more. Their shape also tended to be blockier or rod-like. In contrast, the limestone flakes were the thinnest, with 99% of them shaped like blades and plates. Scorched and blackened faces under the upper layer of spalls provided strong evidence that chalk breakdown took place at an early stage of the fire. The extreme response of the chalks can be explained by the laminar structure of the Nari, which served as planes of weakness for the rock destruction. Three years after the fire, the rocks continue to exfoliate and break down internally. As the harder surface of the Nari was removed, the more brittle underlying chalk is exposed to erosion. If fires can obliterate boulders in a single wildfire event, it follows that wildfires may serve as limiting agents in the geomorphic evolution of slopes. However, it is difficult to estimate the frequency of high-intensity fires in the Carmel region

  18. Elevated carbon dioxide accelerates the spatial turnover of soil microbial communities.

    PubMed

    Deng, Ye; He, Zhili; Xiong, Jinbo; Yu, Hao; Xu, Meiying; Hobbie, Sarah E; Reich, Peter B; Schadt, Christopher W; Kent, Angela; Pendall, Elise; Wallenstein, Matthew; Zhou, Jizhong

    2016-02-01

    Although elevated CO2 (eCO2 ) significantly affects the α-diversity, composition, function, interaction and dynamics of soil microbial communities at the local scale, little is known about eCO2 impacts on the geographic distribution of micro-organisms regionally or globally. Here, we examined the β-diversity of 110 soil microbial communities across six free air CO2 enrichment (FACE) experimental sites using a high-throughput functional gene array. The β-diversity of soil microbial communities was significantly (P < 0.05) correlated with geographic distance under both CO2 conditions, but declined significantly (P < 0.05) faster at eCO2 with a slope of -0.0250 than at ambient CO2 (aCO2 ) with a slope of -0.0231 although it varied within each individual site, indicating that the spatial turnover rate of soil microbial communities was accelerated under eCO2 at a larger geographic scale (e.g. regionally). Both distance and soil properties significantly (P < 0.05) contributed to the observed microbial β-diversity. This study provides new hypotheses for further understanding their assembly mechanisms that may be especially important as global CO2 continues to increase. PMID:26414247

  19. Freshwater ecology. Experimental nutrient additions accelerate terrestrial carbon loss from stream ecosystems.

    PubMed

    Rosemond, Amy D; Benstead, Jonathan P; Bumpers, Phillip M; Gulis, Vladislav; Kominoski, John S; Manning, David W P; Suberkropp, Keller; Wallace, J Bruce

    2015-03-01

    Nutrient pollution of freshwater ecosystems results in predictable increases in carbon (C) sequestration by algae. Tests of nutrient enrichment on the fates of terrestrial organic C, which supports riverine food webs and is a source of CO2, are lacking. Using whole-stream nitrogen (N) and phosphorus (P) additions spanning the equivalent of 27 years, we found that average terrestrial organic C residence time was reduced by ~50% as compared to reference conditions as a result of nutrient pollution. Annual inputs of terrestrial organic C were rapidly depleted via release of detrital food webs from N and P co-limitation. This magnitude of terrestrial C loss can potentially exceed predicted algal C gains with nutrient enrichment across large parts of river networks, diminishing associated ecosystem services. PMID:25745171

  20. Carbon dioxide enrichment alters plant community structure and accelerates shrub growth in the shortgrass steppe.

    PubMed

    Morgan, Jack A; Milchunas, Daniel G; LeCain, Daniel R; West, Mark; Mosier, Arvin R

    2007-09-11

    A hypothesis has been advanced that the incursion of woody plants into world grasslands over the past two centuries has been driven in part by increasing carbon dioxide concentration, [CO(2)], in Earth's atmosphere. Unlike the warm season forage grasses they are displacing, woody plants have a photosynthetic metabolism and carbon allocation patterns that are responsive to CO(2), and many have tap roots that are more effective than grasses for reaching deep soil water stores that can be enhanced under elevated CO(2). However, this commonly cited hypothesis has little direct support from manipulative experimentation and competes with more traditional theories of shrub encroachment involving climate change, management, and fire. Here, we show that, although doubling [CO(2)] over the Colorado shortgrass steppe had little impact on plant species diversity, it resulted in an increasingly dissimilar plant community over the 5-year experiment compared with plots maintained at present-day [CO(2)]. Growth at the doubled [CO(2)] resulted in an approximately 40-fold increase in aboveground biomass and a 20-fold increase in plant cover of Artemisia frigida Willd, a common subshrub of some North American and Asian grasslands. This CO(2)-induced enhancement of plant growth, among the highest yet reported, provides evidence from a native grassland suggesting that rising atmospheric [CO(2)] may be contributing to the shrubland expansions of the past 200 years. Encroachment of shrubs into grasslands is an important problem facing rangeland managers and ranchers; this process replaces grasses, the preferred forage of domestic livestock, with species that are unsuitable for domestic livestock grazing. PMID:17785422

  1. Dissolution kinetics of high-resolution novolac resists

    NASA Astrophysics Data System (ADS)

    Itoh, Katsuyuki; Yamanaka, Koji; Nozue, Hiroshi; Kasama, Kunihiko

    1991-06-01

    Dissolution kinetics, as well as the formation mechanism of a surface insoluble layer produced by dipping into TMAH (tetramethylammonium hydroxide) developer, have been investigated. In the previous paper, we mentioned that dissolution rate characteristics of high resolution novolac resist are clearly divided into three regions. To investigate this dissolution mechanism, we evaluated the temperature dependence of R (Dissolution rate) by changing the exposure dose, PAC (photoactive compound equals dissolution inhibitor) and the TMAH concentration. From Arrhenius Plots of these resist systems, it is considered that R is determined by two competitive reactions in the presence of TMAH; i.e., (a) the complex formation between PAC and novolac resin which produces dissolution inhibition effect, (b) TMAH induced deprotonation of phenolic hydroxy groups in novolac resin which accelerates the dissolution of the resist. Furthermore, we also describe the formation mechanism of a surface insoluble layer produced by dipping into a TMAH developer followed by water rinse, on the basis of the dissolution time of this layer (ts). The resist surface was also analyzed by using FT-IR (Fourier transform infrared spectroscopic measurement) and XPS (X-ray photoelectron spectroscopy). As a result, it was found that (a) water rinse is essential for the surface insoluble layer formation, (b) the ts value is not directly correlated with PAC accumulation in the resist surface and (c) the ts value becomes longer when the amount of penetrated TMAH into the resist increases. These results suggest that the surface insoluble layer is produced via water rinse of PAC-novolac complex described above.

  2. Proper Heat Shock Pretreatment Reduces Acute Liver Injury Induced by Carbon Tetrachloride and Accelerates Liver Repair in Mice

    PubMed Central

    Li, San-Qiang; Wang, Dong-Mei; Shu, You-Ju; Wan, Xue-Dong; Xu, Zheng-Shun; Li, En-Zhong

    2013-01-01

    Whether proper heat shock preconditioning can reduce liver injury and accelerate liver repair after acute liver injury is worth study. So mice received heat shock preconditioning at 40°C for 10 minutes (min), 20 min or 30 min and recovered at room temperature for 8 hours (h) under normal feeding conditions. Then acute liver injury was induced in the heat shock-pretreated mice and unheated control mice by intraperitoneal (i.p.) injection of carbon tetrachloride (CCl4). Hematoxylin and eosin (H&E) staining, serum aspartate aminotransferase (AST) and alanine aminotransferase (ALT) levels and the expression levels of heat shock protein 70 (HSP70), cytochrome P450 1A2 (CYP1A2) and proliferating cell nuclear antigen (PCNA) were detected in the unheated control mice and heat shock-pretreated mice after CCl4 administration. Our results showed that heat shock preconditioning at 40°C for 20 min remarkably improved the mice’s survival rate (P<0.05), lowered the levels of serum AST and ALT (P<0.05), induced HSP70 (P<0.01), CYP1A2 (P<0.01) and PCNA (P<0.05) expression, effectively reduced liver injury (P<0.05) and accelerated the liver repair (P<0.05) compared with heat shock preconditioning at 40°C for 10 min or 30 min in the mice after acute liver injury induced by CCl4 when compared with the control mice. Our results may be helpful in further investigation of heat shock pretreatment as a potential clinical approach to target liver injury PMID:24526809

  3. 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.

  4. Competition among flow, dissolution, and precipitation in porous media

    SciTech Connect

    Rege, S.D.; Fogler, H.S. . Dept. of Chemical Engineering)

    1989-07-01

    A theoretical and experimental study has been carried out on flow, dissolution, and precipitation in porous media. Flow experiments were performed on linear carbonate cores using acidic ferric chloride solutions. Dissolution of the carbonate by the acid causes an increase in the solution pH, thereby precipitating ferric hydroxide. This precipitate plugs up the pore throats in the medium and increases the resistance to fluid flow. Fluctuations in the permeability ratio were observed during core flood experiments, confirming the competition between channel formation due to dissolution and pore plugging due to precipitation. The evolution of the pore structure was characterized. A network model has also been developed to describe flow and reaction in porous media. The model was used to simulate the ferric chloride system, and pressure oscillations predicted by the model show identical trends to those observed experimentally. Additionally, the evolution of pores in the network were graphically represented.

  5. Analytical interfacial studies of double carbonate thermionic oxide cathodes over accelerated operational life

    NASA Astrophysics Data System (ADS)

    Barber, D. K.; Jenkins, S. N.; Whiting, M. J.; Baker, M. A.

    2005-09-01

    Interfacial interactions between the nickel cap and emissive oxide in double carbonate thermionic oxide cathodes have been studied as a function of operational lifetime by SEM, AES, EDX and TEM. The surface of the interface region has been studied by stripping away the oxide from the cap. In cross-section, the interface has been examined by (a) preparing 10° taper cross-sections and (b) cutting FIB sections. Cracks are observed to develop in the bulk Ni and become more pronounced as a function of operational lifetime. Cracks are found both at grain boundaries and close to the surface, parallel to the interface. It is proposed that the cracks develop from voids, formed as a result of the high diffusivity of Mg and Al in the Ni matrix. EDX shows the presence of Al, Mg, Ba, Sr and O within the cracks and it is proposed that MgO and (Ba, Sr)Al 2O 4 are two major reaction products. A thin (skin) layer containing Al, Ba, Sr and O forms at the Ni cap/emissive layer interface, attributed primarily to (Ba, Sr)Al 2O 4 formation.

  6. A spatially resolved surface kinetic model for forsterite dissolution

    NASA Astrophysics Data System (ADS)

    Maher, Kate; Johnson, Natalie C.; Jackson, Ariel; Lammers, Laura N.; Torchinsky, Abe B.; Weaver, Karrie L.; Bird, Dennis K.; Brown, Gordon E.

    2016-02-01

    The development of complex alteration layers on silicate mineral surfaces undergoing dissolution is a widely observed phenomenon. Given the complexity of these layers, most kinetic models used to predict rates of mineral-fluid interactions do not explicitly consider their formation. As a result, the relationship between the development of the altered layers and the final dissolution rate is poorly understood. To improve our understanding of the relationship between the alteration layer and the dissolution rate, we developed a spatially resolved surface kinetic model for olivine dissolution and applied it to a series of closed-system experiments consisting of three-phases (water (±NaCl), olivine, and supercritical CO2) at conditions relevant to in situ mineral carbonation (i.e. 60 °C, 100 bar CO2). We also measured the corresponding δ26/24Mg of the dissolved Mg during early stages of dissolution. Analysis of the solid reaction products indicates the formation of Mg-depleted layers on the olivine surface as quickly as 2 days after the experiment was started and before the bulk solution reached saturation with respect to amorphous silica. The δ26/24Mg of the dissolved Mg decreased by approximately 0.4‰ in the first stages of the experiment and then approached the value of the initial olivine (-0.35‰) as the steady-state dissolution rate was approached. We attribute the preferential release of 24Mg to a kinetic effect associated with the formation of a Mg-depleted layer that develops as protons exchange for Mg2+. We used experimental data to calibrate a surface kinetic model for olivine dissolution that includes crystalline olivine, a distinct "active layer" from which Mg can be preferentially removed, and secondary amorphous silica precipitation. By coupling the spatial arrangement of ions with the kinetics, this model is able to reproduce both the early and steady-state long-term dissolution rates, and the kinetic isotope fractionation. In the early stages of

  7. Impacts of Nickel Nanoparticles on Mineral Carbonation

    PubMed Central

    Bodor, Marius; Santos, Rafael M.; Chiang, Yi Wai; Vlad, Maria; Van Gerven, Tom

    2014-01-01

    This work presents experimental results regarding the use of pure nickel nanoparticles (NiNP) as a mineral carbonation additive. The aim was to confirm if the catalytic effect of NiNP, which has been reported to increase the dissolution of CO2 and the dissociation of carbonic acid in water, is capable of accelerating mineral carbonation processes. The impacts of NiNP on the CO2 mineralization by four alkaline materials (pure CaO and MgO, and AOD and CC steelmaking slags), on the product mineralogy, on the particle size distribution, and on the morphology of resulting materials were investigated. NiNP-containing solution was found to reach more acidic pH values upon CO2 bubbling, confirming a higher quantity of bicarbonate ions. This effect resulted in acceleration of mineral carbonation in the first fifteen minutes of reaction time when NiNP was present. After this initial stage, however, no benefit of NiNP addition was seen, resulting in very similar carbonation extents after one hour of reaction time. It was also found that increasing solids content decreased the benefit of NiNP, even in the early stages. These results suggest that NiNP has little contribution to mineral carbonation processes when the dissolution of alkaline earth metals is rate limiting. PMID:24578669

  8. Impacts of nickel nanoparticles on mineral carbonation.

    PubMed

    Bodor, Marius; Santos, Rafael M; Chiang, Yi Wai; Vlad, Maria; Van Gerven, Tom

    2014-01-01

    This work presents experimental results regarding the use of pure nickel nanoparticles (NiNP) as a mineral carbonation additive. The aim was to confirm if the catalytic effect of NiNP, which has been reported to increase the dissolution of CO₂ and the dissociation of carbonic acid in water, is capable of accelerating mineral carbonation processes. The impacts of NiNP on the CO₂ mineralization by four alkaline materials (pure CaO and MgO, and AOD and CC steelmaking slags), on the product mineralogy, on the particle size distribution, and on the morphology of resulting materials were investigated. NiNP-containing solution was found to reach more acidic pH values upon CO₂ bubbling, confirming a higher quantity of bicarbonate ions. This effect resulted in acceleration of mineral carbonation in the first fifteen minutes of reaction time when NiNP was present. After this initial stage, however, no benefit of NiNP addition was seen, resulting in very similar carbonation extents after one hour of reaction time. It was also found that increasing solids content decreased the benefit of NiNP, even in the early stages. These results suggest that NiNP has little contribution to mineral carbonation processes when the dissolution of alkaline earth metals is rate limiting. PMID:24578669

  9. Influence of processing-induced phase transformations on the dissolution of theophylline tablets.

    PubMed

    Debnath, Smita; Suryanarayanan, Raj

    2004-02-12

    The object of this investigation was to evaluate the influence of (1) processing-induced decrease in drug crystallinity and (2) phase transformations during dissolution, on the performance of theophylline tablet formulations. Anhydrous theophylline underwent multiple transformations (anhydrate --> hydrate --> anhydrate) during processing. Although the crystallinity of the anhydrate obtained finally was lower than that of the unprocessed drug, it dissolved at a slower rate. This decrease in dissolution rate was attributed to the accelerated anhydrate to hydrate transformation during the dissolution run. Water vapor sorption studies proved to be a good predictor of powder dissolution behavior. While a decrease in crystallinity was brought about either by milling or by granulation, the effect on tablet dissolution was pronounced only in the latter. Tablet formulations prepared from the granules exhibited higher hardness, longer disintegration time, and slower dissolution than those containing the milled drug. The granules underwent plastic deformation during compression resulting in harder tablets, with delayed disintegration. The high hardness coupled with rapid anhydrate --> hydrate transformation during dissolution resulted in the formation of a hydrate layer on the tablet surface, which further delayed tablet disintegration and, consequently, dissolution. Phase transformations during processing and, more importantly, during dissolution influenced the observed dissolution rates. Product performance was a complex function of the physical state of the active and the processing conditions. PMID:15198529

  10. Enhanced CO2 Dissolution in Heterogeneous Porous Media

    NASA Astrophysics Data System (ADS)

    Daniels, K.; Neufeld, J. A.; Bickle, M. J.; Hallworth, M. A.

    2014-12-01

    Long-term and secure geological storage of CO2 through technologies such as Carbon Capture and Storage (CCS) within reservoirs is seen as a technological means to reduce anthropogenic CO2 emissions. The long-term viability of this technology is reliant on the structural and secondary trapping of supercritical CO2 within heterogeneous reservoirs. Secondary trapping, primarily through the dissolution of CO2 into ambient reservoir brine to produce a denser fluid, is capable of retaining CO2 in the subsurface and thus reducing the risks of storage. To model secondary trapping we need to understand how the flow of CO2 through heterogeneous reservoir rocks enhances dissolution of supercritical CO2 in reservoir brines. Here we experimentally investigate the dissolution of CO2 in reservoir brines in layered, heterogeneous geological formations. Using analogue experiments, designed to approximate an enhanced oil recovery (EOR) setting, the processes of mixing, dispersion and dissolution are examined. These are compared against test results from non-layered, homogeneous porous media experiments. We find that heterogeneities significantly enhance mixing, particularly between adjacent porous layers. During fluid propagation, pore-scale viscous fingers grow and retreat, thereby providing an increased surface area between the flow and the ambient reservoir fluid. This enhanced mixing is predicted to substantially increase the dissolution of CO2 in reservoir brines. Both permeability and viscosity differences are found to have a significant effect on the interface between the two fluids, and therefore the likely amount of dissolution of CO2.

  11. Mesoscale Approach to Feldspar Dissolution: Quantification of Dissolution Incongruency Based on Al/Si Ordering State

    NASA Astrophysics Data System (ADS)

    Yang, Y.; Min, Y.; Jun, Y.

    2012-12-01

    Dissolution mechanism of aluminosilicates is important for understanding natural and anthropogenic carbon cycles. The total mass of atmospheric CO2 is regulated by the weathering of silicate minerals, and the fate of geologically sequestered CO2 is affected by the interactions between brine, sandstone, caprock, and CO2, which is initiated by mineral dissolution. It has been shown through both experimental and ab initio studies that the dissolution/weathering reactivities of Al and Si in the matrix of an aluminosilicate can be different under many conditions. A subsequent observation is that the release rates of Al and Si, both from the same mineral, may not be stoichiometric when compared to the bulk chemistry of the mineral. For a very long time, the relationship between mineral dissolution incongruency and mineral crystallographic properties remain largely qualitative and descriptive. Here we study the dissolution incongruency of feldspars, the most abundant aluminosilicate on earth. Mineral dissolution experiments for a series of alkali feldspars (albite, anorthoclase, sanidine, and microcline) and plagioclases (oligoclase, andesine, labradorite, bytownite, and anorthite) were conducted at pH 1.68 under ambient conditions. Synchrotron-based X-ray diffraction (HR-XRD), Fourier transform infrared spectroscopy (FTIR), and water chemistry analysis (ICP-MS) are combined to examine the effect of Al/Si ordering on mineral dissolution. Our analysis based on a C1 structure model shows that the incongruency, stemming from the different reactivities of Al-O-Si and Si-O-Si linkages in feldspar's framework, is quantifiable and closely related to the Al/Si ordering state of a feldspar. Our results also suggest that the more random the Al/Si distribution of a mineral, the greater the dissolution incongruency. Our results have significant implications for understanding water-rock interactions. First, when studying the effect of water chemistry on water-rock interaction, smaller

  12. Solar Radiation Management and Olivine Dissolution Methods in Climate Engineering

    NASA Astrophysics Data System (ADS)

    Kone, S.

    2014-12-01

    An overview of solar radiation management and olivine dissolution methods allows to discuss, comparatively, the benefits and consequences of these two geoengineering techniques. The combination of those two techniques allows to concomitantly act on the two main agents intervening in global warming: solar radiation and carbon dioxide. The earth surface temperature increases due mainly to carbon dioxide (a greenhouse gas) that keeps the solar radiation and causes the global warming. Two complementary methods to mitigate climate change are overviewed: SRM method, which uses injected aerosols, aims to reduce the amount of the inbound solar radiation in atmosphere; and olivine dissolution in water, a key chemical reaction envisaged in climate engineering , aiming to reduce the amount of the carbon dioxide in extracting it from atmosphere. The SRM method works on scenarios of solar radiation decrease and the olivine dissolution method works as a carbon dioxide sequestration method. Olivine dissolution in water impacts negatively on the pH of rivers but positively in counteracting ocean acidification and in transporting the silica in ocean, which has benefits for diatom shell formation.

  13. Alunite dissolution rates: Dissolution mechanisms and implications for Mars

    NASA Astrophysics Data System (ADS)

    Miller, J. L.; Elwood Madden, A. S.; Phillips-Lander, C. M.; Pritchett, B. N.; Elwood Madden, M. E.

    2016-01-01

    Alunite (KAl3(SO4)2(OH)6) is a hydrated aluminous sulfate mineral associated with acidic, oxidizing aqueous environments on Earth. Additionally, orbiting spacecraft and rovers on Mars have reported spectral data that indicate a range of mono- and polyhydrated sulfate phases and hydroxysulfate phases, suggesting such conditions also existed on Mars in the past. This study examines alunite dissolution rates in aqueous systems with varying pH, temperature, and solution chemistry conditions. Alunite dissolution rates in dilute solutions are 2-3 orders of magnitude slower than jarosite dissolution rates measured under analogous conditions. Similar to jarosite, alunite dissolution rates vary as a function of activity of H+ and OH- following the rate law log r (mol m-2 s-1) = -0.133(±0.02)pH - 10.65(±0.07) at pH < 5 and log r = 0.194(±0.04)pH - 12.53(±0.26) at pH > 5. However, minimum alunite dissolution rates are shifted to higher pH (5-5.5), likely due to differences in Fe and Al speciation. Alunite and jarosite rates converge in saturated NaCl and CaCl2 brines as the activity of water decreases, suggesting that differences in water exchange rates with Fe3+ and Al3+ control dissolution rates in dilute solutions, while metal-Cl- complexation occurs at similar rates within the brines. Particle lifetimes based on measured dissolution rates in dilute solutions show that alunite particles are expected to be preserved two orders of magnitude longer than jarosite particles over a range of pH and temperature conditions. In particular, alunite is more likely to be preserved in neutral to moderately alkaline systems compared to jarosite, which is expected to be preserved in more acidic conditions. Alunite dissolution produced amorphous Al-rich alteration products at moderate to high pH. Unlike jarosite, alunite dissolution does not show a clear trend as a function of temperature; alunite dissolution rates do not increase with increasing temperature, likely due to lower

  14. Accelerated OH(-) transport in activated carbon air cathode by modification of quaternary ammonium for microbial fuel cells.

    PubMed

    Wang, Xin; Feng, Cuijuan; Ding, Ning; Zhang, Qingrui; Li, Nan; Li, Xiaojing; Zhang, Yueyong; Zhou, Qixing

    2014-04-01

    Activated carbon (AC) is a promising catalyst for the air cathode of microbial fuel cells (MFCs) because of its high performance and low cost. To increase the performance of AC air cathodes, the acceleration of OH(-) transport is one of the most important methods, but it has not been widely investigated. Here we added quaternary ammonium to ACs by in situ anchoring of a quaternary ammonium/epoxide-reacting compound (QAE) or ex situ mixing with anion exchange resins in order to modify ACs from not only the external surface but also inside the pores. In 50 mM phosphate buffer solution (PBS), the in situ anchoring of QAE was a more effective way to increase the power. The highest power density of 2781 ± 36 mW/m(2), which is 10% higher than that of the control, was obtained using QAE-anchored AC cathodes. When the medium was switched to an unbuffered NaCl solution, the increase in maximum power density (885 ± 25 mW/m(2)) was in accordance with the anion exchange capacity (0.219 mmol/g). The highest power density of the anion exchange resin-mixed air cathode was 51% higher than that of the control, indicating that anion exchange is urgently needed in real wastewaters. Excess anchoring of QAE blocked both the mesopores and micropores, causing the power output to be inhibited. PMID:24597673

  15. Statistical comparison of dissolution profiles.

    PubMed

    Wang, Yifan; Snee, Ronald D; Keyvan, Golshid; Muzzio, Fernando J

    2016-05-01

    Statistical methods to assess similarity of dissolution profiles are introduced. Sixteen groups of dissolution profiles from a full factorial design were used to demonstrate implementation details. Variables in the design include drug strength, tablet stability time, and dissolution testing condition. The 16 groups were considered similar when compared using the similarity factor f2 (f2 > 50). However, multivariate ANOVA (MANOVA) repeated measures suggested statistical differences. A modified principal component analysis (PCA) was used to describe the dissolution curves in terms of level and shape. The advantage of the modified PCA approach is that the calculated shape principal components will not be confounded by level effect. Effect size test using omega-squared was also used for dissolution comparisons. Effects indicated by omega-squared are independent of sample size and are a necessary supplement to p value reported from the MANOVA table. Methods to compare multiple groups show that product strength and dissolution testing condition had significant effects on both level and shape. For pairwise analysis, a post-hoc analysis using Tukey's method categorized three similar groups, and was consistent with level-shape analysis. All these methods provide valuable information that is missed using f2 method alone to compare average profiles. The improved statistical analysis approach introduced here enables one to better ascertain both statistical significance and clinical relevance, supporting more objective regulatory decisions. PMID:26294289

  16. Two-phase convective CO2 dissolution in saline aquifers

    DOE PAGESBeta

    Martinez, M. J.; Hesse, M. A.

    2016-01-30

    Geologic carbon storage in deep saline aquifers is a promising technology for reducing anthropogenic emissions into the atmosphere. Dissolution of injected CO2 into resident brines is one of the primary trapping mechanisms generally considered necessary to provide long-term storage security. Given that diffusion of CO2 in brine is woefully slow, convective dissolution, driven by a small increase in brine density with CO2 saturation, is considered to be the primary mechanism of dissolution trapping. Previous studies of convective dissolution have typically only considered the convective process in the single-phase region below the capillary transition zone and have either ignored the overlyingmore » two-phase region where dissolution actually takes place or replaced it with a virtual region with reduced or enhanced constant permeability. Our objective is to improve estimates of the long-term dissolution flux of CO2 into brine by including the capillary transition zone in two-phase model simulations. In the fully two-phase model, there is a capillary transition zone above the brine-saturated region over which the brine saturation decreases with increasing elevation. Our two-phase simulations show that the dissolution flux obtained by assuming a brine-saturated, single-phase porous region with a closed upper boundary is recovered in the limit of vanishing entry pressure and capillary transition zone. For typical finite entry pressures and capillary transition zone, however, convection currents penetrate into the two-phase region. As a result, this removes the mass transfer limitation of the diffusive boundary layer and enhances the convective dissolution flux of CO2 more than 3 times above the rate assuming single-phase conditions.« less

  17. Two-phase convective CO2 dissolution in saline aquifers

    DOE PAGESBeta

    Martinez, Mario J.; Hesse, Marc A.

    2016-01-01

    Geologic carbon storage in deep saline aquifers is a promising technology for reducing anthropogenic emissions into the atmosphere. Dissolution of injected CO2 into resident brines is one of the primary trapping mechanisms generally considered necessary to provide long-term storage security. Given that diffusion of CO2 in brine is woefully slow, convective dissolution, driven by a small increase in brine density with CO2 saturation, is considered to be the primary mechanism of dissolution trapping. Previous studies of convective dissolution have typically only considered the convective process in the single-phase region below the capillary transition zone and have either ignored the overlyingmore » two-phase region where dissolution actually takes place or replaced it with a virtual region with reduced or enhanced constant permeability. Our objective is to improve estimates of the long-term dissolution flux of CO2 into brine by including the capillary transition zone in two-phase model simulations. In the fully two-phase model, there is a capillary transition zone above the brine-saturated region over which the brine saturation decreases with increasing elevation. Our two-phase simulations show that the dissolution flux obtained by assuming a brine-saturated, single-phase porous region with a closed upper boundary is recovered in the limit of vanishing entry pressure and capillary transition zone. For typical finite entry pressures and capillary transition zone, however, convection currents penetrate into the two-phase region. As a result, this removes the mass transfer limitation of the diffusive boundary layer and enhances the convective dissolution flux of CO2 more than 3 times above the rate assuming single-phase conditions.« less

  18. Two-phase convective CO2 dissolution in saline aquifers

    NASA Astrophysics Data System (ADS)

    Martinez, M. J.; Hesse, M. A.

    2016-01-01

    Geologic carbon storage in deep saline aquifers is a promising technology for reducing anthropogenic emissions into the atmosphere. Dissolution of injected CO2 into resident brines is one of the primary trapping mechanisms generally considered necessary to provide long-term storage security. Given that diffusion of CO2 in brine is woefully slow, convective dissolution, driven by a small increase in brine density with CO2 saturation, is considered to be the primary mechanism of dissolution trapping. Previous studies of convective dissolution have typically only considered the convective process in the single-phase region below the capillary transition zone and have either ignored the overlying two-phase region where dissolution actually takes place or replaced it with a virtual region with reduced or enhanced constant permeability. Our objective is to improve estimates of the long-term dissolution flux of CO2 into brine by including the capillary transition zone in two-phase model simulations. In the fully two-phase model, there is a capillary transition zone above the brine-saturated region over which the brine saturation decreases with increasing elevation. Our two-phase simulations show that the dissolution flux obtained by assuming a brine-saturated, single-phase porous region with a closed upper boundary is recovered in the limit of vanishing entry pressure and capillary transition zone. For typical finite entry pressures and capillary transition zone, however, convection currents penetrate into the two-phase region. This removes the mass transfer limitation of the diffusive boundary layer and enhances the convective dissolution flux of CO2 more than 3 times above the rate assuming single-phase conditions.

  19. Systematic review of forsterite dissolution rate data

    NASA Astrophysics Data System (ADS)

    Rimstidt, J. Donald; Brantley, Susan L.; Olsen, Amanda A.

    2012-12-01

    . Comparison of Mg and Si release rates showed that they produced statistically indistinguishable dissolution rates because dissolution was stoichiometric in the experiments over the entire pH range even though the surface concentrations of Mg and Si are known to change with pH. Comparison of rates from experiments with added carbonate, either from CO2 partial pressures greater than atmospheric or added carbonate salts, showed that the existing data set is not sufficient to quantify any effect of dissolved carbonate species on forsterite dissolution rates.

  20. Conversion of batch to molten glass, II: Dissolution of quartz particles

    SciTech Connect

    Hrma, Pavel R.; Marcial, Jose; Swearingen, Kevin J.; Henager, Samuel H.; Schweiger, Michael J.; Tegrotenhuis, Nathan E.

    2011-01-28

    Quartz dissolution during the batch-to-glass conversion influences the melt viscosity and ultimately the temperature at which the glass forms. Batches to make a high-alumina borosilicate glass (formulated for the vitrification of nuclear waste) were heated as 5°C min-1 and quenched from the temperatures of 400-1200°C at 100°C intervals. As a silica source, the batches contained quartz with particles ranging from 5 to 195 µm. The content of unreacted quartz in the samples was determined with x-ray diffraction. Most of fine quartz has dissolved during the early batch reactions (at temperatures <800°C), whereas coarser quartz dissolved mostly in a continuous glass phase via diffusion. The mass-transfer coefficients were assessed from the data as functions of the initial particle sizes and the temperature. A series of batch was also tested that contained nitrated components and additions of sucrose known to accelerate melting. While sucrose addition had no discernible impact on quartz dissolution, nitrate batches melted somewhat more slowly than batches containing carbonates and hydroxides in addition to nitrates.

  1. Two-step accelerated mineral carbonation and decomposition analysis for the reduction of CO₂ emission in the eco-industrial parks.

    PubMed

    Jung, Seok; Wang, Li Pang; Dodbiba, Gjergj; Fujita, Toyohisa

    2014-07-01

    Carbon dioxide (CO₂) emissions are a leading contributor to the negative effects of global warming. Globally, research has focused on effective means of reducing and mitigating CO₂ emissions. In this study, we examined the efficacy of eco-industrial parks (EIPs) and accelerated mineral carbonation techniques in reducing CO₂ emissions in South Korea. First, we used Logarithmic Mean Divisia Index (LMDI) analysis to determine the trends in carbon production and mitigation at the existing EIPs. We found that, although CO₂ was generated as byproducts and wastes of production at these EIPs, improved energy intensity effects occurred at all EIPs, and we strongly believe that EIPs are a strong alternative to traditional industrial complexes for reducing net carbon emissions. We also examined the optimal conditions for using accelerated mineral carbonation to dispose of hazardous fly ash produced through the incineration of municipal solid wastes at these EIPs. We determined that this technique most efficiently sequestered CO₂ when micro-bubbling, low flow rate inlet gas, and ammonia additives were employed. PMID:25079989

  2. MECHANICAL AND CHEMICAL PROPERTIES OF CEMENTITIOUS MATERIALS USING γ-2CaO.SiO2 UNDER THE SEVERAL CONDITIONS IN ACCELERATED CARBONATION CURING

    NASA Astrophysics Data System (ADS)

    Watanabe, Kenzo; Yokozeki, Kosuke; Torichigai, Takeshi; Sakai, Etsuo

    The experiments have been conducted in order to investigate the mechanical and chemical properties of mortar with three different binders under the several conditions in accelerated carbonation curing. As the results, the depth of carbonation varied among each mix proportion. It is proven that by increasing CO2 density in the mortar having γ-2CaO.SiO2, the CaCO3 production will increase, which leads to the increase of filling ability in the pore of mortar. Furthermore, as a result from the calculation of Tritium permeation, it shows that the permeation decreases with an increase of CO2 density.

  3. High rates of carbon storage in old deciduous forests: Emerging mechanisms from the Forest Accelerated Succession ExperimenT (FASET)

    NASA Astrophysics Data System (ADS)

    Gough, C. M.; Nave, L. E.; Hardiman, B. S.; Bohrer, G.; Halperin, A.; Maurer, K.; Le Moine, J.; Nadelhoffer, K.; Vogel, C. S.; Curtis, P.; University Of Michigan Biological Station Forest Ecosystem Study (Umbs-Fest) Team

    2010-12-01

    Deciduous forests of the eastern US are broadly approaching an ecological threshold in which early successional dominant trees are senescing and giving way to later successional species, with unknown consequences for regional carbon (C) cycling. Though recent research demonstrates that forests may accumulate C for centuries, the mechanisms behind sustained rates of C storage in old, particularly deciduous, forests have not been identified. In a regionally representative forest at the University of Michigan Biological Station, we are combining observational and experimental C cycling studies to forecast how forest C storage responds to climate variation, disturbance, and succession. The Forest Accelerated Succession ExperimenT (FASET), in which >6,700 aspen and birch trees (~35 % LAI) were stem girdled within a 39 ha area, is testing the hypothesis that forest production will increase rather than decline with age, due to increases in nitrogen (N) availability, N allocation to the canopy, and the concurrent development of a more biologically and structurally complex canopy. Results thus far support our hypothesis that aging forests in the region may sustain high rates of C storage through shifts in N cycling and increased canopy complexity. Girdling-induced mortality of early successional species reduced soil respiration, accelerated fine root turnover, and prompted the redistribution of N from the foliage of early to later successional species. Nitrogen redistribution increased leaf area index (LAI) production by later successional species, offsetting declines in LAI from senescing early successional species. High rates of net primary production (NPP) were sustained in stands comprising a diverse assemblage of early and later successional species because later successional species, when already present in the canopy, rapidly compensated for declining growth of early successional species. Canopy structural complexity, which increased with forest age, was positively

  4. Small-scale dissolution, precipitation, deformation and fracturing during CO2 sequestration (Invited)

    NASA Astrophysics Data System (ADS)

    Meakin, P.; Austrheim, H.; Huang, H.; Malthe-Sorenssen, A.

    2010-12-01

    The coupling between solute transport, geochemistry and geomechanical processes is critically important in subsurface CO2 sequestration. A better understanding of these processes at small scales could play an important role in the evaluation of large-scale CO2 sequestration reservoir performance and the development of improved CO2 sequestration technology. Insights obtained from the analysis of rock specimens from sites at which natural CO2 sequestration is occurring (the Oman ophiolite, the Solund Basin, Norway and the Snake River Plain), laboratory experiments and computer simulations of dissolution and growth with level set interface capturing and of fracturing due to volume changing solid-solid transformations with discrete element models will be presented. Our results suggest that the coupling between volume changing geochemical processes, deformation and fracturing plays an important role in the weathering of mafic and ultramafic rocks, and that these coupled processes also have an important impact on their CO2 storage capacity. While the growth of solid carbonates and other minerals from supersaturated solutions occludes pore volumes, reducing both permeability and porosity, the disjoining pressure associate with thin liquids films allows growth to continue in mineral filled pores, and the force of crystallization associated with this growth becomes large enough to cause fracturing. Our results suggest that fracturing due to volume increasing, solvent mediated, solid-solid transitions generates new reactive surfaces (surfaces at which dissolution can occur). This accelerates serpentinization and the formation of carbonates in mafic and ultramafic rocks, and increases the extent of reaction (formation of serpentine or carbonates). The characteristic mesh texture associated with serpentinization is attributed to force of crystallization fracturing coupled with growth.

  5. 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

  6. Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

    NASA Astrophysics Data System (ADS)

    Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

    2016-07-01

    Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruent dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). Our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.

  7. Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

    DOE PAGESBeta

    Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

    2016-07-22

    Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruentmore » dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). In conclusion, our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications.« less

  8. Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals

    PubMed Central

    Wang, Yifeng; Jove-Colon, Carlos F.; Kuhlman, Kristopher L.

    2016-01-01

    Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruent dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). Our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications. PMID:27443508

  9. Nonlinear dynamics and instability of aqueous dissolution of silicate glasses and minerals.

    PubMed

    Wang, Yifeng; Jove-Colon, Carlos F; Kuhlman, Kristopher L

    2016-01-01

    Aqueous dissolution of silicate glasses and minerals plays a critical role in global biogeochemical cycles and climate evolution. The reactivity of these materials is also important to numerous engineering applications including nuclear waste disposal. The dissolution process has long been considered to be controlled by a leached surface layer in which cations in the silicate framework are gradually leached out and replaced by protons from the solution. This view has recently been challenged by observations of extremely sharp corrosion fronts and oscillatory zonings in altered rims of the materials, suggesting that corrosion of these materials may proceed directly through congruent dissolution followed by secondary mineral precipitation. Here we show that complex silicate material dissolution behaviors can emerge from a simple positive feedback between dissolution-induced cation release and cation-enhanced dissolution kinetics. This self-accelerating mechanism enables a systematic prediction of the occurrence of sharp dissolution fronts (vs. leached surface layers), oscillatory dissolution behaviors and multiple stages of glass dissolution (in particular the alteration resumption at a late stage of a corrosion process). Our work provides a new perspective for predicting long-term silicate weathering rates in actual geochemical systems and developing durable silicate materials for various engineering applications. PMID:27443508

  10. Interactions between gravity currents and convective dissolution

    NASA Astrophysics Data System (ADS)

    Elenius, M. T.; Voskov, D. V.; Tchelepi, H. A.

    2015-09-01

    Geological storage of carbon dioxide (CO2) is a promising technology for reducing atmospheric emissions. The large discrepancy in the time- and length-scales between up-dip migration of buoyant supercritical CO2 and the sinking fingers of dissolved CO2 poses a challenge for numerical simulations aimed at describing the fate of the plume. Hence, several investigators have suggested methods to simplify the problem, but to date there has been no reference solution with which these simplified models can be compared. We investigate the full problem of Darcy-based two-phase flow with gravity-current propagation and miscible convective mixing, using high-resolution numerical simulations. We build on recent developments of the Automatic Differentiation - General Purpose Research Simulator (AD-GPRS) at Stanford. The results show a CO2 plume that travels for 5000 years reaching a final distance of 14 km up-dip from the injection site. It takes another 2000 years before the CO2 is completely trapped as residual (40%) and dissolved (60%) CO2. Dissolution causes a significant reduction of the plume speed. While fingers of dissolved CO2 appear under the propagating gravity current, the resident brine does not become fully saturated with CO2 anywhere under the plume. The overall mass transfer of CO2 into the brine under the plume remains practically constant for several thousands of years. These results can be used as a benchmark for verification, or improvements, of simplified (reduced-dimensionality, upscaled) models. Our results indicate that simplified models need to account for: (i) reduced dissolution due to interaction with the plume, and (ii) gradual reduction of the local dissolution rate after the fingers begin to interact with the bottom of the aquifer.

  11. Effects of Natural Organic Matter Properties on the Dissolution Kinetics of Zinc Oxide Nanoparticles.

    PubMed

    Jiang, Chuanjia; Aiken, George R; Hsu-Kim, Heileen

    2015-10-01

    The dissolution of zinc oxide (ZnO) nanoparticles (NPs) is a key step of controlling their environmental fate, bioavailability, and toxicity. Rates of dissolution often depend upon factors such as interactions of NPs with natural organic matter (NOM). We examined the effects of 16 different NOM isolates on the dissolution kinetics of ZnO NPs in buffered potassium chloride solution using anodic stripping voltammetry to directly measure dissolved zinc concentrations. The observed dissolution rate constants (kobs) and dissolved zinc concentrations at equilibrium increased linearly with NOM concentration (from 0 to 40 mg C L(-1)) for Suwannee River humic and fulvic acids and Pony Lake fulvic acid. When dissolution rates were compared for the 16 NOM isolates, kobs was positively correlated with certain properties of NOM, including specific ultraviolet absorbance (SUVA), aromatic and carbonyl carbon contents, and molecular weight. Dissolution rate constants were negatively correlated to hydrogen/carbon ratio and aliphatic carbon content. The observed correlations indicate that aromatic carbon content is a key factor in determining the rate of NOM-promoted dissolution of ZnO NPs. The findings of this study facilitate a better understanding of the fate of ZnO NPs in organic-rich aquatic environments and highlight SUVA as a facile and useful indicator of NOM interactions with metal-based nanoparticles. PMID:26355264

  12. Dissolution of amorphous Ti-Zr-Si alloy during anodic oxidation with formation of barrier films

    SciTech Connect

    Isaev, N.I.; Yakovlev, V.B.; Iovdal'skii, A.A.; Gorshkov, T.P.

    1988-07-01

    Radiometric analysis of a solution has been used to study kinetic mechanisms for dissolution of amorphous alloy components in acid aqueous solutions with anodic oxidation in different regimes. In a galvanostatic regime for alloy and crystalline Ti, Zr, and Ta two sections are detected: an initial section of accelerated dissolution and a steady section. An increase in dissolution of zirconium from the alloy has been revealed compared with pure crystalline zirconium. Potentiostatic oxidation is accompanied by a slowdown in dissolution similar to a change in current. Current yield has been analyzed for dissolution of the main elements and nonrectifying impurities of the alloy (for example copper). Gamma spectroscopy using the gamma radiation from neutron-activated isotopes of the components and impurities was performed.

  13. Dissolution of coccolithophorid calcite by microzooplankton and copepod grazing

    NASA Astrophysics Data System (ADS)

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

    2008-01-01

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

  14. Principles of Calcite Dissolution in Human and Artificial Otoconia

    PubMed Central

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

    2014-01-01

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

  15. Brokenhearts: Dissolution of Romantic Relationships.

    ERIC Educational Resources Information Center

    Meeker, F. B.; La Fong, Carl

    Results of an investigation examining the dissolution of romantic relationships are analyzed. Men and women (N=105) who had ended romantic relationships were surveyed in structured individual interviews. Commonalities and differences in respondents' perceptions of the experience were examined. Specific tests were made of a corollary to Waller's…

  16. Formulations for iron oxides dissolution

    DOEpatents

    Horwitz, Earl P.; Chiarizia, Renato

    1992-01-01

    A mixture of a di- or polyphosphonic acid and a reductant wherein each is present in a sufficient amount to provide a synergistic effect with respect to the dissolution of metal oxides and optionally containing corrosion inhibitors and pH adjusting agents.

  17. Optimizing dissolution dynamic nuclear polarization

    NASA Astrophysics Data System (ADS)

    Bornet, Aurélien; Jannin, Sami

    2016-03-01

    This article is a short review of some of our recent developments in dissolution dynamic nuclear polarization (d-DNP). We present the basic principles of d-DNP, and motivate our choice to step away from conventional approaches. We then introduce a modified d-DNP recipe that can be summed up as follows:

  18. Boehmite Actual Waste Dissolutions Studies

    SciTech Connect

    Snow, Lanee A.; Lumetta, Gregg J.; Fiskum, Sandra K.; Peterson, Reid A.

    2008-07-15

    The U.S. Department of Energy plans to vitrify approximately 60,000 metric tons of high-level waste (HLW) sludge from underground storage tanks at the Hanford Nuclear Reservation. To reduce the volume of HLW requiring treatment, a goal has been set to remove a significant quantity of the aluminum, which comprises nearly 70 percent of the sludge. Aluminum is found in the form of gibbsite, sodium aluminate and boehmite. Gibbsite and sodium aluminate can be easily dissolved by washing the waste stream with caustic. Boehmite, which comprises nearly half of the total aluminum, is more resistant to caustic dissolution and requires higher treatment temperatures and hydroxide concentrations. Samples were taken from four Hanford tanks and homogenized in order to give a sample that is representative of REDOX (Reduction Oxidation process for Pu recovery) sludge solids. Bench scale testing was performed on the homogenized waste to study the dissolution of boehmite. Dissolution was studied at three different hydroxide concentrations, with each concentration being run at three different temperatures. Samples were taken periodically over the 170 hour runs in order to determine leaching kinetics. Results of the dissolution studies and implications for the proposed processing of these wastes will be discussed.

  19. Optimizing dissolution dynamic nuclear polarization.

    PubMed

    Bornet, Aurélien; Jannin, Sami

    2016-03-01

    This article is a short review of some of our recent developments in dissolution dynamic nuclear polarization (d-DNP). We present the basic principles of d-DNP, and motivate our choice to step away from conventional approaches. We then introduce a modified d-DNP recipe that can be summed up as follows. PMID:26920826

  20. Forsterite dissolution in saline water at elevated temperature and high CO2 pressure.

    PubMed

    Wang, Fei; Giammar, Daniel E

    2013-01-01

    The rates and mechanisms of magnesium silicate dissolution can control the aqueous chemistry in ways that influence carbonate mineral precipitation during geologic carbon sequestration (GCS). A series of batch experiments was performed with forsterite (Mg(1.81)Fe(0.19)SiO(4)) powder to determine the effects of pressure (10-100 bar CO(2)), temperature (25-100 °C), and salinity (0-50,000 mg/L NaCl) on its dissolution rate at conditions relevant to GCS. Dissolution rates and products were determined by analysis of the aqueous phase, equilibrium and reaction path modeling, and solid phase characterization by scanning electron microscopy and X-ray diffraction. After an initially rapid dissolution period, the dissolution rate declined significantly, an effect that is attributed to the formation of a silica-rich layer at the forsterite surface. The initial dissolution rate increased with increasing temperature and increasing CO(2) pressure; the effect of CO(2) was through its influence on the pH. The dissolution rate was enhanced by NaCl, which may have been due to its inhibition of the formation of a silica-rich surface layer. The experimental results provide information about magnesium silicate dissolution at conditions that will be encountered during GCS that can be used to predict the fate of CO(2) and the evolution of subsurface geochemistry following CO(2) injection. PMID:22650147

  1. Low-z gas stripper as an alternative to carbon foils for the acceleration of high-power uranium beams

    SciTech Connect

    Okuno, H.; Hershcovitch, A.; Fukunishi, N.; Goto, A.; Hasebe, H.; Imao, H.; Kamigaito, O.; Kase, M.; Kuboki, H.; Yano, Y.; Yokouchi, S.

    2011-04-23

    The RIKEN accelerator complex started feeding the next-generation exotic beam facility radioisotope beam factory (RIBF) with heavy-ion beams from 2007 after the successful commissioning of RIBF at the end of 2006. Many improvements made from 2007 to 2010 were instrumental in increasing the intensity of various heavy-ion beams. However, the available beam intensity of very heavy ion beams, especially uranium beams, is far below our goal of 1 p{mu}A (6 x 10{sup 12} particles/s). In order to achieve this goal, upgrade programs are already in progress; the programs include the construction of a new 28-GHz superconducting electron cyclotron resonance ion source and a new injector linac. However, the most serious problem, that of a charge stripper for high-power uranium beams, still remains unsolved, despite extensive research and development work using large foils mounted on a rotating cylinder and a N{sup 2} gas stripper. A gas stripper is free from problems related to lifetime, though the equilibrium charge state in this stripper is considerably lower than that in a carbon foil, owing to the absence of the density effect. Nevertheless, the merits of gas strippers motivated us to develop a low-Z gas stripper to achieve a higher equilibrium charge state even in gases. We measured the electron-loss and electron-capture cross sections of uranium ions in He gas as a function of their charge state at 11, 14, and 15 MeV/nucleon. The equilibrium charge states extracted from the intersection of the lines of the two cross sections were promisingly higher than those in N{sub 2} gas by more than 10. Simple simulations of charge development along the stripper thickness were performed by assuming the measured cross sections. The simulation results show that about 1 mg/cm{sup 2} of He gas should be accumulated to achieve a charge state higher than that of N{sub 2} gas, notwithstanding the difficulty in accumulation of this helium amount owing to its fast dispersion. However, we now

  2. Low-Z gas stripper as an alternative to carbon foils for the acceleration of high-power uranium beams

    NASA Astrophysics Data System (ADS)

    Okuno, H.; Fukunishi, N.; Goto, A.; Hasebe, H.; Imao, H.; Kamigaito, O.; Kase, M.; Kuboki, H.; Yano, Y.; Yokouchi, S.; Hershcovitch, A.

    2011-03-01

    The RIKEN accelerator complex started feeding the next-generation exotic beam facility radioisotope beam factory (RIBF) with heavy-ion beams from 2007 after the successful commissioning of RIBF at the end of 2006. Many improvements made from 2007 to 2010 were instrumental in increasing the intensity of various heavy-ion beams. However, the available beam intensity of very heavy ion beams, especially uranium beams, is far below our goal of 1pμA (6×1012particles/s). In order to achieve this goal, upgrade programs are already in progress; the programs include the construction of a new 28-GHz superconducting electron cyclotron resonance ion source and a new injector linac. However, the most serious problem, that of a charge stripper for high-power uranium beams, still remains unsolved, despite extensive research and development work using large foils mounted on a rotating cylinder and a N2 gas stripper. A gas stripper is free from problems related to lifetime, though the equilibrium charge state in this stripper is considerably lower than that in a carbon foil, owing to the absence of the density effect. Nevertheless, the merits of gas strippers motivated us to develop a low-Z gas stripper to achieve a higher equilibrium charge state even in gases. We measured the electron-loss and electron-capture cross sections of uranium ions in He gas as a function of their charge state at 11, 14, and 15MeV/nucleon. The equilibrium charge states extracted from the intersection of the lines of the two cross sections were promisingly higher than those in N2 gas by more than 10. Simple simulations of charge development along the stripper thickness were performed by assuming the measured cross sections. The simulation results show that about 1mg/cm2 of He gas should be accumulated to achieve a charge state higher than that of N2 gas, notwithstanding the difficulty in accumulation of this helium amount owing to its fast dispersion. However, we now believe that the following two

  3. Extensive dissolution of live pteropods in the Southern Ocean

    NASA Astrophysics Data System (ADS)

    Bednaršek, N.; Tarling, G. A.; Bakker, D. C. E.; Fielding, S.; Jones, E. M.; Venables, H. J.; Ward, P.; Kuzirian, A.; Lézé, B.; Feely, R. A.; Murphy, E. J.

    2012-12-01

    The carbonate chemistry of the surface ocean is rapidly changing with ocean acidification, a result of human activities. In the upper layers of the Southern Ocean, aragonite--a metastable form of calcium carbonate with rapid dissolution kinetics--may become undersaturated by 2050 (ref. ). Aragonite undersaturation is likely to affect aragonite-shelled organisms, which can dominate surface water communities in polar regions. Here we present analyses of specimens of the pteropod Limacina helicina antarctica that were extracted live from the Southern Ocean early in 2008. We sampled from the top 200m of the water column, where aragonite saturation levels were around 1, as upwelled deep water is mixed with surface water containing anthropogenic CO2. Comparing the shell structure with samples from aragonite-supersaturated regions elsewhere under a scanning electron microscope, we found severe levels of shell dissolution in the undersaturated region alone. According to laboratory incubations of intact samples with a range of aragonite saturation levels, eight days of incubation in aragonite saturation levels of 0.94-1.12 produces equivalent levels of dissolution. As deep-water upwelling and CO2 absorption by surface waters is likely to increase as a result of human activities, we conclude that upper ocean regions where aragonite-shelled organisms are affected by dissolution are likely to expand.

  4. A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

    SciTech Connect

    Chen Zhu

    2006-08-31

    Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory measured and field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between laboratory and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO2 injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the second year of the project, we completed CO{sub 2}-Navajo sandstone interaction batch and flow-through experiments and a Navajo sandstone dissolution experiment without the presence of CO{sub 2} at 200 C and 250-300 bars, and initiated dawsonite dissolution and solubility experiments. We also performed additional 5-day experiments at the

  5. A core-top study of dissolution effect on B/Ca in Globigerinoides sacculifer from the tropical Atlantic: Potential bias for paleo-reconstruction of seawater carbonate chemistry

    NASA Astrophysics Data System (ADS)

    Coadic, R.; Bassinot, F.; Dissard, D.; Douville, E.; Greaves, M.; Michel, E.

    2013-04-01

    has been recently shown that B/Ca in planktonic foraminiferal calcite can be used as a proxy for seawater pH. Based on the study of surface sediments (multi-cores) retrieved along a depth transect on the Sierra Leone Rise (Eastern Equatorial Atlantic), we document the decrease of B/Ca and Mg/Ca of Globigerinoides sacculifer shells with increasing water depth and dissolution. This effect of dissolution on B/Ca may potentially represent a severe bias for paleo-pH reconstructions using this species. Samples of G. sacculifer were analyzed independently at two laboratories for B/Ca and Mg/Ca. Both sets of results show a systematic decrease of B/Ca and Mg/Ca along the depth transect, with an overall loss of ~14 µmol/mol (~15%) for B/Ca and of ~0.7 mmol/mol (~21%) for Mg/Ca between the shallowest (2640 m) and the deepest (4950 m) sites. Because of this dissolution effect, surface water pH reconstructed from B/Ca of G. sacculifer decreases by ~0.11 units between the shallowest site and the deepest site, a magnitude similar to the expected glacial/interglacial surface water pH changes.

  6. DISSOLUTION AND CRYSTALLIZATION OF CALCIUM SULFITE PLATELETS

    EPA Science Inventory

    The paper discusses the dissolution and crystallization of calcium sulfite platelets. The rates of calcium sulfite dissolution and crystallization are important in slurry scrubbing processes for flue gas desulfurization. The rates affect the scrubber solution composition, SO2 abs...

  7. DEVELOPMENT OF A CO2 SEQUESTRATION MODULE BY INTEGRATING MINERAL ACTIVATION AND AQUEOUS CARBONATION

    SciTech Connect

    George Alexander; M. Mercedes Maroto-Valer; Parvana Aksoy; Harold Schobert

    2006-03-25

    Mineral carbonation provides a potential option for the long-term storage of carbon dioxide. Serpentine has been chosen as the feedstock mineral, due to its abundance and availability. However, the relatively low reactivity of serpentine has warranted research into physical and chemical treatments that have been shown to greatly increase its reactivity. The use of sulfuric acid as an accelerating medium for the removal of magnesium from serpentine has recently been investigated. In addition to the challenges presented by the dissolution of serpentine, another challenge is the subsequent carbonation of the magnesium ions. A stable hydration sphere for the magnesium ion reduces the carbonation kinetics by obstructing the formation of the carbonation products. Accordingly, this research has evaluated the solubility of carbon dioxide in aqueous solution, the interaction between the dissociation products of carbon dioxide, and the carbonation potential of the magnesium ion.

  8. Effective generation of the spread-out-Bragg peak from the laser accelerated proton beams using a carbon-proton mixed target.

    PubMed

    Yoo, Seung Hoon; Cho, Ilsung; Cho, Sungho; Song, Yongkeun; Jung, Won-Gyun; Kim, Dae-Hyun; Shin, Dongho; Lee, Se Byeong; Pae, Ki-Hong; Park, Sung Yong

    2014-12-01

    Conventional laser accelerated proton beam has broad energy spectra. It is not suitable for clinical use directly, so it is necessary for employing energy selection system. However, in the conventional laser accelerated proton system, the intensity of the proton beams in the low energy regime is higher than that in the high energy regime. Thus, to generate spread-out-Bragg peak (SOBP), stronger weighting value to the higher energy proton beams is needed and weaker weighting value to the lower energy proton beams is needed, which results in the wide range of weighting values. The purpose of this research is to investigate a method for efficient generating of the SOBP with varying magnetic field in the energy selection system using a carbon-proton mixture target. Energy spectrum of the laser accelerated proton beams was acquired using Particle-In-Cell simulations. The Geant4 Monte Carlo simulation toolkit was implemented for energy selection, particle transportation, and dosimetric property measurement. The energy selection collimator hole size of the energy selection system was changed from 1 to 5 mm in order to investigate the effect of hole size on the dosimetric properties for Bragg peak and SOBP. To generate SOBP, magnetic field in the energy selection system was changed during beam irradiation with each beam weighting factor. In this study, our results suggest that carbon-proton mixture target based laser accelerated proton beams can generate quasi-monoenergetic energy distribution and result in the efficient generation of SOBP. A further research is needed to optimize SOBP according to each range and modulated width using an optimized weighting algorithm. PMID:25154880

  9. Dissolution and compaction instabilities in geomaterials

    NASA Astrophysics Data System (ADS)

    Stefanou, I.; Sulem, J.; de Sauvage, J.

    2014-12-01

    Compaction bands play an important role in reservoir engineering and geological storage. Their presence in geological formations may also provide useful information on various geological processes. Several mechanisms can be involved at different scales and may be responsible for compaction band instabilities [1]. Compaction bands can be seen as a particular instability of the governing mathematical system leading to localization of deformation [2-4]. In a saturated porous rock, the progressive mechanical damage of the solid skeleton during compaction, results in the increase of the interface area of the reactants and consequently in the acceleration of the dissolution rate of the solid phase [2,5]. Thus, the solid skeleton is degraded more rapidly (mass removal because of dissolution), the overall mechanical properties of the system diminish (contraction of the elastic domain - chemical softening), deformations increase and the solid skeleton is further damaged (intergranular fractures, debonding, breakage of the porous network etc.). The stability of this positive feedback process is investigated analytically through linear stability analysis by considering the strong chemo-poro-mechanical coupling due to chemical dissolution. The post bifurcation behavior is then studied analytically and numerically revealing the compaction band thickness and periodicity. The effect of various parameters is studied as for instance the influence of the hydraulic diffusivity on the compaction band thickness. [1] P. Baud, S. Vinciguerra, C. David, A. Cavallo, E. Walker and T. Reuschlé (2009), Pure Appl. Geophys., 166(5-7), 869-898 [2] I. Stefanou and J. Sulem (2014), JGR: Solid Earth, 119(2), 880-899. doi:10.1002/2013JB010342I [3] J.W. Rudnicki and J.R. Rice (1975), Journal of the Mechanics and Physics of Solids 23(6),: 371-394 [4] K.A. Issen and J.W. Rudnicki (2000), JGR, 105(B9), 21529. doi:10.1029/2000JB900185 [5] R. Nova, R. Castellanza and C. Tamagnini (2003), International

  10. Contributions to accelerating atmospheric CO2 growth from economic activity, carbon intensity, and efficiency of natural sinks

    SciTech Connect

    Canadella, J.G.; Raupacha, M.R.; Le Quere, C.; Buitenhuis, E.T.; Gillett, N.P.; Field, C.B.; Ciais, P.; Conway, T.J.; Houghton, R.A.; Marland, G.

    2007-11-20

    The growth rate of atmospheric carbon dioxide (CO2), the largest human contributor to human-induced climate change, is increasing rapidly. Three processes contribute to this rapid increase. Two of these processes concern emissions. Recent growth of the world economy combined with an increase in its carbon intensity have led to rapid growth in fossil fuel CO2 emissions since 2000: comparing the 1990s with 2000-2006, the emissions growth rate increased from 1.3% to 3.3%/y. The third process is indicated by increasing evidence (P 0.89) for a long-term (50-year) increase in the airborne fraction (AF) of CO2 emissions, implying a decline in the efficiency of CO2 sinks on land and oceans in absorbing anthropogenic emissions. Since 2000, the contributions of these three factors to the increase in the atmospheric CO2 growth rate have been {approx}65 {+-} 16% from increasing global economic activity, 17 {+-} 6% from the increasing carbon intensity of the global economy, and 18 {+-} 15% from the increase in AF. An increasing AF is consistent with results of climate-carbon cycle models, but the magnitude of the observed signal appears larger than that estimated by models. All of these changes characterize a carbon cycle that is generating stronger-than-expected and sooner-than-expected climate forcing. airborne fraction anthropogenic carbon emissions carbon-climate feedback terrestrial and ocean carbon emissions vulnerabilities of the carbon cycle.

  11. The Use of Artificial Neural Network for Prediction of Dissolution Kinetics

    PubMed Central

    Elçiçek, H.; Akdoğan, E.; Karagöz, S.

    2014-01-01

    Colemanite is a preferred boron mineral in industry, such as boric acid production, fabrication of heat resistant glass, and cleaning agents. Dissolution of the mineral is one of the most important processes for these industries. In this study, dissolution of colemanite was examined in water saturated with carbon dioxide solutions. Also, prediction of dissolution rate was determined using artificial neural networks (ANNs) which are based on the multilayered perceptron. Reaction temperature, total pressure, stirring speed, solid/liquid ratio, particle size, and reaction time were selected as input parameters to predict the dissolution rate. Experimental dataset was used to train multilayer perceptron (MLP) networks to allow for prediction of dissolution kinetics. Developing ANNs has provided highly accurate predictions in comparison with an obtained mathematical model used through regression method. We conclude that ANNs may be a preferred alternative approach instead of conventional statistical methods for prediction of boron minerals. PMID:25028674

  12. The use of artificial neural network for prediction of dissolution kinetics.

    PubMed

    Elçiçek, H; Akdoğan, E; Karagöz, S

    2014-01-01

    Colemanite is a preferred boron mineral in industry, such as boric acid production, fabrication of heat resistant glass, and cleaning agents. Dissolution of the mineral is one of the most important processes for these industries. In this study, dissolution of colemanite was examined in water saturated with carbon dioxide solutions. Also, prediction of dissolution rate was determined using artificial neural networks (ANNs) which are based on the multilayered perceptron. Reaction temperature, total pressure, stirring speed, solid/liquid ratio, particle size, and reaction time were selected as input parameters to predict the dissolution rate. Experimental dataset was used to train multilayer perceptron (MLP) networks to allow for prediction of dissolution kinetics. Developing ANNs has provided highly accurate predictions in comparison with an obtained mathematical model used through regression method. We conclude that ANNs may be a preferred alternative approach instead of conventional statistical methods for prediction of boron minerals. PMID:25028674

  13. A Quantitative Investigation of Cementite Dissolution Kinetics for Continuous Heating of Hypereutectoid Steel

    NASA Astrophysics Data System (ADS)

    Lee, Seok-Jae; Clarke, Kester D.

    2015-09-01

    Cementite dissolution kinetics in austenite was investigated in a hypereutectoid steel alloy during continuous heating. The quantitative change in cementite volume fraction as a function of thermal history was determined from dilation curves by using the martensite start temperature to calculate prior austenite carbon content. Two characteristics of the cementite dissolution kinetics were found: (1) the cementite dissolution rate increased with time regardless of heating rate due to the increased surface area of cementite particles, and (2) the rate of cementite dissolution was strongly affected by heating rate. An empirical equation combining the effects of cementite volume change and heating rate is proposed to describe cementite dissolution kinetics. A continuous heating transformation diagram for hypereutectoid steels was obtained and compared with the DICTRA simulations and metallographic analyses.

  14. Dissolution patterns on caramel blocks

    NASA Astrophysics Data System (ADS)

    Cohen, Caroline; Derr, Julien; Berhanu, Michael; Courrech Du Pont, Sylvain

    2015-11-01

    We investigate erosion by dissolution processes. We perform laboratory experiments on hard caramel bodies, which dissolve on a short timescale, compared to geological material such as limestone. We put a block of caramel, tilted from the horizontal, in a water tank without flow. The dissolution syrup, which is denser than pure water, sinks and the flow detaching from the surface creates patterns underneath the caramel block. These patterns result from the coupled dynamics of the flow detaching and the eroding surface and are reminiscent of scallops observed in the walls of phreatic cave passages. We investigate the mechanisms of formation of these structures and their evolution depending on several parameters such as the fluid density or the flow velocity. We finally parallel the formation of patterns on melting iceberg.

  15. Dissolution Kinetics of Alumina Calcine

    SciTech Connect

    Batcheller, Thomas Aquinas

    2001-09-01

    Dissolution kinetics of alumina type non-radioactive calcine was investigated as part of ongoing research that addresses permanent disposal of Idaho High Level Waste (HLW). Calcine waste was produced from the processing of nuclear fuel at the Idaho Nuclear Technology and Engineering Center (INTEC). Acidic radioactive raffinates were solidified at ~500°C in a fluidized bed reactor to form the dry granular calcine material. Several Waste Management alternatives for the calcine are presented in the Idaho High Level Waste Draft EIS. The Separations Alternative addresses the processing of the calcine so that the HLW is ready for removal to a national geological repository by the year 2035. Calcine dissolution is the key front-end unit operation for the separations alternative.

  16. Development of long-lived thick carbon stripper foils for high energy heavy ion accelerators by a heavy ion beam sputtering method

    NASA Astrophysics Data System (ADS)

    Muto, Hideshi; Ohshiro, Yukimitsu; Kawasaki, Katsunori; Oyaizu, Michihiro; Hattori, Toshiyuki

    2013-04-01

    In the past decade, we have developed extremely long-lived carbon stripper foils of 1-50 μg/cm2 thickness prepared by a heavy ion beam sputtering method. These foils were mainly used for low energy heavy ion beams. Recently, high energy negative Hydrogen and heavy ion accelerators have started to use carbon stripper foils of over 100 μg/cm2 in thickness. However, the heavy ion beam sputtering method was unsuccessful in production of foils thicker than about 50 μg/cm2 because of the collapse of carbon particle build-up from substrates during the sputtering process. The reproduction probability of the foils was less than 25%, and most of them had surface defects. However, these defects were successfully eliminated by introducing higher beam energies of sputtering ions and a substrate heater during the sputtering process. In this report we describe a highly reproducible method for making thick carbon stripper foils by a heavy ion beam sputtering with a Krypton ion beam.

  17. Development of long-lived thick carbon stripper foils for high energy heavy ion accelerators by a heavy ion beam sputtering method

    SciTech Connect

    Muto, Hideshi; Ohshiro, Yukimitsu; Kawasaki, Katsunori; Oyaizu, Michihiro; Hattori, Toshiyuki

    2013-04-19

    In the past decade, we have developed extremely long-lived carbon stripper foils of 1-50 {mu}g/cm{sup 2} thickness prepared by a heavy ion beam sputtering method. These foils were mainly used for low energy heavy ion beams. Recently, high energy negative Hydrogen and heavy ion accelerators have started to use carbon stripper foils of over 100 {mu}g/cm{sup 2} in thickness. However, the heavy ion beam sputtering method was unsuccessful in production of foils thicker than about 50 {mu}g/cm{sup 2} because of the collapse of carbon particle build-up from substrates during the sputtering process. The reproduction probability of the foils was less than 25%, and most of them had surface defects. However, these defects were successfully eliminated by introducing higher beam energies of sputtering ions and a substrate heater during the sputtering process. In this report we describe a highly reproducible method for making thick carbon stripper foils by a heavy ion beam sputtering with a Krypton ion beam.

  18. Carbonate diagenesis and porosity

    SciTech Connect

    Moore, C.H. )

    1989-01-01

    Carbonate diagenesis is a subject of enormous complexity because of the basic chemical reactivity of carbonate minerals. These carbonate minerals react quickly with natural waters that either dissolve the carbonates, or precipitate new carbonates to bring the water into equilibrium with the host carbonate sediments and rocks. These rock-water interactions either create porosity by dissolution, or destroy porosity by the precipitation of carbonate cements into pore spaces. This book examines these relationships in detail.

  19. CO2 sequestration using accelerated gas-solid carbonation of pre-treated EAF steel-making bag house dust.

    PubMed

    El-Naas, Muftah H; El Gamal, Maisa; Hameedi, Suhaib; Mohamed, Abdel-Mohsen O

    2015-06-01

    Mineral CO2 sequestration is a promising process for the reduction of carbon dioxide emissions to the atmosphere. In this paper, alkaline calcium-rich dust particles collected from bag filters of electric arc furnaces (EAF) for steel making were utilized as a viable raw material for mineral CO2 sequestration. The dust particles were pre-treated through hydration, drying and screening. The pre-treated particles were then subjected to direct gas-solid carbonation reaction in a fluidized-bed reactor. The carbonated products were characterized to determine the overall sequestration capacity and the mineralogical structures. Leaching tests were also performed to measure the extracted minerals from the carbonated dust and evaluate the carbonation process on dust stabilization. The experimental results indicated that CO2 could be sequestered using the pre-treated bag house dust. The maximum sequestration of CO2 was 0.657 kg/kg of dust, based on the total calcium content. The highest degree of carbonation achieved was 42.5% and the carbonation efficiency was 69% at room temperature. PMID:25846002

  20. Dissolution and reduction of magnetite by bacteria

    NASA Technical Reports Server (NTRS)

    Kostka, J. E.; Nealson, K. H.

    1995-01-01

    Magnetite (Fe3O4) is an iron oxide of mixed oxidation state [Fe(II), Fe(III)] that contributes largely to geomagnetism and plays a significant role in diagenesis in marine and freshwater sediments. Magnetic data are the primary evidence for ocean floor spreading and accurate interpretation of the sedimentary magnetic record depends on an understanding of the conditions under which magnetite is stable. Though chemical reduction of magnetite by dissolved sulfide is well known, biological reduction has not been considered likely based upon thermodynamic considerations. This study shows that marine and freshwater strains of the bacterium Shewanella putrefaciens are capable of the rapid dissolution and reduction of magnetite, converting millimolar amounts to soluble Fe(II)in a few days at room temperature. Conditions under which magnetite reduction is optimal (pH 5-6, 22-37 degrees C) are consistent with an enzymatic process and not with simple chemical reduction. Magnetite reduction requires viable cells and cell contact, and it appears to be coupled to electron transport and growth. In a minimal medium with formate or lactate as the electron donor, more than 10 times the amount of magnetite was reduced over no carbon controls. These data suggest that magnetite reduction is coupled to carbon metabolism in S. putrefaciens. Bacterial reduction rates of magnetite are of the same order of magnitude as those estimated for reduction by sulfide. If such remobilization of magnetite occurs in nature, it could have a major impact on sediment magnetism and diagenesis.

  1. Dissolution and reduction of magnetite by bacteria.

    PubMed

    Kostka, J E; Nealson, K H

    1995-10-01

    Magnetite (Fe3O4) is an iron oxide of mixed oxidation state [Fe(II), Fe(III)] that contributes largely to geomagnetism and plays a significant role in diagenesis in marine and freshwater sediments. Magnetic data are the primary evidence for ocean floor spreading and accurate interpretation of the sedimentary magnetic record depends on an understanding of the conditions under which magnetite is stable. Though chemical reduction of magnetite by dissolved sulfide is well known, biological reduction has not been considered likely based upon thermodynamic considerations. This study shows that marine and freshwater strains of the bacterium Shewanella putrefaciens are capable of the rapid dissolution and reduction of magnetite, converting millimolar amounts to soluble Fe(II)in a few days at room temperature. Conditions under which magnetite reduction is optimal (pH 5-6, 22-37 degrees C) are consistent with an enzymatic process and not with simple chemical reduction. Magnetite reduction requires viable cells and cell contact, and it appears to be coupled to electron transport and growth. In a minimal medium with formate or lactate as the electron donor, more than 10 times the amount of magnetite was reduced over no carbon controls. These data suggest that magnetite reduction is coupled to carbon metabolism in S. putrefaciens. Bacterial reduction rates of magnetite are of the same order of magnitude as those estimated for reduction by sulfide. If such remobilization of magnetite occurs in nature, it could have a major impact on sediment magnetism and diagenesis. PMID:11539843

  2. Carbon Flux in Drylands: The Forgotten Dimensions?

    NASA Astrophysics Data System (ADS)

    Wainwright, J.; Turnbull, L.

    2014-12-01

    There has been a significant emphasis recently on the rôle of vegetation change and land degradation in drylands on carbon sequestration and the provision of related ecosystem services. Studies have typically focussed on the storage of carbon in biomass over short timescales. Over intermediate timescales, an important component of carbon-related ecohydrological processes is the way in which carbon is transferred from biomass to soil organic matter. These transfers are also significantly affected by land degradation via erosion processes which result in redistribution and net loss of carbon from the local system. Many drylands are underlain by significant stores of inorganic carbon, some of which is deposited from aeolian material, but vertical transfer from the surface stores is also an important process. Numerous studies suggest that these stores are in place from thousands to millions of years and thus contain carbon that has long been taken out of the global cycle. As progressive land degradation occurs, these stores are increasingly being exposed at the surface, and thus reactivated as part of the global cycle. In the context of climate change where increasingly stormy conditions are likely to accelerate the mobilization of sediment and associated carbon, and where increasingly acidic rainfall exacerbates dissolution of inorganic carbon, there is the potential for a significant addition to atmospheric carbon at regional and global scales. We will evaluate the relative importance of this mechanism compared to sequestration in vegetation and discuss the implications for maximizing ecosystem-service provision in drylands.

  3. Dissolution of nickel ferrite in aqueous solutions containing oxalic acid and ferrous salts

    SciTech Connect

    Figueroa, C.A.; Sileo, E.E.; Morando, P.J.; Blesa, M.A.

    2000-05-15

    The dissolution of nickel ferrite in oxalic acid and in ferrous oxalate-oxalic acid aqueous solution was studied. Nickel ferrite was synthesized by thermal decomposition of a mixed tartrate; the particles were shown to be coated with a thin ferric oxide layer. Dissolution takes place in two stages, the first one corresponding to the dissolution of the ferric oxide outer layer and the second one being the dissolution of Ni{sub 1.06}Fe{sub 1.96}O{sub 4}. The kinetics of dissolution during this first stage is typical of ferric oxides: in oxalic acid, both a ligand-assisted and a redox mechanism operates, whereas in the presence of ferrous ions, redox catalysis leads to a faster dissolution. The rate dependence on both oxalic acid and on ferrous ion is described by the Langmuir-Hinshelwood equation. In the second stage, Langmuir-Hinshelwood kinetics also describes the dissolution of iron and nickel from nickel ferrite. It may be concluded that oxalic acid operates to dissolve iron, and the ensuing disruption of the solid framework accelerates the release of nickel.

  4. DISSOLUTION OF NEPTUNIUM OXIDE RESIDUES

    SciTech Connect

    Kyser, E

    2009-01-12

    This report describes the development of a dissolution flowsheet for neptunium (Np) oxide (NpO{sub 2}) residues (i.e., various NpO{sub 2} sources, HB-Line glovebox sweepings, and Savannah River National Laboratory (SRNL) thermogravimetric analysis samples). Samples of each type of materials proposed for processing were dissolved in a closed laboratory apparatus and the rate and total quantity of off-gas were measured. Samples of the off-gas were also analyzed. The quantity and type of solids remaining (when visible) were determined after post-dissolution filtration of the solution. Recommended conditions for dissolution of the NpO{sub 2} residues are: Solution Matrix and Loading: {approx}50 g Np/L (750 g Np in 15 L of dissolver solution), using 8 M nitric acid (HNO{sub 3}), 0.025 M potassium fluoride (KF) at greater than 100 C for at least 3 hours. Off-gas: Analysis of the off-gas indicated nitric oxide (NO), nitrogen dioxide (NO{sub 2}) and nitrous oxide (N{sub 2}O) as the only identified components. No hydrogen (H{sub 2}) was detected. The molar ratio of off-gas produced per mole of Np dissolved ranged from 0.25 to 0.4 moles of gas per mole of Np dissolved. A peak off-gas rate of {approx}0.1 scfm/kg bulk oxide was observed. Residual Solids: Pure NpO{sub 2} dissolved with little or no residue with the proposed flowsheet but the NpCo and both sweepings samples left visible solid residue after dissolution. For the NpCo and Part II Sweepings samples the residue amounted to {approx}1% of the initial material, but for the Part I Sweepings sample, the residue amounted to {approx}8 % of the initial material. These residues contained primarily aluminum (Al) and silicon (Si) compounds that did not completely dissolve under the flowsheet conditions. The residues from both sweepings samples contained minor amounts of plutonium (Pu) particles. Overall, the undissolved Np and Pu particles in the residues were a very small fraction of the total solids.

  5. Physicochemical Hydrodynamics of NAPL Dissolution

    NASA Astrophysics Data System (ADS)

    Doss, S. K.; Ezzedine, S.; Ziagos, J. P.; Hoffman, F.; Gelinas, R. J.

    2001-05-01

    Determining the continually changing interface between the non-aqueous phase liquid (NAPL) and aqueous phase liquid (APL) phases, and the physical and chemical processes by which mass is transferred across the interface is critical to the understanding of NAPL dissolution. Most researchers, however, address only the flux of mass from NAPL into the aqueous phase and the subsequent migration of the dissolved contaminants; little effort has been made to track the NAPL/APL interface. While it is crucial to have an accurate account of mass flux from NAPL to APL in order to design successful remediation strategies, the absence of rigor in tracking the NAPL/APL boundary interface makes such mass flux estimates less reliable. Our studies account for the moving NAPL/APL boundary interface. We introduce a new approach in developing non-linearly coupled flow and transport equations in order to include specific description of chemical dissolution processes.The governing NAPL/APL evolution equations were formulated along principles similar to the Stefan Problem of moving interfaces. Essentially, the diffusion coefficient is allowed to vary in unison with the concentration but with a near discontinuity at the threshold of the NAPL solubility limit. Below the solubility limit, the diffusion takes on its customary value throughout the aqueous phase. Meanwhile, very small values are assigned to the diffusion coefficient within the non-aqueous phase. Along the NAPL/APL interface, the diffusion coefficient is given some transition shape function, which is ultimately determined by calibration to laboratory experiments. In addition to accounting for the continuous erosion of NAPL/APL interface due to the dissolution, blobs of NAPL are allowed to diffuse and move, rather freely, under the influence of prevailing physical forces. Our numerical simulations were obtained using Adaptive Grid, Galerkin Finite Elements technique to solve the coupled flow and transport equations simultaneously

  6. Optimizing dissolution dynamic nuclear polarization

    NASA Astrophysics Data System (ADS)

    Bornet, Aurélien; Jannin, Sami

    2016-03-01

    This article is a short review of some of our recent developments in dissolution dynamic nuclear polarization (d-DNP). We present the basic principles of d-DNP, and motivate our choice to step away from conventional approaches. We then introduce a modified d-DNP recipe that can be summed up as follows: Using broad line polarizing agents to efficiently polarize 1H spins. Increasing the magnetic field to 6.7 T and above. Applying microwave frequency modulation. Applying 1H-13C cross polarization. Transferring hyperpolarized solution through a magnetic tunnel.

  7. Effect of Hot Coiling Under Accelerated Cooling on Development of Non-equiaxed Ferrite in Low Carbon Steel

    NASA Astrophysics Data System (ADS)

    Lanjewar, H. A.; Tripathi, Pranavkumar

    2016-06-01

    Strengthening mechanisms dominant in non-equiaxed ferrite structures are not so familiar and well measured. In present study, non-equiaxed ferritic structures were generated and perceived to be strengthened by grain/crystal refinement, presence of varying substructures, solid solution strengthening, and textural hardening. A Nb-V microalloyed steel was modeled under various accelerated cooling and coiling temperature conditions in a thermo-mechanical simulator. Decrease in coiling temperature in conjunction with accelerated cooling resulted in non-equiaxed ferrite structures with array of phase morphologies. Intermediate transformation conditions produced increase in strength concurrent with observed smallness in crystallite size and high amount of microstrain in the matrix phase indicative of high dislocation densities and crystal imperfections. Increase in strength is partially attributed to solid solution and texture hardening owing to increase in (111) pole intensity in structure.

  8. Effect of Hot Coiling Under Accelerated Cooling on Development of Non-equiaxed Ferrite in Low Carbon Steel

    NASA Astrophysics Data System (ADS)

    Lanjewar, H. A.; Tripathi, Pranavkumar

    2016-04-01

    Strengthening mechanisms dominant in non-equiaxed ferrite structures are not so familiar and well measured. In present study, non-equiaxed ferritic structures were generated and perceived to be strengthened by grain/crystal refinement, presence of varying substructures, solid solution strengthening, and textural hardening. A Nb-V microalloyed steel was modeled under various accelerated cooling and coiling temperature conditions in a thermo-mechanical simulator. Decrease in coiling temperature in conjunction with accelerated cooling resulted in non-equiaxed ferrite structures with array of phase morphologies. Intermediate transformation conditions produced increase in strength concurrent with observed smallness in crystallite size and high amount of microstrain in the matrix phase indicative of high dislocation densities and crystal imperfections. Increase in strength is partially attributed to solid solution and texture hardening owing to increase in (111) pole intensity in structure.

  9. Synthesis of Ultradisperse Carbon Dioxide Powder with Plasma-Dynamic Method in the Coaxial Magneto-Plasma Accelerator

    NASA Astrophysics Data System (ADS)

    Golyanskaya, Evgeniya. O.; Sivkov, Aleksandr A.; Anikina, Zhanna S.

    2016-02-01

    One of the most promising trends in modern physics is the high-temperature superconductivity. Analysis of high-temperature superconductors revealed that almost all of them are complex copper-based oxides. Studies have shown the possibility of using them for the synthesis of coaxial magneto accelerator. Studies have identified the products synthesized soot: Cu, Cu2O, CuO, their shape and size. Also been deciphered and electron microscopy confirmed the composition of the nanopowder obtained in laboratory conditions.

  10. Linear Accelerators

    NASA Astrophysics Data System (ADS)

    Sidorin, Anatoly

    2010-01-01

    In linear accelerators the particles are accelerated by either electrostatic fields or oscillating Radio Frequency (RF) fields. Accordingly the linear accelerators are divided in three large groups: electrostatic, induction and RF accelerators. Overview of the different types of accelerators is given. Stability of longitudinal and transverse motion in the RF linear accelerators is briefly discussed. The methods of beam focusing in linacs are described.

  11. Linear Accelerators

    SciTech Connect

    Sidorin, Anatoly

    2010-01-05

    In linear accelerators the particles are accelerated by either electrostatic fields or oscillating Radio Frequency (RF) fields. Accordingly the linear accelerators are divided in three large groups: electrostatic, induction and RF accelerators. Overview of the different types of accelerators is given. Stability of longitudinal and transverse motion in the RF linear accelerators is briefly discussed. The methods of beam focusing in linacs are described.

  12. Dissolution Rate Enhancement of Clarithromycin Using Ternary Ground Mixtures: Nanocrystal Formation

    PubMed Central

    Shahbaziniaz, Malihe; Foroutan, Seyed Mohsen; Bolourchian, Noushin

    2013-01-01

    Clarithromycin (CLA), a broad-spectrum macrolide, is a poorly soluble drug with dissolution rate limited absorption. The aim of this investigation was to prepare CLA nanoparticles from a ternary ground mixture in the presence of sodium lauryl sulfate (SLS) and polyvinyl pyrrolidone (PVP) as co-grinding water-soluble compounds, in order to improve the drug dissolution rate. Different weight ratios of CLA: SLS: PVP were ground in a dry process by planetary ball mill using different grinding ball size. Following the dissolution rate study, physical properties of the best dissolved co-ground formulation was studied. The accelerated stability studies were also conducted on the co-ground formulation. The results revealed that the dissolution rate of ternary ground mixtures was much higher than that of the intact drug (p < 0.001). Decreasing the grinding ball size and weight with the same rotation speed resulted in particles with decreased dissolution. On the other hand, increasing the PVP concentration in the formulations reduced the drug dissolution. Dissolution efficiencies (DE10 and DE30) for the best dissolved formulation, which consisted of the equal ratio of each co-ground component, were 8.7 and 5 folds higher than the untreated CLA, respectively. This formulation formed nanocrystals with enhanced solubility after dispersing in water. X-ray diffraction, differential scanning calorimetry and infrared spectrophotometry confirmed no chemical interaction and phase transition during the process. Accelerated stability studies confirmed that the co-ground mixture almost remained unchanged in terms of dissolution rate, drug assay and particle size after exposing in stability conditions for three months. PMID:24523739

  13. Dissolution rate enhancement of clarithromycin using ternary ground mixtures: nanocrystal formation.

    PubMed

    Shahbaziniaz, Malihe; Foroutan, Seyed Mohsen; Bolourchian, Noushin

    2013-01-01

    Clarithromycin (CLA), a broad-spectrum macrolide, is a poorly soluble drug with dissolution rate limited absorption. The aim of this investigation was to prepare CLA nanoparticles from a ternary ground mixture in the presence of sodium lauryl sulfate (SLS) and polyvinyl pyrrolidone (PVP) as co-grinding water-soluble compounds, in order to improve the drug dissolution rate. Different weight ratios of CLA: SLS: PVP were ground in a dry process by planetary ball mill using different grinding ball size. Following the dissolution rate study, physical properties of the best dissolved co-ground formulation was studied. The accelerated stability studies were also conducted on the co-ground formulation. The results revealed that the dissolution rate of ternary ground mixtures was much higher than that of the intact drug (p < 0.001). Decreasing the grinding ball size and weight with the same rotation speed resulted in particles with decreased dissolution. On the other hand, increasing the PVP concentration in the formulations reduced the drug dissolution. Dissolution efficiencies (DE10 and DE30) for the best dissolved formulation, which consisted of the equal ratio of each co-ground component, were 8.7 and 5 folds higher than the untreated CLA, respectively. This formulation formed nanocrystals with enhanced solubility after dispersing in water. X-ray diffraction, differential scanning calorimetry and infrared spectrophotometry confirmed no chemical interaction and phase transition during the process. Accelerated stability studies confirmed that the co-ground mixture almost remained unchanged in terms of dissolution rate, drug assay and particle size after exposing in stability conditions for three months. PMID:24523739

  14. Development of a CO2 Sequestration Module by Integrating Mineral Activation and Aqueous Carbonation

    SciTech Connect

    George Alexander; Parvana Aksoy; John Andresen; Mercedes Maroto-Valer; Harold Schobert

    2006-08-14

    Mineral carbonation is a promising concept for permanent CO{sub 2} sequestration due to the vast natural abundance of the raw materials and the permanent storage of CO{sub 2} in solid form as carbonates. The sequestration of CO{sub 2} through the employment of magnesium silicates--olivine and serpentine--is beyond the proof of concept stage. For the work done in this project, serpentine was chosen as the feedstock mineral due to its abundance and availability. Although the reactivity of olivine is greater than that of serpentine, physical and chemical treatments have been shown to increase greatly the reactivity of serpentine. The primary drawback to mineral carbonation is reaction kinetics. To accelerate the carbonation, aqueous processes are preferred, where the minerals are first dissolved in solution. In aqueous carbonation, the key step is the dissolution rate of the mineral, where the mineral dissolution reaction is likely to be surface-controlled. The relatively low reactivity of serpentine has warranted research into physical and chemical treatments that have been shown to greatly increase its reactivity. The use of sulfuric acid as an accelerating medium for the removal of magnesium from serpentine has been investigated. To accelerate the dissolution process, the mineral can be ground to very fine particle size, <37 {micro}m, but this is a very energy-intensive process. Previous work in our laboratory showed that chemical surface activation helps to dissolve magnesium from the serpentine (of particle size {approx} 100 {micro}m) and that the carbonation reaction can be conducted under mild conditions (20 C and 4.6 MPa) compared to previous studies that required >185 C, >13 MPa, and <37 {micro}m particle size. This work also showed that over 70% of the magnesium can be extracted at ambient temperature, leaving an amorphous silica with surface area of about 330 m{sup 2}/g. The overall objective of this research program is to optimize the active carbonation

  15. An effective method of UV-oxidation of dissolved organic carbon in natural waters for radiocarbon analysis by accelerator mass spectrometry

    NASA Astrophysics Data System (ADS)

    Xue, Yuejun; Ge, Tiantian; Wang, Xuchen

    2015-12-01

    Radiocarbon (14C) measurement of dissolved organic carbon (DOC) is a very powerful tool to study the sources, transformation and cycling of carbon in the ocean. The technique, however, remains great challenges for complete and successful oxidation of sufficient DOC with low blanks for high precision carbon isotopic ratio analysis, largely due to the overwhelming proportion of salts and low DOC concentrations in the ocean. In this paper, we report an effective UV-Oxidation method for oxidizing DOC in natural waters for radiocarbon analysis by accelerator mass spectrometry (AMS). The UV-oxidation system and method show 95%±4% oxidation efficiency and high reproducibility for DOC in both river and seawater samples. The blanks associated with the method was also low (about 3 µg C) that is critical for 14C analysis. As a great advantage of the method, multiple water samples can be oxidized at the same time so it reduces the sample processing time substantially compared with other UV-oxidation method currently being used in other laboratories. We have used the system and method for 14C studies of DOC in rivers, estuaries, and oceanic environments and have received promise results.

  16. Plutonium dioxide dissolution in glass

    SciTech Connect

    Vienna, J.D.; Alexander, D.L.; Li, Hong

    1996-09-01

    In the aftermath of the Cold War, the U.S. Department of Energy`s (DOE) Office of Fissile Materials Disposition (OFMD) is charged with providing technical support for evaluation of disposition options for excess fissile materials manufactured for the nation`s defense. One option being considered for the disposition of excess plutonium (Pu) is immobilization by vitrification. The vitrification option entails immobilizing Pu in a host glass and waste package that are criticality-safe (immune to nuclear criticality), proliferation-resistant, and environmentally acceptable for long-term storage or disposal. To prove the technical and economic feasibility of candidate vitrification options it is necessary to demonstrate that PuO{sub 2} feedstock can be dissolved in glass in sufficient quantity. The OFMD immobilization program has set a Pu solubility goal of 10 wt% in glass. The life cycle cost of the vitrification options are strongly influenced by the rate at which PUO{sub 2} dissolves in glass. The total number of process lines needed for vitrification of 50 t of Pu in 10 years is directly dependent upon the time required for Pu dissolution in glass. The objective of this joint Pacific Northwest National Laboratory (PNNL) - Savannah River Technology Center (SRTC) study was to demonstrate a high Pu solubility in glass and to identify on a rough scale the time required for Pu dissolution in the glass. This study was conducted using a lanthanide borosilicate (LaBS) glass composition designed at the SRTC for the vitrification of actinides.

  17. Dissolution studies of hydroxyapatite and glass-reinforced hydroxyapatite ceramics

    SciTech Connect

    Queiroz, A.C.; Santos, J.D.; Monteiro, F.J.; Prado da Silva, M.H

    2003-03-15

    In the continuous agitation assays, glass-reinforced hydroxyapatite (GR-HA) was shown to form a calcium phosphate (CaP) layer, but hydroxyapatite (HA) only formed dispersed precipitates. The formation of this layer was first detected on the GR-HA with a 7.5% glass addition (7.5 GR-HA) after only 3 days of immersion in simulated body fluid (SBF). The time required for layer formation decreased as the amount of glass added to the HA increased. The dissolution rate of the materials followed a similar pattern, i.e. the dissolution rate for GR-HA was higher than for HA, and increased with the addition of glass. The immersion of 7.5 GR-HA in water showed almost linear dissolution kinetics over the immersion periods (3, 7, 15, 30 and 60 days). The concentration of calcium ions in solution and the scanning electron microscopy (SEM) analysis of the 7.5 GR-HA specimens immersed in water and in SBF revealed a clear competition between the material dissolution and the precipitation of a CaP phase. Fourier transformed infrared spectroscopy with alternated total reflectance (FTIR-ATR) analysis indicated that the CaP phase that formed during longer immersion times (30 and 60 days) could be a carbonate-substituted CaP precipitate. As expected from previous work, the GR-HA behavior in terms of its in vitro bioactivity is higher than HA because a homogeneous CaP layer is formed and the precipitation occurs faster. From the dissolution test and in accordance with the chemical composition of the samples, GR-HA was more soluble than HA.

  18. Influence of Carbide Precipitation and Dissolution on the Microstructure of Ultra-Fine-Grained Intercritically Annealed Medium Manganese Steel

    NASA Astrophysics Data System (ADS)

    Lee, Sangwon; De Cooman, Bruno C.

    2016-04-01

    The influence of cementite precipitation and dissolution on the formation of the carbide-free, ultra-fine-grained, ferrite + austenite microstructure of medium manganese steel was analyzed. During heating to the intercritical temperature, cementite nucleates at low-angle lath martensite boundaries, austenite subsequently nucleates at ferrite/cementite boundaries, and the cementite is gradually replaced by the growing austenite grains. The intercritical austenite carbon is therefore due to cementite dissolution, rather than carbon partitioning between ferrite and austenite.

  19. Influence of Carbide Precipitation and Dissolution on the Microstructure of Ultra-Fine-Grained Intercritically Annealed Medium Manganese Steel

    NASA Astrophysics Data System (ADS)

    Lee, Sangwon; De Cooman, Bruno C.

    2016-07-01

    The influence of cementite precipitation and dissolution on the formation of the carbide-free, ultra-fine-grained, ferrite + austenite microstructure of medium manganese steel was analyzed. During heating to the intercritical temperature, cementite nucleates at low-angle lath martensite boundaries, austenite subsequently nucleates at ferrite/cementite boundaries, and the cementite is gradually replaced by the growing austenite grains. The intercritical austenite carbon is therefore due to cementite dissolution, rather than carbon partitioning between ferrite and austenite.

  20. Comparison and modeling of aqueous dissolution rates of various uranium oxides

    SciTech Connect

    Steward, S.A.

    1996-11-01

    Purpose of this work was to measure and model the intrinsic dissolution rates of U oxides under a variety of well-controlled conditions that are relevant to a geologic repository. When exposed to air at elevated temperature, spent fuel may form the stable phase U{sub 3}O{sub 8}. Dehydrated schoepite, UO{sub 3}{center_dot}H{sub 2}O, exists in drip tests on spent fuel. Equivalent sets of U{sub 3}O{sub 8} and UO{sub 3}{center_dot}H{sub 2}O dissolution experiments allowed a systematic examination of the effects of temperature (25-75 C), pH(8-10), and carbonate (2-200x10{sup -4}molar) concentrations at atmospheric oxygen conditions. Results indicate that UO{sub 3}{center_dot}H{sub 2}O has a much higher dissolution rate (at least tenfold) than U{sub 3}O{sub 8} under the same conditions. The intrinsic dissolution rate of unirradiated U{sub 3}O{sub 8} is about twice that of UO{sub 2}. Dissolution of both U{sub 3}O{sub 8} and UO{sub 3}{center_dot}H{sub 2}O shows a very high sensitivity to carbonate concentration. Present results show a 25 to 50-fold increase in room-temperature UO{sub 3}{center_dot}H{sub 2}O dissolution rates between the highest and lowest carbonate concentrations. As with the UO{sub 2} dissolution data, the classical observed chemical kinetic rate law was used to model the U{sub 3}O{sub 8} dissolution rate data. The pH did not have much effect on the models, in agreement with earlier analysis of the UO{sub 2} and spent fuel dissolution data. However, carbonate concentration, not temperature, had the strongest effect on the U{sub 3}O{sub 8} dissolution rate. The U{sub 3}O{sub 8} dissolution activation energy was about 6000 cal/mol, compared with 7300 and 8000 cal/mol for spent fuel and UO{sub 2}, respectively.

  1. CO2 dissolution in water using long serpentine microchannels

    PubMed Central

    Cubaud, Thomas; Sauzade, Martin; Sun, Ruopeng

    2012-01-01

    The evolution of carbon dioxide bubbles dissolving in water is experimentally examined using long microchannels. We study the coupling between bubble hydrodynamics and dissolution in confined geometries. The gas impregnation process in liquid produces significant flow rearrangements. Depending on the initial volumetric liquid fraction, three operating regimes are identified, namely saturating, coalescing, and dissolving. The morphological and dynamical transition from segmented to dilute bubbly flows is investigated. Tracking individual bubbles along the flow direction is used to calculate the temporal evolution of the liquid volumetric fraction and the average flow velocity near reference bubbles over long distances. This method allows us to empirically establish the functional relationship between bubble size and velocity. Finally, we examine the implication of this relationship during the coalescing flow regime, which limits the efficiency of the dissolution process. PMID:22655006

  2. Dissolution of metal and metal oxide nanoparticles in aqueous media.

    PubMed

    Odzak, Niksa; Kistler, David; Behra, Renata; Sigg, Laura

    2014-08-01

    The dissolution of Ag (citrate, gelatin, polyvinylpyrrolidone and chitosan coated), ZnO, CuO and carbon coated Cu nanoparticles (with two nominal sizes each) has been studied in artificial aqueous media, similar in chemistry to environmental waters, for up to 19 days. The dissolved fraction was determined using DGT (Diffusion Gradients in Thin films), dialysis membrane (DM) and ultrafiltration (UF). Relatively small fractions of Ag nanoparticles dissolved, whereas ZnO dissolved nearly completely within few hours. Cu and CuO dissolved as a function of pH. Using DGT, less dissolved Ag was measured compared to UF and DM, likely due to differences in diffusion of organic complexes. Similar dissolved metal concentrations of ZnO, Cu and CuO nanoparticles were determined using DGT and UF, but lower using DM. The results indicate that there is a need to apply complementary techniques to precisely determine dissolution of nanoparticles in aqueous media. PMID:24832924

  3. Instabilities in geomaterials induced by dissolution

    NASA Astrophysics Data System (ADS)

    Stefanou, I.; Sulem, J.

    2015-12-01

    Deformation bands play an important role in reservoir engineering, geological storage, underwater landslides and slow geological procedures. Various mechanisms can be involved at different scales and may be responsible for deformation bands. Mechanical and chemical degradation of the grain skeleton is a softening factor that can lead to compaction, shear or even dilation band formation [1]-[3]. The present study is twofold. On one hand it focuses on the mathematical modeling of chemically induced strain localization instabilities in porous rocks and on the other hand it explores the conditions for their creation [4], [5]. In a saturated porous rock, the progressive mechanical damage of the solid skeleton during deformation, results in the increase of the interface area of the reactants and consequently in the acceleration of the dissolution rate of the solid phase [6]. Under the presence of dissolving fluids the solid skeleton is degraded more rapidly (mass removal because of dissolution), the overall mechanical properties of the system diminish (contraction of the elastic domain - chemical softening), deformations increase and the solid skeleton is further damaged (intergranular fractures, debonding, breakage of the porous network etc.). Based on a micromechanical model, the conditions for deformation band triggering are investigated analytically. The heterogeneity of the microstructure in terms of chemical reactivity of the constituents of the REV is taken into account resulting in a characteristic internal length of the system. The post bifurcation behavior is finally studied both analytically and numerically revealing the thickness of the localized zone. References[1] I. Stefanou and J. Sulem, DOI: 10.1002/2013JB010342 [2] M. Cha and J. C. Santamarina, DOI: 10.1680/geot.14P.115 [3] M. D. Ingraham, K. A. Issen, and D. J. Holcomb, DOI: 10.1007/s11440-013-0275-y [4] K. A. Issen and J. W. Rudnicki, DOI: 10.1029/2000JB900185 [5] J. W. Rudnicki and J. R. Rice, DOI

  4. LIMESTONE AND MARBLE DISSOLUTION BY ACID RAIN: AN ONSITE WEATHERING EXPERIMENT.

    USGS Publications Warehouse

    Reddy, Michael M.; Sherwood, Susan I.; Doe, B.R.

    1986-01-01

    In this paper the authors describe an experimental research program, conducted in conjunction with the National Acidic Precipitation Assessment Program (NAPAP), to quantify acid-rain damage to commercial and cultural carbonate-rock resources. Initial results of this experiment show that carbonate-rock dissolution and associated surface recession increase with increasing acid deposition to the rock surface. A statistically significant linear relation has been found between carbonate-rock surface-recession rate and hydrogen ion loading to the rock surface.

  5. A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

    SciTech Connect

    Chen Zhu; William E. Seyfried

    2005-01-01

    Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory-measured and field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between lab and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO{sub 2} injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the first year of the project, we have successfully developed a sample preparation method and completed three batch feldspar dissolution experiments at 200 C and 300 bars. The changes of solution chemistry as dissolution experiments progressed were monitored with on-line sampling of the aqueous phase at the constant temperature and pressure

  6. In Vivo Predictive Dissolution: Comparing the Effect of Bicarbonate and Phosphate Buffer on the Dissolution of Weak Acids and Weak Bases.

    PubMed

    Krieg, Brian J; Taghavi, Seyed Mohammad; Amidon, Gordon L; Amidon, Gregory E

    2015-09-01

    Bicarbonate is the main buffer in the small intestine and it is well known that buffer properties such as pKa can affect the dissolution rate of ionizable drugs. However, bicarbonate buffer is complicated to work with experimentally. Finding a suitable substitute for bicarbonate buffer may provide a way to perform more physiologically relevant dissolution tests. The dissolution of weak acid and weak base drugs was conducted in bicarbonate and phosphate buffer using rotating disk dissolution methodology. Experimental results were compared with the predicted results using the film model approach of (Mooney K, Mintun M, Himmelstein K, Stella V. 1981. J Pharm Sci 70(1):22-32) based on equilibrium assumptions as well as a model accounting for the slow hydration reaction, CO2 + H2 O → H2 CO3 . Assuming carbonic acid is irreversible in the dehydration direction: CO2 + H2 O ← H2 CO3 , the transport analysis can accurately predict rotating disk dissolution of weak acid and weak base drugs in bicarbonate buffer. The predictions show that matching the dissolution of weak acid and weak base drugs in phosphate and bicarbonate buffer is possible. The phosphate buffer concentration necessary to match physiologically relevant bicarbonate buffer [e.g., 10.5 mM (HCO3 (-) ), pH = 6.5] is typically in the range of 1-25 mM and is very dependent upon drug solubility and pKa . PMID:25980464

  7. Relation between acid dissolution time in the vacuum test tube and time required for graphitization for AMS target preparation

    NASA Astrophysics Data System (ADS)

    Yokoyama, Yusuke; Miyairi, Yousuke; Matsuzaki, Hiroyuki; Tsunomori, Fumiaki

    2007-06-01

    Availability of an effective graphitization system is essential for the successful operation of an AMS laboratory for radiocarbon measurements. We have set up a graphitization system consisting of metal vacuum lines for cleaning CO2 sample gas which is then converted to graphite. CO2 gas from a carbonate sample is produced in vacuum in a test tube by injecting concentrated phosphoric acid. The tube is placed into a heated metal block to accelerate dissolution. However, we have observed systematic differences in the time required to convert the CO2 gas to graphite under a hydrogen atmosphere, from less than 3 h to over 10 h. We have conducted a series of experiments including background measurements and yield measurements to monitor secondary carbon contamination and changes in isotopic fractionation. All of the tests show that the carbon isotope ratios remain unaffected by the duration of the process. We also used a quadrupole mass spectrometer (QMS) to identify possible contaminant gases. Contaminant peaks were identified at high mass (larger than 60) only for long duration experiments. This suggests a possible reaction between the rubber cap and acid fumes producing a contaminant gas that impeded the reduction of CO2.

  8. Direct nanoscale observations of CO2 sequestration during brucite [Mg(OH)2] dissolution.

    PubMed

    Hövelmann, J; Putnis, C V; Ruiz-Agudo, E; Austrheim, H

    2012-05-01

    The dissolution and carbonation of brucite on (001) cleavage surfaces was investigated in a series of in situ and ex situ atomic force microscopy (AFM) experiments at varying pH (2-12), temperature (23-40 °C), aqueous NaHCO(3) concentration (10(-5)-1 M), and PCO(2) (0-1 atm). Dissolution rates increased with decreasing pH and increasing NaHCO(3) concentration. Simultaneously with dissolution of brucite, the growth of a Mg-carbonate phase (probably dypingite) was directly observed. In NaHCO(3) solutions (pH 7.2-9.3,), precipitation of Mg-carbonates was limited. Enhanced precipitation was, however, observed in acidified NaHCO(3) solutions (pH 5, DIC ≈ 25.5 mM) and in solutions that were equilibrated under a CO(2) atmosphere (pH 4, DIC ≈ 25.2 mM). Nucleation predominantly occurred in areas of high dissolution such as deep step edges suggesting that the carbonation reaction is locally diffusion-transport controlled. More extensive particle growth was also observed after ex situ experiments lasting for several hours. This AFM study contributes to an improved understanding of the mechanism of aqueous brucite carbonation at low temperature and pressure conditions and has implications for carbonation reactions in general. PMID:22500652

  9. Accelerator-Based Irradiation Creep of Pyrolytic Carbon Used in TRISO Fuel Particles for the (VHTR) Very Hight Temperature Reactors

    SciTech Connect

    Lumin Wang; Gary Was

    2010-07-30

    Pyrolytic carbon (PyC) is one of the important structural materials in the TRISO fuel particles which will be used in the next generation of gas-cooled very-high-temperature reactors (VHTR). When the TRISO particles are under irradiation at high temperatures, creep of the PyC layers may cause radial cracking leading to catastrophic particle failure. Therefore, a fundamental understanding of the creep behavior of PyC during irradiation is required to predict the overall fuel performance.

  10. Differential dissolution susceptibility of Paleocene foraminiferal assemblage from Farafra Oasis, Egypt

    NASA Astrophysics Data System (ADS)

    Orabi, Orabi H.; Zaky, Amr S.

    2016-01-01

    Four inferred carbonate dissolution intervals are recognized at North Gunna section within the Dakhla and Esna formations (Paleocene) of the Farafra Oasis of Egypt as the following: 1) at the Danian/Selandian boundary (P3a/P3b), 2) at the upper part of Acarinina soldadoensis/Globanomalina pseudomenardii Subzone (P4c), 3) at the upper two third of the Morozvella velascoenis P5 Biozone and 4) at the Paleocene/Eocene boundary of Morozovella velascoensis/Morozovella aragonensis-Morozovelia subbotinae (P5/E5), where the P/E boundary is marked by major hiatus. The essential indicators of dissolution within the four intervals samples are low P/B ratios, high relative abundance of the agglutinated taxa, high relative abundance of calcareous taxa resistant to dissolution, especially Lenticulin, Cibicidoides and Anomalinoides and low relative abundance of susceptible calcareous taxa, such as unilocular, uniserial and biserial taxa for the benthics and non-muricate taxa for the planktonic, associated with the high percentage of organic carbon. The probably factors may contribute to the dissolution of planktonic foraminiferal tests in the four intervals of dissolution at the Farafra Oasis is that acidity produced by the degradation of organic matter promotes dissolution in sediment pore waters.

  11. 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

  12. Can Accelerators Accelerate Learning?

    NASA Astrophysics Data System (ADS)

    Santos, A. C. F.; Fonseca, P.; Coelho, L. F. S.

    2009-03-01

    The 'Young Talented' education program developed by the Brazilian State Funding Agency (FAPERJ) [1] makes it possible for high-schools students from public high schools to perform activities in scientific laboratories. In the Atomic and Molecular Physics Laboratory at Federal University of Rio de Janeiro (UFRJ), the students are confronted with modern research tools like the 1.7 MV ion accelerator. Being a user-friendly machine, the accelerator is easily manageable by the students, who can perform simple hands-on activities, stimulating interest in physics, and getting the students close to modern laboratory techniques.

  13. PARTICLE ACCELERATOR

    DOEpatents

    Teng, L.C.

    1960-01-19

    ABS>A combination of two accelerators, a cyclotron and a ring-shaped accelerator which has a portion disposed tangentially to the cyclotron, is described. Means are provided to transfer particles from the cyclotron to the ring accelerator including a magnetic deflector within the cyclotron, a magnetic shield between the ring accelerator and the cyclotron, and a magnetic inflector within the ring accelerator.

  14. 25 CFR 11.606 - Dissolution proceedings.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... marriage may initiate dissolution proceedings. (b) If a proceeding is commenced by one of the parties, the... proceeding for dissolution of marriage or legal separation shall allege that the marriage is irretrievably... under the jurisdiction of the court of each party; (2) The date of the marriage and the place at...

  15. 25 CFR 11.606 - Dissolution proceedings.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... marriage may initiate dissolution proceedings. (b) If a proceeding is commenced by one of the parties, the... proceeding for dissolution of marriage or legal separation shall allege that the marriage is irretrievably... under the jurisdiction of the court of each party; (2) The date of the marriage and the place at...

  16. Emotional and Cognitive Coping in Relationship Dissolution

    ERIC Educational Resources Information Center

    Wrape, Elizabeth R.; Jenkins, Sharon Rae; Callahan, Jennifer L.; Nowlin, Rachel B.

    2016-01-01

    Dissolution of a romantic relationship can adversely affect functioning among college students and represents one primary reason for seeking campus counseling. This study examined the associations among common coping strategies and distress following relationship dissolution. Avoidance and repetitive negative thinking (RNT) were significantly…

  17. Thermal dissolution of solid fossil fuels

    SciTech Connect

    E.G. Gorlov

    2007-10-15

    The use of oil shales and coals in the processes of thermal dissolution is considered. It is shown that thermal dissolution is a mode of liquefaction of solid fossil fuels and can be used both independently and in combination with liquefaction of coals and processing of heavy petroleum residues.

  18. Stirring effect on kaolinite dissolution rate

    NASA Astrophysics Data System (ADS)

    Metz, Volker; Ganor, Jiwchar

    2001-10-01

    Experiments were carried out measuring kaolinite dissolution rates using stirred and nonstirred flow-through reactors at pHs 2 to 4 and temperatures of 25°C, 50°C, and 70°C. The results show an increase of kaolinite dissolution rate with increasing stirring speed. The stirring effect is reversible, i.e., as the stirring slows down the dissolution rate decreases. The effect of stirring speed on kaolinite dissolution rate is higher at 25°C than at 50°C and 70°C and at pH 4 than at pHs 2 and 3. It is suggested that fine kaolinite particles are formed as a result of stirring-induced spalling or abrasion of kaolinite. These very fine particles have an increased ratio of reactive surface area to specific surface area, which results in enhancement of kaolinite dissolution rate. A balance between production and dissolution of the fine particles explains both the reversibility and the temperature and pH dependence of the stirring effect. Since the stirring effect on kaolinite dissolution rate varies with temperature and pH, measurement of kinetic parameters such as activation energy may be influenced by stirring. Therefore, standard use of nonagitated reaction vessels for kinetic experiments of mineral dissolution and precipitation is recommended, at least for slow reactions that are surface controlled.

  19. Nanosizing of drugs: Effect on dissolution rate

    PubMed Central

    Dizaj, S. Maleki; Vazifehasl, Zh.; Salatin, S.; Adibkia, Kh.; Javadzadeh, Y.

    2015-01-01

    The solubility, bioavailability and dissolution rate of drugs are important parameters for achieving in vivo efficiency. The bioavailability of orally administered drugs depends on their ability to be absorbed via gastrointestinal tract. For drugs belonging to Class II of pharmaceutical classification, the absorption process is limited by drug dissolution rate in gastrointestinal media. Therefore, enhancement of the dissolution rate of these drugs will present improved bioavailability. So far several techniques such as physical and chemical modifications, changing in crystal habits, solid dispersion, complexation, solubilization and liquisolid method have been used to enhance the dissolution rate of poorly water soluble drugs. It seems that improvement of the solubility properties ofpoorly water soluble drugscan translate to an increase in their bioavailability. Nowadays nanotechnology offers various approaches in the area of dissolution enhancement of low aqueous soluble drugs. Nanosizing of drugs in the form of nanoparticles, nanocrystals or nanosuspensions not requiring expensive facilities and equipment or complicated processes may be applied as simple methods to increase the dissolution rate of poorly water soluble drugs. In this article, we attempted to review the effects of nanosizing on improving the dissolution rate of poorly aqueous soluble drugs. According to the reviewed literature, by reduction of drug particle size into nanometer size the total effective surface area is increased and thereby dissolution rate would be enhanced. Additionally, reduction of particle size leads to reduction of the diffusion layer thickness surrounding the drug particles resulting in the increment of the concentration gradient. Each of these process leads to improved bioavailability. PMID:26487886

  20. 25 CFR 11.606 - Dissolution proceedings.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... marriage may initiate dissolution proceedings. (b) If a proceeding is commenced by one of the parties, the... proceeding for dissolution of marriage or legal separation shall allege that the marriage is irretrievably... under the jurisdiction of the court of each party; (2) The date of the marriage and the place at...

  1. 25 CFR 11.606 - Dissolution proceedings.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... marriage may initiate dissolution proceedings. (b) If a proceeding is commenced by one of the parties, the... proceeding for dissolution of marriage or legal separation shall allege that the marriage is irretrievably... under the jurisdiction of the court of each party; (2) The date of the marriage and the place at...

  2. 25 CFR 11.606 - Dissolution proceedings.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... marriage may initiate dissolution proceedings. (b) If a proceeding is commenced by one of the parties, the... proceeding for dissolution of marriage or legal separation shall allege that the marriage is irretrievably... under the jurisdiction of the court of each party; (2) The date of the marriage and the place at...

  3. Evaluation of the electrode performance for PAFC by using acid absorption, acceleration and ac-impedance measurement

    SciTech Connect

    Kim, Chang-Soo; Song, Rak-Hyun; Choi, Byung-Woo

    1996-12-31

    In PAFC, the degradation on cathode electrode caused by carbon corrosion, platinum dissolution and growth is especially severe. An acceleration test is a good technique for evaluating the degradation of electrode performance, because it does not need long time. Coleman et al used thermal cycling and on-off cycling as an acceleration test. Song et al showed that hydrogen shortage decreased the electrode performance more rapidly than that of air shortage in gas shortage test. Honji et al reported that the rate of coarsening of Pt particle is rapid in open circuit potential and this is one of major causes on the performance degradation of electrode. The cathode performance has been studied by using acid absorption, acceleration and ac-impedance measurements as functions of the polytetrafluoroethylene (PTFE) contents and sintering temperatures of the electrode.

  4. Effects of Particle Filters and Accelerated Engine Replacement on Heavy-Duty Diesel Vehicle Emissions of Black Carbon, Nitrogen Oxides, and Ultrafine Particles

    NASA Astrophysics Data System (ADS)

    Kirchstetter, T.; Preble, C.; Dallmann, T. R.; DeMartini, S. J.; Tang, N. W.; Kreisberg, N. M.; Hering, S. V.; Harley, R. A.

    2013-12-01

    Diesel particle filters have become widely used in the United States since the introduction in 2007 of a more stringent exhaust particulate matter emission standard for new heavy-duty diesel vehicle engines. California has instituted additional regulations requiring retrofit or replacement of older in-use engines to accelerate emission reductions and air quality improvements. This presentation summarizes pollutant emission changes measured over several field campaigns at the Port of Oakland in the San Francisco Bay Area associated with diesel particulate filter use and accelerated modernization of the heavy-duty truck fleet. Pollutants in the exhaust plumes of hundreds of heavy-duty trucks en route to the Port were measured in 2009, 2010, 2011, and 2013. Ultrafine particle number, black carbon (BC), nitrogen oxides (NOx), and nitrogen dioxide (NO2) concentrations were measured at a frequency ≤ 1 Hz and normalized to measured carbon dioxide concentrations to quantify fuel-based emission factors (grams of pollutant emitted per kilogram of diesel consumed). The size distribution of particles in truck exhaust plumes was also measured at 1 Hz. In the two most recent campaigns, emissions were linked on a truck-by-truck basis to installed emission control equipment via the matching of transcribed license plates to a Port truck database. Accelerated replacement of older engines with newer engines and retrofit of trucks with diesel particle filters reduced fleet-average emissions of BC and NOx. Preliminary results from the two most recent field campaigns indicate that trucks without diesel particle filters emit 4 times more BC than filter-equipped trucks. Diesel particle filters increase emissions of NO2, however, and filter-equipped trucks have NO2/NOx ratios that are 4 to 7 times greater than trucks without filters. Preliminary findings related to particle size distribution indicate that (a) most trucks emitted particles characterized by a single mode of approximately

  5. Dissolution enthalpies of cellulose in ionic liquids.

    PubMed

    Parviainen, Helena; Parviainen, Arno; Virtanen, Tommi; Kilpeläinen, Ilkka; Ahvenainen, Patrik; Serimaa, Ritva; Grönqvist, Stina; Maloney, Thaddeus; Maunu, Sirkka Liisa

    2014-11-26

    In this work, interactions between cellulose and ionic liquids were studied calorimetrically and by optical microscopy. Two novel ionic liquids (1,5-Diazabicyclo[4.3.0]non-5-enium propionate and N-methyl-1,5-diazabicyclo[4.3.0]non-5-enium dimethyl phosphate) and 1-ethyl-3-methylimidazolium acetate-water mixtures were used as solvents. Optical microscopy served in finding the extent of dissolution and identifying the dissolution pattern of the cellulose sample. Calorimetric studies identified a peak relating to dissolution of cellulose in solvent. The transition did, however, not indicate complete dissolution, but rather dissolution inside fibre or fibrils. This method was used to study differences between four cellulose samples with different pretreatment or origins. PMID:25256460

  6. Calcium Carbonate Phosphate Binding Ion Exchange Filtration and Accelerated Denitrification Improve Public Health Standards and Combat Eutrophication in Aquatic Ecosystems

    PubMed Central

    Yanamadala, Vijay

    2010-01-01

    Cultural eutrophication, the process by which a lake becomes rich in dissolved nutrients as a result of point and nonpoint pollutant sources, is a major cause of the loss of natural lake ecosystems throughout the world. The process occurs naturally in all lakes, but phosphate-rich nutrient runoff from sources such as storm drains and agricultural runoff is a major cause of excess phosphate-induced eutrophication. Especially in Madrona Marsh, one of the last remaining vernal marshes in the greater Los Angeles area, California, cultural eutrophication has become a major problem. In this study, calcium carbonate was found to be an excellent phosphate binder, reducing up to 70% of the phosphates in a given sample of water, and it posed relatively negligent ecological repercussions. This study involved the testing of this principle in both the laboratory and the real ecosystem. A calcium carbonate lacing procedure was first carried out to determine its efficacy in Madrona Marsh. Through this, ammonia was found to interfere with the solubility of calcium carbonate and therefore to be a hindrance to the reduction of phosphate. Therefore, various approaches for reduction of ammonia were tested, including aeration, use of fiber growth media, and plants, mainly Caulerpa verticellata, chosen for it hardiness, primarily in an attempt to increase population of Nitrobacter and Nitrosomonas. All were successful in moderately reducing ammonia levels. In addition, soil sampling, sediment analysis, microscopic plant analysis, microorganism and macroinvertebrate identification, and rate law formulations were conducted. The effect of phosphate and ammonia reduction on the populations of enterobacteria was also an important focus of this experiment. Varying concentrations of phosphate, ammonia, and calcium carbonate in conjunction with phosphate were tested in Madrona Marsh to determine their effects on the populations of enteropathogens on nonspecific blood agar, MacConkey agar, and

  7. Dissolution Dominating Calcification Process in Polar Pteropods Close to the Point of Aragonite Undersaturation

    PubMed Central

    Bednaršek, Nina; Tarling, Geraint A.; Bakker, Dorothee C. E.; Fielding, Sophie; Feely, Richard A.

    2014-01-01

    Thecosome pteropods are abundant upper-ocean zooplankton that build aragonite shells. Ocean acidification results in the lowering of aragonite saturation levels in the surface layers, and several incubation studies have shown that rates of calcification in these organisms decrease as a result. This study provides a weight-specific net calcification rate function for thecosome pteropods that includes both rates of dissolution and calcification over a range of plausible future aragonite saturation states (Ωar). We measured gross dissolution in the pteropod Limacina helicina antarctica in the Scotia Sea (Southern Ocean) by incubating living specimens across a range of aragonite saturation states for a maximum of 14 days. Specimens started dissolving almost immediately upon exposure to undersaturated conditions (Ωar∼0.8), losing 1.4% of shell mass per day. The observed rate of gross dissolution was different from that predicted by rate law kinetics of aragonite dissolution, in being higher at Ωar levels slightly above 1 and lower at Ωar levels of between 1 and 0.8. This indicates that shell mass is affected by even transitional levels of saturation, but there is, nevertheless, some partial means of protection for shells when in undersaturated conditions. A function for gross dissolution against Ωar derived from the present observations was compared to a function for gross calcification derived by a different study, and showed that dissolution became the dominating process even at Ωar levels close to 1, with net shell growth ceasing at an Ωar of 1.03. Gross dissolution increasingly dominated net change in shell mass as saturation levels decreased below 1. As well as influencing their viability, such dissolution of pteropod shells in the surface layers will result in slower sinking velocities and decreased carbon and carbonate fluxes to the deep ocean. PMID:25285916

  8. Variation of crystal dissolution rate based on a dissolution stepwave model.

    PubMed

    Lasaga, A C; Luttge, A

    2001-03-23

    A formulation based on defect-generated dissolution stepwaves of the variation of dissolution rate with the degree of undersaturation is validated by near-atomic-scale observations of surfaces, Monte Carlo simulations, and experimental bulk dissolution rates. The dissolution stepwaves emanating from etch pits provide a train of steps similar to those of a spiral but with different behavior. Their role in accounting for the bulk dissolution rate of crystals provides a conceptual framework for mineral dissolution far from equilibrium. Furthermore, the law extends research to conditions closer to equilibrium and predicts a nonlinear decrease in the rate of dissolution as equilibrium is approached, which has implications for understanding artificial and natural processes involving solid-fluid reactions. PMID:11264534

  9. Dissolution Process of Palladium in Hydrochloric Acid: A Route via Alkali Metal Palladates

    NASA Astrophysics Data System (ADS)

    Kasuya, Ryo; Miki, Takeshi; Morikawa, Hisashi; Tai, Yutaka

    2015-12-01

    To improve the safety of the Pd recovery processes that use toxic oxidizers, dissolution of Pd in hydrochloric acid with alkali metal palladates was investigated. Alkali metal palladates were prepared by calcining a mixture of Pd black and alkali metal (Li, Na, and K) carbonates in air. Almost the entire amount of Pd was converted into Li2PdO2 after calcination at 1073 K (800 °C) using Li2CO3. In contrast, PdO was obtained by calcination at 1073 K (800 °C) using Na and K carbonates. Our results indicated that Li2CO3 is the most active reagent among the examined alkali metal carbonates for the formation of palladates. In addition, dissolution of the resulting Li2PdO2 in HCl solutions was evaluated under various conditions. In particular, Li2PdO2 rapidly dissolved in diluted (0.1 M) HCl at ambient temperature. Solubility of Pd of Li2PdO2 was found to be 99 pct or larger after dissolution treatment at 353 K (80 °C) for 5 minutes; in contrast, PdO hardly dissolved in 0.1 M HCl. The dissolution mechanism of Li2PdO2 in HCl was also elucidated by analysis of crystal structures and particulate properties. Since our process is completely free from toxic oxidizers, the dissolution process via alkali metal palladates is much safer than currently employed methods.

  10. Limestone dissolution in flue gas scrubbing: Effect of sulfite

    SciTech Connect

    Gage, C.L.; Rochelle, G.T. )

    1992-07-01

    Batch limestone dissolution experiments were carried out in a pH stat apparatus at 55 C with CO{sub 2} sparging and dissolved sulfite. Particle size distribution, utilization, sulfite in solution, limestone type, and the approach to calcite equilibrium were all found to contribute to the limestone reactivity. In the absence of sulfite, limestone dissolution was controlled solely by mass transfer. For a given stone under mass transfer control, film thickness was found to be independent of pH. The dissolution rate in the presence of sulfite was controlled by a combined surface kinetics/mass transfer regime. SEM micrographs supported this conclusion. A surface rate correlation was developed which accounted for observed inhibition by an inverse dependence on calcium sulfite concentration at the limestone dependence on calcium sulfite concentration at the limestone surface. While the form of the rate expression was applicable to all stones, the surface rate constant was stone dependent. A computer code which accounted for mass transfer with surface kinetics was tested against experimental observations of four limestone types. Changes in pH and the concentrations of calcium, carbonate, sulfite, sulfate, and adipic acid were accurately modeled.

  11. Effect of protein on the dissolution of HA coatings.

    PubMed

    Bender, S A; Bumgardner, J D; Roach; Bessho, K; Ong, J L

    2000-02-01

    The dissolution behavior of hydroxyapatite (HA) in the presence and absence of protein needs to be investigated in order to fully understand the initial cellular response to HA surfaces. In this study, HA coatings were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy (FTIR) prior to protein study. Fibronectin and albumin adsorption study were also performed. Calcium and phosphorus released in the presence and absence of albumin were measured. pH of the solution was measured daily. From the materials characterization, it was observed that the coatings exhibit a HA-type structure, with traces of sodium on the surface. FTIR indicated the possible presence of carbonates on the coatings. From the adsorption study, the amount of albumin adsorbed (0.052+/-0.005 microg/mm2) was statistically higher than the amount of fibronectin adsorbed on HA surfaces (0.035+/-0.002 microg/mm2). Flame atomic absorption indicated a significantly higher calcium ions released initially for HA coatings incubated with proteins as compared to coatings in the absence of proteins. However, after 7 days incubation, no significant difference in calcium ions release was observed between the HA coatings in the presence and absence of proteins. Phosphorus dissolution on HA coatings was not significantly affected by the presence of proteins. Thus, it was suggested from this study that the initial dissolution properties of calcium ions from HA coatings was dependent on the media. PMID:10646947

  12. 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

  13. Carbon dioxide sequestration by aqueous mineral carbonation of magnesium silicate minerals

    SciTech Connect

    Gerdemann, Stephen J.; Dahlin, David C.; O'Connor, William K.; Penner, Larry R.

    2003-01-01

    The dramatic increase in atmospheric carbon dioxide since the Industrial Revolution has caused concerns about global warming. Fossil-fuel-fired power plants contribute approximately one third of the total human-caused emissions of carbon dioxide. Increased efficiency of these power plants will have a large impact on carbon dioxide emissions, but additional measures will be needed to slow or stop the projected increase in the concentration of atmospheric carbon dioxide. By accelerating the naturally occurring carbonation of magnesium silicate minerals it is possible to sequester carbon dioxide in the geologically stable mineral magnesite (MgCO3). The carbonation of two classes of magnesium silicate minerals, olivine (Mg2SiO4) and serpentine (Mg3Si2O5(OH)4), was investigated in an aqueous process. The slow natural geologic process that converts both of these minerals to magnesite can be accelerated by increasing the surface area, increasing the activity of carbon dioxide in the solution, introducing imperfections into the crystal lattice by high-energy attrition grinding, and in the case of serpentine, by thermally activating the mineral by removing the chemically bound water. The effect of temperature is complex because it affects both the solubility of carbon dioxide and the rate of mineral dissolution in opposing fashions. Thus an optimum temperature for carbonation of olivine is approximately 185 degrees C and 155 degrees C for serpentine. This paper will elucidate the interaction of these variables and use kinetic studies to propose a process for the sequestration of the carbon dioxide.

  14. A global experiment suggests climate warming will not accelerate litter decomposition in streams but might reduce carbon sequestration.

    PubMed

    Boyero, Luz; Pearson, Richard G; Gessner, Mark O; Barmuta, Leon A; Ferreira, Verónica; Graça, Manuel A S; Dudgeon, David; Boulton, Andrew J; Callisto, Marcos; Chauvet, Eric; Helson, Julie E; Bruder, Andreas; Albariño, Ricardo J; Yule, Catherine M; Arunachalam, Muthukumarasamy; Davies, Judy N; Figueroa, Ricardo; Flecker, Alexander S; Ramírez, Alonso; Death, Russell G; Iwata, Tomoya; Mathooko, Jude M; Mathuriau, Catherine; Gonçalves, José F; Moretti, Marcelo S; Jinggut, Tajang; Lamothe, Sylvain; M'Erimba, Charles; Ratnarajah, Lavenia; Schindler, Markus H; Castela, José; Buria, Leonardo M; Cornejo, Aydeé; Villanueva, Verónica D; West, Derek C

    2011-03-01

    The decomposition of plant litter is one of the most important ecosystem processes in the biosphere and is particularly sensitive to climate warming. Aquatic ecosystems are well suited to studying warming effects on decomposition because the otherwise confounding influence of moisture is constant. By using a latitudinal temperature gradient in an unprecedented global experiment in streams, we found that climate warming will likely hasten microbial litter decomposition and produce an equivalent decline in detritivore-mediated decomposition rates. As a result, overall decomposition rates should remain unchanged. Nevertheless, the process would be profoundly altered, because the shift in importance from detritivores to microbes in warm climates would likely increase CO(2) production and decrease the generation and sequestration of recalcitrant organic particles. In view of recent estimates showing that inland waters are a significant component of the global carbon cycle, this implies consequences for global biogeochemistry and a possible positive climate feedback. PMID:21299824

  15. Molecular dynamic simulations of ocular tablet dissolution.

    PubMed

    Ru, Qian; Fadda, Hala M; Li, Chung; Paul, Daniel; Khaw, Peng T; Brocchini, Steve; Zloh, Mire

    2013-11-25

    Small tablets for implantation into the subconjunctival space in the eye are being developed to inhibit scarring after glaucoma filtration surgery (GFS). There is a need to evaluate drug dissolution at the molecular level to determine how the chemical structure of the active may correlate with dissolution in the nonsink conditions of the conjunctival space. We conducted molecular dynamics simulations to study the dissolution process of tablets derived from two drugs that can inhibit fibrosis after GFS, 5-fluorouracil (5-FU) and the matrix metalloprotease inhibitor (MMPi), ilomastat. The dissolution was simulated in the presence of simple point charge (SPC) water molecules, and the liquid turnover of the aqueous humor in the subconjunctival space was simulated by removal of the dissolved drug molecules at regular intervals and replacement by new water molecules. At the end of the simulation, the total molecular solvent accessible surface area of 5-FU tablets increased by 60 times more than that of ilomastat as a result of tablet swelling and release of molecules into solution. The tablet dissolution pattern shown in our molecular dynamic simulations tends to correlate with experimental release profiles. This work indicates that a series of molecular dynamic simulations can be used to predict the influence of the molecular properties of a drug on its dissolution profile and could be useful during preformulation where sufficient amounts of the drug are not always available to perform dissolution studies. PMID:24073784

  16. Characterization and dissolution properties of ruthenium oxides.

    PubMed

    Luxton, Todd P; Eick, Matthew J; Scheckel, Kirk G

    2011-07-01

    Ruthenium oxides (RuO(2)·1·10H(2)O and RuO(2)) have been synthesized by forced hydrolysis and oxidation of ruthenium chloride. The resulting materials were extensively characterized to determine the crystallinity, surface area, and ruthenium oxidation state. Surface charging experiments indicate a large quantity of reactive functional groups for both materials and a decrease in the acidity of the surface functional groups with crystallization of the hydrous oxide. Dissolution studies conducted in acidic and basic pH environments indicate Ru-oxides are insoluble in 0.1 M HCl and slightly soluble in 0.1 M NaOH. Oxalate and ascorbate (5 mM) promoted dissolution of RuO(2)·1·10H(2)O demonstrated an increase in dissolution rates with decreasing pH and increasing ligand surface coverage. XPS analysis of the RuO(2)·1·10H(2)O surface after ligand promoted dissolution revealed the reduction of Ru(IV) to Ru(III) indicating that both ascorbate and oxalate reductively dissolve RuO(2)·1·10H(2)O. Dissolution experiments with RuO(2) resulted in dissolution only for 5 mM oxalate at pH 3. Dissolution rates calculated for RuO(2)·1·10H(2)O and RuO(2) are compared with previously published dissolution rates for iron oxides, demonstrating an order of magnitude decrease in the oxalate and ascorbate promoted dissolution. PMID:21511266

  17. Microbial extracellular polysaccharides and plagioclase dissolution

    SciTech Connect

    Welch, S.A.; Barker, W.W.; Banfield, J.F.

    1999-05-01

    Bytownite feldspar was dissolved in batch reactors in solutions of starch (glucose polymer), gum xanthan (glucose, mannose, glucuronic acid), pectin (poly-galacturonic acid), and four alginates (mannuronic and guluronic acid) with a range of molecular weights (low, medium, high and uncharacterized) to evaluate the effect of extracellular microbial polymers on mineral dissolution rates. Solutions were analyzed for dissolved Si and Al as an indicator of feldspar dissolution. At neutral pH, feldspar dissolution was inhibited by five of the acid polysaccharides, gum xanthan, pectin, alginate low, alginate medium, alginate high, compared to an organic-free control. An uncharacterized alginate substantially enhanced both Si and Al release from the feldspar. Starch, a neutral polysaccharide, had no apparent effect. Under mildly acidic conditions, initial pH {approx} 4, all of the polymers enhanced feldspar dissolution compared to the inorganic controls. Si release from feldspar in starch solution exceeded the control by a factor of three. Pectin and gum xanthan increased feldspar dissolution by a factor of 10, and the alginates enhanced feldspar dissolution by a factor of 50 to 100. Si and Al concentrations increased with time, even though solutions were supersaturated with respect to several possible secondary phases. Under acidic conditions, initial pH {approx} 3, below the pK{sub a} of the carboxylic acid groups, dissolution rates increased, but the relative increase due to the polysaccharides is lower, approximately a factor of two to ten. Microbial extracellular polymers play a complex role in mineral weathering. Polymers appear to inhibit dissolution under some conditions, possibly by irreversibly binding to the mineral surfaces. The extracellular polysaccharides can also enhance dissolution by providing protons and complexing with ions in solution.

  18. 10 CFR 960.4-2-6 - Dissolution.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... host rock within the site was subject to significant dissolution during the Quaternary Period. (c..., dissolution cavities, significant volumetric reduction of the host rock or surrounding strata, or...

  19. In situ Characterization of Photoresist Dissolution

    NASA Astrophysics Data System (ADS)

    Itani, Toshiro; Santillan, Julius Joseph

    2010-06-01

    The dissolution process plays an important role in optimizing photoresist materials and processes for next-generation lithographic technologies. In this paper, we describe the application of high-speed atomic force microscopy for in situ analysis and characterization of photoresist dissolution. In particular, the physical changes in an exposed extreme ultraviolet (EUV) photoresist film are analyzed in real time - before, during, and after the development process. In this initial work, we report the dissolution characteristics of an EUV-exposed poly(4-hyrdroxystyrene)-based polymer resist processed with a tetramethylammonium hydroxide developer solution.

  20. Accelerated glacier melt on Snow Dome, Mount Olympus, Washington, USA, due to deposition of black carbon and mineral dust from wildfire

    NASA Astrophysics Data System (ADS)

    Kaspari, Susan; McKenzie Skiles, S.; Delaney, Ian; Dixon, Daniel; Painter, Thomas H.

    2015-04-01

    Assessing the potential for black carbon (BC) and dust deposition to reduce albedo and accelerate glacier melt is of interest in Washington because snow and glacier melt are an important source of water resources, and glaciers are retreating. In August 2012 on Snow Dome, Mount Olympus, Washington, we measured snow surface spectral albedo and collected surface snow samples and a 7 m ice core. The snow and ice samples were analyzed for iron (Fe, used as a dust proxy) via inductively coupled plasma sector field mass spectrometry, total impurity content gravimetrically, BC using a single-particle soot photometer (SP2), and charcoal through microscopy. In the 2012 summer surface snow, BC (54 ± 50 µg/L), Fe (367±236 µg/L) and gravimetric impurity (35 ± 18 mg/L) concentrations were spatially variable, and measured broadband albedo varied between 0.67-0.74. BC and dust concentrations in the ice core 2011 summer horizon were a magnitude higher (BC = 3120 µg/L, Fe = 22000 µg/L, and gravimetric impurity = 1870 mg/L), corresponding to a modeled broadband albedo of 0.45 based on the measured BC and gravimetric impurity concentrations. The Big Hump forest fire is the likely source for the higher concentrations. Modeling constrained by measurements indicates that the all-sky 12 h daily mean radiative forcings in summer 2012 and 2011 range between 37-53 W m-2 and 112-149 W m-2, respectively, with the greater forcings in 2011 corresponding to a 29-38 mm/d enhancement in snowmelt. The timing of the forest fire impurity deposition is coincident with an increase in observed discharge in the Hoh River, highlighting the potential for BC and dust deposition on glaciers from forest fires to accelerate melt.

  1. Accelerated killing of cancer cells using a multifunctional single-walled carbon nanotube-based system for targeted drug delivery in combination with photothermal therapy

    PubMed Central

    Jeyamohan, Prashanti; Hasumura, Takashi; Nagaoka, Yutaka; Yoshida, Yasuhiko; Maekawa, Toru; Kumar, D Sakthi

    2013-01-01

    The photothermal effect of single-walled carbon nanotubes (SWCNTs) in combination with the anticancer drug doxorubicin (DOX) for targeting and accelerated destruction of breast cancer cells is demonstrated in this paper. A targeted drug-delivery system was developed for selective killing of breast cancer cells with polyethylene glycol biofunctionalized and DOX-loaded SWCNTs conjugated with folic acid. In our work, in vitro drug-release studies showed that the drug (DOX) binds at physiological pH (pH 7.4) and is released only at a lower pH, ie, lysosomal pH (pH 4.0), which is the characteristic pH of the tumor environment. A sustained release of DOX from the SWCNTs was observed for a period of 3 days. SWCNTs have strong optical absorbance in the near-infrared (NIR) region. In this special spectral window, biological systems are highly transparent. Our study reports that under laser irradiation at 800 nm, SWCNTs exhibited strong light–heat transfer characteristics. These optical properties of SWCNTs open the way for selective photothermal ablation in cancer therapy. It was also observed that internalization and uptake of folate-conjugated NTs into cancer cells was achieved by a receptor-mediated endocytosis mechanism. Results of the in vitro experiments show that laser was effective in destroying the cancer cells, while sparing the normal cells. When the above laser effect was combined with DOX-conjugated SWCNTs, we found enhanced and accelerated killing of breast cancer cells. Thus, this nanodrug-delivery system, consisting of laser, drug, and SWCNTs, looks to be a promising selective modality with high treatment efficacy and low side effects for cancer therapy. PMID:23926428

  2. Rate of production, dissolution and accumulation of biogenic solids in the ocean

    NASA Technical Reports Server (NTRS)

    Arrhenius, G.

    1988-01-01

    The equatorial current system, by its response to global circulation changes, provides a unique recording mechanism for long range climatic oscillations. A permanent record of the changes in rate of upwelling and organic production is generated in the equatorial deep sea sediments, particularly by such biogenic components which are unaffected by secondary dissolution. In order to determine the rates of accumulation of various sedimentary components, a reliable differential measurement of age of the strata must be obtained. Various approaches to this problem are reviewed, and sources of error discussed. Secondary dissolution of calcium carbonate introduces a substantial and variable difference between the dissolution-modified, and hence a priori unknown, rate of deposition on one hand and the rate of accumulation, derivable from the observed concentration, on the other. The cause and magnitude of these variations are of importance, particularly since some current dating schemes are based on assumed constancy in the rate of accumulation of this and, in some cases, also all other sedimentary components. The concepts used in rate evaluation are discussed with emphasis on the difference between the state of dissolution, an observable property of the sediment, and the rate of dissolution, a parameter that requires deduction of the carbonate fraction dissolved, and of the time differential. As a most likely cause of the enhanced state of dissolution of the interglacial carbonate sediments is proposed the lowered rates of biogenic production and deposition, which cause longer exposure of the carbonate microfossils to corrosion in the bioturbated surface layer of the sediment. Historical perspective is included in the discussion in view of the dedication of the Symposium to Hans Pettersson, the leader of the Swedish Deep Sea Expedition 1947-1948, an undertaking that opened a new era in deep sea research and planetary dynamics.

  3. Kinetics and roles of solution and surface species of chalcopyrite dissolution at 650 mV

    NASA Astrophysics Data System (ADS)

    Li, Yubiao; Qian, Gujie; Li, Jun; Gerson, Andrea R.

    2015-07-01

    To better understand chalcopyrite dissolution in hydrogeochemical processes and the related environmental issue of acid and metalliferous drainage (AMD), the kinetics as well as the influence of solution composition and the nature of surface species formed during chalcopyrite dissolution have been examined under the controlled conditions of Eh 650 mV (SHE), pH 1.0-2.0 and 75 °C, with/without 4 mM Fe2+ addition. SEM and XPS analyses indicate that the surface products, both at micro- and nano-scales, did not passivate dissolution under the conditions examined. Extensive S0 was formed mostly as discrete particles rather than coatings on the chalcopyrite surface. Jarosite was only observed for dissolution at pH 2.0 with 4 mM added Fe2+. Without Fe2+ addition, the initial dissolution rate was observed to be only correlated to H+ activity as aH+0.12(±0.01), indicating chalcopyrite dissolution was controlled via chemical oxidation of chalcopyrite by H+/O2. When reaction between chalcopyrite and Fe3+ predominated chalcopyrite dissolution (i.e. later stage of dissolution without Fe2+ addition), the dissolution rate was found to be positively correlated to the activities of Fe3+, as aFe3+1.54(±0.07), and H+, as aH+0.13(±0.05). When 4 mM Fe2+ was added, no clear correlation was observed between the dissolution rate and the activities of either Fe3+or H+. It is proposed that the relative reactive surface area may not be proportional to that predicted by a shrinking sphere model as was assumed for derivation of the rate laws for the systems without added Fe2+, with the predicted rate being greater than the measured rate. Irrespective, it is clear that the addition of a relatively low Fe2+ concentration plays an important role in accelerating the copper dissolution rate at this Eh.

  4. Microfluidics experiments of dissolution in a fracture. Influence of Damköhler and Péclet numbers, and of the geometry on the dissolution pattern

    NASA Astrophysics Data System (ADS)

    Osselin, Florian; Budek, Agnieszka; Cybulski, Olgierd; Szymczak, Piotr

    2015-04-01

    Dissolution of natural rocks is an ever present phenomenon in nature. The shaping of natural landscapes by the dissolution of limestone gives for example birth to exceptional features like karsts. Currently dissolution is also at the heart of key research topics as Carbon Capture and Storage or Enhanced Oil Recovery. The basics principles of dissolution are well-known, however, the sheer amount of different patterns arising from these mechanisms and the strong dependency on parameters such as pore network, chemical composition and flow rate, make it particularly difficult to study theoretically and experimentally. In this study we present a microfluidic experiment simulating the behavior of a dissolving fluid in a fracture. The experiments consist of a chip of gyspum inserted between two polycarbonate plates and subjected to a constant flow rate of pure water. The point in using microfluidics is that it allows a complete control on the experimental parameters such as geometry and chemical composition of the porous medium, flow rate, fracture aperture, roughness of the fracture walls, and an in situ observation of the geometry evolution which is impossible with 3D natural rocks. Thanks to our experiments we have been able to cover the whole range of dissolution patterns, from wormholing or DLA fingering to homogeneous dissolution, by changing Péclet and Damköhler numbers. Moreover, we have been able to tweak the geometry of our artificial fracture, inserting finger seeds or non-dissolvable obstacles. The comparison of the experimental patterns with the numerical dissolution code dissol (Szymczak and Ladd 2011) has then shown a very good correlation of the patterns, giving confidence in both experiments and modeling.

  5. Leaching modelling of slurry-phase carbonated steel slag.

    PubMed

    Costa, G; Polettini, A; Pomi, R; Stramazzo, A

    2016-01-25

    In the present work the influence of accelerated mineral carbonation on the leaching behaviour of basic oxygen furnace steel slag was investigated. The environmental behaviour of the material as evaluated through the release of major elements and toxic metals under varying pH conditions was the main focus of the study. Geochemical modelling of the eluates was used to derive a theoretical description of the underlying leaching phenomena for the carbonated material as compared to the original slag. Among the investigated elements, Ca and Si were most appreciably affected by carbonation. A very clear effect of carbonation on leaching was observed for silicate phases, and lower-Ca/Si-ratio minerals were found to control leaching in carbonated slag eluates as compared to the corresponding untreated slag sample as a result of Ca depletion from the residual slag particles. Clear evidence was also gained of solubility control for Ca, Mg and Mn by a number of carbonate minerals, indicating a significant involvement of the original slag constituents in the carbonation process. The release of toxic metals (Zn, V, Cr, Mo) was found to be variously affected by carbonation, owing to different mechanisms including pH changes, dissolution/precipitation of carbonates as well as sorption onto reactive mineral surfaces. The leaching test results were used to derive further considerations on the expected metal release levels on the basis of specific assumptions on the relevant pH domains for the untreated and carbonated slag. PMID:26489916

  6. Experimental investigation of the dissolution of fractures. From early stage instability to phase diagram

    NASA Astrophysics Data System (ADS)

    Osselin, Florian; Budek, Agnieszka; Cybulski, Olgierd; Kondratiuk, Pawel; Garstecki, Piotr; Szymczak, Piotr

    2016-04-01

    Dissolution of natural rocks is a fundamental geological process and a key part of landscape formation and weathering processes. Moreover, in current hot topics like Carbon Capture and Storage or Enhanced Oil Recovery, mastering dissolution of the host rock is fundamental for the efficiency and the security of the operation. The basic principles of dissolution are well-known and the theory of the reactive infiltration instability has been extensively studied. However, the experimental aspect has proved very challenging because of the strong dependence of the outcome with pore network, chemical composition, flow rate... In this study we are trying to tackle this issue by using a very simple and efficient device consisting of a chip of pure gypsum inserted between two polycarbonate plates and subjected to a constant flow rate of pure water. Thanks to this device, we are able to control all parameters such as flow rate, fracture aperture, roughness of the walls... but also to observe in situ the progression of the dissolution thanks to the transparency of the polycarbonate which is impossible with 3D rocks. We have been using this experimental set-up to explore and investigate all aspects of the dissolution in a fracture, such as initial instability and phase diagram of different dissolution patterns, and to compare it with theory and simulations, yielding very good agreement and interesting feedbacks on the coupling between flow and chemistry in geological media

  7. Chemistry of proposed calcination/dissolution processing of Hanford Site tank wastes

    SciTech Connect

    Delegard, C.H.

    1995-01-01

    Plans exist to separate radioactive waste stored in underground tanks at the US Department of Energy`s Hanford Site in south central Washington State into low-level and high-level fractions, and to immobilize the separate fractions in high-integrity vitrified forms for long-term disposal. Calcination with water dissolution has been proposed as a possible treatment for achieving low/high-level separation. Chemistry development activities conducted since 1992 with simulated and genuine tank waste show that calcination/dissolution destroys organic carbon and converts nitrate and nitrite to hydroxide and benign offgases. The process also dissolves significant quantities of bulk chemicals (aluminum, chromium, and phosphate), allowing their redistribution from the high-level to the low-level fraction. Present studies of the chemistry of calcination/dissolution processing of genuine wastes, conducted in the period October 1993 to September 1994, show the importance of sodium fluoride phosphate double salt in controlling phosphate dissolution. Peptization of waste solids is of concern if extensive washing occurs. Strongly oxidizing conditions imposed by calcination reactions were found to convert transition metals to soluble anions in the order chromate > manganate > > ferrate. In analogy with manganese behavior, plutonium dissolution, presumably by oxidation to more soluble anionic species, also occurs by calcination/dissolution. Methods to remove plutonium from the product low-level solution stream must be developed.

  8. An atomic force microscopy study of the dissolution of calcite in the presence of phosphate ions

    NASA Astrophysics Data System (ADS)

    Klasa, J.; Ruiz-Agudo, E.; Wang, L. J.; Putnis, C. V.; Valsami-Jones, E.; Menneken, M.; Putnis, A.

    2013-09-01

    Dissolution of calcite in the presence of phosphate solutions was studied in situ by Atomic Force Microscopy. Results of experiments in slightly alkaline (NH4)2HPO4 solutions showed that dissolution, measured from etch pit spreading, is significantly reduced compared to that observed in pure deionized water, confirming an inhibitory effect of (NH4)2HPO4 on calcite dissolution. However, rates measured in the presence of Na-phosphate solutions at the same pH remained close to that in pure water. This would indicate that the inhibitory effect could be caused by the presence of the NH4+ group. Moreover, for phosphate solution concentrations >5 mM, the precipitation of a calcium phosphate phase occurred simultaneously while calcite was dissolving, despite the continuous flow of the reaction solution. Such reactions may play an important role in phosphorus recovery from P-bearing solutions. Importantly this study gives insights into the mechanism of interface-coupled dissolution-precipitation reactions occurring during the interaction of phosphate-bearing solutions with calcium carbonate minerals and emphasizes the importance of performing direct observations when determining the kinetics of dissolution reactions, as they can be significantly affected by the precipitation of secondary phases that could alter dissolution rates determined from measurements of bulk solution composition.

  9. Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

    SciTech Connect

    Ravichandran, M.; Ryan, J.N.; Aiken, G.R.; Reddy, M.M.

    1998-11-01

    Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca{sup 2+}. Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in Dl water had no detectable dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates correlated positively with enhanced cinnabar dissolution. {zeta}-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.

  10. Dissolution and Separation of Aluminum and Aluminosilicates

    DOE PAGESBeta

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; Felker, Leslie Kevin; Mattus, Catherine H.

    2015-12-19

    The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as amore » function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.« less

  11. Dissolution and Separation of Aluminum and Aluminosilicates

    SciTech Connect

    McFarlane, Joanna; Benker, Dennis; DePaoli, David W.; Felker, Leslie Kevin; Mattus, Catherine H.

    2015-12-19

    The selection of an aluminum alloy for target irradiation affects post-irradiation target dissolution and separations. Recent tests with aluminum alloy 6061 yielded greater than expected precipitation in the dissolver, forming up to 10 wt.% solids of aluminum hydroxides and aluminosilicates. Aluminosilicate dissolution presents challenges in a number of different areas, metals extraction from minerals, flyash treatment, and separations from aluminum alloys. We present experimental work that attempts to maximize dissolution of aluminum metal, along with silicon, magnesium, and copper impurities, through control of temperature, the rate of reagent addition, and incubation time. Aluminum phase transformations have been identified as a function of time and temperature, using X-ray diffraction. Solutions have been analyzed using wet chemical methods and X-ray fluorescence. Our data have been compared with published calculations of aluminum phase diagrams. Approaches are given to enhance the dissolution of aluminum and aluminosilicate phases in caustic solution.

  12. Nylon Dissolution in Nitric Acid Solutions

    SciTech Connect

    KESSINGER, GLENF.

    2004-06-16

    H Area Operations is planning to process Pu-contaminated uranium scrap in support of de-inventory efforts. Nylon bags will be used to hold materials to be dissolved in H-Canyon. Based on this set of twelve nylon dissolutions, it is concluded that (when other variables are held constant): increased acid concentration results in increased dissolution rates; increased acid concentration results in a lower dissolution onset temperature; little, if any, H plus is consumed during the depolymerization process; and 2.0-3.0 M HNO3, with 0.025 M KF and 2 g/L B, is satisfactory for the dissolution of nylon bag materials to be used during H-Canyon processing.

  13. Neutralization of ADAM8 ameliorates liver injury and accelerates liver repair in carbon tetrachloride-induced acute liver injury.

    PubMed

    Li, San-Qiang; Zhu, Sha; Wan, Xue-Dong; Xu, Zheng-Shun; Ma, Zhao

    2014-04-01

    Although some studies have described the function of ADAM8 (a disintegrin and metalloprotease 8) related with rheumatoid arthritis, cancer and asthma, etc., the concrete role of ADAM8 in acute liver injury is still unknown. So mice respectively received anti-ADAM8 monoclonal antibody (mAb) of 100 μg/100 μl, 200 μg/100 μl or 300 μg/100 μl in PBS or PBS pre-injection. Then acute liver injury was induced in the mice by intraperitoneal (i.p.) injection of carbon tetrachloride (CCl₄). Serum AST and ALT level, Haematoxylin-eosin (H&E) staining, the expression level of vascular endothelial growth factor (VEGF), cytochrome P450 1A2 (CYP1A2) and proliferating cell nuclear antigen (PCNA) were detected in the mice after CCl4 administration. Our results showed that anti-ADAM8 mAb pre-injection could effectively lower AST and ALT levels (P < 0.05 or P < 0.01) and reduce liver injury (P < 0.05 or P <0.01), induce the expression of VEGF, CYP1A2 and PCNA (P <0.05 or P < 0.01) in dose-dependent manner compared with the control mice which received PBS pre-injection. In summary, our study suggested that ADAM8 might promote liver injury by inhibiting the proliferation of hepatocytes, angiogenesis and affecting the metabolism function of liver during acute liver injury induced by CCl₄. Anti-ADAM8 mAb injection might be suitable as a potential method for acute liver injury therapy. PMID:24646716

  14. Dissolution rates of prehnite, epidote, and albite

    SciTech Connect

    Rosemary, N.M. )

    1991-11-01

    Dissolution rates of prehnite and epidote in aqueous solutions were measured in the temperature range 25 to 90C, and as a function of pH. The dissolution rate of albite was measured at pH 1.4 at temperatures between 25 and 90C. Batch experiments using low ionic strength pH buffers in constant temperature water batch or ovens provided data on cumulative element release as a function of time. Steady state Si, Ca, Na, and Al release data obtained from these experiments were used to obtain limiting dissolution rates, where the term limiting rate denotes dissolution of a bulk mineral under conditions where it is far from equilibrium with the fluid. At 90C and at pH 1.4 to 6, prehnite and epidote dissolution rates decrease and are proportional to approximately {minus}0.3 pH for prehnite and {minus}0.2 pH for epidote. Above pH 6, prehnite dissolution becomes pH independent, by epidote dissolution increases with rates that are proportional to between +0.3 and +0.6 pH. Prehnite and epidote dissolution is linear and stoichiometric at low pH. At pH greater than 7, both minerals initially display preferential release of Si and Al relative to Ca; however, with increasing reaction dissolution becomes stoichiometric. This suggests that a Ca-enriched layer forms but reaches a steady state thickness which does not impede subsequent linear stoichiometric release. At pH 1.4, the limiting dissolution rate for albite is linear and stoichiometric. At pH 1.4, the activation energies are 18.12 {plus minus} 0.81 kcal mol{sup {minus}1} for prehnite, 19.76 {plus minus} 1.2 kcal mol{sup {minus}1} for epidote and 17.07 {plus minus} 1.6 kcal mol{sup {minus}1} for albite. At pH 6.5, the activation energy for prehnite dissolution is 20.73 {plus minus} 3.2 kcal mol{sup {minus}1}.

  15. Conceptual and instrumental progress in dissolution DNP

    NASA Astrophysics Data System (ADS)

    Jähnig, Fabian; Kwiatkowski, Grzegorz; Ernst, Matthias

    2016-03-01

    We discuss conceptual and instrumental progress in dissolution DNP since its introduction in 2003. In our view there are three critical steps in the dissolution DNP process: (i) The achievable polarization level in a sample. (ii) The time required to build up the polarization. (iii) The transfer of the sample to the measurement system with minimum loss of polarization. In this review we describe in detail these steps and the different methodological and instrumental implementations, which have been proposed to optimize them.

  16. DETERMINATION OF CORROSION INHIBITOR CRITERIA FOR TYPE III IIIA TANKS DURING SALT DISSOLUTION OPERATIONS

    SciTech Connect

    Wiersma, B

    2008-01-04

    Preparation of high level waste for vitrification involves in part the dissolution of salt cake from the carbon steel storage tanks. The salt crystals composing this cake are high in nitrate concentration with the interstitial liquid being high in hydroxide and nitrite concentration. During the salt dissolution process, a stage is reached in which the inhibitors, hydroxide and nitrite, are insufficient to prevent nitrate stress corrosion cracking (SCC) and fall outside the requirements of the corrosion control program. Additional inhibitors, which are necessary to meet the requirements, may be counterproductive to the efficiency of the process and waste minimization. Corrosion testing was initiated to better characterize the necessary inhibitor concentration for high nitrate waste during salt dissolution processing. A four-phase test program is being conducted: (1) electrochemical characterization, (2) accelerated or polarized U-bend testing, (3) long-term (non-polarized) U-bend testing and (4) vapor space U-bend tests. Electrochemical testing, which included cyclic potentiodynamic polarization (CPP), linear polarization resistance (LPR) and open-circuit potential (OCP) measurements, was performed to identify stress corrosion cracking susceptibility, to characterize pitting resistance and to determine the general corrosion rate. Polarized U-bend tests were utilized to assess the effect of minimum inhibitor concentrations and heat treatment on SCC and to determine test parameters for future long-term U-bend testing. Results from CPP, LPR and OCP tests demonstrated that carbon steel formed a protective oxide film and the potential became electropositive during exposure to the waste at all inhibitor concentrations. The tenacity of this film improved as the inhibitor concentration level was increased and the temperature was decreased. This passive film increased the resistance to localized corrosion significantly. Therefore if any of these inhibitor levels are selected

  17. Dolomite-rich coralline algae in reefs resist dissolution in acidified conditions

    NASA Astrophysics Data System (ADS)

    Nash, M. C.; Opdyke, B. N.; Troitzsch, U.; Russell, B. D.; Adey, W. H.; Kato, A.; Diaz-Pulido, G.; Brent, C.; Gardner, M.; Prichard, J.; Kline, D. I.

    2013-03-01

    Coral reef ecosystems develop best in high-flow environments but their fragile frameworks are also vulnerable to high wave energy. Wave-resistant algal rims, predominantly made up of the crustose coralline algae (CCA) Porolithon onkodes and P. pachydermum, are therefore critical structural elements for the survival of many shallow coral reefs. Concerns are growing about the susceptibility of CCA to ocean acidification because CCA Mg-calcite skeletons are more susceptible to dissolution under low pH conditions than coral aragonite skeletons. However, the recent discovery of dolomite (Mg0.5Ca0.5(CO3)), a stable carbonate, in P. onkodes cells necessitates a reappraisal of the impacts of ocean acidification on these CCA. Here we show, using a dissolution experiment, that dried dolomite-rich CCA have 6-10 times lower rates of dissolution than predominantly Mg-calcite CCA in both high-CO2 (~ 700ppm) and control (~ 380ppm) environments, respectively. We reveal this stabilizing mechanism to be a combination of reduced porosity due to dolomite infilling and selective dissolution of other carbonate minerals. Physical break-up proceeds by dissolution of Mg-calcite walls until the dolomitized cell eventually drops out intact. Dolomite-rich CCA frameworks are common in shallow coral reefs globally and our results suggest that it is likely that they will continue to provide protection and stability for coral reef frameworks as CO2 rises.

  18. Experimental determination of chlorite dissolution rates

    SciTech Connect

    Rochelle, C.A.; Bateman, K.; MacGregor, R.; Pearce, J.M.; Wetton, P.D.; Savage, D.

    1995-12-31

    Current concepts of the geological disposal of low- and intermediate-level radioactive wastes in the UK envisage the construction of a mined facility (incorporating cementitious engineered barriers) in chlorite-bearing rocks. To model accurately the fluid-rock reactions within the disturbed zone surrounding a repository requires functions that describe mineral dissolution kinetics under pH conditions that vary from near neutral to highly alkaline. Therefore, an experimental study to determine the dissolution rates of Fe-rich chlorite has been undertaken as part of the Nirex Safety Assessment Research Program. Four experiments have been carried out at 25 C and four at 70 C, both sets using a range of NaCl/NaOH solutions of differing pH (of nominal pH 9.0, 10.3, 11.6 and 13.0 [at 25 C]). Dissolution rates have been calculated and were found to increase with increasing pH and temperature. However, increased pH resulted in non-stoichiometric dissolution possibly due to preferential dissolution of part of the chlorite structure relative to another, or reprecipitation of some elements as thin hydroxide or oxyhydroxide surface coatings on the chlorite. These results also show that chlorite dissolution is appreciably slower than that of albite and quartz at both 25 and 70 C, but slightly faster than that of muscovite at 70 C.

  19. Kinetics of anorthite dissolution in basaltic melt

    NASA Astrophysics Data System (ADS)

    Yu, Yi; Zhang, Youxue; Chen, Yang; Xu, Zhengjiu

    2016-04-01

    We report convection-free anorthite dissolution experiments in a basaltic melt at 1280-1500 °C and 0.5 GPa on two different crystallographic surfaces, (1 2 1 bar) and (3 bar 0 2) to investigate dissolution kinetics. The anisotropy of the anorthite dissolution rate along these two surfaces is negligible. Time series experiments at ∼1280 °C show that anorthite dissolution is mainly controlled by diffusion in the melt within experimental uncertainty. Analytical solutions were used to model the dissolution and diffusion processes, and to obtain the diffusivities and the saturation concentrations of the equilibrium-determining component (Al2O3) for anorthite dissolution into the basaltic melt. For the first time, we are able to show the physical and chemical characteristics of quench growth effect on the near-interface melt using high spatial resolution (0.3 μm) EDS analyses. For anorthite (An# ⩾ 90) saturation in a melt with 39-53 wt% SiO2 and ⩽0.4 wt% H2O, the concentration of Al2O3 in wt% depends on temperature as follows:

  20. Two-phase convective CO2 dissolution in saline aquifers

    SciTech Connect

    Martinez, Mario J.; Hesse, Marc A.

    2016-01-01

    Geologic carbon storage in deep saline aquifers is a promising technology for reducing anthropogenic emissions into the atmosphere. Dissolution of injected CO2 into resident brines is one of the primary trapping mechanisms generally considered necessary to provide long-term storage security. Given that diffusion of CO2 in brine is woefully slow, convective dissolution, driven by a small increase in brine density with CO2 saturation, is considered to be the primary mechanism of dissolution trapping. Previous studies of convective dissolution have typically only considered the convective process in the single-phase region below the capillary transition zone and have either ignored the overlying two-phase region where dissolution actually takes place or replaced it with a virtual region with reduced or enhanced constant permeability. Our objective is to improve estimates of the long-term dissolution flux of CO2 into brine by including the capillary transition zone in two-phase model simulations. In the fully two-phase model, there is a capillary transition zone above the brine-saturated region over which the brine saturation decreases with increasing elevation. Our two-phase simulations show that the dissolution flux obtained by assuming a brine-saturated, single-phase porous region with a closed upper boundary is recovered in the limit of vanishing entry pressure and capillary transition zone. For typical finite entry pressures and capillary transition zone, however, convection currents penetrate into the two-phase region. As a result, this removes the mass transfer limitation of the diffusive boundary layer and enhances the convective dissolution flux of CO2 more than 3 times above the rate assuming single-phase conditions.

  1. [In vitro dissolution rate of Liuwei Wuling tablet based on biological potency and integrated dissolution].

    PubMed

    Zheng, Juan; Cheng, Ling; Shen, Cheng-ying; Li, Juan-juan; Qiu, Ling; Shen, Gang; Han, Jin; Yuan, Hai-long

    2015-11-01

    To explore the feasibility of chemical and biological method in evaluation of the in vitro dissolution rate of Liuwei Wuling tablet (LWT), this experiment investigated the inhibitory effect of LWT dissolving solutions on LX-2 hepatic stellate cells in 0.1% SDS dissolution medium in different dissolving periods. From these results, the cumulative dissolution rate of LWT was obtained based on the cell inhibitory rate. The dissolution rates of deoxyschizandrin, phillyrin, and Specnuezhenide were determined by HPLC method. A novel approach of self-defined weighting coefficient had been created to establish the integrated dissolution rate model. Then f2 similar factor method was used to evaluate the relevance of these two methods. The results showed that f2 values for deoxyschizandrin, phillyrin, Specnuezhenide, and the integrated dissolution were 61, 43, 61 and 75 respectively, indicating that the dissolution of multi-component integration could fully reflect the biological potency of the whole recipe. The dissolution evaluation method for multicomponent integration based on biological activity is expected to be one of the effective means for in vitro dissolution test of LWT. PMID:27097413

  2. Plasma accelerators

    SciTech Connect

    Ruth, R.D.; Chen, P.

    1986-03-01

    In this paper we discuss plasma accelerators which might provide high gradient accelerating fields suitable for TeV linear colliders. In particular we discuss two types of plasma accelerators which have been proposed, the Plasma Beat Wave Accelerator and the Plasma Wake Field Accelerator. We show that the electric fields in the plasma for both schemes are very similar, and thus the dynamics of the driven beams are very similar. The differences appear in the parameters associated with the driving beams. In particular to obtain a given accelerating gradient, the Plasma Wake Field Accelerator has a higher efficiency and a lower total energy for the driving beam. Finally, we show for the Plasma Wake Field Accelerator that one can accelerate high quality low emittance beams and, in principle, obtain efficiencies and energy spreads comparable to those obtained with conventional techniques.

  3. A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

    SciTech Connect

    Young, Alan; Colbow, Vesna; Harvey, David; Rogers, Erin; Wessel, Silvia

    2013-01-01

    The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stress test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.

  4. [Effect of accelerated heavy ions of carbon 12C, neon 20Ne and iron 56Fe on the chromosomal apparatus of human blood lymphocytes in vitro].

    PubMed

    Repina, L A

    2011-01-01

    Cytogenetic assay of the chromosomal apparatus of human blood lymphocytes was carried out after in vitro irradiation by heavy charged particles with high LET values. Blood plasm samples enriched with lymphocytes were irradiated by accelerated ions of carbon 12C (290 MeV/nucleon and LET = 70 keV/microm), neon 20Ne (400 MeV/nucleon and LET = 70 keV/microm), and iron 56Fe (500 MeV/nucleon and LET = 200 keV/microm) in the dose range from 0.25 to 1 Gy. Rate of chromosome aberrations showed a linear dependence on doses from the densely ionizing radiations with high LET values. Frequency of dicentrics and centric rings in human lymphocytes irradiated by 12C with the energy of 290 MeV/nucleon was maximal at 1 Gy (p < 0.05) relative to the other heavy particles. It was found that relative biological effectiveness of heavy nuclei is several times higher than of 60Co gamma-radiation throughout the range of doses in this investigation. PMID:22312859

  5. Modeling accelerated and decelerated drug release in terms of fractional release rate.

    PubMed

    Weiss, Michael

    2015-02-20

    The model of a proportional change in fractional dissolution rate was used to quantify influences on the vitro dissolution process. After fitting the original dissolution profile with an empirical model (inverse Gaussian distribution), acceleration and deceleration effects due to dissolution conditions or formulation parameters could be described by one parameter only. Acceleration of dissolution due to elevated temperature and deceleration by increasing the content of glyceryl monostearate in theophylline tablets are presented as examples. Likewise, this approach was applied to in vitro-in vivo correlation (IVIVC). It is shown that the model is appropriate when the plot of the in vivo versus in vivo times is nonlinear and can be described by a power function. The results demonstrate the utility of the model in dissolution testing and IVIVC assessment. PMID:25486334

  6. DISSOLUTION OF FISSILE MATERIALS CONTAINING TANTALUM METAL

    SciTech Connect

    Rudisill, T; Mark Crowder, M; Michael Bronikowski, M

    2007-05-29

    The dissolution of composite materials containing plutonium (Pu) and tantalum (Ta) metals is currently performed in Phase I of the HB-Line facility. The conditions for the present flowsheet are the dissolution of 500 g of Pu metal in the 15 L dissolver using a 4 M nitric acid (HNO{sub 3}) solution containing 0.2 M potassium fluoride (KF) at 95 C for 4-6 h.[1] The Ta metal, which is essentially insoluble in HNO{sub 3}/fluoride solutions, is rinsed with process water to remove residual acid, and then burned to destroy classified information. During the initial dissolution campaign, the total mass of Pu and Ta in the dissolver charge was limited to nominally 300 g. The reduced amount of Pu in the dissolver charge coupled with significant evaporation of solution during processing of several dissolver charges resulted in the precipitation of a fluoride salt contain Pu. Dissolution of the salt required the addition of aluminum nitrate (Al(NO{sub 3}){sub 3}) and a subsequent undesired 4 h heating cycle. As a result of this issue, HB-Line Engineering requested the Savannah River National Laboratory (SRNL) to optimize the dissolution flowsheet to reduce the cycle time, reduce the risk of precipitating solids, and obtain hydrogen (H{sub 2}) generation data at lower fluoride concentrations.[2] Using samples of the Pu/Ta composite material, we performed three experiments to demonstrate the dissolution of the Pu metal using HNO{sub 3} solutions containing 0.15 and 0.175 M KF. When 0.15 M KF was used in the dissolving solution, 95.5% of the Pu in the sample dissolved in approximately 6 h. The undissolved material included a small amount of Pu metal and plutonium oxide (PuO{sub 2}) solids. Complete dissolution of the metal would have likely occurred if the dissolution time had been extended. This assumption is based on the steady increase in the Pu concentration observed during the last several hours of the experiment. We attribute the formation of PuO{sub 2} to the complexation

  7. Understanding the Mechanisms Enabling an Ultra-high Efficiency Moving Wire Interface for Real-time Carbon 14 Accelerator Mass Spectrometry Quantitation of Samples Suspended in Solvent

    NASA Astrophysics Data System (ADS)

    Thomas, Avraham Thaler

    Carbon 14 (14C) quantitation by accelerator mass spectrometry (AMS) is a powerfully sensitive and uniquely quantitative tool for tracking labeled carbonaceous molecules in biological systems. This is due to 14C's low natural abundance of 1 ppt, the nominal difference in biological activity between an unlabeled and a 14C-labeled molecule, and the ability of AMS to measure isotopic ratios independently of a sample's other characteristics. To make AMS more broadly accessible, a moving wire interface for real-time coupling of high pressure liquid chromatography (HPLC) to AMS and high throughput AMS quantitation of minute single samples has been developed. Prior to this work, samples needed to be converted to solid carbon before measurement. This conversion process has many steps and requires that the sample size be large enough to allow precise handling of the resulting graphite. These factors make the process susceptible to error and time consuming, as well as requiring 0.5 ug of carbon. Samples which do not contain enough carbon, such as HPLC fractions, must be bulked up. This adds background and increases effort. The moving wire interface overcomes these limitations by automating sample processing. Samples placed on the wire are transported through a solvent removal stage followed by a combustion stage after which the combustion products are directed to a gas accepting ion source. The ion source converts the carbon from the CO2 combustion product into C ions, from which an isotopic ratio can be determined by AMS. Although moving wire interfaces have been implemented for various tasks since 1964, the efficiency of these systems at transferring fluid from an HPLC to the wire was only 3%, the efficiency of transferring combustion products from the combustion oven to ion source was only 30%, the flow and composition of the carrier gas from the combustion oven to the ion source needed to be optimized for coupling to an AMS gas accepting ion source and the drying ovens

  8. Dissolution of K-feldspar at CO2-saturated conditions

    NASA Astrophysics Data System (ADS)

    Rosenqvist, Jörgen; Kilpatrick, Andrew D.; Yardley, Bruce W. D.; Rochelle, Christopher A.

    2014-05-01

    Underground storage of carbon dioxide on a very large scale is widely considered to be an essential part of any strategy to reduce greenhouse gas emissions to the atmosphere. Aquifers in deep sedimentary basins have been identified as suitable targets for geological carbon dioxide storage, especially aquifers located in sandstone host rock. This has led to renewed interest in studying the interaction between sandstone minerals and aqueous fluids, as there is a paucity of data for CO2-containing systems at relevant conditions. In an attempt to improve data coverage for important silicate minerals, we have measured the dissolution kinetics of K-feldspar in CO2-saturated fluids over a range of temperatures. K-feldspar fragments were hand-picked from a larger sample, crushed to a narrow size range and cleaned. The grains were reacted with water in batch-type reactors at temperatures from 20°C to 200°C and pressures up to 200 bar, and the dissolution was followed by periodic withdrawal of aliquots of solution. The mineral grains were allowed to react with pure water for a number of weeks before injection of CO2 into the system. Excess CO2 was provided to ensure CO2 saturation in the experimental systems. While the reaction time before injection was not long enough to attain complete equilibrium, it did considerably lower the degree of undersaturation with respect to K-feldspar and helped highlight the effect of CO2 injection into a rock-equilibrated aqueous fluid. At all temperatures studied, injection of CO2 resulted in a rapid increase in the soluble concentrations of K and Si (and also Na from a plagioclase component). The dissolution then reached apparent steady state conditions after a few days, with observed dissolution rates in the range of 1E-9 to 1E-12 mol/m2/s over the temperature range studied. The CO2-saturated solutions maintained mildly acidic conditions throughout the experiments and the observed rates therefore fall roughly between rates measured in

  9. Effect of bacteria and dissolved organics on mineral dissolution kinetics:

    NASA Astrophysics Data System (ADS)

    Pokrovsky, Oleg; Shirokova, Liudmila; Benezeth, Pascale; Zabelina, Svetlana

    2010-05-01

    Quantification of the effect of microorganisms and associated organic ligands on mineral dissolution rate is one among the last remaining challenges in modeling of water-rock interactions under earth surface and subsurface environments. This is especially true for deep underground settings within the context of CO2 capture, sequestration and storage. First, elevated CO2 pressures create numerous experimental difficulties for performing robust flow-through experiments at a given saturation state. Second, reactivity of main rock-forming minerals in abiotic systems at pCO2 >> 1 atm and circumneutral pH is still poorly constrained. And third, most of microbial habitats of the subsurface biosphere are not suitable for routine culturing in the laboratory, many of them are anaerobic and even strictly anaerobic, and many bacteria and archae cultures can live only in the consortium of microorganisms which is very hard to maintain at a controlled and stable biomass concentration. For experimental modeling of bio-mineral interactions in the laboratory, two other main conceptual challenges exist. Typical concentration of dissolved organic carbon that serves as a main nutrient for heterotrophic bacteria in underground waters rarely exceeds 3-5 mg/L. Typical concentration of DOC in nutrient media used for bacteria culturing is between 100 and 10,000 mg/L. Therefore, performing mineral-bacteria interactions in the laboratory under environmentally-sound conditions requires significant dilution of the nutrient media or the use of flow-through reactors. Concerning the effect of organic ligands and bacterial excudates on rock-forming mineral dissolution, at the present time, mostly empirical (phenomenological) approach can be used. Indeed, the pioneering studies of Stumm and co-workers have established a firm basis for modeling the catalyzing and inhibiting effects of ligands on metal oxide dissolution rate. This approach, very efficient for studying the interaction of organic and

  10. In situ Microscopic Observation of Sodium Deposition/Dissolution on Sodium Electrode

    NASA Astrophysics Data System (ADS)

    Yui, Yuhki; Hayashi, Masahiko; Nakamura, Jiro

    2016-03-01

    Electrochemical sodium deposition/dissolution behaviors in propylene carbonate-based electrolyte solution were observed by means of in situ light microscopy. First, granular sodium was deposited at pits in a sodium electrode in the cathodic process. Then, the sodium particles grew linearly from the electrode surface, becoming needle-like in shape. In the subsequent anodic process, the sodium dissolved near the base of the needles on the sodium electrode and the so-called “dead sodium” broke away from the electrode. The mechanisms of electrochemical sodium deposition and dissolution on a copper electrode were similar to those on the sodium electrode.

  11. In situ Microscopic Observation of Sodium Deposition/Dissolution on Sodium Electrode

    PubMed Central

    Yui, Yuhki; Hayashi, Masahiko; Nakamura, Jiro

    2016-01-01

    Electrochemical sodium deposition/dissolution behaviors in propylene carbonate-based electrolyte solution were observed by means of in situ light microscopy. First, granular sodium was deposited at pits in a sodium electrode in the cathodic process. Then, the sodium particles grew linearly from the electrode surface, becoming needle-like in shape. In the subsequent anodic process, the sodium dissolved near the base of the needles on the sodium electrode and the so-called “dead sodium” broke away from the electrode. The mechanisms of electrochemical sodium deposition and dissolution on a copper electrode were similar to those on the sodium electrode. PMID:26925554

  12. Can the dissolution rates of individual minerals be used to describe whole rock dissolution?

    NASA Astrophysics Data System (ADS)

    Critelli, Teresa; Marini, Luigi; Schott, Jacques; Mavromatis, Vasileios; Apollaro, Carmine; Rinder, Thomas; De Rosa, Rosanna; Oelkers, Eric H.

    2014-05-01

    There have been an exhaustive number of laboratory studies determining the dissolution rates of individual minerals, but few have focused on the dissolution rates of minerals in multi-mineralic rocks. As a result, geochemical modeling of the temporal evolution of water-rock interaction is generally based on the assumption that the dissolution rate of minerals within a rock is equal to that measured in the laboratory on individual minerals. To verify this hypothesis, we have determined experimentally the dissolution rates of a well characterized metabasalt rock (Apollaro et al., 2011; Bloise et al., 2012) from the Mt. Reventino area (Southern Italy) at 25°C in mixed flow reactors. From these experiments and rock modal analysis we have deduced the dissolution rates of the minerals present in the rock (actinolite, albite, chlorite, epidote, and phengite). The major observation of this effort include: (i) only small differences in the dissolution rates of the individual minerals were observed; these rates are close to the whole-rock dissolution rate and (ii) the dissolution rates of albite and chlorite are in close agreement with laboratory rates obtained from individual mineral dissolution experiments, whereas those of actinolite, phengite, and epidote are not consistent with those reported in literature by 1-2 orders of magnitude. These results demonstrate that the dissolution rate of a given mineral in a multi-phase rock can be affected by the presence of the other minerals. Rock dissolution kinetics are likely constrained by the dissolution rates of the more abundant, lesser reactive mineral or minerals in the rock. These unreactive minerals can prevent the dissolution of the more rapidly dissolving mineral grains by keeping them out of contact with the aqueous phase. This implies that the overall weathering rate of rocks cannot be modelled from the measured dissolution rates of its individual minerals. If confirmed through further studies, this conclusion may

  13. Towards a less biased dissolution of chitosan.

    PubMed

    Thevarajah, Joel J; Bulanadi, Jerikho C; Wagner, Manfred; Gaborieau, Marianne; Castignolles, Patrice

    2016-09-01

    The dissolution of polysaccharides is notoriously challenging, especially when one needs a "true" solution. Factors influencing chitosan's solubility include composition, also known as degree of acetylation (DA). The dissolution of chitosan was investigated by visual observation, size-exclusion chromatography (SEC), pressure mobilization (PM), free-solution capillary electrophoresis (CE) and real-time solution-state NMR spectroscopy. Aqueous HCl dissolves around 15% more chitosan than the commonly used aqueous acetic acid (AcOH), however aggregates were detected in SEC suggesting incomplete dissolution. Significant deacetylation of chitosan over the period needed for dissolution at high temperature was observed by NMR spectroscopy in DCl by about 20% of the initial DA value. Accurate DA determination by NMR spectroscopy may thus be possible only in the solid state (with a precision within 1% on the DA % scale above a DA of 10%). Overall a compromise between maximum solubilization and minimum degradation is required in attempting to obtain a "true" solution of chitosan. The completeness of the dissolution may be more influenced by the average DA than by molar mass. PMID:27543035

  14. Reductive dissolution of goethite by phenolic reductants

    NASA Astrophysics Data System (ADS)

    LaKind, Judy S.; Stone, Alan T.

    1989-05-01

    The reductive dissolution of goethite (α-FeOOH) and hematite (α-Fe 2O 3) by phenolic reductants has been examined in order to improve the understanding of iron transformations in soils, sediments and aquifers. Rates of goethite reductive dissolution by hydroquinone increased as the pH was increased from pH 1.8 to 4.65, arid the following reaction stoichiometry was obeyed: 2 α- FeOOH + QH2 = 2 Fe2+ + Q + 4 OH-. As the pH was increased from pH 4.5 to 6.0, the reductive dissolution rate decreased to below the detection limit. At pH 3.4, the reductive dissolution of hematite was two orders of magnitude slower than goethite. The relationship between structure and reactivity was examined for a series of mono-, di-, and tri-hydroxybenzene reductants. Rates of reductive dissolution decreased in the following order: catechol ˜- hydroquinone > 3,4-dihydroxybenzoic acid > resorcinol-phenol-4-hydroxybenzoic acid.

  15. Visualizing nanoparticle dissolution by imaging mass spectrometry.

    PubMed

    Szakal, Christopher; Ugelow, Melissa S; Gorham, Justin M; Konicek, Andrew R; Holbrook, R David

    2014-04-01

    We demonstrate the ability to visualize nanoparticle dissolution while simultaneously providing chemical signatures that differentiate between citrate-capped silver nanoparticles (AgNPs), AgNPs forced into dissolution via exposure to UV radiation, silver nitrate (AgNO3), and AgNO3/citrate deposited from aqueous solutions and suspensions. We utilize recently developed inkjet printing (IJP) protocols to deposit the different solutions/suspensions as NP aggregates and soluble species, which separate onto surfaces in situ, and collect mass spectral imaging data via time-of-flight secondary ion mass spectrometry (TOF-SIMS). Resulting 2D Ag(+) chemical images provide the ability to distinguish between the different Ag-containing starting materials and, when coupled with mass spectral peak ratios, provide information-rich data sets for quick and reproducible visualization of NP-based aqueous constituents. When compared to other measurements aimed at studying NP dissolution, the IJP-TOF-SIMS approach offers valuable information that can potentially help in understanding the complex equilibria in NP-containing solutions and suspensions, including NP dissolution kinetics and extent of overall dissolution. PMID:24611464

  16. The kinetics of Dissolution of Biologically Formed Calcific Deposits.

    NASA Astrophysics Data System (ADS)

    Rokidi, Stamatia; Koutsoukos, Petros

    2015-04-01

    order (ca.3) for the biominerals. This mode of dependence for both minerals studied, suggested surface diffusion controlled mechanism for their dissolution. The apparent rates of dissolution of the calcific deposits were higher in comparison to the corresponding value of the stoichiometric HAP. This finding is due to the higher apparent solubility of the carbonate and other metals containing biominerals. It should be noted that the dissolution affected the morphology of the prismatic crystallites which became thinner and shorter suggesting that the dissolution was rather uniform in the a, b and c axes of the prismatic crystallites. ACKNOWLEGMENT This research was partially funded by the European Union (European Social Fund-ESF) and Greek National Funds through the Operational program Education and Lifelong Learning' under the action Aristeia II (Code No 4420).

  17. Lattice Boltzmann simulation of chemical dissolution in porous media.

    PubMed

    Kang, Qinjun; Zhang, Dongxiao; Chen, Shiyi; He, Xiaoyi

    2002-03-01

    In this paper, we develop a lattice Boltzmann model for simulating the transport and reaction of fluids in porous media. To simulate such a system, we account for the interaction of forced convection, molecular diffusion, and surface reaction. The problem is complicated by the evolution of the porous media geometry due to chemical reactions, which may significantly and continuously modify the hydrologic properties of the media. The particular application that motivates the present study is acid stimulation, a common technique used to increase production from petroleum reservoirs. This technique involves the injection of acid (e.g., hydrochloric acid, HCl, acetic acid, HAc) into the formation to dissolve minerals comprising the rock. As acid is injected, highly conductive channels or "wormholes" may be formed. The dissolution of carbonate rocks in 0.5M HCl and 0.5M HAc is simulated with the lattice Boltzmann model developed in this study. The dependence of dissolution process and the geometry of the final wormhole pattern on the acid type and the injection rate is studied. The results agree qualitatively with the experimental and theoretical analyses of others and substantiate the previous finding that there exists an optimal injection rate at which the wormhole is formed as well as the number of pore volumes of the injected fluid to break through is minimized. This study also confirms the experimentally observed phenomenon that the optimal injection rate decreases and the corresponding minimized number of pore volumes to break through increases as the acid is changed from HCl to HAc. Simulations suggest that the proposed lattice Boltzmann model may serve as an alternative reliable quantitative approach to study chemical dissolution in porous media. PMID:11909255

  18. Criticality safety in high explosives dissolution

    SciTech Connect

    Troyer, S.D.

    1997-06-01

    In 1992, an incident occurred at the Pantex Plant in which the cladding around a fissile material component (pit) cracked during dismantlement of the high explosives portion of a nuclear weapon. Although the event did not result in any significant contamination or personnel exposures, concerns about the incident led to the conclusion that the current dismantlement process was unacceptable. Options considered for redesign, dissolution tooling design considerations, dissolution tooling design features, and the analysis of the new dissolution tooling are summarized. The final tooling design developed incorporated a number of safety features and provides a simple, self-contained, low-maintenance method of high explosives removal for nuclear explosive dismantlement. Analyses demonstrate that the tooling design will remain subcritical under normal, abnormal, and credible accident scenarios. 1 fig.

  19. Dissolution DNP for in vivo preclinical studies

    NASA Astrophysics Data System (ADS)

    Comment, Arnaud

    2016-03-01

    The tremendous polarization enhancement afforded by dissolution dynamic nuclear polarization (DNP) can be taken advantage of to perform preclinical in vivo molecular and metabolic imaging. Following the injection of molecules that are hyperpolarized via dissolution DNP, real-time measurements of their biodistribution and metabolic conversion can be recorded. This technology therefore provides a unique and invaluable tool for probing cellular metabolism in vivo in animal models in a noninvasive manner. It gives the opportunity to follow and evaluate disease progression and treatment response without requiring ex vivo destructive tissue assays. Although its considerable potential has now been widely recognized, hyperpolarized magnetic resonance by dissolution DNP remains a challenging method to implement for routine in vivo preclinical measurements. The aim of this article is to provide an overview of the current state-of-the-art technology for preclinical applications and the challenges that need to be addressed to promote it and allow its wider dissemination in the near future.

  20. Formation and dissolution of bacterial colonies.

    PubMed

    Weber, Christoph A; Lin, Yen Ting; Biais, Nicolas; Zaburdaev, Vasily

    2015-09-01

    Many organisms form colonies for a transient period of time to withstand environmental pressure. Bacterial biofilms are a prototypical example of such behavior. Despite significant interest across disciplines, physical mechanisms governing the formation and dissolution of bacterial colonies are still poorly understood. Starting from a kinetic description of motile and interacting cells we derive a hydrodynamic equation for their density on a surface, where most of the kinetic coefficients are estimated from experimental data for N. gonorrhoeae bacteria. We use it to describe the formation of multiple colonies with sizes consistent with experimental observations. Finally, we show how the changes in the cell-to-cell interactions lead to the dissolution of the bacterial colonies. The successful application of kinetic theory to a complex far from equilibrium system such as formation and dissolution of living bacterial colonies potentially paves the way for the physical quantification of the initial stages of biofilm formation. PMID:26465495

  1. Formation and dissolution of bacterial colonies

    NASA Astrophysics Data System (ADS)

    Weber, Christoph A.; Lin, Yen Ting; Biais, Nicolas; Zaburdaev, Vasily

    2015-09-01

    Many organisms form colonies for a transient period of time to withstand environmental pressure. Bacterial biofilms are a prototypical example of such behavior. Despite significant interest across disciplines, physical mechanisms governing the formation and dissolution of bacterial colonies are still poorly understood. Starting from a kinetic description of motile and interacting cells we derive a hydrodynamic equation for their density on a surface, where most of the kinetic coefficients are estimated from experimental data for N. gonorrhoeae bacteria. We use it to describe the formation of multiple colonies with sizes consistent with experimental observations. Finally, we show how the changes in the cell-to-cell interactions lead to the dissolution of the bacterial colonies. The successful application of kinetic theory to a complex far from equilibrium system such as formation and dissolution of living bacterial colonies potentially paves the way for the physical quantification of the initial stages of biofilm formation.

  2. Dissolution DNP for in vivo preclinical studies.

    PubMed

    Comment, Arnaud

    2016-03-01

    The tremendous polarization enhancement afforded by dissolution dynamic nuclear polarization (DNP) can be taken advantage of to perform preclinical in vivo molecular and metabolic imaging. Following the injection of molecules that are hyperpolarized via dissolution DNP, real-time measurements of their biodistribution and metabolic conversion can be recorded. This technology therefore provides a unique and invaluable tool for probing cellular metabolism in vivo in animal models in a noninvasive manner. It gives the opportunity to follow and evaluate disease progression and treatment response without requiring ex vivo destructive tissue assays. Although its considerable potential has now been widely recognized, hyperpolarized magnetic resonance by dissolution DNP remains a challenging method to implement for routine in vivo preclinical measurements. The aim of this article is to provide an overview of the current state-of-the-art technology for preclinical applications and the challenges that need to be addressed to promote it and allow its wider dissemination in the near future. PMID:26920829

  3. Occupational exposure to complex mixtures of volatile organic compounds in ambient air: desorption from activated charcoal using accelerated solvent extraction can replace carbon disulfide?

    PubMed

    Fabrizi, Giovanni; Fioretti, Marzia; Rocca, Lucia Mainero

    2013-01-01

    A desorption study of 57 volatile organic compounds (VOCs) has been conducted by use of accelerated solvent extraction (ASE) and gas chromatography-mass spectrometry. Different solvents were tested to extract activated charcoal tubes with the objective of replacing carbon disulfide, used in official methods, because of its highly toxic health and environmental effects. Extraction conditions, for example temperature and number of cycles, were investigated and optimized. The definitive extraction procedure selected was use of acetone at 150 °C and two consecutive extraction cycles at a pressure of 1,500 psi. Considering a sample volume of 0.005 Nm(3), corresponding to a sampling time of 8 h at a flow rate of 0.01 L min(-1), the method was validated over the concentration range 65-26,300 μg Nm(-3). The lowest limit of quantification was 6 μg Nm(-3), and recovery for the 93 % of analytes ranged from 65 to 102 %. For most of the compounds, relative standard deviations were less than 15 % for inter and intra-day precision. Uncertainty of measurement was also determined: the relative expanded uncertainty was always below 29.6 %, except for dichlorodifluoromethane. This work shows that use of friendlier solvent, for example acetone, coupled with use of ASE, can replace use of CS(2) for chemical removal of VOCs from activated charcoal. ASE has several advantages over traditional solvent-extraction methods, including shorter extraction time, minimum sample manipulation, high reproducibility, and less extraction discrimination. No loss of sensitivity occurs and there is also a salutary effect on bench workers' health and on the smell of laboratory air. PMID:22968683

  4. Combination of cathodic reduction with adsorption for accelerated removal of Cr(VI) through reticulated vitreous carbon electrodes modified with sulfuric acid-glycine co-doped polyaniline.

    PubMed

    Mo, Xi; Yang, Zhao-hui; Xu, Hai-yin; Zeng, Guang-ming; Huang, Jing; Yang, Xia; Song, Pei-pei; Wang, Li-ke

    2015-04-01

    Improving the reduction kinetics is crucial in the electroreduction process of Cr(VI). In this study, we developed a novel adsorption-electroreduction system for accelerated removal of Cr(VI) by employing reticulated vitreous carbon electrode modified with sulfuric acid-glycine co-doped polyaniline (RVC/PANI-SA-GLY). Firstly, response surface methodology confirmed the optimum polymerization condition of co-doped polyaniline for modifying electrodes (Aniline, sulfuric acid and glycine, respectively, of 0.2 mol/L, 0.85 mol/L, 0.93 mol/L) when untraditional dopant glycine was added. Subsequently, RVC/PANI-SA-GLY showed higher Cr(VI) removal percentages in electroreduction experiments over RVC electrode modified with sulfuric acid doped polyaniline (RVC/PANI-SA) and bare RVC electrode. In contrast to RVC/PANI-SA, the improvement by RVC/PANI-SA-GLY was more significant and especially obvious at more negative potential, lower initial Cr(VI) concentration, relatively less acidic solution and higher current densities, best achieving 7.84% higher removal efficiency with entire Cr(VI) eliminated after 900 s. Current efficiencies were likewise enhanced by RVC/PANI-SA-GLY under quite negative potentials. Fourier transform infrared (FTIR) and energy dispersive spectrometer (EDS) analysis revealed a possible adsorption-reduction mechanism of RVC/PANI-SA-GLY, which greatly contributed to the faster reduction kinetics and was probably relative to the absorption between protonated amine groups of glycine and HCrO4(-). Eventually, the stability of RVC/PANI-SA-GLY was proven relatively satisfactory. PMID:25603298

  5. Radiolytic modelling of spent fuel oxidative dissolution mechanism. Calibration against UO 2 dynamic leaching experiments

    NASA Astrophysics Data System (ADS)

    Merino, J.; Cera, E.; Bruno, J.; Quiñones, J.; Casas, I.; Clarens, F.; Giménez, J.; de Pablo, J.; Rovira, M.; Martínez-Esparza, A.

    2005-11-01

    Calibration and testing are inherent aspects of any modelling exercise and consequently they are key issues in developing a model for the oxidative dissolution of spent fuel. In the present work we present the outcome of the calibration process for the kinetic constants of a UO 2 oxidative dissolution mechanism developed for using in a radiolytic model. Experimental data obtained in dynamic leaching experiments of unirradiated UO 2 has been used for this purpose. The iterative calibration process has provided some insight into the detailed mechanism taking place in the alteration of UO 2, particularly the role of rad OH radicals and their interaction with the carbonate system. The results show that, although more simulations are needed for testing in different experimental systems, the calibrated oxidative dissolution mechanism could be included in radiolytic models to gain confidence in the prediction of the long-term alteration rate of the spent fuel under repository conditions.

  6. Comparison of three preservation techniques for slowing dissolution of calcareous nannofossils in organic rich sediments

    USGS Publications Warehouse

    Seefelt, Ellen L.; Self-Trail, Jean; Schultz, Arthur P.

    2015-01-01

    In an attempt to halt or reduce dissolution of calcareous nannofossils in organic and/or pyrite-rich sediments, three different methods of short-term storage preservation were tested for efficacy: vacuum packing, argon gas replacement, and buffered water. Abundance counts of calcareous nannofossil assemblages over a six month period showed that none of the three preservation methods were consistently effective in reducing assemblage loss due to dissolution. In most cases, the control slides made at the drill site had more abundant calcareous nannofossil assemblages than those slides made from sediments stored via vacuum packing, argon gas replacement, or buffered water. Thin section and XRD analyses showed that in most cases, <1% pyrite was needed to drive the oxidation-reduction reaction that resulted in dissolution, even in carbonate-rich sediments.

  7. Dissolution of biogenic ooze over basement edifices in the equatorial Pacific with implications for hydrothermal ventilation of the oceanic crust

    USGS Publications Warehouse

    Bekins, B.A.; Spivack, A.J.; Davis, E.E.; Mayer, L.A.

    2007-01-01

    Recent observations indicate that curious closed depressions in carbonate sediments overlying basement edifices are widespread in the equatorial Pacific. A possible mechanism for their creation is dissolution by fluids exiting basement vents from off-axis hydrothermal flow. Quantitative analysis based on the retrograde solubility of calcium carbonate and cooling of basement fluids during ascent provides an estimate for the dissolution capacity of the venting fluids. Comparison of the dissolution capacity and fluid flux with typical equatorial Pacific carbonate mass accumulation rates shows that this mechanism is feasible. By maintaining sediment-free basement outcrops, the process may promote widespread circulation of relatively unaltered seawater in the basement in an area where average sediment thicknesses are 300-500 m. The enhanced ventilation can explain several previously puzzling observations in this region, including anomalously low heat flux, relatively unaltered seawater in the basement, and aerobic and nitrate-reducing microbial activity at the base of the sediments. ?? 2007 The Geological Society of America.