CO{sub 2} emissions: mineral carbonation and Finnish pulp and paper industry (CO{sub Nordic Plus}) and use of serpentinites in energy and metal industry (ECOSERP); Hiilidioksidipaeaestoet: Mineraalikarbonointi ja Suomen massaja paperiteollisuus (CO{sub 2} Nordic plus) ja serpentiinin hyoetykaeyttoe energia- ja metalliteollisuudessa (ECOSERP)

Energy Technology Data Exchange (ETDEWEB)

Fogelholm, C.J.; Raiski, T.; Teir, S. [Helsinki Univ. of Technology, Espoo (Finland). Lab of Energy Engineering and Environmental Protection

2006-12-19

Mineral carbonation has been investigated at Helsinki University of Technology (TKK), laboratory of energy engineering and environmental protection since year 2000. The Finnish Technology Agency Tekes and the Finnish Recovery Boiler Committee are funding through the ClimBus technology programme, in conjunction with the Nordic Energy Research Programme, the research regarding the application of ex situ mineral carbonation processes. One aspect is to verify the possible use of mineral carbonation for the separation, utilisation and long-term storage of carbon dioxide (CO2) in the pulp and paper industry. The Geological Survey of Finland (GTK) has been screening since 2004 the location, quality and suitability of the Finnish processed serpentine and stopped serpentinite storage of mines and in situ serpentinite bodies of ultramafic rock formations for mineral carbonation of CO2. Tekes and the GTK are funding development work through the ClimBus technology programme on the utilisation of serpentine and serpentinite for CO2 sequestration purposes, based on economical and environmental evaluation of mineral and mining processing operations. Also the options for other use of serpentine and serpentinite are evaluated. The most promising magnesium and calcium-based sources for carbonation are by products of mining processes of ultramafic rocks (such as serpentinites and serpentine) and steelmaking slags. Carbonated minerals could possibly be used as paper coating materials (PCC), fillers or construction materials. For magnesium carbonate new markets and applications must be developed. (orig.)

Tailings and mineral carbonation : the potential for atmospheric CO{sub 2} sequestration

Energy Technology Data Exchange (ETDEWEB)

Rollo, H.A. [Lorax Environmental Services Ltd., Vancouver, BC (Canada); Jamieson, H.E. [Queen' s Univ., Kingston, ON (Canada). Dept. of Geological Sciences and Geological Engineering; Lee, C.A. [Dillon Consulting Ltd., Cambridge, ON (Canada)

2009-02-15

Carbon dioxide (CO{sub 2}) sequestration includes geological storage, ocean storage, organic storage, and mineral storage (mineral carbonation). This presentation discussed tailings and mineral carbonation and the potential for atmospheric CO{sub 2} sequestration. In particular, it outlined CO{sub 2} sequestration and presented a history of investigations. The Ekati Diamond Mine was discussed with particular reference to its location, geology, and processing. Other topics that were presented included mineralogy; water chemistry; modeling results; and estimates of annual CO{sub 2} sequestration. Conclusions and implications were also presented. It was concluded that ore processing at mines with ultramafic host rocks have the potential to partially offset CO{sub 2} emissions. In addition, it was found that existing tailings at ultramafic deposits may be viable source materials for CO{sub 2} sequestration by mineral carbonation. tabs., figs.

CO2 emissions: mineral carbonation and Finnish pulp and paper industry (CONordicPlus) and use of serpentinites in energy and metal industry (ECOSERP)

International Nuclear Information System (INIS)

Fogelholm, C.J.; Raiski, T.; Teir, S.

2006-01-01

Mineral carbonation has been investigated at Helsinki University of Technology (TKK), laboratory of energy engineering and environmental protection since year 2000. The Finnish Technology Agency Tekes and the Finnish Recovery Boiler Committee are funding through the ClimBus technology programme, in conjunction with the Nordic Energy Research Programme, the research regarding the application of ex situ mineral carbonation processes. One aspect is to verify the possible use of mineral carbonation for the separation, utilisation and long-term storage of carbon dioxide (CO2) in the pulp and paper industry. The Geological Survey of Finland (GTK) has been screening since 2004 the location, quality and suitability of the Finnish processed serpentine and stopped serpentinite storage of mines and in situ serpentinite bodies of ultramafic rock formations for mineral carbonation of CO2. Tekes and the GTK are funding development work through the ClimBus technology programme on the utilisation of serpentine and serpentinite for CO2 sequestration purposes, based on economical and environmental evaluation of mineral and mining processing operations. Also the options for other use of serpentine and serpentinite are evaluated. The most promising magnesium and calcium-based sources for carbonation are by products of mining processes of ultramafic rocks (such as serpentinites and serpentine) and steelmaking slags. Carbonated minerals could possibly be used as paper coating materials (PCC), fillers or construction materials. For magnesium carbonate new markets and applications must be developed. (orig.)

Hydrothermal Valorization of Steel Slags—Part I: Coupled H2 Production and CO2 Mineral Sequestration

Directory of Open Access Journals (Sweden)

Camille Crouzet

2017-10-01

Full Text Available A new process route for the valorization of BOF steel slags combining H2 production and CO2 mineral sequestration is investigated at 300°C (HT under hydrothermal conditions. A BOF steel slag stored several weeks outdoor on the production site was used as starting material. To serve as a reference, room temperature (RT carbonation of the same BOF steel slag has been monitored with in situ Raman spectroscopy and by measuring pH and PCO2 on a time-resolved basis. CO2 uptake under RT and HT are, respectively, 243 and 327 kg CO2/t of fresh steel slag, which add up with the 63 kg of atmospheric CO2 per ton already uptaken by the starting steel slag on the storage site. The CO2 gained by the sample at HT is bounded to the carbonation of brownmillerite. H2 yield decreased by about 30% in comparison to the same experiment performed without added CO2, due to sequestration of ferrous iron in a Mg-rich siderite phase. Ferric iron, initially present in brownmillerite, is partitioned between an Fe-rich clay mineral of saponite type and metastable hematite. Saponite is likely stabilized by the presence of Al, whereas hematite may represent a metastable product of brownmillerite carbonation. Mg-rich wüstite is involved in at least two competing reactions, i.e., oxidation into magnetite and carbonation into siderite. Results of both water-slag and water-CO2-slag experiments after 72 h are consistent with a kinetics enhancement of the former reaction when a CO2 partial pressure imposes a pH between 5 and 6. Three possible valorization routes, (1 RT carbonation prior to hydrothermal oxidation, (2 RT carbonation after hydrothermal treatment, and (3 combined HT carbonation and oxidation are discussed in light of the present results and literature data.

Mineral CO2 sequestration by steel slag carbonation

International Nuclear Information System (INIS)

Huijgen, W.J.J.; Comans, R.N.J.; Witkamp, G.J.

2005-12-01

Mineral CO2 sequestration, i.e., carbonation of alkaline silicate Ca/Mg minerals, analogous to natural weathering processes, is a possible technology for the reduction of carbon dioxide emissions to the atmosphere. In this paper, alkaline Ca-rich industrial residues are presented as a possible feedstock for mineral CO2 sequestration. These materials are cheap, available near large point sources of CO2, and tend to react relatively rapidly with CO2 due to their chemical instability. Ground steel slag was carbonated in aqueous suspensions to study its reaction mechanisms. Process variables, such as particle size, temperature, carbon dioxide pressure, and reaction time, were systematically varied, and their influence on the carbonation rate was investigated. The maximum carbonation degree reached was 74% of the Ca content in 30 min at 19 bar pressure, 100C, and a particle size of <38 μm. The two must important factors determining the reaction rare are particle size (<2 mm to <38 μm) and reaction temperature (25-225C). The carbonation reaction was found to occur in two steps: (1) leaching of calcium from the steel slag particles into the solution; (2) precipitation of calcite on the surface of these particles. The first step and, more in particular, the diffusion of calcium through the solid matrix toward the surface appeared to be the rate-determining reaction step, The Ca diffusion was found to be hindered by the formation of a CaCO3-coating and a Ca-depleted silicate zona during the carbonation process. Research on further enhancement of the reaction rate, which would contribute to the development of a cost-effective CO2-sequestration process, should focus particularly on this mechanism

Impact of elevated CO_2 concentrations on carbonate mineral precipitation ability of sulfate-reducing bacteria and implications for CO_2 sequestration

International Nuclear Information System (INIS)

Paul, Varun G.; Wronkiewicz, David J.; Mormile, Melanie R.

2017-01-01

Interest in anthropogenic CO_2 release and associated global climatic change has prompted numerous laboratory-scale and commercial efforts focused on capturing, sequestering or utilizing CO_2 in the subsurface. Known carbonate mineral precipitating microorganisms, such as the anaerobic sulfate-reducing bacteria (SRB), could enhance the rate of conversion of CO_2 into solid minerals and thereby improve long-term storage of captured gasses. The ability of SRB to induce carbonate mineral precipitation, when exposed to atmospheric and elevated pCO_2, was investigated in laboratory scale tests with bacteria from organic-rich sediments collected from hypersaline Lake Estancia, New Mexico. The enriched SRB culture was inoculated in continuous gas flow and batch reactors under variable headspace pCO_2 (0.0059 psi to 20 psi). Solution pH, redox conditions, sulfide, calcium and magnesium concentrations were monitored in the reactors. Those reactors containing SRB that were exposed to pCO_2 of 14.7 psi or less showed Mg-calcite precipitation. Reactors exposed to 20 psi pCO_2 did not exhibit any carbonate mineralization, likely due to the inhibition of bacterial metabolism caused by the high levels of CO_2. Hydrogen, lactate and formate served as suitable electron donors for the SRB metabolism and related carbonate mineralization. Carbon isotopic studies confirmed that ∼53% of carbon in the precipitated carbonate minerals was derived from the CO_2 headspace, with the remaining carbon being derived from the organic electron donors, and the bicarbonate ions available in the liquid medium. The ability of halotolerant SRB to induce the precipitation of carbonate minerals can potentially be applied to the long-term storage of anthropogenic CO_2 in saline aquifers and other ideal subsurface rock units by converting the gas into solid immobile phases. - Highlights: • SRB under study are capable of precipitating calcite up to 14.7 psi pCO_2. • At 20 psi pCO_2, bacterial activity

Experiment and simulation study on the effects of cement minerals on the water-rock-CO2 interaction during CO2 geological storage

Science.gov (United States)

Liu, N.; Cheng, J.

2016-12-01

The CO2 geological storage is one of the most promising technology to mitigate CO2 emission. The fate of CO2 underground is dramatically affected by the CO2-water-rock interaction, which are mainly dependent on the initial aquifer mineralogy and brine components. The cement minerals are common materials in sandstone reservoir but few attention has been paid for its effects on CO2-water-rock interaction. Five batch reactions, in which 5% cement minerals were assigned to be quartz, calcite, dolomite, chlorite and Ca-montmorillonite, respectively, were conducted to understanding the cement minerals behaviors and its corresponding effects on the matrix minerals alterations during CO2 geological storage. Pure mineral powders were selected to mix and assemble the 'sandstone rock' with different cement components meanwhile keeping the matrix minerals same for each group as 70% quartz, 20% K-feldspar and 5% albite. These `rock' reacted with 750ml deionized water and CO2 under 180° and 18MPa for 15 days, during which the water chemistry evolution and minerals surface micromorphology changes has been monitored. The minerals saturation indexes calculation and phase diagram as well as the kinetic models were made by PHREEQC to uncover the minerals reaction paths. The experiment results indicated that the quartz got less eroded, on the contrary, K-feldspar and albite continuously dissolved to favor the gibbsite and kaolinite precipitations. The carbonates cement minerals quickly dissolved to reach equilibrium with the pH buffered and in turn suppressed the alkali feldspar dissolutions. No carbonates minerals precipitations occurred until the end of reactions for all groups. The simulation results were basically consistent with the experiment record but failed to simulate the non-stoichiometric reactions and the minerals kinetic rates seemed underestimated at the early stage of reactions. The cement minerals significantly dominated the reaction paths during CO2 geological

An experimental study on mineral sequestration of CO2 in basics and ultra basics rocks

International Nuclear Information System (INIS)

Dufaud, F.

2006-11-01

The first part of the thesis is dedicated to dissolution data of siderite FeCO 3 and magnetite Fe 3 O 4 which have been monitored in situ on the FAME beamline of the european synchrotron radiation facility in Grenoble. Iron in solution close to siderite single crystals is shown to be divalent hydrated. The small size of the experimentally investigated volume of solution (200 *400 micrometer and 3 mm height) allowed to work with single crystals in well defined geometries. No specific interaction was observed between iron (II) and dissolved inorganic carbon, suggesting that modelling siderite evolution under high CO 2 pressures by using CO 2 -less very acidic (pH 1-2) solutions is adequate. Using initial reaction rates, we get an activation energy for siderite dissolution of 62 kJ.mol -1 , consistent with existing literature data. Such a value is suggestive of a mineral/solution interface mechanism.. Data from this study and from literature are consistent over a temperature range 25 C - 125 C and a pH range pH 1-7 with an empirical law: pk = pH + E a /(ln(10)*RT(K)) - log(S/V) - 10,5 where E a = 62 kJ.mol -1 and S/V is the ratio between solid surface S and fluid volume V. A value of activation energy of 73.5 kJ.mol -1 is obtained in the case of magnetite, also consistent with mineral/solution processes. The second and major part of the thesis work is the realization of analogical experiments for simulating carbonation of basic and ultra basic minerals. Experiments were carried out on consolidated rock cores at 90 C and 280 bar of CO 2 (low temperature experiments) and on powders contained in metallic capsules at 400-500 C and 1000-1700 bars of CO 2 (high temperature experiments). The rate of mineral storage of CO 2 was defined as the molar ratio of solid carbonate formed over total CO 2 injected. It is of about 1% in three months in low temperature experiments whereas it reaches several tens of percents per hour in high temperature experiments. In all cases

Energy consumption and net CO2 sequestration of aqueous mineral carbonation

International Nuclear Information System (INIS)

Huijgen, W.J.J.; Ruijg, G.J.; Comans, R.N.J.; Witkamp, G.J.

2006-12-01

Aqueous mineral carbonation is a potentially attractive sequestration technology to reduce CO2 emissions. The energy consumption of this technology, however, reduces the net amount of CO2 sequestered. Therefore, the energetic CO2 sequestration efficiency of aqueous mineral carbonation was studied in dependence of various process variables using either wollastonite (CaSiO3) or steel slag as feedstock. For wollastonite, the maximum energetic CO2 sequestration efficiency within the ranges of process conditions studied was 75% at 200C, 20 bar CO2, and a particle size of <38μm. The main energy-consuming process steps were the grinding of the feedstock and the compression of the CO2 feed. At these process conditions, a significantly lower efficiency was determined for steel slag (69%), mainly because of the lower Ca content of the feedstock. The CO2 sequestration efficiency might be improved substantially for both types of feedstock by, e.g., reducing the amount of process water applied and further grinding of the feedstock. The calculated energetic efficiencies warrant a further assessment of the (energetic) feasibility of CO2 sequestration by aqueous mineral carbonation on the basis of a pilot-scale process

Simplified models of rates of CO2 mineralization in Geologic Carbon Storage

Science.gov (United States)

DePaolo, D. J.; Zhang, S.

2017-12-01

Geologic carbon storage (GCS) reverses the flow of carbon to the atmosphere, returning the carbon to long-term geologic storage. Models suggest that most of the injected CO2 will be "trapped" in the subsurface by physical means, but the most risk-free and permanent form of carbon storage is as carbonate minerals (Ca,Mg,Fe)CO3. The transformation of CO2 to carbonate minerals requires supply of divalent cations by dissolution of silicate minerals. Available data suggest that rates of transformation are difficult to predict. We show that the chemical kinetic observations and experimental results, when reduced to a single timescale that describes the fractional rate at which cations are released to solution by mineral dissolution, show sufficiently systematic behavior that the rates of mineralization can be estimated with reasonable certainty. Rate of mineralization depends on both the abundance (determined by the reservoir rock mineralogy) and the rate at which cations are released by dissolution into pore fluid that has been acidified with dissolved CO2. Laboratory-measured rates and field observations give values spanning 8 to 10 orders of magnitude, but when evaluated in the context of reservoir-scale reactive transport simulations, this range becomes much smaller. Reservoir scale simulations indicate that silicate mineral dissolution and subsequent carbonate mineral precipitation occur at pH 4.5 to 6, fluid flow velocity less than 5m/yr, and 50-100 years or more after the start of injection. These constraints lead to estimates of 200 to 2000 years for conversion of 60-90% of injected CO2 when the reservoir rock has a sufficient volume fraction of divalent cation-bearing silicate minerals (ca. 20%), and confirms that when reservoir rock mineralogy is not favorable the fraction of CO2 converted to carbonate minerals is minimal over 104 years. A sufficient amount of reactive minerals represents the condition by which the available cations per volume of rock plus pore

In-situ Optical Spectroscopy Investigation of Water and Its influence on Forsterite Transformation in Supercritical CO2

Science.gov (United States)

Wang, Z.; Thompson, C. J.; Joly, A. G.; Sklarew, D. S.; Poindexter, L.; Rosso, K. M.

2009-12-01

Carbon capture and sequestration (CCS) from coal/gas-burning power plants is currently viewed as one of the most promising technologies for mitigating green house gas emissions. This strategy involves injection of supercritical CO2 (scCO2) into deep geological formations such as depleted oil and gas reservoirs and deep saline aquifers. The feasibility of this approach and the ultimate fate of the stored CO2 are determined by the interactions between scCO2, various minerals in the rock formations, and the host fluids. Currently, there is only limited knowledge about both the thermodynamic and kinetic aspects of the physical and chemical processes that occur between scCO2 and relevant minerals, such as metal silicates and metal aluminosilicates, and the role of water activity for catalyzing mineral transformation reactions. In this work, we have developed a modular in situ optical spectroscopic platform that integrates a scCO2 generation and manipulation system with an array of optical and laser spectroscopies including UV-visible, IR, Raman and laser fluorescence spectroscopy. We have used the system to study i) the dissolution and quantification of H2O/D2O in scCO2 and ii) interaction between scCO2 and a model metal silicate, forsterite (Mg2SiO4), and the effects of the presence of water under variable pressure, temperature and water content. Our results showed that H2O and D2O have unique IR spectral features over a broad spectral range from 700 cm-1 to ~ 2900 cm-1 in scCO2 and their concentrations are directly proportional to the characteristic IR bands that correspond to their stretching (D2O) and bending frequencies (both D2O and H2O). These bands offer a unique spectroscopic signature useful for qualitative and quantitative analysis of the properties and reactivity of small amounts of H2O in scCO2. metal carbonation reactions relevant to sequestration.

Analysis of mineral trapping for CO{sub 2} disposal in deep aquifers

Energy Technology Data Exchange (ETDEWEB)

Xu, Tianfu; Apps, John A.; Pruess, Karsten

2001-07-20

CO{sub 2} disposal into deep aquifers has been suggested as a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO{sub 2} disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO{sub 2} injection, we have analyzed the impact of CO{sub 2} immobilization through carbonate precipitation. A survey of all major classes of rock-forming minerals, whose alteration would lead to carbonate precipitation, indicated that very few minerals are present in sufficient quantities in aquifer host rocks to permit significant sequestration of CO{sub 2}. We performed batch reaction modeling of the geochemical evolution of three different aquifer mineralogies in the presence of CO{sub 2} at high pressure. Our modeling considered (1) redox processes that could be important in deep subsurface environments, (2) the presence of organic matter, (3) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, and (4) CO{sub 2} solubility dependence on pressure, temperature and salinity of the system. The geochemical evolution under both natural background and CO{sub 2} injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO{sub 2} sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO{sub 2} that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO{sub 2} dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of ferric mineral precursors such as glauconite, which in turn is dependent on the reactivity of associated organic material. The accumulation of carbonates in

Numerical simulation of CO2 disposal by mineral trapping in deep aquifers

International Nuclear Information System (INIS)

Xu Tianfu; Apps, John A.; Pruess, Karsten

2004-01-01

Carbon dioxide disposal into deep aquifers is a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO 2 disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO 2 injection, the authors have analyzed the impact of CO 2 immobilization through carbonate mineral precipitation. Batch reaction modeling of the geochemical evolution of 3 different aquifer mineral compositions in the presence of CO 2 at high pressure were performed. The modeling considered the following important factors affecting CO 2 sequestration: (1) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, (2) CO 2 solubility dependence on pressure, temperature and salinity of the system, and (3) redox processes that could be important in deep subsurface environments. The geochemical evolution under CO 2 injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO 2 sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO 2 that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO 2 dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of Fe(III) mineral precursors such as goethite or glauconite. The accumulation of carbonates in the rock matrix leads to a considerable decrease in porosity. This in turn adversely affects permeability and fluid flow in the aquifer. The numerical experiments described here provide useful insight into sequestration mechanisms, and their controlling geochemical conditions and parameters

In situ evidence of mineral physical protection and carbon stabilization revealed by nanoscale 3-D tomography

Science.gov (United States)

Weng, Yi-Tse; Wang, Chun-Chieh; Chiang, Cheng-Cheng; Tsai, Heng; Song, Yen-Fang; Huang, Shiuh-Tsuen; Liang, Biqing

2018-05-01

An approach for nanoscale 3-D tomography of organic carbon (OC) and associated mineral nanoparticles was developed to illustrate their spatial distribution and boundary interplay, using synchrotron-based transmission X-ray microscopy (TXM). The proposed 3-D tomography technique was first applied to in situ observation of a laboratory-made consortium of black carbon (BC) and nanomineral (TiO2, 15 nm), and its performance was evaluated using dual-scan (absorption contrast and phase contrast) modes. This novel tool was then successfully applied to a natural OC-mineral consortium from mountain soil at a spatial resolution of 60 nm, showing the fine structure and boundary of OC, the distribution of abundant nano-sized minerals, and the 3-D organo-mineral association in situ. The stabilization of 3500-year-old natural OC was mainly attributed to the physical protection of nano-sized iron (Fe)-containing minerals (Fe oxyhydroxides including ferrihydrite, goethite, and lepidocrocite), and the strong organo-mineral complexation. In situ evidence revealed an abundance of mineral nanoparticles, in dense thin layers or nano-aggregates/clusters, instead of crystalline clay-sized minerals on or near OC surfaces. The key working minerals for C stabilization were reactive short-range-order (SRO) mineral nanoparticles and poorly crystalline submicron-sized clay minerals. Spectroscopic analyses demonstrated that the studied OC was not merely in crisscross co-localization with reactive SRO minerals; there could be a significant degree of binding between OC and the minerals. The ubiquity and abundance of mineral nanoparticles on the OC surface, and their heterogeneity in the natural environment may have been severely underestimated by traditional research approaches. Our in situ description of organo-mineral interplay at the nanoscale provides direct evidence to substantiate the importance of mineral physical protection for the long-term stabilization of OC. This high-resolution 3-D

Hydrothermal Valorization of Steel Slags—Part I: Coupled H{sub 2} Production and CO{sub 2} Mineral Sequestration

Energy Technology Data Exchange (ETDEWEB)

Crouzet, Camille [University Grenoble Alpes, University Savoie Mont Blanc, CNRS, IRD, IFSTTAR, ISTerre, Grenoble (France); LRCS and RS2E, CNRS-UMR7314, University Picardie Jules Verne, Amiens (France); Aix Marseille University, CNRS, Centrale Marseille, M2P2, Marseille (France); Brunet, Fabrice, E-mail: fabrice.brunet@univ-grenoble-alpes.fr; Montes-Hernandez, German [University Grenoble Alpes, University Savoie Mont Blanc, CNRS, IRD, IFSTTAR, ISTerre, Grenoble (France); Recham, Nadir [LRCS and RS2E, CNRS-UMR7314, University Picardie Jules Verne, Amiens (France); Findling, Nathaniel [University Grenoble Alpes, University Savoie Mont Blanc, CNRS, IRD, IFSTTAR, ISTerre, Grenoble (France); Ferrasse, Jean-Henry [Aix Marseille University, CNRS, Centrale Marseille, M2P2, Marseille (France); Goffé, Bruno [Aix-Marseille University, CNRS, IRD, Coll. de France, CEREGE, Aix-en-Provence (France)

2017-10-30

A new process route for the valorization of BOF steel slags combining H{sub 2} production and CO{sub 2} mineral sequestration is investigated at 300°C (HT) under hydrothermal conditions. A BOF steel slag stored several weeks outdoor on the production site was used as starting material. To serve as a reference, room temperature (RT) carbonation of the same BOF steel slag has been monitored with in situ Raman spectroscopy and by measuring pH and P{sub CO2} on a time-resolved basis. CO{sub 2} uptake under RT and HT are, respectively, 243 and 327 kg CO{sub 2}/t of fresh steel slag, which add up with the 63 kg of atmospheric CO{sub 2} per ton already uptaken by the starting steel slag on the storage site. The CO{sub 2} gained by the sample at HT is bounded to the carbonation of brownmillerite. H{sub 2} yield decreased by about 30% in comparison to the same experiment performed without added CO{sub 2}, due to sequestration of ferrous iron in a Mg-rich siderite phase. Ferric iron, initially present in brownmillerite, is partitioned between an Fe-rich clay mineral of saponite type and metastable hematite. Saponite is likely stabilized by the presence of Al, whereas hematite may represent a metastable product of brownmillerite carbonation. Mg-rich wüstite is involved in at least two competing reactions, i.e., oxidation into magnetite and carbonation into siderite. Results of both water-slag and water-CO{sub 2}-slag experiments after 72 h are consistent with a kinetics enhancement of the former reaction when a CO{sub 2} partial pressure imposes a pH between 5 and 6. Three possible valorization routes, (1) RT carbonation prior to hydrothermal oxidation, (2) RT carbonation after hydrothermal treatment, and (3) combined HT carbonation and oxidation are discussed in light of the present results and literature data.

Continuing Studies on Direct Aqueous Mineral Carbonation of CO{sub 2} Sequestration

Energy Technology Data Exchange (ETDEWEB)

O' Connor, W.K.; Dahlin, D.C.; Nilsen, D.N.; Gerdemann, S.J.; Rush, G.E.; Penner, L.R.; Walters, R.P.; Turner, P.C.

2002-03-04

Direct aqueous mineral carbonation has been investigated as a process to convert gaseous CO{sub 2} into a geologically stable, solid final form. The process utilizes a solution of sodium bicarbonate (NaHCO{sub 3}), sodium chloride (NaCl), and water, mixed with a mineral reactant, such as olivine (Mg{sub 2}SiO{sub 4}) or serpentine [Mg{sub 3}Si{sub 2}O{sub 5}(OH){sub 4}]. Carbon dioxide is dissolved into this slurry, by diffusion through the surface and gas dispersion within the aqueous phase. The process includes dissolution of the mineral and precipitation of the magnesium carbonate mineral magnesite (MgCO{sub 3}) in a single unit operation. Activation of the silicate minerals has been achieved by thermal and mechanical means, resulting in up to 80% stoichiometric conversion of the silicate to the carbonate within 30 minutes. Heat treatment of the serpentine, or attrition grinding of the olivine and/or serpentine, appear to activate the minerals by the generation of a non-crystalline phase. Successful conversion to the carbonate has been demonstrated at ambient temperature and relatively low (10 atm) partial pressure of CO{sub 2} (P{sub CO2}). However, optimum results have been achieved using the bicarbonate-bearing solution, and high P{sub CO2}. Specific conditions include: 185 C; P{sub CO2}=150 atm; 30% solids. Studies suggest that the mineral dissolution rate is not solely surface controlled, while the carbonate precipitation rate is primarily dependent on the bicarbonate concentration of the slurry. Current and future activities include further examination of the reaction pathways and pretreatment options, the development of a continuous flow reactor, and an evaluation of the economic feasibility of the process.

Retrieval of average CO2 fluxes by combining in situ CO2 measurements and backscatter lidar information

Science.gov (United States)

Gibert, Fabien; Schmidt, Martina; Cuesta, Juan; Ciais, Philippe; Ramonet, Michel; Xueref, IrèNe; Larmanou, Eric; Flamant, Pierre Henri

2007-05-01

The present paper deals with a boundary layer budgeting method which makes use of observations from various in situ and remote sensing instruments to infer regional average net ecosystem exchange (NEE) of CO2. Measurements of CO2 within and above the atmospheric boundary layer (ABL) by in situ sensors, in conjunction with a precise knowledge of the change in ABL height by lidar and radiosoundings, enable to infer diurnal and seasonal NEE variations. Near-ground in situ CO measurements are used to discriminate natural and anthropogenic contributions of CO2 diurnal variations in the ABL. The method yields mean NEE that amounts to 5 μmol m-2 s-1 during the night and -20 μmol m-2 s-1 in the middle of the day between May and July. A good agreement is found with the expected NEE accounting for a mixed wheat field and forest area during winter season, representative of the mesoscale ecosystems in the Paris area according to the trajectory of an air column crossing the landscape. Daytime NEE is seen to follow the vegetation growth and the change in the ratio diffuse/direct radiation. The CO2 vertical mixing flux during the rise of the atmospheric boundary layer is also estimated and seems to be the main cause of the large decrease of CO2 mixing ratio in the morning. The outcomes on CO2 flux estimate are compared to eddy-covariance measurements on a barley field. The importance of various sources of error and uncertainty on the retrieval is discussed. These errors are estimated to be less than 15%; the main error resulted from anthropogenic emissions.

Quantitative comparison of in situ soil CO2 flux measurement methods

Science.gov (United States)

Jennifer D. Knoepp; James M. Vose

2002-01-01

Development of reliable regional or global carbon budgets requires accurate measurement of soil CO2 flux. We conducted laboratory and field studies to determine the accuracy and comparability of methods commonly used to measure in situ soil CO2 fluxes. Methods compared included CO2...

Improved solar-driven photocatalytic performance of Ag_2CO_3/(BiO)_2CO_3 prepared in-situ

International Nuclear Information System (INIS)

Zhong, Junbo; Li, Jianzhang; Huang, Shengtian; Cheng, Chaozhu; Yuan, Wei; Li, Minjiao; Ding, Jie

2016-01-01

Highlights: • Ag_2CO_3/(BiO)_2CO_3 photocatalysts were prepared in-situ. • The photo-induced charge separation rate has been greatly increased. • The photocatalytic activity has been greatly promoted. - Abstract: Ag_2CO_3/(BiO)_2CO_3 composites have been fabricated in-situ via a facile parallel flaw co-precipitation method. The specific surface area, structure, morphology, and the separation rate of photo-induced charge pairs of the photocatalysts were characterized by Brunauer–Emmett–Teller (BET) method, X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy(DRS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and surface photovoltage (SPV) spectroscopy, respectively. XRD patterns and DRS demonstrated that Ag_2CO_3 has no effect on the crystal phase and bandgap of (BiO)_2CO_3. The existence of Ag_2CO_3 in the composites enhances the separation rate of photo-induced charge pairs of the photocatalysts. The photocatalytic performance of Ag_2CO_3/(BiO)_2CO_3 was evaluated by the decolorization of methyl orange (MO) aqueous solution under simulated solar irradiation. It was found that the simulated solar-induced photocatalytic activity of Ag_2CO_3/(BiO)_2CO_3 copmposites was significantly improved, which was mainly attributed to the enhanced surface area and the separation rate of photo-induced charge pairs.

Mineral Carbonation Potential of CO2 from Natural and Industrial-based Alkalinity Sources

Science.gov (United States)

Wilcox, J.; Kirchofer, A.

2014-12-01

Mineral carbonation is a Carbon Capture and Storage (CSS) technology where gaseous CO2 is reacted with alkaline materials (such as silicate minerals and alkaline industrial wastes) and converted into stable and environmentally benign carbonate minerals (Metz et al., 2005). Here, we present a holistic, transparent life cycle assessment model of aqueous mineral carbonation built using a hybrid process model and economic input-output life cycle assessment approach. We compared the energy efficiency and the net CO2 storage potential of various mineral carbonation processes based on different feedstock material and process schemes on a consistent basis by determining the energy and material balance of each implementation (Kirchofer et al., 2011). In particular, we evaluated the net CO2 storage potential of aqueous mineral carbonation for serpentine, olivine, cement kiln dust, fly ash, and steel slag across a range of reaction conditions and process parameters. A preliminary systematic investigation of the tradeoffs inherent in mineral carbonation processes was conducted and guidelines for the optimization of the life-cycle energy efficiency are provided. The life-cycle assessment of aqueous mineral carbonation suggests that a variety of alkalinity sources and process configurations are capable of net CO2 reductions. The maximum carbonation efficiency, defined as mass percent of CO2 mitigated per CO2 input, was 83% for CKD at ambient temperature and pressure conditions. In order of decreasing efficiency, the maximum carbonation efficiencies for the other alkalinity sources investigated were: olivine, 66%; SS, 64%; FA, 36%; and serpentine, 13%. For natural alkalinity sources, availability is estimated based on U.S. production rates of a) lime (18 Mt/yr) or b) sand and gravel (760 Mt/yr) (USGS, 2011). The low estimate assumes the maximum sequestration efficiency of the alkalinity source obtained in the current work and the high estimate assumes a sequestration efficiency

Cost evaluation of CO2 sequestration by aqueous mineral carbonation

International Nuclear Information System (INIS)

Huijgen, Wouter J.J.; Comans, Rob N.J.; Witkamp, Geert-Jan

2007-01-01

A cost evaluation of CO 2 sequestration by aqueous mineral carbonation has been made using either wollastonite (CaSiO 3 ) or steel slag as feedstock. First, the process was simulated to determine the properties of the streams as well as the power and heat consumption of the process equipment. Second, a basic design was made for the major process equipment, and total investment costs were estimated with the help of the publicly available literature and a factorial cost estimation method. Finally, the sequestration costs were determined on the basis of the depreciation of investments and variable and fixed operating costs. Estimated costs are 102 and 77 EUR/ton CO 2 net avoided for wollastonite and steel slag, respectively. For wollastonite, the major costs are associated with the feedstock and the electricity consumption for grinding and compression (54 and 26 EUR/ton CO 2 avoided, respectively). A sensitivity analysis showed that additional influential parameters in the sequestration costs include the liquid-to-solid ratio in the carbonation reactor and the possible value of the carbonated product. The sequestration costs for steel slag are significantly lower due to the absence of costs for the feedstock. Although various options for potential cost reduction have been identified, CO 2 sequestration by current aqueous carbonation processes seems expensive relative to other CO 2 storage technologies. The permanent and inherently safe sequestration of CO 2 by mineral carbonation may justify higher costs, but further cost reductions are required, particularly in view of (current) prices of CO 2 emission rights. Niche applications of mineral carbonation with a solid residue such as steel slag as feedstock and/or a useful carbonated product hold the best prospects for an economically feasible CO 2 sequestration process. (author)

Analysis of mineral trapping for CO(sub 2) disposal in deep aquifers; TOPICAL

International Nuclear Information System (INIS)

Xu, Tianfu; Apps, John A.; Pruess, Karsten

2001-01-01

CO(sub 2) disposal into deep aquifers has been suggested as a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO(sub 2) disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO(sub 2) injection, we have analyzed the impact of CO(sub 2) immobilization through carbonate precipitation. A survey of all major classes of rock-forming minerals, whose alteration would lead to carbonate precipitation, indicated that very few minerals are present in sufficient quantities in aquifer host rocks to permit significant sequestration of CO(sub 2). We performed batch reaction modeling of the geochemical evolution of three different aquifer mineralogies in the presence of CO(sub 2) at high pressure. Our modeling considered (1) redox processes that could be important in deep subsurface environments, (2) the presence of organic matter, (3) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, and (4) CO(sub 2) solubility dependence on pressure, temperature and salinity of the system. The geochemical evolution under both natural background and CO(sub 2) injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO(sub 2) sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO(sub 2) that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO(sub 2) dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of ferric mineral precursors such as glauconite, which in turn is dependent on the reactivity of associated organic material. The accumulation of carbonates in

Mechanisms for chemostatic behavior in catchments: implications for CO2 consumption by mineral weathering

Science.gov (United States)

Clow, David W.; Mast, M. Alisa

2010-01-01

Concentrations of weathering products in streams often show relatively little variation compared to changes in discharge, both at event and annual scales. In this study, several hypothesized mechanisms for this “chemostatic behavior” were evaluated, and the potential for those mechanisms to influence relations between climate, weathering fluxes, and CO2 consumption via mineral weathering was assessed. Data from Loch Vale, an alpine catchment in the Colorado Rocky Mountains, indicates that cation exchange and seasonal precipitation and dissolution of amorphous or poorly crystalline aluminosilicates are important processes that help regulate solute concentrations in the stream; however, those processes have no direct effect on CO2 consumption in catchments. Hydrograph separation analyses indicate that old water stored in the subsurface over the winter accounts for about one-quarter of annual streamflow, and almost one-half of annual fluxes of Na and SiO2 in the stream; thus, flushing of old water by new water (snowmelt) is an important component of chemostatic behavior. Hydrologic flushing of subsurface materials further induces chemostatic behavior by reducing mineral saturation indices and increasing reactive mineral surface area, which stimulate mineral weathering rates. CO2 consumption by carbonic acid mediated mineral weathering was quantified using mass-balance calculations; results indicated that silicate mineral weathering was responsible for approximately two-thirds of annual CO2 consumption, and carbonate weathering was responsible for the remaining one-third. CO2 consumption was strongly dependent on annual precipitation and temperature; these relations were captured in a simple statistical model that accounted for 71% of the annual variation in CO2 consumption via mineral weathering in Loch Vale.

In situ spectroscopic monitoring of CO2 reduction at copper oxide electrode.

Science.gov (United States)

Wang, Liying; Gupta, Kalyani; Goodall, Josephine B M; Darr, Jawwad A; Holt, Katherine B

2017-04-28

Copper oxide modified electrodes were investigated as a function of applied electrode potential using in situ infrared spectroscopy and ex situ Raman and X-ray photoelectron spectroscopy. In deoxygenated KHCO 3 electrolyte bicarbonate and carbonate species were found to adsorb to the electrode during reduction and the CuO was reduced to Cu(i) or Cu(0) species. Carbonate was incorporated into the structure and the CuO starting material was not regenerated on cycling to positive potentials. In contrast, in CO 2 saturated KHCO 3 solution, surface adsorption of bicarbonate and carbonate was not observed and adsorption of a carbonato-species was observed with in situ infrared spectroscopy. This species is believed to be activated, bent CO 2 . On cycling to negative potentials, larger reduction currents were observed in the presence of CO 2 ; however, less of the charge could be attributed to the reduction of CuO. In the presence of CO 2 CuO underwent reduction to Cu 2 O and potentially Cu, with no incorporation of carbonate. Under these conditions the CuO starting material could be regenerated by cycling to positive potentials.

Analysis of ex situ processes of CO2 sequestration. Final report

International Nuclear Information System (INIS)

Touze, S.; Bourgeois, F.; Baranger, P.; Durst, P.

2004-01-01

The aim of this study is to bring quantitative elements to evaluate the validation of the CO 2 mineral sequestration to limit the greenhouse effect gases. This analysis aims to calculate the CO 2 accounting of the system (internal energy production balance the energy expend) sequestrated CO 2 and produced CO 2 . The first part detailed the possible experimental solutions. Then two carbonation processes, direct and indirect, have been chosen of the analysis. (A.L.B.)

Negative CO2 emissions via subsurface mineral carbonation in fractured peridotite

Science.gov (United States)

Kelemen, P. B.; Matter, J.

2014-12-01

Uptake of CO2 from surface water via mineral carbonation in peridotite can be engineered to achieve negative CO2 emissions. Reaction with peridotite, e.g., CO2 + olivine (A), serpentine (B) and brucite (C), forms inert, non-toxic, solid carbonates such as magnesite. Experimental studies show that A can be 80% complete in a few hours with 30 micron powders and elevated P(CO2) [1,2,3]. B is slower, but in natural systems the rate of B+C is significant [4]. Methods for capture of dilute CO2 via mineral carbonation [4,5,6,7] are not well known, though CO2 storage via mineral carbonation has been discussed for decades [8,9]. Where crushed peridotite is available, as in mine tailings, increased air or water flow could enhance CO2 uptake at a reasonable cost [4,5]. Here we focus on enhancing subsurface CO2 uptake from surface water flowing in fractured peridotite, in systems driven by thermal convection such as geothermal power plants. Return of depleted water to the surface would draw down CO2 from the air [6,7]. CO2 uptake from water, rate limited by flow in input and output wells, could exceed 1000 tons CO2/yr [7]. If well costs minus power sales were 0.1M to 1M and each system lasts 10 years this costs oil industry. Uptake of 1 Gt CO2/yr at 1000 t/well/yr requires 1M wells, comparable to the number of producing oil and gas wells in the USA. Subsurface CO2 uptake could first be applied in coastal, sub-seafloor peridotite with onshore drilling. Sub-seafloor peridotite is extensive off Oman, New Caledonia and Papua New Guinea, with smaller amounts off Spain, Morocco, USA, etc. This would be a regional contribution, used in parallel with other methods elsewhere. To achieve larger scale is conceivable. There is a giant mass of seafloor peridotite along slow-spreading mid-ocean ridges. Could robotic drills enhance CO2 uptake at a reasonable cost, while fabric chimneys transport CO2-depleted water to the sea surface? Does anyone know James Cameron's phone number? [1] O

Spatial variation of sediment mineralization supports differential CO2 emissions from a tropical hydroelectric reservoir

Directory of Open Access Journals (Sweden)

Simone Jaqueline Cardoso

2013-04-01

Full Text Available Substantial amounts of organic matter (OM from terrestrial ecosystems are buried as sediments in inland waters. It is still unclear to what extent this OM constitutes a sink of carbon, and how much of it is returned to the atmosphere upon mineralization to carbon dioxide (CO2. The construction of reservoirs affects the carbon cycle by increasing OM sedimentation at the regional scale. In this study we determine the OM mineralization in the sediment of three zones (river, transition and dam of a tropical hydroelectric reservoir in Brazil as well as identify the composition of the carbon pool available for mineralization. We measured sediment OC mineralization rates and related them to the composition of the OM, bacterial abundance and pCO2 of the surface water of the reservoir. Terrestrial OM was an important substrate for the mineralization. In the river and transition zones most of the OM was allochthonous (56 % and 48 %, respectively while the dam zone had the lowest allochthonous contribution (7 %. The highest mineralization rates were found in the transition zone (154.80 ± 33.50 mg C m-2 d-1 and the lowest in the dam (51.60 ± 26.80 mg C m-2 d-1. Moreover, mineralization rates were significantly related to bacterial abundance (r2 = 0.50, p < 0.001 and pCO2 in the surface water of the reservoir (r2 = 0.73, p < 0.001. The results indicate that allochthonous OM has different contributions to sediment mineralization in the three zones of the reservoir. Further, the sediment mineralization, mediated by heterotrophic bacteria metabolism, significantly contributes to CO2 supersaturation in the water column, resulting in higher pCO2 in the river and transition zones in comparison with the dam zone, affecting greenhouse gas emission estimations from hydroelectric reservoirs.

Fundamental study of CO2-H2O-mineral interactions for carbon sequestration, with emphasis on the nature of the supercritical fluid-mineral interface.

Energy Technology Data Exchange (ETDEWEB)

Bryan, Charles R.; Dewers, Thomas A.; Heath, Jason E.; Wang, Yifeng; Matteo, Edward N.; Meserole, Stephen P.; Tallant, David Robert

2013-09-01

In the supercritical CO2-water-mineral systems relevant to subsurface CO2 sequestration, interfacial processes at the supercritical fluid-mineral interface will strongly affect core- and reservoir-scale hydrologic properties. Experimental and theoretical studies have shown that water films will form on mineral surfaces in supercritical CO2, but will be thinner than those that form in vadose zone environments at any given matric potential. The theoretical model presented here allows assessment of water saturation as a function of matric potential, a critical step for evaluating relative permeabilities the CO2 sequestration environment. The experimental water adsorption studies, using Quartz Crystal Microbalance and Fourier Transform Infrared Spectroscopy methods, confirm the major conclusions of the adsorption/condensation model. Additional data provided by the FTIR study is that CO2 intercalation into clays, if it occurs, does not involve carbonate or bicarbonate formation, or significant restriction of CO2 mobility. We have shown that the water film that forms in supercritical CO2 is reactive with common rock-forming minerals, including albite, orthoclase, labradorite, and muscovite. The experimental data indicate that reactivity is a function of water film thickness; at an activity of water of 0.9, the greatest extent of reaction in scCO2 occurred in areas (step edges, surface pits) where capillary condensation thickened the water films. This suggests that dissolution/precipitation reactions may occur preferentially in small pores and pore throats, where it may have a disproportionately large effect on rock hydrologic properties. Finally, a theoretical model is presented here that describes the formation and movement of CO2 ganglia in porous media, allowing assessment of the effect of pore size and structural heterogeneity on capillary trapping efficiency. The model results also suggest possible engineering approaches for optimizing trapping capacity and for

Flexible metal-organic framework compounds: In situ studies for selective CO{sub 2} capture

Energy Technology Data Exchange (ETDEWEB)

Allen, A.J., E-mail: andrew.allen@nist.gov [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899-8520 (United States); Espinal, L.; Wong-Ng, W. [Material Measurement Laboratory, National Institute of Standards and Technology (NIST), Gaithersburg, MD 20899-8520 (United States); Queen, W.L. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); The Molecular Foundry, Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA 94720 (United States); Brown, C.M. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716 (United States); Kline, S.R. [NIST Center for Neutron Research, Gaithersburg, MD 20899-6102 (United States); Kauffman, K.L. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States); Culp, J.T. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States); URS Corporation, South Park, PA 15219 (United States); Matranga, C. [National Energy Technology Laboratory (NETL), US Department of Energy, Pittsburgh, PA 15236 (United States)

2015-10-25

Results are presented that explore the dynamic structural changes occurring in two highly flexible nanocrystalline metal-organic framework (MOF) compounds during the adsorption and desorption of pure gases and binary mixtures. The Ni(1,2-bis(4-pyridyl)ethylene)[Ni(CN){sub 4}] and catena-bis(dibenzoylmethanato)-(4,4′-bipyridyl)nickel(II) chosen for this study are 3-D and 1-D porous coordination polymers (PCP) with a similar gate opening pressure response for CO{sub 2} isotherms at 303 K, but with differing degrees of flexibility for structural change to accommodate guest molecules. As such, they serve as a potential model system for evaluating the complex kinetics associated with dynamic structure changes occurring in response to gas adsorption in flexible MOF systems. Insights into the crystallographic changes occurring as the MOF pore structure expands and contracts in response to interactions with CO{sub 2}, N{sub 2}, and CO{sub 2}/N{sub 2} mixtures have been obtained from in situ small-angle neutron scattering and neutron diffraction, combined with ex situ X-ray diffraction structure measurements. The role of structure in carbon capture functionality is discussed with reference to the ongoing characterization challenges and a possible materials-by-design approach. - Graphical abstract: We present in situ small-angle neutron scattering results for two flexible metal-organic frameworks (MOFs). The figure shows that for one (NiBpene, high CO{sub 2} adsorption) the intensity of the Bragg peak for the expandable d-spacing most associated with CO{sub 2} adsorption varies approximately with the isotherm, while for the other (NiDBM-Bpy, high CO{sub 2} selectivity) the d-spacing, itself, varies with the isotherm. The cartoons show the proposed modes of structural change. - Highlights: • Dynamic structures of two flexible MOF CO{sub 2} sorbent compounds are compared in situ. • These porous solid sorbents serve as models for pure & dual gas adsorption. • Different

Kinetics of carbonate mineral dissolution in CO2-acidified brines at storage reservoir conditions.

Science.gov (United States)

Peng, Cheng; Anabaraonye, Benaiah U; Crawshaw, John P; Maitland, Geoffrey C; Trusler, J P Martin

2016-10-20

We report experimental measurements of the dissolution rate of several carbonate minerals in CO 2 -saturated water or brine at temperatures between 323 K and 373 K and at pressures up to 15 MPa. The dissolution kinetics of pure calcite were studied in CO 2 -saturated NaCl brines with molalities of up to 5 mol kg -1 . The results of these experiments were found to depend only weakly on the brine molality and to conform reasonably well with a kinetic model involving two parallel first-order reactions: one involving reactions with protons and the other involving reaction with carbonic acid. The dissolution rates of dolomite and magnesite were studied in both aqueous HCl solution and in CO 2 -saturated water. For these minerals, the dissolution rates could be explained by a simpler kinetic model involving only direct reaction between protons and the mineral surface. Finally, the rates of dissolution of two carbonate-reservoir analogue minerals (Ketton limestone and North-Sea chalk) in CO 2 -saturated water were found to follow the same kinetics as found for pure calcite. Vertical scanning interferometry was used to study the surface morphology of unreacted and reacted samples. The results of the present study may find application in reactive-flow simulations of CO 2 -injection into carbonate-mineral saline aquifers.

Experimental and simulation studies on mineral trapping of CO2 with brine

International Nuclear Information System (INIS)

Soong, Y.; Goodman, A.L.; McCarthy-Jones, J.R.; Baltrus, J.P.

2004-01-01

The reaction of carbon dioxide (CO 2 ) with brine samples collected from the Oriskany Formation in Indiana County, PA, was investigated in an autoclave reactor under various conditions. A geochemical code, PHREEQC, was used as to simulate the reaction in the autoclave reactor. The combined experimental and modeling data suggests that pH (pH > 9) plays a key role in the formation of carbonate minerals. The effects of temperature and CO 2 pressure have a lesser impact on the formation of carbonate minerals

Carbon dioxide sequestration by mineral carbonation. Feasibility of enhanced natural weathering as a CO2 emission reduction technology

International Nuclear Information System (INIS)

Huijgen, W.J.J.

2007-01-01

A possible technology that can contribute to the reduction of carbon dioxide emissions is CO2 sequestration by mineral carbonation. The basic concept behind mineral CO2 sequestration is the mimicking of natural weathering processes in which calcium or magnesium containing minerals react with gaseous CO2 and form solid calcium or magnesium carbonates. Potential advantages of mineral CO2 sequestration compared to, e.g., geological CO2 storage include (1) the permanent and inherently safe sequestration of CO2, due to the thermodynamic stability of the carbonate product formed and (2) the vast potential sequestration capacity, because of the widespread and abundant occurrence of suitable feedstock. In addition, carbonation is an exothermic process, which potentially limits the overall energy consumption and costs of CO2 emission reduction. However, weathering processes are slow, with timescales at natural conditions of thousands to millions of years. For industrial implementation, a reduction of the reaction time to the order of minutes has to be achieved by developing alternative process routes. The aim of this thesis is an investigation of the technical, energetic, and economic feasibility of CO2 sequestration by mineral carbonation. In Chapter 1 the literature published on CO2 sequestration by mineral carbonation is reviewed. Among the potentially suitable mineral feedstock for mineral CO2 sequestration, Ca-silicates, more particularly wollastonite (CaSiO3), a mineral ore, and steel slag, an industrial alkaline solid residue, are selected for further research. Alkaline Ca-rich residues seem particularly promising, since these materials are inexpensive and available near large industrial point sources of CO2. In addition, residues tend to react relatively rapidly with CO2 due to their (geo)chemical instability. Various process routes have been proposed for mineral carbonation, which often include a pre-treatment of the solid feedstock (e.g., size reduction and

Chemical and Biological Catalytic Enhancement of Weathering of Silicate Minerals and industrial wastes as a Novel Carbon Capture and Storage Technology

Science.gov (United States)

Park, A. H. A.

2014-12-01

Increasing concentration of CO2 in the atmosphere is attributed to rising consumption of fossil fuels around the world. The development of solutions to reduce CO2 emissions to the atmosphere is one of the most urgent needs of today's society. One of the most stable and long-term solutions for storing CO2 is via carbon mineralization, where minerals containing metal oxides of Ca or Mg are reacted with CO2 to produce thermodynamically stable Ca- and Mg-carbonates that are insoluble in water. Carbon mineralization can be carried out in-situ or ex-situ. In the case of in-situ mineralization, the degree of carbonation is thought to be limited by both mineral dissolution and carbonate precipitation reaction kinetics, and must be well understood to predict the ultimate fate of CO2 within geological reservoirs. While the kinetics of in-situ mineral trapping via carbonation is naturally slow, it can be enhanced at high temperature and high partial pressure of CO2. The addition of weak organic acids produced from food waste has also been shown to enhance mineral weathering kinetics. In the case of the ex-situ carbon mineralization, the role of these ligand-bearing organic acids can be further amplified for silicate mineral dissolution. Unfortunately, high mineral dissolution rates often lead to the formation of a silica-rich passivation layer on the surface of silicate minerals. Thus, the use of novel solvent mixture that allows chemically catalyzed removal of this passivation layer during enhanced Mg-leaching surface reaction has been proposed and demonstrated. Furthermore, an engineered biological catalyst, carbonic anhydrase, has been developed and evaluated to accelerate the hydration of CO2, which is another potentially rate-limiting step of the carbonation reaction. The development of these novel catalytic reaction schemes has significantly improved the overall efficiency and sustainability of in-situ and ex-situ mineral carbonation technologies and allowed direct

Commentary: Ex Situ Aqueous Mineral Carbonation

Energy Technology Data Exchange (ETDEWEB)

Gadikota, Greeshma, E-mail: gadikota@princeton.edu [Department of Civil and Environmental Engineering, Princeton University, Princeton, NJ (United States)

2016-05-26

CO{sub 2} conversion to calcium and magnesium carbonates has garnered considerable attention since it is a thermodynamically downhill pathway to safely and permanently sequester large quantities of CO{sub 2}. This seminal work performed at The National Energy Technology Laboratory in Albany (NETL-Albany) reports the conversion of calcium- and magnesium-bearing silicate minerals, such as olivine [(Mg, Fe){sub 2}SiO{sub 4}], wollastonite (CaSiO{sub 3}), and serpentine [Mg{sub 3}Si{sub 2}O{sub 5}(OH){sub 4}], as they are reacted with CO{sub 2} in an aqueous environment to form magnesium or calcium carbonates. This paper discusses various pretreatment methods of the starting materials, such as grinding or heat treatment of hydroxylated Mg silicates, to enhance the reaction kinetics. The effects of various chemical additives (e.g., NaCl and NaHCO{sub 3}), and reaction parameters, such as temperature, pressure, and reaction time, on the conversion are investigated. Feasibility assessments and energy and economic analyses of the direct carbonation of calcium- and magnesium-bearing minerals are presented.

In situ x-ray fluorescence and californium-252 neutron activation analysis for marine and terrestrial mineral exploration

International Nuclear Information System (INIS)

Wogman, N.A.

1976-12-01

Instrumentation has been designed for in situ analysis of marine and terrestrial minerals using the techniques of x-ray fluorescence and neutron activation analysis. The energy-dispersive x-ray fluorescence analyzer allows more than 20 elements to be quantitatively measured at the 10 ppM level in water depths to 300 m. The analyzer consists of a solid cryogen-cooled Si(Li) detector, a 50 mCi 109 Cd or 57 Co excitation source, and an analyzer-computer system for data storage and manipulation. The neutron activation analysis, which is designed to measure up to 30 elements at parts per hundred to ppM levels, utilizes the man-made element 252 Cf as its neutron activation source. The resulting radioelements which emit characteristic gamma radiation are then analyzed in situ during 2- to 200-s counting intervals with Ge(Li) or NaI(T1) detector systems. An extension of this latter technique, which uses a 252 Cf- 235 U fueled subcritical multiplier, is also being studied. The subcritical facility allows the neutrons from the 252 Cf source to be multiplied, thus providing greater neutron flux. Details of these in situ analysis systems, actual in situ spectra, and recorded data are discussed with respect to the detection of minerals at their varying concentration levels. The system response of each illustrates its usefulness for various rapid environmental mineral exploration studies. These techniques can be utilized on terrestrial surfaces and marine or fresh water sediments. 5 figures, 2 tables

An experimental study on mineral sequestration of CO{sub 2} in basics and ultra basics rocks; Etude experimentale des reactions de carbonatation minerale du CO{sub 2} dans les roches basiques et ultrabasiques

Energy Technology Data Exchange (ETDEWEB)

Dufaud, F

2006-11-15

The first part of the thesis is dedicated to dissolution data of siderite FeCO{sub 3} and magnetite Fe{sub 3}O{sub 4} which have been monitored in situ on the FAME beamline of the european synchrotron radiation facility in Grenoble. Iron in solution close to siderite single crystals is shown to be divalent hydrated. The small size of the experimentally investigated volume of solution (200 *400 micrometer and 3 mm height) allowed to work with single crystals in well defined geometries. No specific interaction was observed between iron (II) and dissolved inorganic carbon, suggesting that modelling siderite evolution under high CO{sub 2} pressures by using CO{sub 2}-less very acidic (pH 1-2) solutions is adequate. Using initial reaction rates, we get an activation energy for siderite dissolution of 62 kJ.mol{sup -1}, consistent with existing literature data. Such a value is suggestive of a mineral/solution interface mechanism.. Data from this study and from literature are consistent over a temperature range 25 C - 125 C and a pH range pH 1-7 with an empirical law: pk = pH + E{sub a}/(ln(10)*RT(K)) - log(S/V) - 10,5 where E{sub a} = 62 kJ.mol{sup -1} and S/V is the ratio between solid surface S and fluid volume V. A value of activation energy of 73.5 kJ.mol{sup -1} is obtained in the case of magnetite, also consistent with mineral/solution processes. The second and major part of the thesis work is the realization of analogical experiments for simulating carbonation of basic and ultra basic minerals. Experiments were carried out on consolidated rock cores at 90 C and 280 bar of CO{sub 2} (low temperature experiments) and on powders contained in metallic capsules at 400-500 C and 1000-1700 bars of CO{sub 2} (high temperature experiments). The rate of mineral storage of CO{sub 2} was defined as the molar ratio of solid carbonate formed over total CO{sub 2} injected. It is of about 1% in three months in low temperature experiments whereas it reaches several tens of

Field Tests of Real-time In-situ Dissolved CO2 Monitoring for CO2 Leakage Detection in Groundwater

Science.gov (United States)

Yang, C.; Zou, Y.; Delgado, J.; Guzman, N.; Pinedo, J.

2016-12-01

Groundwater monitoring for detecting CO2 leakage relies on groundwater sampling from water wells drilled into aquifers. Usually groundwater samples are required be collected periodically in field and analyzed in the laboratory. Obviously groundwater sampling is labor and cost-intensive for long-term monitoring of large areas. Potential damage and contamination of water samples during the sampling process can degrade accuracy, and intermittent monitoring may miss changes in the geochemical parameters of groundwater, and therefore signs of CO2 leakage. Real-time in-situ monitoring of geochemical parameters with chemical sensors may play an important role for CO2 leakage detection in groundwater at a geological carbon sequestration site. This study presents field demonstration of a real-time in situ monitoring system capable of covering large areas for detection of low levels of dissolved CO2 in groundwater and reliably differentiating natural variations of dissolved CO2 concentration from small changes resulting from leakage. The sand-alone system includes fully distributed fiber optic sensors for carbon dioxide detection with a unique sensor technology developed by Intelligent Optical Systems. The systems were deployed to the two research sites: the Brackenridge Field Laboratory where the aquifer is shallow at depths of 10-20 ft below surface and the Devine site where the aquifer is much deeper at depths of 140 to 150 ft. Groundwater samples were periodically collected from the water wells which were installed with the chemical sensors and further compared to the measurements of the chemical sensors. Our study shows that geochemical monitoring of dissolved CO2 with fiber optic sensors could provide reliable CO2 leakage signal detection in groundwater as long as CO2 leakage signals are stronger than background noises at the monitoring locations.

Adsorption of Dissolved Gases (CH4, CO2, H2, Noble Gases) by Water-Saturated Smectite Clay Minerals

Science.gov (United States)

Bourg, I. C.; Gadikota, G.; Dazas, B.

2016-12-01

Adsorption of dissolved gases by water-saturated clay minerals plays important roles in a range of fields. For example, gas adsorption in on clay minerals may significantly impact the formation of CH4 hydrates in fine-grained sediments, the behavior of CH4 in shale, CO2 leakage across caprocks of geologic CO2 sequestration sites, H2 leakage across engineered clay barriers of high-level radioactive waste repositories, and noble gas geochemistry reconstructions of hydrocarbon migration in the subsurface. Despite its importance, the adsorption of gases on clay minerals remains poorly understood. For example, some studies have suggested that clay surfaces promote the formation of CH4 hydrates, whereas others indicate that clay surfaces inhibit the formation of CH4 hydrates. Here, we present molecular dynamics (MD) simulations of the adsorption of a range of gases (CH4, CO2, H2, noble gases) on clay mineral surfaces. Our results indicate that the affinity of dissolved gases for clay mineral surfaces has a non-monotone dependence on the hydrated radius of the gas molecules. This non-monotone dependence arises from a combination of two effects: the polar nature of certain gas molecules (in particular, CO2) and the templating of interfacial water structure by the clay basal surface, which results in the presence of interfacial water "cages" of optimal size for intermediate-size gas molecules (such as Ne or Ar).

Rapid solubility and mineral storage of CO₂ in basalt

DEFF Research Database (Denmark)

Gislason, Sigurdur R.; Broecker, W.S.; Gunnlaugsson, E.

2014-01-01

The long-term security of geologic carbon storage is critical to its success and public acceptance. Much of the security risk associated with geological carbon storage stems from its buoyancy. Gaseous and supercritical CO2 are less dense than formation waters, providing a driving force for it to ......The long-term security of geologic carbon storage is critical to its success and public acceptance. Much of the security risk associated with geological carbon storage stems from its buoyancy. Gaseous and supercritical CO2 are less dense than formation waters, providing a driving force...... for it to escape back to the surface. This buoyancy can be eliminated by the dissolution of CO2 into water prior to, or during its injection into the subsurface. The dissolution makes it possible to inject into fractured rocks and further enhance mineral storage of CO2 especially if injected into silicate rocks...... rich in divalent metal cations such as basalts and ultra-mafic rocks. We have demonstrated the dissolution of CO2 into water during its injection into basalt leading to its geologic solubility storage in less than five minutes and potential geologic mineral storage within few years after injection [1...

Experimental Studies on the Interaction of scCO2 and scCO2-SO2 With Rock Forming Minerals at Conditions of Geologic Carbon Storages - First Results

Science.gov (United States)

Erzinger, J.; Wilke, F.; Wiersberg, T.; Vasquez Parra, M.

2010-12-01

Co-injection of SO2 (plus possibly NOx and O2) during CO2 storage in deep saline aquifers may cause stronger brine acidification than CO2 alone. Because of that, we investigate chemical corrosion of rocks and rock-forming minerals with impure supercritical CO2 (scCO2) at possible storage conditions of >73.7 bar and >31°C. Contaminates were chosen with respect to the composition of CO2 captured industrially from coal-fired power plants using the oxyfuel technology. The resulting data should build a base for the long-term prediction of the behavior of CO2 in geologic storage reservoirs. Experiments of up to 1000 hrs duration have been performed with 10 natural mineral concentrates (calcite, dolomite, siderite, anhydrite, hematite, albite, microcline, kaolinite, muscovite, biotite) in 3n NaCl solution and pure scCO2 or scCO2+SO2 (99.5+0.5 vol%). The NaCl reaction fluid resembles the average salinity of deep formation waters of the North German Basin and is not free of oxygen. To increase reaction rates all minerals were ground and the reagents agitated either by stirring or shaking in autoclaves of about one liter in volume. The autoclaves consist of Hastelloy™ or ferromagnetic stainless steel fully coated with PTFE. We used in average 15 g of solids, 700 ml liquid, and the vessels were pressurized up to 100 bars with CO2 or CO2-SO2 mixture. Experiments were run at temperatures up to 90°C. Before, during and after the experiments small amounts fluids were sampled and analyzed for dissolved constituents and pH. Solid phases were characterized by XRF, XRD, and EMPA before and after the experiments. Pure scCO2 corrodes all carbonates, reacts only slightly with anhydrite, albite, and microcline at a minimum pH of 4, and does not recognizably interact with the others. After the experiment, albite has gained in a, not yet fully identified, carbonate phase which might be dawsonite. Reaction fluids of the experiments with scCO2+SO2 have mostly lower pH than using scCO2

Numerical modeling of injection and mineral trapping of CO2 withH2S and SO2 in a Sandstone Formation

Energy Technology Data Exchange (ETDEWEB)

Xu, Tianfu; Apps, John A.; Pruess, Karsten; Yamamoto, Hajime

2004-09-07

Carbon dioxide (CO{sub 2}) injection into deep geologic formations could decrease the atmospheric accumulation of this gas from anthropogenic sources. Furthermore, by co-injecting H{sub 2}S or SO{sub 2}, the products respectively of coal gasification or combustion, with captured CO{sub 2}, problems associated with surface disposal would be mitigated. We developed models that simulate the co-injection of H{sub 2}S or SO{sub 2} with CO{sub 2} into an arkose formation at a depth of about 2 km and 75 C. The hydrogeology and mineralogy of the injected formation are typical of those encountered in Gulf Coast aquifers of the United States. Six numerical simulations of a simplified 1-D radial region surrounding the injection well were performed. The injection of CO{sub 2} alone or co-injection with SO{sub 2} or H{sub 2}S results in a concentrically zoned distribution of secondary minerals surrounding a leached and acidified region adjacent to the injection well. Co-injection of SO{sub 2} with CO{sub 2} results in a larger and more strongly acidified zone, and alteration differs substantially from that caused by the co-injection of H{sub 2}S or injection of CO{sub 2} alone. Precipitation of carbonates occurs within a higher pH (pH > 5) peripheral zone. Significant quantities of CO{sub 2} are sequestered by ankerite, dawsonite, and lesser siderite. The CO{sub 2} mineral-trapping capacity of the formation can attain 40-50 kg/m{sup 3} medium for the selected arkose. In contrast, secondary sulfates precipitate at lower pH (pH < 5) within the acidified zone. Most of the injected SO{sub 2} is transformed and immobilized through alunite precipitation with lesser amounts of anhydrite and minor quantities of pyrite. The dissolved CO{sub 2} increases with time (enhanced solubility trapping). The mineral alteration induced by injection of CO{sub 2} with either SO{sub 2} or H{sub 2}S leads to corresponding changes in porosity. Significant increases in porosity occur in the acidified

ATOMIC-LEVEL IMAGING OF CO2 DISPOSAL AS A CARBONATE MINERAL: OPTIMIZING REACTION PROCESS DESIGN; A

International Nuclear Information System (INIS)

M.J. McKelvy; R. Sharma; A.V.G. Chizmeshya; H. Bearat; R.W. Carpenter

2001-01-01

Fossil fuels, especially coal, can support the energy demands of the world for centuries to come, if the environmental problems associated with CO(sub 2) emissions can be overcome. Permanent and safe methods for CO(sub 2) capture and disposal/storage need to be developed. Mineralization of stationary-source CO(sub 2) emissions as carbonates can provide such safe capture and long-term sequestration. Mg-rich lamellar-hydroxide based minerals (e.g., brucite and serpentine) offer a class of widely available, low-cost materials, with intriguing mineral carbonation potential. Carbonation of such materials inherently involves dehydroxylation, which can disrupt the material down to the atomic level. As such, controlled dehydroxylation, before and/or during carbonation, may provide an important parameter for enhancing carbonation reaction processes. Mg(OH)(sub 2) was chosen as the model material for investigating lamellar hydroxide mineral dehydroxylation/carbonation mechanisms due to (i) its structural and chemical simplicity, (ii) interest in Mg(OH)(sub 2) gas-solid carbonation as a potentially cost-effective CO(sub 2) mineral sequestration process component, and (iii) its structural and chemical similarity to other lamellar-hydroxide-based minerals (e.g., serpentine-based minerals) whose carbonation reaction processes are being explored due to their low-cost CO(sub 2) sequestration potential. Fundamental understanding of the mechanisms that govern dehydroxylation/carbonation processes is essential for minimizing the cost of any lamellar-hydroxide-based mineral carbonation sequestration process. This report covers the third year progress of this grant, as well as providing an integrated overview of the progress in years 1-3, as we have been granted a one-year no-cost extension to wrap up a few studies and publications to optimize project impact

Improved solar-driven photocatalytic performance of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} prepared in-situ

Energy Technology Data Exchange (ETDEWEB)

Zhong, Junbo, E-mail: junbozhong@163.com [Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Li, Jianzhang, E-mail: lschmanuscript@163.com [Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Huang, Shengtian; Cheng, Chaozhu; Yuan, Wei [Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Li, Minjiao [Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China); Sichuan Provincial Academician (Expert) Workstation, Sichuan University of Science and Engineering, Zigong 643000 (China); Ding, Jie [Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan, College of Chemistry and Pharmaceutical Engineering, Sichuan University of Science and Engineering, Zigong 643000 (China)

2016-05-15

Highlights: • Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} photocatalysts were prepared in-situ. • The photo-induced charge separation rate has been greatly increased. • The photocatalytic activity has been greatly promoted. - Abstract: Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} composites have been fabricated in-situ via a facile parallel flaw co-precipitation method. The specific surface area, structure, morphology, and the separation rate of photo-induced charge pairs of the photocatalysts were characterized by Brunauer–Emmett–Teller (BET) method, X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy(DRS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and surface photovoltage (SPV) spectroscopy, respectively. XRD patterns and DRS demonstrated that Ag{sub 2}CO{sub 3} has no effect on the crystal phase and bandgap of (BiO){sub 2}CO{sub 3}. The existence of Ag{sub 2}CO{sub 3} in the composites enhances the separation rate of photo-induced charge pairs of the photocatalysts. The photocatalytic performance of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} was evaluated by the decolorization of methyl orange (MO) aqueous solution under simulated solar irradiation. It was found that the simulated solar-induced photocatalytic activity of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} copmposites was significantly improved, which was mainly attributed to the enhanced surface area and the separation rate of photo-induced charge pairs.

Dissolved organic carbon and nitrogen mineralization strongly affect co2 emissions following lime application to acidic soil

International Nuclear Information System (INIS)

Shaaban, M.; Peng, Q.; Lin, S.; Wu, Y.

2014-01-01

Emission of greenhouse gases from agricultural soils has main contribution to the climatic change and global warming. Dynamics of dissolved organic carbon (DOC) and nitrogen mineralization can affect CO/sub 2/ emission from soils. Influence of DOC and nitrogen mineralization on CO/sub 2/ emissions following lime application to acidic soil was investigated in current study. Laboratory experiment was conducted under aerobic conditions with 25% moisture contents (66% water-filled pore space) at 25 degree C in the dark conditions. Different treatments of lime were applied to acidic soil as follows: CK (control), L (low rate of lime: 0.2g lime / 100 g soil) and H (high rate of lime: 0.5g lime /100g soil). CO/sub 2/ emissions were measured by gas chromatography and dissolved organic carbon, NH4 +-N, NO/sub 3/ --N and soil pH were measured during incubation study. Addition of lime to acidic soil significantly increased the concentration of DOC and N mineralization rate. Higher concentrations of DOC and N mineralization, consequently, increased the CO/sub 2/ emissions from lime treated soils. Cumulative CO/sub 2/ emission was 75% and 71% higher from L and H treatments as compared to CK. The results of current study suggest that DOC and N mineralization are critical in controlling gaseous emissions of CO/sub 2/ from acidic soils following lime application. (author)

The CarbFix Pilot Project in Iceland - CO2 capture and mineral storage in basaltic rocks

Science.gov (United States)

Sigurdardottir, H.; Sigfusson, B.; Aradottir, E. S.; Gunnlaugsson, E.; Gislason, S. R.; Alfredsson, H. A.; Broecker, W. S.; Matter, J. M.; Stute, M.; Oelkers, E.

2010-12-01

The overall objective of the CarbFix project is to develop and optimize a practical and cost-effective technology for capturing CO2 and storing it via in situ mineral carbonation in basaltic rocks, as well as to train young scientist to carry the corresponding knowledge into the future. The project consists of a field injection of CO2 charged water at the Hellisheidi geothermal power plant in SW Iceland, laboratory experiments, numerical reactive transport modeling, tracer tests, natural analogue and cost analysis. The CO2 injection site is situated about 3 km south of the Hellisheidi geothermal power plant. Reykjavik Energy operates the power plant, which currently produces 60,000 tons/year CO2 of magmatic origin. The produced geothermal gas mainly consists of CO2 and H2S. The two gases will be separated in a pilot gas treatment plant, and CO2 will be transported in a pipeline to the injection site. There, CO2 will be fully dissolved in 20 - 25°C water during injection at 25 - 30 bar pressure, resulting in a single fluid phase entering the storage formation, which consists of relatively fresh basaltic lavas. The CO2 charged water is reactive and will dissolve divalent cations from the rock, which will combine with the dissolved carbon to form solid thermodynamically stable carbonate minerals. The injection test is designed to inject 2200 tons of CO2 per year. In the past three years the CarbFix project has been addressing background fluid chemistries at the injection site and characterizing the target reservoir for the planned CO2 injection. Numerous groundwater samples have been collected and analysed. A monitoring and accounting plan has been developed, which integrates surface, subsurface and atmospheric monitoring. A weather station is operating at the injection site for continuous monitoring of atmospheric CO2 and to track all key parameters for the injection. Environmental authorities have granted licenses for the CO2 injection and the use of tracers, based

Interactions between CO2, saline water and minerals during geological storage of CO2

International Nuclear Information System (INIS)

Hellevang, Helge

2006-06-01

The topic of this thesis is to gain a better understanding of interactions between injected CO 2 , aqueous solutions and formation mineralogies. The main focus is concerned with the potential role mineral reactions play in safe long term storage of CO 2 . The work is divided into an experimental part concentrated on the potential of dawsonite (NaAl(OH) 2 CO 3 ) as a permanent storage host of CO 2 , and the development of a new geochemical code ACCRETE that is coupled with the ATHENA multiphase flow simulator. The thesis is composed of two parts: (I) the first part introducing CO 2 storage, geochemical interactions and related work; and (II) the second part that consists of the papers. Part I is composed as follows: Chapter 2 gives a short introduction to geochemical reactions considered important during CO 2 storage, including a thermodynamic framework. Chapter 3 presents objectives of numerical work related to CO 2 -water-rock interactions including a discussion of factors that influence the outcome of numerical simulations. Chapter 4 presents the main results from paper A to E. Chapter 5 give some details about further research that we propose based on the present work and related work in the project. Several new activities have emerged from research on CO 2 -water-rock interaction during the project. Several of the proposed activities are already initiated. Papers A to F are then listed in Part II of the thesis after the citation list. The thesis presents the first data on the reaction kinetics of dawsonite at different pH (Paper A), and comprehensive numerical simulations, both batch- and large scale 3D reactive transport, that illustrate the role different carbonates have for safe storage of CO 2 in geological formations (Papers C to F). The role of dawsonite in CO 2 storage settings is treated throughout the study (Papers A to E) After the main part of the thesis (Part I and II), two appendices are included: Appendix A lists reactions that are included in the

Cost Evaluation of CO2 Sequestration by Aqueous Mineral Carbonation

NARCIS (Netherlands)

Huijgen, W.J.J.; Comans, R.N.J.; Witkamp, G.J.

2007-01-01

A cost evaluation of CO2 sequestration by aqueous mineral carbonation has been made using either wollastonite (CaSiO3) or steel slag as feedstock. First, the process was simulated to determine the properties of the streams as well as the power and heat consumption of the process equipment. Second, a

Carbon Mineralization by Aqueous Precipitation for Beneficial Use of CO2 from Flue Gas

Energy Technology Data Exchange (ETDEWEB)

Devenney, Martin; Gilliam, Ryan; Seeker, Randy

2014-06-01

The objective of this project is to demonstrate an innovative process to mineralize CO2 from flue gas directly to reactive carbonates and maximize the value and versatility of its beneficial use products. The program scope includes the design, construction, and testing of a CO2 Conversion to Material Products (CCMP) Pilot Demonstration Plant utilizing CO2 from the flue gas of a power production facility in Moss Landing, CA as well as flue gas from coal combustion. This topical report covers Phase 2b, which is the construction phase of pilot demonstration subsystems that make up the integrated plant. The subsystems included are the mineralization subsystem, the Alkalinity Based on Low Energy (ABLE) subsystem, the waste calcium oxide processing subsystem, and the fiber cement board production subsystem. The fully integrated plant is now capable of capturing CO2 from various sources (gas and coal) and mineralizing into a reactive calcium carbonate binder and subsequently producing commercial size (4ftx8ft) fiber cement boards. The topical report provides a description of the “as built” design of these subsystems and the results of the commissioning activities that have taken place to confirm operability. At the end of Phase 2b, the CCMP pilot demonstration is fully ready for testing.

In Situ Mineralization of Magnetite Nanoparticles in Chitosan Hydrogel

Science.gov (United States)

Wang, Yongliang; Li, Baoqiang; Zhou, Yu; Jia, Dechang

2009-09-01

Based on chelation effect between iron ions and amino groups of chitosan, in situ mineralization of magnetite nanoparticles in chitosan hydrogel under ambient conditions was proposed. The chelation effect between iron ions and amino groups in CS-Fe complex, which led to that chitosan hydrogel exerted a crucial control on the magnetite mineralization, was proved by X-ray photoelectron spectrum. The composition, morphology and size of the mineralized magnetite nanoparticles were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy and thermal gravity. The mineralized nanoparticles were nonstoichiometric magnetite with a unit formula of Fe2.85O4 and coated by a thin layer of chitosan. The mineralized magnetite nanoparticles with mean diameter of 13 nm dispersed in chitosan hydrogel uniformly. Magnetization measurement indicated that superparamagnetism behavior was exhibited. These magnetite nanoparticles mineralized in chitosan hydrogel have potential applications in the field of biotechnology. Moreover, this method can also be used to synthesize other kinds of inorganic nanoparticles, such as ZnO, Fe2O3 and hydroxyapatite.

In Situ Mineralization of Magnetite Nanoparticles in Chitosan Hydrogel

Directory of Open Access Journals (Sweden)

Wang Yongliang

2009-01-01

Full Text Available Abstract Based on chelation effect between iron ions and amino groups of chitosan, in situ mineralization of magnetite nanoparticles in chitosan hydrogel under ambient conditions was proposed. The chelation effect between iron ions and amino groups in CS–Fe complex, which led to that chitosan hydrogel exerted a crucial control on the magnetite mineralization, was proved by X-ray photoelectron spectrum. The composition, morphology and size of the mineralized magnetite nanoparticles were characterized by X-ray diffraction, Raman spectroscopy, transmission electron microscopy and thermal gravity. The mineralized nanoparticles were nonstoichiometric magnetite with a unit formula of Fe2.85O4and coated by a thin layer of chitosan. The mineralized magnetite nanoparticles with mean diameter of 13 nm dispersed in chitosan hydrogel uniformly. Magnetization measurement indicated that superparamagnetism behavior was exhibited. These magnetite nanoparticles mineralized in chitosan hydrogel have potential applications in the field of biotechnology. Moreover, this method can also be used to synthesize other kinds of inorganic nanoparticles, such as ZnO, Fe2O3and hydroxyapatite.

In situ NMR observation of the lithium extraction/insertion from LiCoO2 cathode

International Nuclear Information System (INIS)

Shimoda, Keiji; Murakami, Miwa; Takamatsu, Daiko; Arai, Hajime; Uchimoto, Yoshiharu; Ogumi, Zempachi

2013-01-01

Abstract: Rechargeable lithium-ion batteries (LIBs) are currently accepted to be one of the most suitable energy storage resources in portable electronic devices because of their high gravimetric and volumetric energy density. To understand the behavior of Li + ions on electrochemical lithium extraction/insertion process, we performed in situ 7 Li nuclear magnetic resonance (NMR) measurements for LiCoO 2 cathode in a plastic cell battery, and the spectral evolutions of the 7 Li NMR signal of Li x CoO 2 (0 ≤ x ≤ 1) were well investigated. Very narrow solid solution region of Li x CoO 2 (∼0.99 ≤ x 2 signal at ∼0 ppm, which is related to the localized nature of the electronic spin of paramagnetic Co 4+ ion formed at the very early delithiation stage. With further decreasing the signal intensity of LiCoO 2 , a Knight-shifted signal corresponding to an electrically conductive Li x CoO 2 phase emerged at x = 0.97, which then monotonously decreased in intensity for x x CoO 2 . These observations acquired in situ fully confirm the earlier studies obtained in ex situ measurements, although the present study offers more quantitative information. Moreover, it was shown that the peak position of the NMR shift for Li x CoO 2 moved as a function of lithium content, which behavior is analogous to the change in its c lattice parameter. Also, the growth and consumption of dendritic/mossy metallic lithium on the counter electrode was clearly observed during the charge/discharge cycles

Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

Science.gov (United States)

Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

2012-02-07

Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

Evaluation of Southern Quebec asbestos residues for CO2 sequestration by mineral carbonation

Energy Technology Data Exchange (ETDEWEB)

Beaudoin, G.; Hebert, R.; Constantin, M. [Laval Univ., Quebec City, PQ (Canada); Bonin, G. [LAB Chrysotile Inc., Black Lake, PQ (Canada); Dipple, G. [British Columbia Univ., Vancouver, BC (Canada)

2003-08-01

One alternative to help reduce carbon dioxide (CO{sub 2}) levels in the atmosphere is to sequester CO{sub 2} by mineral carbonation using ultramafic rock-hosted magnesian silicates (serpentine, olivine, talc). The carbonation process produces magnesite, which is a geologically stable and an environmentally safe magnesium carbonate. Three CO{sub 2} sinks exist in southern Quebec use such silicates. They are: (1) asbestos mill residues, (2) associated mine waste, and (3) ultramafic bedrock. Extraction of asbestos in the region has been accomplished from serpentinized harzburgite located in the Thetford Mines and Asbestos ophiolitic massifs and also from the highly sheared Pennington Sheet. The physical and chemical properties of magnesium silicate deposits greatly determine their carbonation potential. A wide range of properties was observed in samples obtained from almost all asbestos mill residues and waste. The reaction which takes place depends on the mineral content. The kinetics of the reactions are influenced by humidity and grain size.

In situ X-ray ptychography imaging of high-temperature CO2 acceptor particle agglomerates

DEFF Research Database (Denmark)

Høydalsvik, Kristin; Fløystad, Jostein Bø; Zhao, Tiejun

2014-01-01

be used for in situ phase contrast imaging in structure studies at atmospheric pressure and elevated temperatures. Lithium zirconate, a candidate CO2 capture material, was studied at a pressure of one atmosphere in air and in CO2, at temperatures exceeding 600 °C. Images with a spatial resolution better...

Fabrication of superhydrophobic surfaces via CaCO3 mineralization mediated by poly(glutamic acid)

Science.gov (United States)

Cao, Heng; Yao, Jinrong; Shao, Zhengzhong

2013-03-01

Surfaces with micrometer and nanometer sized hierarchical structures were fabricated by an one-step in situ additive controlled CaCO3 mineralization method. After chemical modification, the surfaces with various morphologies showed superhydrophobicity in different states, which could be easily adjusted by the initial supersaturation of the mineralization solution (concentration of calcium ion and poly(glutamic acid)). Generally, the "lotus state" surface which was covered by a thick layer of tetrahedron-shaped CaCO3 particles to exhibit a contact angle (CA) of 157±1° and a very low contact angle hysteresis (CAH) (roll-off angle=1°) was produced under high supersaturation. On the other hands, the petal-like surface with flower-shaped calcite spherulites was obtained in a relative low supersaturation, which showed both high CA (156±2°) and CAH (180°) in a "Cassie impregnating wetting state".

Spatial variation of sediment mineralization supports differential CO2 emissions from a tropical hydroelectric reservoir.

Science.gov (United States)

Cardoso, Simone J; Vidal, Luciana O; Mendonça, Raquel F; Tranvik, Lars J; Sobek, Sebastian; Fábio, Roland

2013-01-01

Substantial amounts of organic matter (OM) from terrestrial ecosystems are buried as sediments in inland waters. It is still unclear to what extent this OM constitutes a sink of carbon, and how much of it is returned to the atmosphere upon mineralization to carbon dioxide (CO2). The construction of reservoirs affects the carbon cycle by increasing OM sedimentation at the regional scale. In this study we determine the OM mineralization in the sediment of three zones (river, transition, and dam) of a tropical hydroelectric reservoir in Brazil as well as identify the composition of the carbon pool available for mineralization. We measured sediment organic carbon mineralization rates and related them to the composition of the OM, bacterial abundance and pCO2 of the surface water of the reservoir. Terrestrial OM was an important substrate for the mineralization. In the river and transition zones most of the OM was allochthonous (56 and 48%, respectively) while the dam zone had the lowest allochthonous contribution (7%). The highest mineralization rates were found in the transition zone (154.80 ± 33.50 mg C m(-) (2) d(-) (1)) and the lowest in the dam (51.60 ± 26.80 mg C m(-) (2) d(-) (1)). Moreover, mineralization rates were significantly related to bacterial abundance (r (2) = 0.50, p hydroelectric reservoirs.

Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system

Science.gov (United States)

Marion, Giles M.

2001-06-01

Carbonate minerals have played an important role in the geochemical evolution of Earth, and may have also played an important role in the geochemical evolution of Mars and Europa. Several models have been published in recent years that describe chloride and sulfate mineral solubilities in concentrated brines using the Pitzer equations. Few of these models are parameterized for subzero temperatures, and those that are do not include carbonate chemistry. The objectives of this work are to estimate Pitzer-equation bicarbonate-carbonate parameters and carbonate mineral solubility products and to incorporate them into the FREZCHEM model to predict carbonate mineral solubilities in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system at low temperatures (≤25°C) with a special focus on subzero temperatures. Most of the Pitzer-equation parameters and equilibrium constants are taken from the literature and extrapolated into the subzero temperature range. Solubility products for 14 sodium, potassium, magnesium, and calcium bicarbonate and carbonate minerals are included in the model. Most of the experimental data are at temperatures ≥ -8°C; only for the NaHCO 3-NaCl-H 2O and Na 2CO 3-NaCl-H 2O systems are there bicarbonate and carbonate data to temperatures as low as -21.6°C. In general, the fit of the model to the experimental data is good. For example, calculated eutectic temperatures and compositions for NaHCO 3, Na 2CO 3, and their mixtures with NaCl and Na 2SO 4 salts are in good agreement with experimental data to temperatures as low as -21.6°C. Application of the model to eight saline, alkaline carbonate waters give predicted pHs ranging from 9.2 to 10.2, in comparison with measured pHs that range from 8.7 to 10.2. The model suggests that the CaCO 3 mineral that precipitates during seawater freezing is probably calcite and not ikaite. The model demonstrates that a proposed salt assemblage for the icy surface of Europa consisting of highly hydrated MgSO 4

Reverse osmosis treatment in CO_2 + O_2 to the application of the in-situ leaching of uranium

International Nuclear Information System (INIS)

Ruan Zhilong; Li Xilong; Yang Shaowu

2014-01-01

Advantages and disadvantages of various groundwater management methods, combined with CO_2 + O_2 characteristics of in situ leaching uranium mining process, use reverse osmosis wastewater treatment technology, has carried on the laboratory test, field condition test and industrial test. Obtained by indoor experiment and field conditions for Cl"- ion concentration variation characteristics; Reverse osmosis treatment effect of wastewater is verified by industrial test, obtained the technical parameters and consumption data, as well as the leaching liquid and adsorption tail liquid pH, SO_4"2"-; Cl"- in the plasma concentration monitoring, and further prove that the reverse osmosis treatment technology is suitable for in-situ leaching of uranium in CO_2 + O_2 in wastewater treatment. (authors)

Calcium Carbonate Precipitation for CO2 Storage and Utilization: A Review of the Carbonate Crystallization and Polymorphism

Directory of Open Access Journals (Sweden)

Ribooga Chang

2017-07-01

Full Text Available The transformation of CO2 into a precipitated mineral carbonate through an ex situ mineral carbonation route is considered a promising option for carbon capture and storage (CCS since (i the captured CO2 can be stored permanently and (ii industrial wastes (i.e., coal fly ash, steel and stainless-steel slags, and cement and lime kiln dusts can be recycled and converted into value-added carbonate materials by controlling polymorphs and properties of the mineral carbonates. The final products produced by the ex situ mineral carbonation route can be divided into two categories—low-end high-volume and high-end low-volume mineral carbonates—in terms of their market needs as well as their properties (i.e., purity. Therefore, it is expected that this can partially offset the total cost of the CCS processes. Polymorphs and physicochemical properties of CaCO3 strongly rely on the synthesis variables such as temperature, pH of the solution, reaction time, ion concentration and ratio, stirring, and the concentration of additives. Various efforts to control and fabricate polymorphs of CaCO3 have been made to date. In this review, we present a summary of current knowledge and recent investigations entailing mechanistic studies on the formation of the precipitated CaCO3 and the influences of the synthesis factors on the polymorphs.

Activation of magnesium rich minerals as carbonation feedstock materials for CO2 sequestration

International Nuclear Information System (INIS)

Maroto-Valer, M.M.; Kuchta, M.E.; Zhang, Y.; Andresen, J.M.; Fauth, D.J.

2005-01-01

Mineral carbonation, the reaction of magnesium-rich minerals such as olivine and serpentine with CO 2 to form stable mineral carbonates, is a novel and promising approach to carbon sequestration. However, the preparation of the minerals prior to carbonation can be energy intensive, where some current studies have been exploring extensive pulverization of the minerals below 37 μm, heat treatment of minerals up to 650 o C, prior separation of CO 2 from flue gases, and carbonation at high pressures, temperatures and long reaction times of up to 125 atm, 185 o C and 6 h, respectively. Thus, the objective of the mineral activation concept is to promote and accelerate carbonation reaction rates and efficiencies through surface activation to the extent that such rigorous reaction conditions were not required. The physical activations were performed with air and steam, while chemical activations were performed with a suite of acids and bases. The parent serpentine, activated serpentines, and carbonation products were characterized to determine their surface properties and assess their potential as carbonation minerals. The results indicate that the surface area of the raw serpentine, which is approximately 8 m 2 /g, can be increased through physical and chemical activation methods to over 330 m 2 /g. The chemical activations were more effective than the physical activations at increasing the surface area, with the 650 o C steam activated serpentine presenting a surface area of only 17 m 2 /g. Sulfuric acid was the most effective acid used during the chemical activations, resulting in surface areas greater than 330 m 2 /g. Several of the samples produced underwent varying degrees of carbonation. The steam activated serpentine underwent a 60% conversion to magnesite at 155 o C and 126 atm in 1 h, while the parent sample only exhibited a 7% conversion. The most promising results came from the carbonation of the extracted Mg(OH) 2 solution, where, based on the amount of

Evaluation of the CO2 sequestration capacity for coal fly ash using a flow-through column reactor under ambient conditions

International Nuclear Information System (INIS)

Jo, Ho Young; Ahn, Joon-Hoon; Jo, Hwanju

2012-01-01

Highlights: ► A conceptual in-situ mineral carbonation method using a coal ash pond is proposed. ► CO 2 uptake occurred by carbonation reaction of CO 2 with Ca 2+ ions from coal fly ash. ► The CO 2 sequestration capacity was affected by the solid dosage. ► Seawater can be used as a solvent for mineral carbonation of coal fly ash. - Abstract: An in-situ CO 2 sequestration method using coal ash ponds located in coastal regions is proposed. The CO 2 sequestration capacity of coal fly ash (CFA) by mineral carbonation was evaluated in a flow-through column reactor under various conditions (solid dosage: 100–330 g/L, CO 2 flow rate: 20–80 mL/min, solvent type: deionized (DI) water, 1 M NH 4 Cl solution, and seawater). The CO 2 sequestration tests were conducted on CFA slurries using flow-through column reactors to simulate more realistic flow-through conditions. The CO 2 sequestration capacity increased when the solid dosage was increased, whereas it was affected insignificantly by the CO 2 flow rate. A 1 M NH 4 Cl solution was the most effective solvent, but it was not significantly different from DI water or seawater. The CO 2 sequestration capacity of CFA under the flow-through conditions was approximately 0.019 g CO 2 /g CFA under the test conditions (solid dosage: 333 g/L, CO 2 flow rate: 40 mL/min, and solvent: seawater).

Thermal decomposition of dolomite under CO2: insights from TGA and in situ XRD analysis.

Science.gov (United States)

Valverde, Jose Manuel; Perejon, Antonio; Medina, Santiago; Perez-Maqueda, Luis A

2015-11-28

Thermal decomposition of dolomite in the presence of CO2 in a calcination environment is investigated by means of in situ X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The in situ XRD results suggest that dolomite decomposes directly at a temperature around 700 °C into MgO and CaO. Immediate carbonation of nascent CaO crystals leads to the formation of calcite as an intermediate product of decomposition. Subsequently, decarbonation of this poorly crystalline calcite occurs when the reaction is thermodynamically favorable and sufficiently fast at a temperature depending on the CO2 partial pressure in the calcination atmosphere. Decarbonation of this dolomitic calcite occurs at a lower temperature than limestone decarbonation due to the relatively low crystallinity of the former. Full decomposition of dolomite leads also to a relatively low crystalline CaO, which exhibits a high reactivity as compared to limestone derived CaO. Under CO2 capture conditions in the Calcium-Looping (CaL) process, MgO grains remain inert yet favor the carbonation reactivity of dolomitic CaO especially in the solid-state diffusion controlled phase. The fundamental mechanism that drives the crystallographic transformation of dolomite in the presence of CO2 is thus responsible for its fast calcination kinetics and the high carbonation reactivity of dolomitic CaO, which makes natural dolomite a potentially advantageous alternative to limestone for CO2 capture in the CaL technology as well as SO2in situ removal in oxy-combustion fluidized bed reactors.

Calcium Carbonate Precipitation for CO{sub 2} Storage and Utilization: A Review of the Carbonate Crystallization and Polymorphism

Energy Technology Data Exchange (ETDEWEB)

Chang, Ribooga; Kim, Semin; Lee, Seungin; Choi, Soyoung; Kim, Minhee; Park, Youngjune, E-mail: young@gist.ac.kr [Carbon and Energy Systems, School of Earth Sciences and Environmental Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju (Korea, Republic of)

2017-07-10

The transformation of CO{sub 2} into a precipitated mineral carbonate through an ex situ mineral carbonation route is considered a promising option for carbon capture and storage (CCS) since (i) the captured CO{sub 2} can be stored permanently and (ii) industrial wastes (i.e., coal fly ash, steel and stainless-steel slags, and cement and lime kiln dusts) can be recycled and converted into value-added carbonate materials by controlling polymorphs and properties of the mineral carbonates. The final products produced by the ex situ mineral carbonation route can be divided into two categories—low-end high-volume and high-end low-volume mineral carbonates—in terms of their market needs as well as their properties (i.e., purity). Therefore, it is expected that this can partially offset the total cost of the CCS processes. Polymorphs and physicochemical properties of CaCO{sub 3} strongly rely on the synthesis variables such as temperature, pH of the solution, reaction time, ion concentration and ratio, stirring, and the concentration of additives. Various efforts to control and fabricate polymorphs of CaCO{sub 3} have been made to date. In this review, we present a summary of current knowledge and recent investigations entailing mechanistic studies on the formation of the precipitated CaCO{sub 3} and the influences of the synthesis factors on the polymorphs.

Mineral composition of durum wheat grain and pasta under increasing atmospheric CO2 concentrations.

Science.gov (United States)

Beleggia, Romina; Fragasso, Mariagiovanna; Miglietta, Franco; Cattivelli, Luigi; Menga, Valeria; Nigro, Franca; Pecchioni, Nicola; Fares, Clara

2018-03-01

The concentrations of 10 minerals were investigated in the grain of 12 durum wheat genotypes grown under free air CO 2 enrichment conditions, and in four of their derived pasta samples, using inductively coupled plasma mass spectrometry. Compared to ambient CO 2 (400ppm; AMB), under elevated CO 2 (570ppm; ELE), the micro-element and macro-element contents showed strong and significant decreases in the grain: Mn, -28.3%; Fe, -26.7%; Zn, -21.9%; Mg, -22.7%; Mo, -40.4%; K, -22.4%; and Ca, -19.5%. These variations defined the 12 genotypes as sensitive or non-sensitive to ELE. The pasta samples under AMB and ELE showed decreased mineral contents compared to the grain. Nevertheless, the contributions of the pasta to the recommended daily allowances remained relevant, also for the micro-elements under ELE conditions (range, from 18% of the recommended daily allowance for Zn, to 70% for Mn and Mo). Copyright © 2017 Elsevier Ltd. All rights reserved.

NOVEL IN-SITU METAL AND MINERAL EXTRACTION TECHNOLOGY

Energy Technology Data Exchange (ETDEWEB)

Glenn O' Gorman; Hans von Michaelis; Gregory J. Olson

2004-09-22

This white paper summarizes the state of art of in-situ leaching of metals and minerals, and describes a new technology concept employing improved fragmentation of ores underground in order to prepare the ore for more efficient in-situ leaching, combined with technology to continuously improve solution flow patterns through the ore during the leaching process. The process parameters and economic benefits of combining the new concept with chemical and biological leaching are described. A summary is provided of the next steps required to demonstrate the technology with the goal of enabling more widespread use of in-situ leaching.

Waste water treatment of CO2+O2 in-situ leaching uranium

International Nuclear Information System (INIS)

Xu Lechang; Liu Naizhong; Du Zhiming; Wang Hongying

2012-01-01

An in-situ leaching uranium mine located in Northern China uses CO 2 +O 2 leaching process to leach uranium. The consumption of industrial reagent and water, and generation and discharge of waste water are minimized by comprehensive waste water treatment technology with process water recycle, reverse osmosis and natural evaporation. The process water of the mine that can be recycled and reused includes barren fluid, solution washing loaded resin, precipitating mother solution and filtered liquor of yellow cake. Solution regenerating barren resin is treated by reverse osmosis. Concentrated water from reverse osmosis and solution washing barren resin are naturally evaporated. (authors)

Evaluation of southern Quebec asbestos residues for CO{sub 2} sequestration by mineral carbonation : preliminary result

Energy Technology Data Exchange (ETDEWEB)

Huot, F. [Geo-conseils, Cap-Rouge, PQ (Canada); Beaudoin, G.; Hebert, R.; Constantin, M. [Laval Univ., Dept. of Geology and Geological Engineering, Quebec City, PQ (Canada); Bonin, G. [LAB Chrysotile Inc., Black Lake, PQ (Canada); Dipple, G.M. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Earth and Ocean Sciences

2003-07-01

Carbon dioxide (CO{sub 2}) sequestration is one approach that can help reduce CO{sub 2} levels in the atmosphere. This paper discusses CO{sub 2} sequestration by mineral carbonation using ultramafic rock-hosted magnesian silicates (serpentine, olivine, talc). The carbonation process produces magnesite, which is a geologically stable and an environmentally safe magnesium carbonate. There are 3 potential CO{sub 2} sinks in southern Quebec that use such silicates. They are: (1) asbestos mill residues, (2) associated mine waste, and (3) ultramafic bedrock. Asbestos is extracted from serpentinized harzburgite located in the Thetford Mines and Asbestos ophiolitic massifs and also from the highly sheared Pennington Sheet. The physical and chemical properties of magnesium silicate deposits greatly determine their carbonation potential. A wide range of properties was observed in samples obtained from almost all asbestos mill residues and waste. The reaction which takes place depends on the mineral content. The kinetics of the reactions are influenced by humidity and grain size.

CO2 Mineralization and Utilization using Steel Slag for Establishing a Waste-to-Resource Supply Chain.

Science.gov (United States)

Pan, Shu-Yuan; Chung, Tai-Chun; Ho, Chang-Ching; Hou, Chin-Jen; Chen, Yi-Hung; Chiang, Pen-Chi

2017-12-08

Both steelmaking via an electric arc furnace and manufacturing of portland cement are energy-intensive and resource-exploiting processes, with great amounts of carbon dioxide (CO 2 ) emission and alkaline solid waste generation. In fact, most CO 2 capture and storage technologies are currently too expensive to be widely applied in industries. Moreover, proper stabilization prior to utilization of electric arc furnace slag are still challenging due to its high alkalinity, heavy metal leaching potentials and volume instability. Here we deploy an integrated approach to mineralizing flue gas CO 2 using electric arc furnace slag while utilizing the reacted product as supplementary cementitious materials to establish a waste-to-resource supply chain toward a circular economy. We found that the flue gas CO 2 was rapidly mineralized into calcite precipitates using electric arc furnace slag. The carbonated slag can be successfully utilized as green construction materials in blended cement mortar. By this modulus, the global CO 2 reduction potential using iron and steel slags was estimated to be ~138 million tons per year.

The thermal behaviour and structural stability of nesquehonite, MgCO3.3H2O, evaluated by in situ laboratory parallel-beam X-ray powder diffraction: New constraints on CO2 sequestration within minerals.

Science.gov (United States)

Ballirano, Paolo; De Vito, Caterina; Ferrini, Vincenzo; Mignardi, Silvano

2010-06-15

In order to gauge the appropriateness of CO(2) reaction with Mg chloride solutions as a process for storing carbon dioxide, the thermal behaviour and structural stability of its solid product, nesquehonite (MgCO(3).3H(2)O), were investigated in situ using real-time laboratory parallel-beam X-ray powder diffraction. The results suggest that the nesquehonite structure remains substantially unaffected up to 373 K, with the exception of a markedly anisotropic thermal expansion acting mainly along the c axis. In the 371-390 K range, the loss of one water molecule results in the nucleation of a phase of probable composition MgCO(3).2H(2)O, which is characterized by significant structural disorder. At higher temperatures (423-483 K), both magnesite and MgO.2MgCO(3) coexist. Finally, at 603 K, periclase nucleation starts and the disappearance of carbonate phases is completed at 683 K. Consequently, the structural stability of nesquehonite at high temperatures suggests that it will remain stable under the temperature conditions that prevail at the Earth's surface. These results will help (a) to set constraints on the temperature conditions under which nesquehonite may be safely stored and (b) to develop CO(2) sequestration via the synthesis of nesquehonite for industrial application. Copyright 2010 Elsevier B.V. All rights reserved.

Progress Toward Measuring CO2 Isotopologue Fluxes in situ with the LLNL Miniature, Laser-based CO2 Sensor

Science.gov (United States)

Osuna, J. L.; Bora, M.; Bond, T.

2015-12-01

One method to constrain photosynthesis and respiration independently at the ecosystem scale is to measure the fluxes of CO2­ isotopologues. Instrumentation is currently available to makes these measurements but they are generally costly, large, bench-top instruments. Here, we present progress toward developing a laser-based sensor that can be deployed directly to a canopy to passively measure CO2 isotopologue fluxes. In this study, we perform initial proof-of-concept and sensor characterization tests in the laboratory and in the field to demonstrate performance of the Lawrence Livermore National Laboratory (LLNL) tunable diode laser flux sensor. The results shown herein demonstrate measurement of bulk CO2 as a first step toward achieving flux measurements of CO2 isotopologues. The sensor uses a Vertical Cavity Surface Emitting Laser (VCSEL) in the 2012 nm range. The laser is mounted in a multi-pass White Cell. In order to amplify the absorption signal of CO2 in this range we employ wave modulation spectroscopy, introducing an alternating current (AC) bias component where f is the frequency of modulation on the laser drive current in addition to the direct current (DC) emission scanning component. We observed a strong linear relationship (r2 = 0.998 and r2 = 0.978 at all and low CO2 concentrations, respectively) between the 2f signal and the CO2 concentration in the cell across the range of CO2 concentrations relevant for flux measurements. We use this calibration to interpret CO2 concentration of a gas flowing through the White cell in the laboratory and deployed over a grassy field. We will discuss sensor performance in the lab and in situ as well as address steps toward achieving canopy-deployed, passive measurements of CO2 isotopologue fluxes. This work performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. LLNL-ABS-675788

Hydrogeochemical and stable isotopic investigations on CO2-rich mineral waters from Harghita Mts. (Eastern Carpathians, Romania)

Science.gov (United States)

Kis, Boglárka-Mercedesz; Baciu, Călin; Kármán, Krisztina; Kékedy-Nagy, Ladislau; Francesco, Italiano

2013-04-01

There is a worldwide interest on geothermal, mineral and groundwater as a resource for energy, drinking water supply and therapeutic needs. The increasing trend in replacing tap water with commercial bottled mineral water for drinking purposes has become an economic, hydrogeologic and medical concern in the last decades. Several investigations have been carried out worldwide on different topics related to geothermal and mineral waters, dealing with mineral water quality assessment, origin of geothermal and mineral waters, geochemical processes that influence water chemistry and water-rock interaction In Romania, the Călimani-Gurghiu-Harghita Neogene to Quaternary volcanic chain (Eastern Carpathians) is one of the most important areas from the point of view of CO2-rich mineral waters. These mineral water springs occur within other post-volcanic phenomena like dry CO2 emissions, moffettes, bubbling pools, H2S gas emissions etc. Mineral waters from this area are used for bottling, local spas and drinking purposes for local people. The number of springs, around 2000 according to literature data, shows that there is still a significant unexploited potential for good quality drinking water in this area. Within the youngest segment of the volcanic chain, the Harghita Mts., its volcaniclastic aprons and its boundary with the Transylvanian Basin, we have carried out an investigation on 23 CO2-rich mineral water springs from a hydrogeochemical and stable isotopic point of view. The mineral waters are Ca-Mg-HCO3 to Na-Cl type. Sometimes mixing between the two types can be observed. We have detected a great influence of water-rock interaction on the stable isotopic composition of the mineral waters, shown by isotopic shifts to the heavier oxygen isotope, mixing processes between shallow and deeper aquifers and local thermal anomalies. Acknowledgements: The present work was financially supported by the Romanian National Research Council, Project PN-II-ID-PCE-2011-3-0537 and by

In-Situ Hydrothermal Synthesis of Bi-Bi2O2CO3 Heterojunction Photocatalyst with Enhanced Visible Light Photocatalytic Activity

Science.gov (United States)

Kar, Prasenjit; Maji, Tuhin Kumar; Nandi, Ramesh; Lemmens, Peter; Pal, Samir Kumar

2017-04-01

Bismuth containing nanomaterials recently received increasing attention with respect to environmental applications because of their low cost, high stability and nontoxicity. In this work, Bi-Bi2O2CO3 heterojunctions were fabricated by in-situ decoration of Bi nanoparticles on Bi2O2CO3 nanosheets via a simple hydrothermal synthesis approach. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) were used to confirm the morphology of the nanosheet-like heterostructure of the Bi-Bi2O2CO3 composite. Detailed ultrafast electronic spectroscopy reveals that the in-situ decoration of Bi nanoparticles on Bi2O2CO3 nanosheets exhibit a dramatically enhanced electron-hole pair separation rate, which results in an extraordinarily high photocatalytic activity for the degradation of a model organic dye, methylene blue (MB) under visible light illumination. Cycling experiments revealed a good photochemical stability of the Bi-Bi2O2CO3 heterojunction under repeated irradiation. Photocurrent measurements further indicated that the heterojunction incredibly enhanced the charge generation and suppressed the charge recombination of photogenerated electron-hole pairs.

Crystal-field-driven redox reactions: How common minerals split H2O and CO2 into reduced H2 and C plus oxygen

Science.gov (United States)

Freund, F.; Batllo, F.; Leroy, R. C.; Lersky, S.; Masuda, M. M.; Chang, S.

1991-01-01

It is difficult to prove the presence of molecular H2 and reduced C in minerals containing dissolved H2 and CO2. A technique was developed which unambiguously shows that minerals grown in viciously reducing environments contain peroxy in their crystal structures. The peroxy represent interstitial oxygen atoms left behind when the solute H2O and/or CO2 split off H2 and C as a result of internal redox reactions, driven by the crystal field. The observation of peroxy affirms the presence of H2 and reduced C. It shows that the solid state is indeed an unusual reaction medium.

In-Situ X-ray Tomography Study of Cement Exposed to CO2 Saturated Brine

DEFF Research Database (Denmark)

Chavez Panduro, E. A.; Torsæter, M.; Gawel, K.

2017-01-01

For successful CO2 storage in underground reservoirs, the potential problem of CO2 leakage needs to be addressed. A profoundly improved understanding of the behavior of fractured cement under realistic subsurface conditions including elevated temperature, high pressure and the presence of CO2...... saturated brine is required. Here, we report in situ X-ray micro computed tomography (μ-CT) studies visualizing the microstructural changes upon exposure of cured Portland cement with an artificially engineered leakage path (cavity) to CO2 saturated brine at high pressure. Carbonation of the bulk cement......, self-healing of the leakage path in the cement specimen, and leaching of CaCO3 were thus directly observed. The precipitation of CaCO3, which is of key importance as a possible healing mechanism of fractured cement, was found to be enhanced in confined regions having limited access to CO2...

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CO2: Implications for Caprock Integrity

Science.gov (United States)

Loring, J. S.; Chen, J.; Thompson, C.; Schaef, T.; Miller, Q. R.; Martin, P. F.; Ilton, E. S.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

2012-12-01

The effectiveness of geologic sequestration as an enterprise for CO2 storage depends partly on the reactivity of supercritical CO2 (scCO2) with caprock minerals. Injection of scCO2 will displace formation water, and the pore space adjacent to overlying caprocks could eventually be dominated by dry to water-saturated scCO2. Caprock formations have high concentrations of clay minerals, including expandable montmorillonites. Water-bearing scCO2 is highly reactive and capable of hydrating or dehydrating clays, possibly leading to porosity and permeability changes that directly impact caprock performance. Dehydration will cause montmorillonite clay minerals in caprocks to contract, thereby decreasing solid volume and possibly increasing caprock permeability and porosity. On the other hand, water intercalation will cause these clays to expand, thereby increasing solid volume and possibly leading to self-sealing of caprock fractures. Pacific Northwest National Laboratory's Carbon Sequestration Initiative is developing capabilities for studying wet scCO2-mineral reactions in situ. Here, we introduce novel in situ infrared (IR) spectroscopic instrumentation that enables quantitative titrations of reactant minerals with water in scCO2. Results are presented for the infrared spectroscopic titrations of Na-, Ca-, and Mg-saturated Wyoming betonites with water over concentrations ranging from zero to scCO2 saturated. These experiments were carried out at 50°C and 90 bar. Transmission IR spectroscopy was used to measure concentrations of water dissolved in the scCO2 or intercalated into the clays. The titration curves evaluated from the transmission-IR data are compared between the three types of clays to assess the effects of the cation on water partitioning. Single-reflection attenuated total reflection (ATR) IR spectroscopy was used to collect the spectrum of the clays as they hydrate at every total water concentration during the titration. Clay hydration is evidenced by

Carbon Mineralization by Aqueous Precipitation for Beneficial Use of CO₂ from Flue Gas

Energy Technology Data Exchange (ETDEWEB)

Devenney, Martin [Calera Corporation, Moss Landing, CA (United States); Gilliam, Ryan [Calera Corporation, Moss Landing, CA (United States); Seeker, Randy [Calera Corporation, Moss Landing, CA (United States)

2015-06-30

The objective of this project was to demonstrate an innovative process to mineralize CO₂ from flue gas directly to reactive carbonates and maximize the value and versatility of its beneficial use products. The program scope includes the design, construction, and testing of a CO₂ Conversion to Material Products (CCMP) Pilot Demonstration Plant utilizing CO₂ from the flue gas of a power production facility in Moss Landing, CA as well as flue gas from coal combustion. This final report details all development, analysis, design and testing of the project. Also included in the final report are an updated Techno-Economic Analysis and CO₂ Lifecycle Analysis. The subsystems included in the pilot demonstration plant are the mineralization subsystem, the Alkalinity Based on Low Energy (ABLE) subsystem, the waste calcium oxide processing subsystem, and the fiber cement board production subsystem. The fully integrated plant was proven to be capable of capturing CO₂ from various sources (gas and coal) and mineralizing it into a reactive calcium carbonate binder and subsequently producing commercial size (4ftx8ft) fiber cement boards. The final report provides a description of the “as built” design of these subsystems and the results of the commissioning activities that have taken place to confirm operability. The report also discusses the results of the fully integrated operation of the facility. Fiber cement boards have been produced in this facility exclusively using reactive calcium carbonate from captured CO₂ from flue gas. These boards meet all US and China appropriate acceptance standards. Use demonstrations for these boards are now underway.

[Temperature sensitivity of CO2 fluxes from rhizosphere soil mineralization and root decomposition in Pinus massoniana and Castanopsis sclerophylla forests].

Science.gov (United States)

Liu, Yu; Hu, Xiao-Fei; Chen, Fu-Sheng; Yuan, Ping-Cheng

2013-06-01

Rhizospheric and non-rhizospheric soils and the absorption, transition, and storage roots were sampled from the mid-subtropical Pinus massoniana and Castanopsis sclerophylla forests to study the CO2 fluxes from soil mineralization and root decomposition in the forests. The samples were incubated in closed jars at 15 degrees C, 25 degrees C, 35 degrees C, and 45 degrees C, respectively, and alkali absorption method was applied to measure the CO2 fluxes during 53 days incubation. For the two forests, the rhizospheric effect (ratio of rhizospheric to non-rhizospheric soil) on the CO2 flux from soil mineralization across all incubation temperature ranged from 1.12 to 3.09, with a decreasing trend along incubation days. There was no significant difference in the CO2 flux from soil mineralization between the two forests at 15 degrees C, but the CO2 flux was significantly higher in P. massoniana forest than in C. sclerophylla forest at 25 degrees C and 35 degrees C, and in an opposite pattern at 45 degrees C. At all incubation temperature, the CO2 release from the absorption root decomposition was higher than that from the transition and storage roots decomposition, and was smaller in P. massoniana than in C. sclerophylla forest for all the root functional types. The Q10 values of the CO2 fluxes from the two forests were higher for soils (1.21-1.83) than for roots (0.96-1.36). No significant differences were observed in the Q10 values of the CO2 flux from soil mineralization between the two forests, but the Q10 value of the CO2 flux from root decomposition was significantly higher in P. massoniana than in C. sclerophylla forest. It was suggested that the increment of CO2 flux from soil mineralization under global warming was far higher than that from root decomposition, and for P. massoniana than for C. sclerophylla forest. In subtropics of China, the adaptability of zonal climax community to global warming would be stronger than that of pioneer community.

Application of oxy-fuel CO2 capture for In-situ bitumen extraction from Canada's oil sands

Energy Technology Data Exchange (ETDEWEB)

Bohm, Mark; Goold, Scott; Laux, Stefan; Sharma, Apoorva; Aasen, Knut; Neu, Ben

2010-09-15

The CO2 Capture Project, along with Praxair, Devon Canada, Cenovus Energy and Statoil are executing a project to demonstrate oxy-fuel combustion as a practical and economic method for CO2 capture from once-through steam generators used in the in-situ production of bitumen in the Canadian Oil Sands. The goal of the project is to develop a reliable, lower cost solution for capturing CO2 that will eliminate up to 90% of the GHG emissions from in-situ operations. The participants will present results of Phase I of this project, and will also outline the future Phases to pilot this technology.

An in-situ IR study on the adsorption of CO2 and H2O on hydrotalcites

NARCIS (Netherlands)

Coenen, K.T.; Gallucci, F.; Mezari, B.; Hensen, E.J.M.; van Sint Annaland, M.

2018-01-01

In-situ IR technique was used to study the reversible adsorption of CO2 and H2O at elevated temperatures on a potassium-promoted hydrotalcite for its use in sorption-enhanced water-gas shift (SEWGS). It was found that mainly bidentate carbonate species are responsible for the reversible (cyclic)

Radiocarbon as a Reactive Tracer for Tracking Permanent CO₂ Storage in Basaltic Rocks

Energy Technology Data Exchange (ETDEWEB)

Matter, Juerg [Columbia Univ., New York, NY (United States); Stute, Martin [Columbia Univ., New York, NY (United States); Schlosser, Peter [Columbia Univ., New York, NY (United States); Broecker, Wallace [Columbia Univ., New York, NY (United States)

2015-09-30

In view of concerns about the long-term integrity and containment of CO₂ storage in geologic reservoirs, many efforts have been made to improve the monitoring, verification and accounting methods for geologically stored CO₂. Our project aimed to demonstrate that carbon-14 (¹⁴C) could be used as a reactive tracer to monitor geochemical reactions and evaluate the extent of mineral trapping of CO₂ in basaltic rocks. The capacity of a storage reservoir for mineral trapping of CO₂ is largely a function of host rock composition. Mineral carbonation involves combining CO₂ with divalent cations including Ca²⁺, Mg²⁺ and Fe²⁺. The most abundant geological sources for these cations are basaltic rocks. Based on initial storage capacity estimates, we know that basalts have the necessary capacity to store million to billion tons of CO₂ via in situ mineral carbonation. However, little is known about CO2-fluid-rock reactions occurring in a basaltic storage reservoir during and post-CO₂ injection. None of the common monitoring and verification techniques have been able to provide a surveying tool for mineral trapping. The most direct method for quantitative monitoring and accounting involves the tagging of the injected CO₂ with 14C because 14C is not present in deep geologic reservoirs prior to injection. Accordingly, we conducted two CO₂ injection tests at the CarbFix pilot injection site in Iceland to study the feasibility of 14C as a reactive tracer for monitoring CO₂-fluid-rock reactions and CO₂ mineralization. Our newly developed monitoring techniques, using 14C as a reactive tracer, have been successfully demonstrated. For the first time, permanent and safe disposal of CO₂ as environmentally benign carbonate minerals in basaltic rocks could be shown. Over 95% of the injected CO₂ at the Carb

Hidden shift of the ionome of plants exposed to elevated CO2 depletes minerals at the base of human nutrition

Science.gov (United States)

Loladze, Irakli

2014-01-01

Mineral malnutrition stemming from undiversified plant-based diets is a top global challenge. In C3 plants (e.g., rice, wheat), elevated concentrations of atmospheric carbon dioxide (eCO2) reduce protein and nitrogen concentrations, and can increase the total non-structural carbohydrates (TNC; mainly starch, sugars). However, contradictory findings have obscured the effect of eCO2 on the ionome—the mineral and trace-element composition—of plants. Consequently, CO2-induced shifts in plant quality have been ignored in the estimation of the impact of global change on humans. This study shows that eCO2 reduces the overall mineral concentrations (−8%, 95% confidence interval: −9.1 to −6.9, p carbon:minerals in C3 plants. The meta-analysis of 7761 observations, including 2264 observations at state of the art FACE centers, covers 130 species/cultivars. The attained statistical power reveals that the shift is systemic and global. Its potential to exacerbate the prevalence of ‘hidden hunger’ and obesity is discussed. DOI: http://dx.doi.org/10.7554/eLife.02245.001 PMID:24867639

CO{sub 2} Energy Reactor – Integrated Mineral Carbonation: Perspectives on Lab-Scale Investigation and Products Valorization

Energy Technology Data Exchange (ETDEWEB)

Santos, Rafael M., E-mail: rafael.santos@alumni.utoronto.ca [Chemical and Environmental Laboratories (CEL), School of Applied Chemical and Environmental Sciences, Sheridan Institute of Technology, Brampton, ON (Canada); Knops, Pol C. M.; Rijnsburger, Keesjan L. [Innovation Concepts B.V., Twello (Netherlands); Chiang, Yi Wai [School of Engineering, University of Guelph, Guelph, ON (Canada)

2016-02-15

To overcome the challenges of mineral CO{sub 2} sequestration, Innovation Concepts B.V. is developing a unique proprietary gravity pressure vessel (GPV) reactor technology and has focussed on generating reaction products of high economic value. The GPV provides intense process conditions through hydrostatic pressurization and heat exchange integration that harvests exothermic reaction energy, thereby reducing energy demand of conventional reactor designs, in addition to offering other benefits. In this paper, a perspective on the status of this technology and outlook for the future is provided. To date, laboratory-scale tests of the envisioned process have been performed in a tubular “rocking autoclave” reactor. The mineral of choice has been olivine [~Mg{sub 1.6}Fe{sup 2+}{sub 0.4}(SiO{sub 4}) + ppm Ni/Cr], although asbestos, steel slags, and oil shale residues are also under investigation. The effect of several process parameters on reaction extent and product properties has been tested: CO{sub 2} pressure, temperature, residence time, additives (buffers, lixiviants, chelators, oxidizers), solids loading, and mixing rate. The products (carbonates, amorphous silica, and chromite) have been physically separated (based on size, density, and magnetic properties), characterized (for chemistry, mineralogy, and morphology), and tested in intended applications (as pozzolanic carbon-negative building material). Economically, it is found that product value is the main driver for mineral carbonation, rather than, or in addition to, the sequestered CO{sub 2}. The approach of using a GPV and focusing on valuable reaction products could thus make CO{sub 2} mineralization a feasible and sustainable industrial process.

The formation mechanism of a textured ceramic of thermoelectric [Ca2CoO3](0.62)[CoO2] on beta-Co(OH)2 templates through in situ topotactic conversion.

Science.gov (United States)

Itahara, Hiroshi; Seo, Won-Seon; Lee, Sujeong; Nozaki, Hiroshi; Tani, Toshihiko; Koumoto, Kunihito

2005-05-04

We investigated the formation mechanism of thermoelectric [Ca(2)CoO(3)](0.62)[CoO(2)] (CCO) on beta-Co(OH)(2) templates with maintained orientations by identifying the intermediate phases and specifying the relationship between their crystallographic orientations. We mixed beta-Co(OH)(2) templates with the complementary reactant CaCO(3) and prepared a compact by tape casting, with the developed (001) plane of the templates aligned along the casting plane. High-temperature XRD of the compact revealed that beta-Co(OH)(2) decomposed into Co(3)O(4) by 873 K, and Co(3)O(4) reacted with CaO to form CCO by 1193 K via the formation of the newly detected intermediate phase beta-Na(x)()CoO(2)-type Ca(x)()CoO(2) at 913-973 K. Pole figure measurements and SEM and TEM observations revealed that the relationship between the crystallographic planes was (001) beta-Co(OH)(2)//{111} Co(3)O(4)//(001) Ca(x)()CoO(2)//(001) CCO. The crystal structures of the four materials possess the common CoO(2) layer (or similar), which is composed of edge-sharing CoO(6) octahedra, parallel to the planes. The cross-sectional HRTEM analysis of an incompletely reacted specimen showed transient lattice images from Ca(x)()CoO(2) into CCO, in which every other CoO(2) layer of Ca(x)()CoO(2) was preserved. Thus, it was demonstrated that a textured CCO ceramic is produced through a series of in situ topotactic conversion reactions with a preserved CoO(2) layer of its template.

Evaluation of the CO{sub 2} sequestration capacity for coal fly ash using a flow-through column reactor under ambient conditions

Energy Technology Data Exchange (ETDEWEB)

Jo, Ho Young, E-mail: hyjo@korea.ac.kr [Department of Earth and Environmental Sciences, Korea University, Anam-dong, Seongbuk-gu, Seoul 136-713 (Korea, Republic of); Ahn, Joon-Hoon; Jo, Hwanju [Department of Earth and Environmental Sciences, Korea University, Anam-dong, Seongbuk-gu, Seoul 136-713 (Korea, Republic of)

2012-11-30

Highlights: Black-Right-Pointing-Pointer A conceptual in-situ mineral carbonation method using a coal ash pond is proposed. Black-Right-Pointing-Pointer CO{sub 2} uptake occurred by carbonation reaction of CO{sub 2} with Ca{sup 2+} ions from coal fly ash. Black-Right-Pointing-Pointer The CO{sub 2} sequestration capacity was affected by the solid dosage. Black-Right-Pointing-Pointer Seawater can be used as a solvent for mineral carbonation of coal fly ash. - Abstract: An in-situ CO{sub 2} sequestration method using coal ash ponds located in coastal regions is proposed. The CO{sub 2} sequestration capacity of coal fly ash (CFA) by mineral carbonation was evaluated in a flow-through column reactor under various conditions (solid dosage: 100-330 g/L, CO{sub 2} flow rate: 20-80 mL/min, solvent type: deionized (DI) water, 1 M NH{sub 4}Cl solution, and seawater). The CO{sub 2} sequestration tests were conducted on CFA slurries using flow-through column reactors to simulate more realistic flow-through conditions. The CO{sub 2} sequestration capacity increased when the solid dosage was increased, whereas it was affected insignificantly by the CO{sub 2} flow rate. A 1 M NH{sub 4}Cl solution was the most effective solvent, but it was not significantly different from DI water or seawater. The CO{sub 2} sequestration capacity of CFA under the flow-through conditions was approximately 0.019 g CO{sub 2}/g CFA under the test conditions (solid dosage: 333 g/L, CO{sub 2} flow rate: 40 mL/min, and solvent: seawater).

Carbon dioxide sequestration by direct mineral carbonation with carbonic acid

Energy Technology Data Exchange (ETDEWEB)

O' Connor, W.K.; Dahlin, D.C.; Nilsen, D.N.; Walters, R.P.; Turner, P.C.

2000-07-01

The Albany Research Center (ARC) of the US Department of Energy (DOE) has been conducting a series of mineral carbonation tests at its Albany, Oregon, facility over the past 2 years as part of a Mineral Carbonation Study Program within the DOE. The ARC tests have focused on ex-situ mineral carbonation in an aqueous system. The process developed at ARC utilizes a slurry of water mixed with a magnesium silicate mineral, olivine [forsterite and member (mg{sub 2}SiO{sub 4})], or serpentine [Mg{sub 3}Si{sub 2}O{sub 5}(OH){sub 4}]. This slurry is reacted with supercritical carbon dioxide (CO{sub 2}) to produce magnesite (MgCO{sub 3}). The CO{sub 2} is dissolved in water to form carbonic acid (H{sub 2}CO{sub 3}), which dissociates to H{sup +} and HCO{sub 3}{sup {minus}}. The H{sup +} reacts with the mineral, liberating Mg{sup 2+} cations which react with the bicarbonate to form the solid carbonate. The process is designed to simulate the natural serpentinization reaction of ultramafic minerals, and for this reason, these results may also be applicable to in-situ geological sequestration regimes. Results of the baseline tests, conducted on ground products of the natural minerals, have been encouraging. Tests conducted at ambient temperature (22 C) and subcritical CO{sub 2} pressures (below 73 atm) resulted in very slow conversion to the carbonate. However, when elevated temperatures and pressures are utilized, coupled with continuous stirring of the slurry and gas dispersion within the water column, significant reaction occurs within much shorter reaction times. Extent of reaction, as measured by the stoichiometric conversion of the silicate mineral (olivine) to the carbonate, is roughly 90% within 24 hours, using distilled water, and a reaction temperature of 185 C and a partial pressure of CO{sub 2} (P{sub CO{sub 2}}) of 115 atm. Recent tests using a bicarbonate solution, under identical reaction conditions, have achieved roughly 83% conversion of heat treated serpentine

Estimation of the reactive mineral surface area during CO2-rich fluid-rock interaction: the influence of neogenic phases

Science.gov (United States)

Scislewski, A.; Zuddas, P.

2010-12-01

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water-rock interaction. It is however, difficult to estimate and well normalize bulk reaction rates if the mineral surface area exposed to the aqueous solution and effectively participating on the reactions is unknown. We evaluated the changing of the reactive mineral surface area during the interaction between CO2-rich fluids and Albitite/Granitoid rocks (similar mineralogy but different abundances), reacting under flow-through conditions. Our methodology, adopting an inverse modeling approach, is based on the estimation of dissolution rate and reactive surface area of the different minerals participating in the reactions by the reconstruction the chemical evolution of the interacting fluids. The irreversible mass-transfer processes is defined by a fractional degree of advancement, while calculations were carried out for Albite, Microcline, Biotite and Calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite. Irrespective of the mineral abundance in granite and albitite, we found that mineral dissolution rates did not change significantly in the investigated range of time where output solution’s pH remained in the range between 6 and 8, indicating that the observed variation in fluid composition depends not on pH but rather on the variation of the parent mineral’s reactive surface area. We found that the reactive surface area of Albite varied by more than 2 orders of magnitude, while Microcline, Calcite and Biotite surface areas changed by 1-2 orders of magnitude. We propose that parent mineral chemical heterogeneity and, particularly, the stability of secondary mineral phases may explain the observed variation of the reactive surface area of the minerals. Formation of coatings at the dissolving parent mineral surfaces significantly reduced the amount of surface available to react

Procedure to use phosphogypsum industrial waste for mineral CO2 sequestration

International Nuclear Information System (INIS)

Cárdenas-Escudero, C.; Morales-Flórez, V.; Pérez-López, R.; Santos, A.; Esquivias, L.

2011-01-01

Highlights: ► Phosphogypsum wastes are proposed to reduce CO 2 greenhouse gas emissions. ► Phosphogypsum dissolution with NaOH results in Ca(OH) 2 precipitation and Na 2 SO 4 . ► Aqueous carbonation of Ca(OH) 2 with CO 2 results in the CaCO 3 precipitation. ► Metals contained in the phosphogypsum are transferred to the final calcite. ► Applications of CaCO 3 and Na 2 SiO 4 by-products are proposed to improve viability. - Abstract: Industrial wet phosphoric acid production in Huelva (SW Spain) has led to the controversial stockpiling of waste phosphogypsum by-products, resulting in the release of significant quantities of toxic impurities in salt marshes in the Tinto river estuary. In the framework of the fight against global climate change and the effort to reduce carbon dioxide emissions, a simple and efficient procedure for CO 2 mineral sequestration is presented in this work, using phosphogypsum waste as a calcium source. Our results demonstrate the high efficiency of portlandite precipitation by phosphogypsum dissolution using an alkaline soda solution. Carbonation experiments performed at ambient pressure and temperature resulted in total conversion of the portlandite into carbonate. The fate of trace elements present in the phosphogypsum waste was also investigated, and trace impurities were found to be completely transferred to the final calcite. We believe that the procedure proposed here should be considered not only as a solution for reducing old stockpiles of phosphogypsum wastes, but also for future phosphoric acid and other gypsum-producing industrial processes, resulting in more sustainable production.

Coupled multiphase reactive flow and mineral dissolution-precipitation kinetics: Examples of long-term CO2 sequestration in Utsira Sand, Norway and Mt. Simon Formation, Midwest USA

Science.gov (United States)

Zhang, Y.; Zhang, G.; Lu, P.; Hu, B.; Zhu, C.

2017-12-01

The extent of CO2 mineralization after CO2 injection into deep saline aquifers is a result of the complex coupling of multiphase fluid flow, mass transport, and brine-mineral reactions. The effects of dissolution rate laws and groundwater flow on the long-term fate of CO2 have been seriously overlooked. To investigate these effects, we conducted multiphase (CO2 and brine) coupled reactive transport modeling of CO2 storage in two sandy formations (Utsira Sand, Norway1,2 and Mt. Simon formation, USA 3) using ToughReact and simulated a series of scenarios. The results indicated that: (1) Different dissolution rate laws for feldspars can significantly affect the amount of CO2 mineralization. Increased feldspar dissolution will promote CO2 mineral trapping through the coupling between feldspar dissolution and carbonate mineral precipitation at raised pH. The predicted amount of CO2 mineral trapping when using the principle of detailed balancing-based rate law for feldspar dissolution is about twice as much as that when using sigmoidal rate laws in the literature. (2) Mineral trapping is twice as much when regional groundwater flow is taken into consideration in long-term simulations (e.g., 10,000 years) whereas most modeling studies neglected the regional groundwater flow back and effectively simulated a batch reactor process. Under the influence of regional groundwater flow, the fresh brine from upstream continuously dissolves CO2 at the tail of CO2 plume, generating a large acidified area where large amount of CO2 mineralization takes place. The upstream replenishment of groundwater results in ˜22% mineral trapping at year 10,000, compared to ˜4% when this effect is ignored. Refs: 1Zhang, G., Lu, P., Wei, X., Zhu, C. (2016). Impacts of Mineral Reaction Kinetics and Regional Groundwater Flow on Long-Term CO2 Fate at Sleipner. Energy & Fuels, 30(5), 4159-4180. 2Zhu, C., Zhang, G., Lu, P., Meng, L., Ji, X. (2015). Benchmark modeling of the Sleipner CO2 plume

Towards Molecular Characterization of Mineral-Organic Matter Interface Using In Situ Liquid Secondary Ion Mass Spectrometry

Science.gov (United States)

Zhu, Z.; Yu, X. Y.

2017-12-01

Organo-Mineral-Microbe interactions in terrestrial ecosystems are of great interest. Quite a few models have been developed through extensive efforts in this field. However, predictions from current models are far from being accurate, and many debates still exist. One of the major reasons is that most experimental data generated from bulk analysis, and the information of molecular dynamics occurring at mineral-organic matter interface is rare. Such information has been difficult to obtain, due to lack of suitable in situ analysis tools. Recently, we have developed in situ liquid secondary ion mass spectrometry (SIMS) at Pacific Northwest National Laboratory1, and it has shown promise to provide both elemental and molecular information at vacuum-liquid and solid-liquid interfaces.2 In this presentation, we demonstrate that in situ liquid SIMS can provide critical molecular information at solid substrate-live biofilm interface.3 Shewanella oneidensis is used as a model micro-organism and silicon nitride as a model mineral surface. Of particular interest, biologically relevant water clusters have been first observed in the living biofilms. Characteristic fragments of biofilm matrix components such as proteins, polysaccharides, and lipids can be molecularly examined. Furthermore, characteristic fatty acids (e.g., palmitic acid), quinolone signal, and riboflavin fragments were found to respond after the biofilm is treated with Cr(VI), leading to biofilm dispersal. Significant changes in water clusters and quorum sensing signals indicative of intercellular communication in the aqueous environment were observed, suggesting that they might result in fatty acid synthesis and inhibition of riboflavin production. The Cr(VI) reduction seems to follow the Mtr pathway leading to Cr(III) formation. Our approach potentially opens a new avenue for in-situ understanding of mineral-organo or mineral-microbe interfaces using in situ liquid SIMS and super resolution fluorescence

In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO2

International Nuclear Information System (INIS)

Patridge, Christopher J.; Love, Corey T.; Swider-Lyons, Karen E.; Twigg, Mark E.; Ramaker, David E.

2013-01-01

The local structure of nanoscale (∼10–40 nm) LiCoO 2 is monitored during electrochemical cycling utilizing in-situ X-ray absorption spectroscopy (XAS). The high surface area of the LiCoO 2 nanoparticles not only enhances capacity fade, but also provides a large signal from the particle surface relative to the bulk. Changes in the nanoscale LiCoO 2 metal-oxide bond lengths, structural disorder, and chemical state are tracked during cycling by adapting the delta mu (Δμ) technique in complement with comprehensive extended X-ray absorption fine structure (EXAFS) modeling. For the first time, we use a Δμ EXAFS method, and by comparison of the difference EXAFS spectra, extrapolate significant coordination changes and reduction of cobalt species with cycling. This combined approach suggests Li–Co site exchange at the surface of the nanoscale LiCoO 2 as a likely factor in the capacity fade and irreversible losses in practical, microscale LiCoO 2 . - Graphical abstract: Electrochemical cycling of Li-ion batteries has strong impact on the structure and integrity of the cathode active material particularly near the surface/electrolyte interface. In developing a new method, we have used in-situ X-ray absorption spectroscopy during electrochemical cycling of nanoscale LiCoO 2 to track changes during charge and discharge and between subsequent cycles. Using difference spectra, several small changes in Co-O bond length, Co-O and Co-Co coordination, and site exchange between Co and Li sites can be tracked. These methods show promise as a new technique to better understand processes which lead to capacity fade and loss in Li-ion batteries. - Highlights: • A new method is developed to understand capacity fade in Li-ion battery cathodes. • Structural changes are tracked during Li intercalation/deintercalation of LiCoO 2 . • Surface structural changes are emphasized using nanoscale-LiCoO 2 and difference spectra. • Full multiple scattering calculations are used to

Carbon dioxide sequestration by direct mineral carbonation with carbonic acid

Energy Technology Data Exchange (ETDEWEB)

O' Connor, William K.; Dahlin, David C.; Nilsen, David N.; Walters, Richard P.; Turner, Paul C.

2000-01-01

The Albany Research Center (ARC) of the U.S. Dept. of Energy (DOE) has been conducting a series of mineral carbonation tests at its Albany, Oregon, facility over the past 2 years as part of a Mineral Carbonation Study Program within the DOE. Other participants in this Program include the Los Alamos National Laboratory, Arizona State University, Science Applications International Corporation, and the DOE National Energy Technology Laboratory. The ARC tests have focused on ex-situ mineral carbonation in an aqueous system. The process developed at ARC utilizes a slurry of water mixed with a magnesium silicate mineral, olivine [forsterite end member (Mg2SiO4)], or serpentine [Mg3Si2O5(OH)4]. This slurry is reacted with supercritical carbon dioxide (CO2) to produce magnesite (MgCO3). The CO2 is dissolved in water to form carbonic acid (H2CO3), which dissociates to H+ and HCO3 -. The H+ reacts with the mineral, liberating Mg2+ cations which react with the bicarbonate to form the solid carbonate. The process is designed to simulate the natural serpentinization reaction of ultramafic minerals, and for this reason, these results may also be applicable to in-situ geological sequestration regimes. Results of the baseline tests, conducted on ground products of the natural minerals, have been encouraging. Tests conducted at ambient temperature (22 C) and subcritical CO2 pressures (below 73 atm) resulted in very slow conversion to the carbonate. However, when elevated temperatures and pressures are utilized, coupled with continuous stirring of the slurry and gas dispersion within the water column, significant reaction occurs within much shorter reaction times. Extent of reaction, as measured by the stoichiometric conversion of the silicate mineral (olivine) to the carbonate, is roughly 90% within 24 hours, using distilled water, and a reaction temperature of 185?C and a partial pressure of CO2 (PCO2) of 115 atm. Recent tests using a bicarbonate solution, under identical reaction

In-situ nanoscale imaging of clay minerals with atomic force microscopy

International Nuclear Information System (INIS)

Bosbach, D.

2010-01-01

Document available in extended abstract form only. Clay minerals play a key role in many concepts for high-level nuclear waste repository systems in deep geological formations. Various aspects related to the long-term safety of nuclear disposal are linked to their fundamental physical-chemical properties, in particular with respect to their reactivity in aqueous environments. Atomic Force Microscopy (AFM) allows high resolution imaging of clay minerals in-situ while they are exposed to an aqueous solution. The presentation is intended to provide an overview of examples of AFM studies on clay minerals: 1. AFM is an ideal tool to visualize the shape of individual clay particles down to molecular scales including a quantitative description of for example their aspect ratio. Furthermore, the particle size can be easily extracted from AFM data for individual particles as well as particle size distribution. 2. Surface area of clay minerals is a key issue when discussing heterogeneous reactions such as dissolution, adsorption or (surface) precipitation - total surface area, BET surface area, reactive surface area need to be distinguished. In particular reactive surface area is linked to specific reactive surface sites. AFM is of course able to identify such sites and consequently AFM data allow to characterize and to quantify reactive surface area. 3. The reactivity of clay mineral surfaces in aqueous environments controls the behaviour of clay minerals under repository conditions and also affects the migration/retention of radionuclides. It could be shown that the dissolution of smectite particles under acidic conditions at room temperature primarily occurs at (hk0) particle edges, whereas the reactivity of the (001) basal surfaces is very limited. The heterogeneous (surface) precipitation of secondary iron (hydr)oxides phase could be unraveled by AFM observations. Surface precipitation occurs preferentially at (hk0) edges surfaces. Ignoring the surface site specific

Experimental Investigation and Simplistic Geochemical Modeling of CO2 Mineral Carbonation Using the Mount Tawai Peridotite

Directory of Open Access Journals (Sweden)

Omeid Rahmani

2016-03-01

Full Text Available In this work, the potential of CO2 mineral carbonation of brucite (Mg(OH2 derived from the Mount Tawai peridotite (forsterite based (Mg2SiO4 to produce thermodynamically stable magnesium carbonate (MgCO3 was evaluated. The effect of three main factors (reaction temperature, particle size, and water vapor were investigated in a sequence of experiments consisting of aqueous acid leaching, evaporation to dryness of the slurry mass, and then gas-solid carbonation under pressurized CO2. The maximum amount of Mg converted to MgCO3 is ~99%, which occurred at temperatures between 150 and 175 °C. It was also found that the reduction of particle size range from >200 to <75 µm enhanced the leaching rate significantly. In addition, the results showed the essential role of water vapor in promoting effective carbonation. By increasing water vapor concentration from 5 to 10 vol %, the mineral carbonation rate increased by 30%. This work has also numerically modeled the process by which CO2 gas may be sequestered, by reaction with forsterite in the presence of moisture. In both experimental analysis and geochemical modeling, the results showed that the reaction is favored and of high yield; going almost to completion (within about one year with the bulk of the carbon partitioning into magnesite and that very little remains in solution.

Application of in-situ stress measurement on bursts disasters of rock and CO{sub 2} in coal mine

Energy Technology Data Exchange (ETDEWEB)

Lian-Jie Wang; Dong-Sheng Sun; Li-Rong Zhang; Guan-Wu Zhou [Ministry of Land and Resources, Beijing (China)

2009-01-15

For the purpose of reduction and prevention of rock burst disasters and CO{sub 2}, measurements were made of in-situ stress and mechanical parameters of rock in Yingcheng mine. Geological structure and gas measurements were studied and the stress field was simulated and distribution of stress field was obtained in this area. On the basis of the study, the danger areas of rockbursts and CO{sub 2} were predicted. Preventive measures were suggested to decrease gas pressure and in-situ stress in front of the working face with advance boreholes relieving blasting. 12 refs., 5 figs., 1 tab.

CO2 fixation using magnesium silicate minerals part 1: Process description and performance

International Nuclear Information System (INIS)

Fagerlund, Johan; Nduagu, Experience; Romão, Inês; Zevenhoven, Ron

2012-01-01

This paper describes a staged carbonation process for magnesium silicate mineral carbonation. This carbon dioxide capture and storage (CCS) alternative involves the production of magnesium hydroxide, followed by its carbonation in a pressurised fluidised bed (PFB) reactor. The goal is to utilise the heat of the carbonation reaction to drive the Mg(OH) 2 production step. The results show that Mg(OH) 2 can be produced successfully (up to 78% Mg extraction extent achieved so far) and efficiently from different serpentinite minerals from locations worldwide (Finland, Lithuania, Australia, Portugal…). From the extraction step, ammonium sulphate is recovered while iron oxides (from the mineral) are obtained as by-products. The carbonation step, while still being developed, resulted in >50%-wt conversion in 10 min (500 °C, 20 bar) for > 300 μm serpentinite-derived Mg(OH) 2 particles. Thus the reaction rate achieved so far is much faster than what is currently being considered fast in the field of mineral carbonation. -- Highlights: ► Magnesium silicate-based rock can sequester CO 2 as stable magnesium carbonate. ► Abundance of rock material offers a larger capacity than other CCS methods. ► Mg(OH) 2 production is followed by its carbonation in a pressurised fluidised bed. ► Carbonation reaches >50% in around 10 min for >0.3 mm particles. ► Mg(OH) 2 produced from different rock material show the same performance.

Facile synthesis of surface N-doped Bi_2O_2CO_3: Origin of visible light photocatalytic activity and in situ DRIFTS studies

International Nuclear Information System (INIS)

Zhou, Ying; Zhao, Ziyan; Wang, Fang; Cao, Kun; Doronkin, Dmitry E.; Dong, Fan; Grunwaldt, Jan-Dierk

2016-01-01

Graphical abstract: Surfactant (CTAB) can induce nitrogen interstitially doping in the Bi_2O_2CO_3 surface, leading to the formation of localized states from N−O bond, which probably account for the origin of the visible light activity. Moreover, the photocatalytic NO oxidation processes over Bi_2O_2CO_3 were successfully monitored for the first time by in situ DRIFTS. - Highlights: • Interstitially doping N in the Bi_2O_2CO_3 surface was achieved at room temperature. • N-doped Bi_2O_2CO_3 exhibited significantly enhanced visible light photocatalytic activity compared to the pristine Bi_2O_2CO_3. • The formation of localized states from N−O bond could account for the visible light activity of Bi_2O_2CO_3. • The photocatalytic NO oxidation process was monitored by in situ DRIFTS. - Abstract: Bi_2O_2CO_3 nanosheets with exposed {001} facets were prepared by a facile room temperature chemical method. Due to the high oxygen atom density in {001} facets of Bi_2O_2CO_3, the addition of cetyltrimethylammonium bromide (CTAB) does not only influence the growth of crystalline Bi_2O_2CO_3, but also modifies the surface properties of Bi_2O_2CO_3 through the interaction between CTAB and Bi_2O_2CO_3. Nitrogen from CTAB as dopant interstitially incorporates in the Bi_2O_2CO_3 surface evidenced by both experimental and theoretical investigations. Hence, the formation of localized states from N−O bond improves the visible light absorption and charge separation efficiency, which leads to an enhancement of visible light photocatalytic activity toward to the degradation of Rhodamine B (RhB) and oxidation of NO. In addition, the photocatalytic NO oxidation over Bi_2O_2CO_3 nanosheets was successfully monitored for the first time using in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS). Both bidentate and monodentate nitrates were identified on the surface of catalysts during the photocatalytic reaction process. The application of this strategy to

The influence of included minerals on the intrinsic reactivity of chars prepared under N{sub 2} and CO{sub 2} environment

Energy Technology Data Exchange (ETDEWEB)

Zhang, Hong; Li, Huan; Chen, Jiabao; Zhao, Bo; Hu, Guangzhou [China Univ. of Mining and Technology, Jiangsu (China). School of Chemical Engineering

2013-07-01

Oxy-fuel technology could be successfully used to retrofit existing coal-fired power plants or alternatively be used to design and build new coal-fired power plants with almost zero emissions. Char reactivity under oxy-fuel conditions will have a significant impact on the coal burnout. In this paper, two fractions, representing organic-rich particles and organic particles with included minerals, were separated from each of three Chinese coals of different rank. They were then devolatilized at 1,450 C in a drop tube furnace (DTF) under N{sub 2} and CO{sub 2} environment, respectively. The chars were subjected to nitrogen adsorption study, thermogravimetric analysis and XRD analysis. It was found that char reactivity of all three pairs of chars were increased under CO{sub 2} environment as compared with that under N{sub 2} environment, but with differing trend. For the organic-rich samples the reactivity difference is increased with decreasing rank. On the contrary, for the samples of organic particles with included minerals, the reactivity difference is decreased with decreasing rank. Mechanism analysis showed that they are resulted not from gasification, but from a combination of changes in surface area and in the orderness of carbon structure in the chars, both of which, in turn, are resulted from the higher heat capacity of CO{sub 2} and the interaction between metastable liquid phase and the included minerals.

To accelerate technology of in situ leaching and heap leaching for mining mineral resources of China

International Nuclear Information System (INIS)

Luo Mei

1999-01-01

Recently, in situ leaching and heap leaching are the most advanced technology for mining low-grade mineral resources in the world. The author briefly expounds the basic concept and advantages of in situ leaching and heap leaching and deals with the main research content of the hydrometallurgical technology of in situ leaching and heap leaching, its development and present application at home and abroad. Having expounded the gap existing between China's technology of in situ leaching and heap leaching and the foreign technology, the author forecasts the prospects of accelerating the mining of China's mineral resources by using the technology of in situ leaching and heap leaching

In situ X-ray and neutron diffraction of the Ruddlesden-Popper compounds (RE2-xSrx)0.98(Fe0.8Co0.2)1-yMgyO4-δ (RE=La, Pr): Structure and CO2 stability

DEFF Research Database (Denmark)

Chatzichristodoulou, Christodoulos; Hauback, B.C.; Hendriksen, Peter Vang

2013-01-01

The crystal structure of the Ruddlesden-Popper compounds (La 1.0Sr1.0)0.98Fe0.8Co 0.2O4-δ and (La1.2Sr0.8) 0.98(Fe0.8Co0.2)0.8Mg 0.2O4-δ was investigated at 1000 °C in N 2 (aO2=1×10-4) by in-situ powder neutron diffraction. In-situ powder X-ray diffraction (PXD) was also employed to investigate....... The equivalent pseudo-cubic thermal and chemical expansion coefficients are in agreement with values determined by dilatometry. The chemical stability in CO2 containing environments of various Ruddlesden-Popper compounds with chemical formula (RE2-xSr x)0.98(Fe0.8Co0.2) 1-yMgyO4-δ (RE=La, Pr), as well...

In-situ X-ray absorption spectroscopy analysis of capacity fade in nanoscale-LiCoO{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Patridge, Christopher J. [NRC/NRL Cooperative Research Associate, U.S. Naval Research Laboratory, Washington, DC 20375 (United States); Love, Corey T., E-mail: corey.love@nrl.navy.mil [Chemistry Division, Code 6113, U.S. Naval Research Laboratory, Washington, DC 20375 (United States); Swider-Lyons, Karen E. [Chemistry Division, Code 6113, U.S. Naval Research Laboratory, Washington, DC 20375 (United States); Twigg, Mark E. [Electronics Science and Technology Division, Code 6812, U.S. Naval Research Laboratory, Washington, DC 20375 (United States); Ramaker, David E. [Chemistry Division, Code 6189, U.S. Naval Research laboratory, Washington, DC 20375 (United States)

2013-07-15

The local structure of nanoscale (∼10–40 nm) LiCoO{sub 2} is monitored during electrochemical cycling utilizing in-situ X-ray absorption spectroscopy (XAS). The high surface area of the LiCoO{sub 2} nanoparticles not only enhances capacity fade, but also provides a large signal from the particle surface relative to the bulk. Changes in the nanoscale LiCoO{sub 2} metal-oxide bond lengths, structural disorder, and chemical state are tracked during cycling by adapting the delta mu (Δμ) technique in complement with comprehensive extended X-ray absorption fine structure (EXAFS) modeling. For the first time, we use a Δμ EXAFS method, and by comparison of the difference EXAFS spectra, extrapolate significant coordination changes and reduction of cobalt species with cycling. This combined approach suggests Li–Co site exchange at the surface of the nanoscale LiCoO{sub 2} as a likely factor in the capacity fade and irreversible losses in practical, microscale LiCoO{sub 2}. - Graphical abstract: Electrochemical cycling of Li-ion batteries has strong impact on the structure and integrity of the cathode active material particularly near the surface/electrolyte interface. In developing a new method, we have used in-situ X-ray absorption spectroscopy during electrochemical cycling of nanoscale LiCoO{sub 2} to track changes during charge and discharge and between subsequent cycles. Using difference spectra, several small changes in Co-O bond length, Co-O and Co-Co coordination, and site exchange between Co and Li sites can be tracked. These methods show promise as a new technique to better understand processes which lead to capacity fade and loss in Li-ion batteries. - Highlights: • A new method is developed to understand capacity fade in Li-ion battery cathodes. • Structural changes are tracked during Li intercalation/deintercalation of LiCoO{sub 2}. • Surface structural changes are emphasized using nanoscale-LiCoO{sub 2} and difference spectra. • Full multiple

On the interaction of pure and impure supercritical CO2 with rock forming minerals in saline aquifers: An experimental geochemical approach

International Nuclear Information System (INIS)

Wilke, Franziska D.H.; Vásquez, Mónica; Wiersberg, Thomas; Naumann, Rudolf; Erzinger, Jörg

2012-01-01

The aim of this experimental study was to evaluate and compare the geochemical impact of pure and impure CO 2 on rock forming minerals of possible CO 2 storage reservoirs. This geochemical approach takes into account the incomplete purification of industrial captured CO 2 and the related effects during injection, and provides relevant data for long-term storage simulations of this specific greenhouse gas. Batch experiments were conducted to investigate the interactions of supercritical CO 2 , brine and rock-forming mineral concentrates (albite, microcline, kaolinite, biotite, muscovite, calcite, dolomite and anhydrite) using a newly developed experimental setup. After up to 42 day (1000 h) experiments using pure and impure supercritical CO 2 the dissolution and solution characteristics were examined by XRD, XRF, SEM and EDS for the solid, and ICP–MS and IC for the fluid reactants, respectively. Experiments with mixtures of supercritical CO 2 (99.5 vol.%) and SO 2 or NO 2 impurities (0.5 vol.%) suggest the formation of H 2 SO 4 and HNO 3 , reflected in pH values between 1 and 4 for experiments with silicates and anhydrite and between 5 and 6 for experiments with carbonates. These acids should be responsible for the general larger amount of cations dissolved from the mineral phases compared to experiments using pure CO 2 . For pure CO 2 a pH of around 4 was obtained using silicates and anhydrite, and 7–8 for carbonates. Dissolution of carbonates was observed after both pure and impure CO 2 experiments. Anhydrite was corroded by approximately 50 wt.% and gypsum precipitated during experiments with supercritical CO 2 + NO 2 . Silicates do not exhibit visible alterations during all experiments but released an increasing amount of cations in the reaction fluid during experiments with impure CO 2 . Nonetheless, precipitated secondary carbonates could not be identified.

Simulation of CO2–water–rock interactions on geologic CO2 sequestration under geological conditions of China

International Nuclear Information System (INIS)

Wang, Tianye; Wang, Huaiyuan; Zhang, Fengjun; Xu, Tianfu

2013-01-01

Highlights: • We determined the feasibilities of geologic CO 2 sequestration in China. • We determined the formation of gibbsite suggested CO 2 can be captured by rocks. • We suggested the mechanisms of CO 2 –water–rock interactions. • We found the corrosion and dissolution of the rock increased as temperature rose. -- Abstract: The main purpose of this study focused on the feasibility of geologic CO 2 sequestration within the actual geological conditions of the first Carbon Capture and Storage (CCS) project in China. This study investigated CO 2 –water–rock interactions under simulated hydrothermal conditions via physicochemical analyses and scanning electron microscopy (SEM). Mass loss measurement and SEM showed that corrosion of feldspars, silica, and clay minerals increased with increasing temperature. Corrosion of sandstone samples in the CO 2 -containing fluid showed a positive correlation with temperature. During reaction at 70 °C, 85 °C, and 100 °C, gibbsite (an intermediate mineral product) formed on the sample surface. This demonstrated mineral capture of CO 2 and supported the feasibility of geologic CO 2 sequestration. Chemical analyses suggested a dissolution–reprecipitation mechanism underlying the CO 2 –water–rock interactions. The results of this study suggested that mineral dissolution, new mineral precipitation, and carbonic acid formation-dissociation are closely interrelated in CO 2 –water–rock interactions

Community-level sensitivity of a calcifying ecosystem to acute in situ CO2 enrichment

KAUST Repository

Burdett, HL

2017-11-23

The rate of change in ocean carbonate chemistry is a vital determinant in the magnitude of effects observed. Benthic marine ecosystems are facing an increasing risk of acute CO2 exposure that may be natural or anthropogenically derived (e.g. engineering and industrial activities). However, our understanding of how acute CO2 events impact marine life is restricted to individual organisms, with little understanding for how this manifests at the community level. Here, we investigated in situ the effect of acute CO2 enrichment on the coralline algal ecosystem—a globally ubiquitous, ecologically and economically important habitat, but one which is likely to be sensitive to CO2 enrichment due to its highly calcified reef-like structures engineered by coralline algae. Most notably, we observed a rapid community-level shift to favour net dissolution rather than net calcification. Smaller changes from net respiration to net photosynthesis were also observed. There was no effect on the net flux of DMS/DMSP (algal secondary metabolites), nor on the nutrients nitrate and phosphate. Following return to ambient CO2 levels, only a partial recovery was seen within the monitoring timeframe. This study highlights the sensitivity of biogenic carbonate marine communities to acute CO2 enrichment and raises concerns over the capacity for the system to ‘bounce back’ if subjected to repeated acute high-CO2 events.

Facile formation of 2D Co2P@Co3O4 microsheets through in-situ toptactic conversion and surface corrosion: Bifunctional electrocatalysts towards overall water splitting

Science.gov (United States)

Yao, Lihua; Zhang, Nan; Wang, Yin; Ni, Yuanman; Yan, Dongpeng; Hu, Changwen

2018-01-01

Exploring efficient non-precious electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for many renewable energy conversion processes. In this work, we report that 2D Co2P@Co3O4 microsheets can be prepared through an in-situ toptactic conversion from single-crystal β-Co(OH)2 microplatelets, associated with a surface phosphatization and corrosion process. The resultant Co2P@Co3O4 2D hybrid materials can further serve as self-supported bifunctional catalytic electrodes to drive the overall water splitting for HER and OER simultaneously, with low overpotentials and high long-term stability. Furthermore, a water electrolyzer based on Co2P@Co3O4 hybrid as both anode and cathode is fabricated, which achieves 10 mA cm-2 current at only 1.57 V during water splitting process. Therefore, this work provides a facile strategy to obtain 2D Co2P-based micro/nanostructures, which act as low-cost and highly active electrocatalysts towards overall water splitting application.

In Situ Local Contact Angle Measurement in a CO2-Brine-Sand System Using Microfocused X-ray CT.

Science.gov (United States)

Lv, Pengfei; Liu, Yu; Wang, Zhe; Liu, Shuyang; Jiang, Lanlan; Chen, Junlin; Song, Yongchen

2017-04-11

The wettability of porous media is of major interest in a broad range of natural and engineering applications. The wettability of a fluid on a solid surface is usually evaluated by the contact angle between them. While in situ local contact angle measurements are complicated by the topology of porous media, which can make it difficult to use traditional methods, recent advances in microfocused X-ray computed tomography (micro-CT) and image processing techniques have made it possible to measure contact angles on the scale of the pore sizes in such media. However, the effects of ionic strength, CO 2 phase, and flow pattern (drainage or imbibition) on pore-scale contact angle distribution are still not clear and have not been reported in detail in previous studies. In this study, we employed a micro-CT scanner for in situ investigation of local contact angles in a CO 2 -brine-sand system under various conditions. The effects of ionic strength, CO 2 phase, and flow pattern on the local contact-angle distribution were examined in detail. The results showed that the local contact angles vary over a wide range as a result of the interaction of surface contaminants, roughness, pore topology, and capillarity. The wettability of a porous surface could thus slowly weaken with increasing ionic strength, and the average contact angle could significantly increase when gaseous CO 2 (gCO 2 ) turns into supercritical CO 2 (scCO 2 ). Contact angle hysteresis also occurred between drainage and imbibition procedures, and the hysteresis was more significant under gCO 2 condition.

In Situ analysis of CO2 laser irradiation on controlling progression of erosive lesions on dental enamel.

Science.gov (United States)

Lepri, Taísa Penazzo; Scatolin, Renata Siqueira; Colucci, Vivian; De Alexandria, Adílis Kalina; Maia, Lucianne Cople; Turssi, Cecília Pedroso; Corona, Silmara Aparecida Milori

2014-08-01

The present study aimed to evaluate in situ the effect of CO2 laser irradiation to control the progression of enamel erosive lesions. Fifty-six slabs of bovine incisors enamel (5 × 3 × 2.5 mm(3) ) were divided in four distinct areas: (1) sound (reference area), (2) initial erosion, (3) treatment (irradiated or nonirradiated with CO2 laser), (4) final erosion (after in situ phase). The initial erosive challenge was performed with 1% citric acid (pH = 2.3), for 5 min, 2×/day, for 2 days. The slabs were divided in two groups according to surface treatment: irradiated with CO2 laser (λ = 10.6 µm; 0.5 W) and nonirradiate. After a 2-day lead-in period, 14 volunteers wore an intraoral palatal appliance containing two slabs (irradiated and nonirradiated), in two intraoral phases of 5 days each. Following a cross-over design during the first intraoral phase, half of the volunteers immersed the appliance in 100 mL of citric acid for 5 min, 3×/day, while other half of the volunteers used deionized water (control). The volunteers were crossed over in the second phase. Enamel wear was determined by an optical 3D profilometer. Three-way ANOVA for repeated measures revealed that there was no significant interaction between erosive challenge and CO2 laser irradiation (P = 0.419). Erosive challenge significantly increased enamel wear (P = 0.001), regardless whether or not CO2 laser irradiation was performed. There was no difference in enamel wear between specimens CO2 -laser irradiated and non-irradiated (P = 0.513). Under intraoral conditions, CO2 laser irradiation did not control the progression of erosive lesions in enamel caused by citric acid. © 2014 Wiley Periodicals, Inc.

Monitoring of the microbial community composition of the saline aquifers during CO2 storage by fluorescence in situ hybridisation

OpenAIRE

Daria Morozova; M. Wandrey; Mashal Alawi; Martin Zimmer; Andrea Vieth-Hillebrand [Vieth; M. Zettlitzer; Hilke Würdemann

2010-01-01

This study reveals the first analyses of the composition and activity of the microbial community of a saline CO2 storage aquifer. Microbial monitoring during CO2 injection has been reported. By using fluorescence in situ hybridisation (FISH), we have shown that the microbial community was strongly influenced by the CO2 injection. Before CO2 arrival, up to 6 × 106 cells ml−1 were detected by DAPI staining at a depth of 647 m below the surface. The microbial community was dominated by the dom...

Modeling of fate and transport of co-injection of H2S with CO2 in deep saline formations

Energy Technology Data Exchange (ETDEWEB)

Zhang, W.; Xu, T.; Li, Y.

2010-12-15

The geological storage of CO{sub 2} in deep saline formations is increasing seen as a viable strategy to reduce the release of greenhouse gases into the atmosphere. However, costs of capture and compression of CO{sub 2} from industrial waste streams containing small quantities of sulfur and nitrogen compounds such as SO{sub 2}, H{sub 2}S and N{sub 2} are very expensive. Therefore, studies on the co-injection of CO{sub 2} containing other acid gases from industrial emissions are very important. In this paper, numerical simulations were performed to study the co-injection of H{sub 2}S with CO{sub 2} in sandstone and carbonate formations. Results indicate that the preferential dissolution of H{sub 2}S gas (compared with CO{sub 2} gas) into formation water results in the delayed breakthrough of H{sub 2}S gas. Co-injection of H{sub 2}S results in the precipitation of pyrite through interactions between the dissolved H{sub 2}S and Fe{sup 2+} from the dissolution of Fe-bearing minerals. Additional injection of H{sub 2}S reduces the capabilities for solubility and mineral trappings of CO{sub 2} compared to the CO{sub 2} only case. In comparison to the sandstone (siliciclastic) formation, the carbonate formation is less favorable to the mineral sequestration of CO{sub 2}. Different from CO{sub 2} mineral trapping, the presence of Fe-bearing siliciclastic and/or carbonate is more favorable to the H{sub 2}S mineral trapping.

Magnesium hydroxide extracted from a magnesium-rich mineral for CO2 sequestration in a gas-solid system.

Science.gov (United States)

Lin, Pao-Chung; Huang, Cheng-Wei; Hsiao, Ching-Ta; Teng, Hsisheng

2008-04-15

Magnesium hydroxide extracted from magnesium-bearing minerals is considered a promising agent for binding CO2 as a carbonate mineral in a gas-solid reaction. An efficient extraction route consisting of hydrothermal treatment on serpentine in HCl followed by NaOH titration for Mg(OH)2 precipitation was demonstrated. The extracted Mg(OH)2 powder had a mean crystal domain size as small as 12 nm and an apparent surface area of 54 m2/g. Under one atmosphere of 10 vol% CO2/N2, carbonation of the serpentine-derived Mg(OH)2 to 26% of the stoichiometric limit was achieved at 325 degrees C in 2 h; while carbonation of a commercially available Mg(OH)2, with a mean crystal domain size of 33 nm and an apparent surface area of 3.5 m2/g, reached only 9% of the stoichiometric limit. The amount of CO2 fixation was found to be inversely proportional to the crystal domain size of the Mg(OH)2 specimens. The experimental data strongly suggested that only a monolayer of carbonates was formed on the crystal domain boundary in the gas-solid reaction, with little penetration of the carbonates into the crystal domain.

Nuclear techniques for in situ evaluation of coal and mineral deposits

International Nuclear Information System (INIS)

Borsaru, M.

1993-01-01

This paper reviews developments in in situ analysis of minerals and coal by nuclear borehole logging. Developments in the oil, gas and uranium industries are not discussed in the present paper unless they have direct applications in the mineral industry (e.g. multi-element analysis and development of spectral litho-density tools). The review covers techniques developed mostly in the last decade and is based on work published in North America, Europe and Australia. (author)

In situ photodeposition of amorphous CoSx on the TiO2 towards hydrogen evolution

Science.gov (United States)

Chen, Feng; Luo, Wei; Mo, Yanping; Yu, Huogen; Cheng, Bei

2018-02-01

Cocatalyst modification of photocatalysts is an important strategy to enhance the photocatalytic performance by promoting effective separation of photoinduced electron-hole pairs and providing abundant active sites. In this study, a facile in situ photodeposition method was developed to prepare amorphous CoSx-modified TiO2 photocatalysts. It was found that amorphous CoSx nanoparticles were solidly loaded on the TiO2 surface, resulting in a greatly improved photocatalytic H2-evolution performance. When the amount of amorphous CoSx was 10 wt%, the hydrogen evolution rate of the CoSx/TiO2 reached 119.7 μmol h-1, which was almost 16.7 times that of the pure TiO2. According to the above experimental results, a reasonable mechanism of improved photocatalytic performance is proposed for the CoSx/TiO2 photocatalysts, namely, the photogenerated electrons of TiO2 can rapidly transfer to amorphous CoSx nanoparticles due to the solid contact between them, and then amorphous CoSx can provide plenty of sulfur active sites to rapidly adsorb protons from solution to produce hydrogen by the photogenerated electrons. Considering the facile synthesis method, the present cheap and highly efficient amorphous CoSx-modified TiO2 photocatalysts would have great potential for practical use in photocatalytic H2 production.

Reactivity of micas and cap-rock in wet supercritical CO_2 with SO_2 and O_2 at CO_2 storage conditions

International Nuclear Information System (INIS)

Pearce, Julie K.; Dawson, Grant K.W.; Law, Alison C.K.; Biddle, Dean; Golding, Suzanne D.

2016-01-01

Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO_2, O_2, and NOx, may be present in CO_2 streams from coal combustion sources. SO_2 and O_2 have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO_2 fluid may also come into contact with the base of cap-rock after CO_2 injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation. The first observation of mineral dissolution and precipitation on phyllosilicates and CO_2 storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO_2 reactions with industrial impurities SO_2 and O_2 at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO_2 containing SO_2, or SO_2 and O_2, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO_2 dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO_2 containing SO_2 or in pure supercritical CO_2. In the presence of SO_2, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was

Hot and cold CO{sub 2}-rich mineral waters in Chaves geothermal area (northern Portugal)

Energy Technology Data Exchange (ETDEWEB)

Aires-Barros, Luis; Marques, Jose Manuel; Graca, Rui Cores; Matias, Maria Jose [Universidade Tecnica de Lisboa, Lab. de Mineralogia e Petrologia (LAMPIST), Lisboa (Portugal); Weijden, Cornelis H. van der; Kreulen, Rob [Utrecht Univ., Dept. of Geochemistry, Utrecht (Netherlands); Eggenkamp, Hermanus Gerardus M. [Utrecht Univ., Dept. of Geochemistry, Utrecht (Netherlands); Reading Univ., Postgraduate Research Inst. for Sedimentology, Reading (United Kingdom)

1998-02-01

In order to update the geohydrologic characterisation of Chaves geothermal area, coupled isotopic and chemical studies have been carried out on hot and cold CO{sub 2}-rich mineral waters discharging, in northern Portugal, along one of the major regional NNE-trending faults (the so-called Verin-Chaves-Penacova Depression). Based upon their location, and chemical and isotopic composition, the analysed waters can be divided into two groups. The northern group belongs to the HCO{sub 3}/Na/CO{sub 2}-rich type, and consists of the hot spring waters of Chaves and the cold spring waters of Vilarelho da Raia. The {delta}D and {delta}{sup 18}O values show that these waters are of meteoric origin. The lack of an {sup 18}O shift indicates that there is no evidence of water/rock interaction at high temperatures. The southern group includes the cold spring waters of Campilho/Vidago and Sabroso/Pedras Salgadas. Their chemistry is similar to that of the northern group but their heavier {delta}D and {delta}{sup 18}O values could be attributed to different recharge altitudes. Mixing between deep mineralised waters and dilute superficial waters of meteoric origin might explain the higher {sup 3}H activity found in the Vidago and Pedras Salgadas mineral waters. Alternatively, they could be mainly related to shallow underground flowpaths. The {delta}{sup 13}C values support a deep-seated origin for the CO{sub 2}. The {delta}{sup 37}Cl is comparable in all the mineral waters of the study areas, indicating a common origin of Cl. The {sup 87}Sr/{sup 86}Sr ratios in waters seem to be dominated by the dissolution of plagioclases or granitic rocks. (Author)

Environmental Benign Synthesis of Lithium Silicates and Mg-Al Layered Double Hydroxide from Vermiculite Mineral for CO2 Capture

Directory of Open Access Journals (Sweden)

Yu Zhang

2017-04-01

Full Text Available This research introduces a completely new environmental benign synthesis route for obtaining two kinds of inter-mediate and high temperature CO2 sorbents, Mg-Al layered double hydroxide (LDH and Li4SiO4, from vermiculite. The mineral vermiculite was leached with acid, from which the obtained SiO2 was used for the synthesis of Li4SiO4 and the leaching waste water was used for the synthesis of Mg-Al LDH. Therefore, no waste was produced during the whole process. Both Li4SiO4 and Mg-Al LDH sorbents were carefully characterized using XRD, SEM, and BET analyses. The CO2 capturing performance of these two sorbents was comprehensively evaluated. The influence of the Li/Si ratio, calcination temperature, calcination time, and sorption temperature on the CO2 sorption capacity of Li4SiO4, and the sorption temperature on the CO2 sorption capacity of LDH, were investigated. The optimal leaching acid concentration for vermiculite and the CO2 sorption/desorption cycling performance of both the Li4SiO4 and Mg-Al LDH sorbents were determined. In sum, this demonstrated a unique and environment-friendly scheme for obtaining two CO2 sorbents from cheap raw materials, and this idea is applicable to the efficient utilization of other minerals.

Procedure to use phosphogypsum industrial waste for mineral CO{sub 2} sequestration

Energy Technology Data Exchange (ETDEWEB)

Cardenas-Escudero, C. [Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Sevilla, Av. Reina Mercedes s/n, 41012 Seville (Spain); Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Av. Americo Vespucio, 49, 41092 Seville (Spain); Morales-Florez, V., E-mail: victor.morales@icmse.csic.es [Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Av. Americo Vespucio, 49, 41092 Seville (Spain); Perez-Lopez, R. [Departamento de Geologia, Facultad de Ciencias Experimentales, Universidad de Huelva, Campus Universitario Campus del Carmen, Avenida de las Fuerzas Armadas, 21071 Huelva (Spain); Instituto de Diagnostico Ambiental y Estudios del Agua (IDAeA-CSIC), Jordi Girona 18, 08034 Barcelona (Spain); Santos, A. [Departamento de Ciencias de la Tierra, Universidad de Cadiz, Campus del Rio San Pedro, Av. Republica Saharaui s/n, 11510 Puerto Real (Spain); Esquivias, L. [Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Sevilla, Av. Reina Mercedes s/n, 41012 Seville (Spain); Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Av. Americo Vespucio, 49, 41092 Seville (Spain)

2011-11-30

Highlights: Black-Right-Pointing-Pointer Phosphogypsum wastes are proposed to reduce CO{sub 2} greenhouse gas emissions. Black-Right-Pointing-Pointer Phosphogypsum dissolution with NaOH results in Ca(OH){sub 2} precipitation and Na{sub 2}SO{sub 4}. Black-Right-Pointing-Pointer Aqueous carbonation of Ca(OH){sub 2} with CO{sub 2} results in the CaCO{sub 3} precipitation. Black-Right-Pointing-Pointer Metals contained in the phosphogypsum are transferred to the final calcite. Black-Right-Pointing-Pointer Applications of CaCO{sub 3} and Na{sub 2}SiO{sub 4} by-products are proposed to improve viability. - Abstract: Industrial wet phosphoric acid production in Huelva (SW Spain) has led to the controversial stockpiling of waste phosphogypsum by-products, resulting in the release of significant quantities of toxic impurities in salt marshes in the Tinto river estuary. In the framework of the fight against global climate change and the effort to reduce carbon dioxide emissions, a simple and efficient procedure for CO{sub 2} mineral sequestration is presented in this work, using phosphogypsum waste as a calcium source. Our results demonstrate the high efficiency of portlandite precipitation by phosphogypsum dissolution using an alkaline soda solution. Carbonation experiments performed at ambient pressure and temperature resulted in total conversion of the portlandite into carbonate. The fate of trace elements present in the phosphogypsum waste was also investigated, and trace impurities were found to be completely transferred to the final calcite. We believe that the procedure proposed here should be considered not only as a solution for reducing old stockpiles of phosphogypsum wastes, but also for future phosphoric acid and other gypsum-producing industrial processes, resulting in more sustainable production.

On the potential for CO2 mineral storage in continental flood basalts – PHREEQC batch- and 1D diffusion–reaction simulations

Directory of Open Access Journals (Sweden)

Van Pham Thi

2012-06-01

Full Text Available Abstract Continental flood basalts (CFB are considered as potential CO2 storage sites because of their high reactivity and abundant divalent metal ions that can potentially trap carbon for geological timescales. Moreover, laterally extensive CFB are found in many place in the world within reasonable distances from major CO2 point emission sources. Based on the mineral and glass composition of the Columbia River Basalt (CRB we estimated the potential of CFB to store CO2 in secondary carbonates. We simulated the system using kinetic dependent dissolution of primary basalt-minerals (pyroxene, feldspar and glass and the local equilibrium assumption for secondary phases (weathering products. The simulations were divided into closed-system batch simulations at a constant CO2 pressure of 100 bar with sensitivity studies of temperature and reactive surface area, an evaluation of the reactivity of H2O in scCO2, and finally 1D reactive diffusion simulations giving reactivity at CO2 pressures varying from 0 to 100 bar. Although the uncertainty in reactive surface area and corresponding reaction rates are large, we have estimated the potential for CO2 mineral storage and identified factors that control the maximum extent of carbonation. The simulations showed that formation of carbonates from basalt at 40 C may be limited to the formation of siderite and possibly FeMg carbonates. Calcium was largely consumed by zeolite and oxide instead of forming carbonates. At higher temperatures (60 – 100 C, magnesite is suggested to form together with siderite and ankerite. The maximum potential of CO2 stored as solid carbonates, if CO2 is supplied to the reactions unlimited, is shown to depend on the availability of pore space as the hydration and carbonation reactions increase the solid volume and clog the pore space. For systems such as in the scCO2 phase with limited amount of water, the total carbonation potential is limited by the amount of water present

Long-term C-CO2 emissions and carbon crop residue mineralization in an oxisol under different tillage and crop rotation systems

Directory of Open Access Journals (Sweden)

Ben-Hur Costa de Campos

2011-06-01

Full Text Available Soil C-CO2 emissions are sensitive indicators of management system impacts on soil organic matter (SOM. The main soil C-CO2 sources at the soil-plant interface are the decomposition of crop residues, SOM turnover, and respiration of roots and soil biota. The objectives of this study were to evaluate the impacts of tillage and cropping systems on long-term soil C-CO2 emissions and their relationship with carbon (C mineralization of crop residues. A long-term experiment was conducted in a Red Oxisol in Cruz Alta, RS, Brazil, with subtropical climate Cfa (Köppen classification, mean annual precipitation of 1,774 mm and mean annual temperature of 19.2 ºC. Treatments consisted of two tillage systems: (a conventional tillage (CT and (b no tillage (NT in combination with three cropping systems: (a R0- monoculture system (soybean/wheat, (b R1- winter crop rotation (soybean/wheat/soybean/black oat, and (c R2- intensive crop rotation (soybean/ black oat/soybean/black oat + common vetch/maize/oilseed radish/wheat. The soil C-CO2 efflux was measured every 14 days for two years (48 measurements, by trapping the CO2 in an alkaline solution. The soil gravimetric moisture in the 0-0.05 m layer was determined concomitantly with the C-CO2 efflux measurements. The crop residue C mineralization was evaluated with the mesh-bag method, with sampling 14, 28, 56, 84, 112, and 140 days after the beginning of the evaluation period for C measurements. Four C conservation indexes were used to assess the relation between C-CO2 efflux and soil C stock and its compartments. The crop residue C mineralization fit an exponential model in time. For black oat, wheat and maize residues, C mineralization was higher in CT than NT, while for soybean it was similar. Soil moisture was higher in NT than CT, mainly in the second year of evaluation. There was no difference in tillage systems for annual average C-CO2 emissions, but in some individual evaluations, differences between

Headspace analysis gas-phase infrared spectroscopy: a study of xanthate decomposition on mineral surfaces

Science.gov (United States)

Vreugdenhil, Andrew J.; Brienne, Stephane H. R.; Markwell, Ross D.; Butler, Ian S.; Finch, James A.

1997-03-01

The O-ethyldithiocarbonate (ethyl xanthate, CH 3CH 2OCS -2) anion is a widely used reagent in mineral processing for the separation of sulphide minerals by froth flotation. Ethyl xanthate interacts with mineral powders to produce a hydrophobic layer on the mineral surface. A novel infrared technique, headspace analysis gas-phase infrared spectroscopy (HAGIS) has been used to study the in situ thermal decomposition products of ethyl xanthate on mineral surfaces. These products include CS 2, COS, CO 2, CH 4, SO 2, and higher molecular weight alkyl-containing species. Decomposition pathways have been proposed with some information determined from 2H- and 13C-isotope labelling experiments.

Synthesis and detection the oxidization of Co cores of Co@SiO2 core-shell nanoparticles by in situ XRD and EXAFS.

Science.gov (United States)

Zhang, Kunhao; Zhao, Ziyan; Wu, Zhonghua; Zhou, Ying

2015-01-01

In this paper, the Co@SiO2 core-shell nanoparticles were prepared by the sol-gel method. The oxidization of Co core nanoparticles was studied by the synchrotron radiation-based techniques including in situ X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS) up to 800°C in air and N2 protection conditions, respectively. It was found that the oxidization of Co cores is undergoing three steps regardless of being in air or in N2 protection condition. In the first step ranging from room temperature to 200°C, the Co cores were dominated by Co(0) state as well as small amount of Co(2+) ions. When temperature was above 300°C, the interface between Co cores and SiO2 shells was gradually oxidized into Co(2+), and the CoO layer was observed. As the temperature increasing to 800°C, the Co cores were oxidized to Co3O4 or Co3O4/CoO. Nevertheless, the oxidization kinetics of Co cores is different for the Co@SiO2 in air and N2 gas conditions. Generally, the O2 in the air could get through the SiO2 shells easily onto the Co core surface and induce the oxidization of the Co cores due to the mesoporous nature of the SiO2 shells. However, in N2 gas condition, the O atoms can only be from the SiO2 shells, so the diffusion effect of O atoms in the interface between Co core and SiO2 shell plays a key role.

Oxide ion diffusion mechanism related to Co and Fe ions in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ using in-situ X-ray absorption spectroscopy

Science.gov (United States)

Itoh, Takanori; Imai, Hideto

2018-03-01

The time changes of the white line and pre-edge intensities of Co and Fe K-edge in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ (BSCF) were observed to estimate the oxide ion diffusion related to Co and Fe ions by using in - situ X-ray absorption spectroscopy (XAS) during oxidation. The 20 μm self-standing BSCF film was prepared for in - situ XAS measurements. The time changes of absorption were fitted to the exponential decay function with two terms. The longer relaxation time (τ), related to the oxide ion diffusion during the oxidation of BSCF, is dependent on temperature. The oxide ion diffusion coefficients (D) were calculated from the τ s estimated by in - situ XAS. The values of the activation energy (Ea) for D related to Co K-edge white line, Co pre-edge, and Fe pre-edge were 1.8-2.0 eV. The value of Ea for D related to Fe K-edge white line, however, was higher than other absorption values at approximately 2.3 eV. We discussed the oxide ion diffusion mechanism related to Co and Fe ions in BSCF using in - situ XAS.

Study on adsorption of 60Co in soils and minerals and transportation of 60Co in bean-soil system

International Nuclear Information System (INIS)

Feng Yonghong; Chen Chuanqun; Wang Shouxiang; Zhang Yongxi; Sun Zhiming

1998-02-01

The adsorption and desorption of 60 Co in soils and minerals, and the transportation, accumulation, distribution in bean-soil system are studied. The results are as follows: (1) 60 Co was adsorbed rapidly and desorbed difficultly by soils and minerals. The order of the saturated adsorption rate and K d (distribution coefficient) of 60 Co at the balance value was: kieselguhr>paddy soil (loamy clay)>yellowish red soil>kaoline>perlite>silt-loamy soil. The order of D f (desorption factor) value was: yellowish red soil>silt-loamy soil>kaoline>perlite>paddy soil (loamy clay)>kieselguhr. The dynamic behavior of 60 Co in the soils and minerals could be described as a closed two--compartment model. (2) After 60 Co was introduced to the bean-soil system, the concentration of 60 Co in the root is about 10.4∼23.3 times of that in the stalk, and 30 times of that in the bean pod. The negative correlation between the concentration of 60 Co in the soil and depth was detected, over 90 per cent of 60 Co was retained within 6 centimeters of the surface layer, the half residual depth was 2 centimeters. An opened two-compartment model was applied to describe the behavior of 60 Co in the bean-soil system

Re- and Demineralization Characteristics of Enamel Depending on Baseline Mineral Loss and Lesion Depth in situ.

Science.gov (United States)

Wierichs, Richard J; Lausch, Julian; Meyer-Lueckel, Hendrik; Esteves-Oliveira, Marcella

2016-01-01

The aim of this double-blinded, randomized, cross-over in situ study was to evaluate the re- and demineralization characteristics of sound enamel as well as lowly and highly demineralized caries-like enamel lesions after the application of different fluoride compounds. In each of three experimental legs of 4 weeks, 21 participants wore intraoral mandibular appliances containing 4 bovine enamel specimens (2 lowly and 2 highly demineralized). Each specimen included one sound enamel and either one lowly demineralized (7 days, pH 4.95) or one highly demineralized (21 days, pH 4.95) lesion, and was positioned 1 mm below the acrylic under a plastic mesh. The three randomly allocated treatments (application only) included the following dentifrices: (1) 1,100 ppm F as NaF, (2) 1,100 ppm F as SnF2 and (3) 0 ppm F (fluoride-free) as negative control. Differences in integrated mineral loss (x0394;x0394;Z) and lesion depth (x0394;LD) were calculated between values before and after the in situ period using transversal microradiography. Of the 21 participants, 6 did not complete the study and 2 were excluded due to protocol violation. Irrespectively of the treatment, higher baseline mineral loss and lesion depth led to a less pronounced change in mineral loss and lesion depth. Except for x0394;x0394;Z of the dentifrice with 0 ppm F, sound surfaces showed significantly higher x0394;x0394;Z and x0394;LD values compared with lowly and highly demineralized lesions (p test). Re- and demineralization characteristics of enamel depended directly on baseline mineral loss and lesion depth. Treatment groups should therefore be well balanced with respect to baseline mineral loss and lesion depth. © 2016 S. Karger AG, Basel.

Synchrotron X-ray scattering studies at mineral-water interfaces

International Nuclear Information System (INIS)

Chiarello, R.P.; Sturchio, N.C.

1995-01-01

Synchrotron X-ray scattering techniques provide a powerful tool for the in situ study of atomic scale processes occurring at solid-liquid interfaces. We have applied these techniques to characterize and study reactions at mineral-water interfaces. Here we present two examples. The first is the characterization of the calcite (CaCO 3 ) (10 bar 14) cleavage surface, in equilibrium with deionized water, by crystal truncation rod measurements. The second is the in situ study of the heteroepitaxial growth of otavite (CdCO 3 ) on the calcite (10 bar 14) cleavage surface. The results of such studies will lead to significant progress in understanding mineral-water interface geochemistry

Process-based modeling of silicate mineral weathering responses to increasing atmospheric CO2 and climate change

Science.gov (United States)

Banwart, Steven A.; Berg, Astrid; Beerling, David J.

2009-12-01

A mathematical model describes silicate mineral weathering processes in modern soils located in the boreal coniferous region of northern Europe. The process model results demonstrate a stabilizing biological feedback mechanism between atmospheric CO2 levels and silicate weathering rates as is generally postulated for atmospheric evolution. The process model feedback response agrees within a factor of 2 of that calculated by a weathering feedback function of the type generally employed in global geochemical carbon cycle models of the Earth's Phanerozoic CO2 history. Sensitivity analysis of parameter values in the process model provides insight into the key mechanisms that influence the strength of the biological feedback to weathering. First, the process model accounts for the alkalinity released by weathering, whereby its acceleration stabilizes pH at values that are higher than expected. Although the process model yields faster weathering with increasing temperature, because of activation energy effects on mineral dissolution kinetics at warmer temperature, the mineral dissolution rate laws utilized in the process model also result in lower dissolution rates at higher pH values. Hence, as dissolution rates increase under warmer conditions, more alkalinity is released by the weathering reaction, helping maintain higher pH values thus stabilizing the weathering rate. Second, the process model yields a relatively low sensitivity of soil pH to increasing plant productivity. This is due to more rapid decomposition of dissolved organic carbon (DOC) under warmer conditions. Because DOC fluxes strongly influence the soil water proton balance and pH, this increased decomposition rate dampens the feedback between productivity and weathering. The process model is most sensitive to parameters reflecting soil structure; depth, porosity, and water content. This suggests that the role of biota to influence these characteristics of the weathering profile is as important, if not

The Force of Crystallization and Fracture Propagation during In-Situ Carbonation of Peridotite

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Reinier van Noort

2017-10-01

Full Text Available Subsurface mineralization of CO2 by injection into (hydro-fractured peridotites has been proposed as a carbon sequestration method. It is envisaged that the expansion in solid volume associated with the mineralization reaction leads to a build-up of stress, resulting in the opening of further fractures. We performed CO2-mineralization experiments on simulated fractures in peridotite materials under confined, hydrothermal conditions, to directly measure the induced stresses. Only one of these experiments resulted in the development of a stress, which was less than 5% of the theoretical maximum. We also performed one method control test in which we measured stress development during the hydration of MgO. Based on microstructural observations, as well as XRD and TGA measurements, we infer that, due to pore clogging and grain boundary healing at growing mineral interfaces, the transport of CO2, water and solutes into these sites inhibited reaction-related stress development. When grain boundary healing was impeded by the precipitation of silica, a small stress did develop. This implies that when applied to in-situ CO2-storage, the mineralization reaction will be limited by transport through clogged fractures, and proceed at a rate that is likely too slow for the process to accommodate the volumes of CO2 expected for sequestration.

Review of CO2 Reduction Technologies using Mineral Carbonation of Iron and Steel Making Slag in Malaysia

Science.gov (United States)

Norhana Selamat, Siti; Nor, Nik Hisyamudin Muhd; Rashid, Muhammad Hanif Abdul; Fauzi Ahmad, Mohd; Mohamad, Fariza; Ismail, Al Emran; Fahrul Hassan, Mohd; Turan, Faiz Mohd; Zain, Mohd Zamzuri Mohd; Abu Bakar, Elmi; Seiji, Yokoyama

2017-10-01

Climate change, greenhouse gas effect, and global warming is envisioning to turn more awful and more terrible by year. Since the leading cause of global warming is uncontrolled CO2 in atmosphere. The amount of unused steel slag is expected to increment later on, steel industries is one of the mechanical industries that contribute the CO2 emission. That because this businesses deliver carbon in light of powers reductant and substantial volume of steel. The changes of atmosphere these day is truly developing concern and that make steel creator are confronted with test of discovering methods for bringing down CO2 emission. Malaysia is working decidedly in the diminishment of CO2 gas. There are a few techniques in decreasing the amount of CO2 in the air as underlined by the Intergovernmental Panel of Climate Change (IPCC), an organization under the United Country however CCS is an extremely encouraging innovation to moderate CO2 emission in air. Mineral carbonation is another technique to store carbon dioxide permanently, long term stability and vast capacity.

Verification of geomechanical integrity and prediction of long-term mineral trapping for the Ketzin CO2 storage pilot site

Science.gov (United States)

Kempka, Thomas; De Lucia, Marco; Kühn, Michael

2014-05-01

Static and dynamic numerical modelling generally accompany the entire CO2 storage site life cycle. Thereto, it is required to match the employed models with field observations on a regular basis in order to predict future site behaviour. We investigated the coupled processes at the Ketzin CO2 storage pilot site [1] using a model coupling concept focusing on the temporal relevance of processes involved (hydraulic, chemical and mechanical) at given time-scales (site operation, abandonment and long-term stabilization). For that purpose, long-term dynamic multi-phase flow simulations [2], [3] established the basis for all simulations discussed in the following. Hereby, pressure changes resulting in geomechanical effects are largest during site operation, whereas geochemical reactions are governed by slow kinetics resulting in a long-term stabilization. To account for mechanical integrity, which may be mainly affected during site operation, we incorporated a regional-scale coupled hydro-mechanical model. Our simulation results show maximum ground surface displacements of about 4 mm, whereas shear and tensile failure are not observed. Consequently, the CO2 storage operation at the Ketzin pilot site does not compromise reservoir, caprock and fault integrity. Chemical processes responsible for mineral trapping are expected to mainly occur during long-term stabilization at the Ketzin pilot site [4]. Hence, our previous assessment [3] was extended by integrating two long-term mineral trapping scenarios. Thereby, mineral trapping contributes to the trapping mechanisms with 11.7 % after 16,000 years of simulation in our conservative and with 30.9 % in our maximum reactivity scenarios. Dynamic flow simulations indicate that only 0.2 % of the CO2 injected (about 67,270 t CO2 in total) is in gaseous state, but structurally trapped after 16,000 years. Depending on the studied long-term scenario, CO2 dissolution is the dominating trapping mechanism with 68.9 % and 88

Study on tertiary in-situ leachable uranium mineralization conditions in South Songliao basin

International Nuclear Information System (INIS)

Zhang Zhenqiang; Li Guokuan; Zhao Zonghua; Zhang Jingxun

2001-01-01

Tertiary in-situ leachable mineralization in Songliao Basin was analyzed in theory in the past. Since 1998, regional investigation at 1:200000 scale has been done with about 120 holes drilled. Based on drill holes recording, section compiling and sample analysis, the authors investigate into the Tertiary in-situ leachable conditions including rock character, sedimentary facies, rock chemistry, organic substances, uranium content, sandstone porosity, sandstone bodies, interlayer oxidation, and hydro-dynamic value. The study would play important role in prospecting for in-situ leachable uranium in South Songliao basin

In Situ Raman Analysis of CO2—Assisted Drying of Fruit-Slices

Directory of Open Access Journals (Sweden)

Andreas Siegfried Braeuer

2017-05-01

Full Text Available This work explores the feasibility of applying in situ Raman spectroscopy for the online monitoring of the supercritical carbon dioxide (SC-CO2 drying of fruits. Specifically, we investigate two types of fruits: mango and persimmon. The drying experiments were carried out inside an optical accessible vessel at 10 MPa and 313 K. The Raman spectra reveal: (i the reduction of the water from the fruit slice and (ii the change of the fruit matrix structure during the drying process. Two different Raman excitation wavelengths were compared: 532 nm and 785 nm. With respect to the quality of the obtained spectra, the 532 nm excitation wavelength was superior due to a higher signal-to-noise ratio and due to a resonant excitation scheme of the carotenoid molecules. It was found that the absorption of CO2 into the fruit matrix enhances the extraction of water, which was expressed by the obtained drying kinetic curve.

In Situ Raman Analysis of CO2—Assisted Drying of Fruit-Slices

Science.gov (United States)

Braeuer, Andreas Siegfried; Schuster, Julian Jonathan; Gebrekidan, Medhanie Tesfay; Bahr, Leo; Michelino, Filippo; Zambon, Alessandro; Spilimbergo, Sara

2017-01-01

This work explores the feasibility of applying in situ Raman spectroscopy for the online monitoring of the supercritical carbon dioxide (SC-CO2) drying of fruits. Specifically, we investigate two types of fruits: mango and persimmon. The drying experiments were carried out inside an optical accessible vessel at 10 MPa and 313 K. The Raman spectra reveal: (i) the reduction of the water from the fruit slice and (ii) the change of the fruit matrix structure during the drying process. Two different Raman excitation wavelengths were compared: 532 nm and 785 nm. With respect to the quality of the obtained spectra, the 532 nm excitation wavelength was superior due to a higher signal-to-noise ratio and due to a resonant excitation scheme of the carotenoid molecules. It was found that the absorption of CO2 into the fruit matrix enhances the extraction of water, which was expressed by the obtained drying kinetic curve. PMID:28505120

Facile synthesis of surface N-doped Bi{sub 2}O{sub 2}CO{sub 3}: Origin of visible light photocatalytic activity and in situ DRIFTS studies

Energy Technology Data Exchange (ETDEWEB)

Zhou, Ying, E-mail: yzhou@swpu.edu.cn [State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Xindu Rd. 8, Chengdu 610500 (China); The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University, Xindu Rd. 8, Chengdu 610500 (China); Insititute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe (Germany); Zhao, Ziyan [State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Xindu Rd. 8, Chengdu 610500 (China); The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University, Xindu Rd. 8, Chengdu 610500 (China); Wang, Fang; Cao, Kun [The Center of New Energy Materials and Technology, School of Materials Science and Engineering, Southwest Petroleum University, Xindu Rd. 8, Chengdu 610500 (China); Doronkin, Dmitry E. [Insititute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe (Germany); Dong, Fan [College of Environmental and Biological Engineering, Chonqing Technology and Business University, Chongqing 400067 (China); Grunwaldt, Jan-Dierk, E-mail: grunwaldt@kit.edu [Insititute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe (Germany)

2016-04-15

Graphical abstract: Surfactant (CTAB) can induce nitrogen interstitially doping in the Bi{sub 2}O{sub 2}CO{sub 3} surface, leading to the formation of localized states from N−O bond, which probably account for the origin of the visible light activity. Moreover, the photocatalytic NO oxidation processes over Bi{sub 2}O{sub 2}CO{sub 3} were successfully monitored for the first time by in situ DRIFTS. - Highlights: • Interstitially doping N in the Bi{sub 2}O{sub 2}CO{sub 3} surface was achieved at room temperature. • N-doped Bi{sub 2}O{sub 2}CO{sub 3} exhibited significantly enhanced visible light photocatalytic activity compared to the pristine Bi{sub 2}O{sub 2}CO{sub 3}. • The formation of localized states from N−O bond could account for the visible light activity of Bi{sub 2}O{sub 2}CO{sub 3}. • The photocatalytic NO oxidation process was monitored by in situ DRIFTS. - Abstract: Bi{sub 2}O{sub 2}CO{sub 3} nanosheets with exposed {001} facets were prepared by a facile room temperature chemical method. Due to the high oxygen atom density in {001} facets of Bi{sub 2}O{sub 2}CO{sub 3}, the addition of cetyltrimethylammonium bromide (CTAB) does not only influence the growth of crystalline Bi{sub 2}O{sub 2}CO{sub 3}, but also modifies the surface properties of Bi{sub 2}O{sub 2}CO{sub 3} through the interaction between CTAB and Bi{sub 2}O{sub 2}CO{sub 3}. Nitrogen from CTAB as dopant interstitially incorporates in the Bi{sub 2}O{sub 2}CO{sub 3} surface evidenced by both experimental and theoretical investigations. Hence, the formation of localized states from N−O bond improves the visible light absorption and charge separation efficiency, which leads to an enhancement of visible light photocatalytic activity toward to the degradation of Rhodamine B (RhB) and oxidation of NO. In addition, the photocatalytic NO oxidation over Bi{sub 2}O{sub 2}CO{sub 3} nanosheets was successfully monitored for the first time using in situ diffuse reflectance infrared Fourier

CoMet: an airborne mission to simultaneously measure CO2 and CH4 using lidar, passive remote sensing, and in-situ techniques

Science.gov (United States)

Fix, Andreas; Amediek, Axel; Bovensmann, Heinrich; Ehret, Gerhard; Gerbig, Christoph; Gerilowski, Konstantin; Pfeilsticker, Klaus; Roiger, Anke; Zöger, Martin

2018-04-01

TIn order to improve our current knowledge on the budgets of the two most important anthropogenic greenhouse gases, CO2 and CH4, an airborne mission on board the German research aircraft HALO in coordination with two smaller Cessna aircraft is going to be conducted in April/May 2017. The goal of CoMet is to combine a suite of the best currently available active (lidar) and passive remote sensors as well as in-situ instruments to provide regional-scale data of greenhouse gases which are urgently required.

CO2 Energy Reactor - Integrated Mineral Carbonation: Perspectives on Lab-Scale Investigation and Products Valorization

OpenAIRE

Rafael M Santos; Pol CM Knops; Keesjan L Rijnsburger; Yi Wai eChiang

2016-01-01

To overcome the challenges of mineral CO2 sequestration, Innovation Concepts B.V. is developing a unique proprietary gravity pressure vessel (GPV) reactor technology and has focussed on generating reaction products of high economic value. The GPV provides intense process conditions through hydrostatic pressurization and heat exchange integration that harvests exothermic reaction energy, thereby reducing energy demand of conventional reactor designs, in addition to offering other benefits. In ...

Supplying synthetic crude oil from Canadian oil sands: A comparative study of the costs and CO2 emissions of mining and in-situ recovery

International Nuclear Information System (INIS)

Méjean, Aurélie; Hope, Chris

2013-01-01

High crude oil prices and the eventual decline of conventional oil production raise the issue of alternative fuels such as non-conventional oil. The paper describes a simple probabilistic model of the costs of synthetic crude oil produced from Canadian oil sands. Synthetic crude oil is obtained by upgrading bitumen that is first produced through mining or in-situ recovery techniques. This forward-looking analysis quantifies the effects of learning and production constraints on the costs of supplying synthetic crude oil. The sensitivity analysis shows that before 2035, the most influential parameters are the learning parameter in the case of in-situ bitumen and the depletion parameter in the case of mined bitumen. After 2035, depletion dominates in both cases. The results show that the social cost of CO 2 has a large impact on the total costs of synthetic crude oil, in particular in the case of synthetic crude oil from in-situ bitumen, due to the carbon intensity of the recovery techniques: taking into account the social cost of CO 2 adds more than half to the cost of producing synthetic crude oil from mined bitumen in 2050 (mean value), while the cost of producing synthetic crude oil from in-situ bitumen more than doubles. - Highlights: • We model the cost of Canadian synthetic crude oil (SCO) using Monte-Carlo techniques. • We reveal the uncertainty associated with each input parameter. • We quantify the effect of learning, depletion and CO 2 using sensitivity analyses. • Accounting for the social cost of CO 2 doubles the cost of SCO from in-situ bitumen. • CO 2 pricing could have a large effect on the economics of the oil sands

Adsorption of methane and CO2 onto olivine surfaces in Martian dust conditions

Science.gov (United States)

Escamilla-Roa, Elizabeth; Martin-Torres, Javier; Sainz-Díaz, C. Ignacio

2018-04-01

Methane has been detected on all planets of our Solar System, and most of the larger moons, as well as in dwarf-planets like Pluto and Eric. The presence of this molecule in rocky planets is very interesting because its presence in the Earth's atmosphere is mainly related to biotic processes. Space instrumentation in orbiters around Mars has detected olivine on the Martian soil and dust. On the other hand the measurements of methane from the Curiosity rover report detection of background levels of atmospheric methane with abundance that is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, elevated levels of methane about this background have been observed implying that Mars is episodically producing methane from an additional unknown source, making the reasons of these temporal fluctuations of methane a hot topic in planetary research. The goal of this study is to investigate at atomic level the interactions during the adsorption processes of methane and other Mars atmospheric species (CO2, H2O) on forsterite surfaces, through electronic structure calculations based on the Density Functional Theory (DFT). We propose two models to simulate the interaction of adsorbates with the surface of dust mineral, such as binary mixtures (5CH4+5H2O/5CH4+5CO2) and as a semi-clathrate adsorption. We have obtained interesting results of the adsorption process in the mixture 5CH4+5CO2. Associative and dissociative adsorptions were observed for water and CO2 molecules. The methane molecules were only trapped and held by water or CO2 molecules. In the dipolar surface, the adsorption of CO2 molecules produced new species: one CO from a CO2 dissociation, and, two CO2 molecules chemisorbed to mineral surface forming in one case a carbonate group. Our results suggest that CO2 has a strong interaction with the mineral surface when methane is present. These results could be confirmed after the

In-Situ MVA of CO₂ Sequestration Using Smart Field Technology

Energy Technology Data Exchange (ETDEWEB)

Mohaghegh, Shahab D. [West Virginia Univ. Research Corporation, Morgantown, WV (United States)

2014-09-01

Capability of underground carbon dioxide storage to confine and sustain injected CO₂ for a long period of time is the main concern for geologic CO₂ sequestration. If a leakage from a geological CO₂ sequestration site occurs, it is crucial to find the approximate amount and the location of the leak, in a timely manner, in order to implement proper remediation activities. An overwhelming majority of research and development for storage site monitoring has been concentrated on atmospheric, surface or near surface monitoring of the sequestered CO₂ . This study aims to monitor the integrity of CO₂ storage at the reservoir level. This work proposes developing in-situ CO₂ Monitoring and Verification technology based on the implementation of Permanent Down-hole Gauges (PDG) or “Smart Wells” along with Artificial Intelligence and Data Mining (AI&DM). The technology attempts to identify the characteristics of the CO₂ leakage by de-convolving the pressure signals collected from Permanent Down-hole Gauges (PDG). Citronelle field, a saline aquifer reservoir, located in the U.S. was considered as the basis for this study. A reservoir simulation model for CO₂ sequestration in the Citronelle field was developed and history matched. PDGs were installed, and therefore were considered in the numerical model, at the injection well and an observation well. Upon completion of the history matching process, high frequency pressure data from PDGs were generated using the history matched numerical model using different CO₂ leakage scenarios. Since pressure signal behaviors were too complicated to de-convolute using any existing mathematical formulations, a Machine Learning-based technology was introduced for this purpose. An Intelligent Leakage Detection System (ILDS) was developed as the result of this effort using the machine learning and pattern recognition technologies. The ILDS

Microbiological and Geochemical Survey of CO2-Dominated Mofette and Mineral Waters of the Cheb Basin, Czech Republic

Directory of Open Access Journals (Sweden)

Patryk Krauze

2017-12-01

Full Text Available The Cheb Basin (NW Bohemia, Czech Republic is a shallow, neogene intracontinental basin. It is a non-volcanic region which features frequent earthquake swarms and large-scale diffuse degassing of mantle-derived CO2 at the surface that occurs in the form of CO2-rich mineral springs and wet and dry mofettes. So far, the influence of CO2 degassing onto the microbial communities has been studied for soil environments, but not for aquatic systems. We hypothesized, that deep-trenching CO2 conduits interconnect the subsurface with the surface. This admixture of deep thermal fluids should be reflected in geochemical parameters and in the microbial community compositions. In the present study four mineral water springs and two wet mofettes were investigated through an interdisciplinary survey. The waters were acidic and differed in terms of organic carbon and anion/cation concentrations. Element geochemical and isotope analyses of fluid components were used to verify the origin of the fluids. Prokaryotic communities were characterized through quantitative PCR and Illumina 16S rRNA gene sequencing. Putative chemolithotrophic, anaerobic and microaerophilic organisms connected to sulfur (e.g., Sulfuricurvum, Sulfurimonas and iron (e.g., Gallionella, Sideroxydans cycling shaped the core community. Additionally, CO2-influenced waters form an ecosystem containing many taxa that are usually found in marine or terrestrial subsurface ecosystems. Multivariate statistics highlighted the influence of environmental parameters such as pH, Fe2+ concentration and conductivity on species distribution. The hydrochemical and microbiological survey introduces a new perspective on mofettes. Our results support that mofettes are either analogs or rather windows into the deep biosphere and furthermore enable access to deeply buried paleo-sediments.

In situ X-ray and neutron diffraction of the Ruddlesden–Popper compounds (RE2−xSrx)0.98(Fe0.8Co0.2)1−yMgyO4−δ (RE=La, Pr): Structure and CO2 stability

International Nuclear Information System (INIS)

Chatzichristodoulou, C.; Hauback, B.C.; Hendriksen, P.V.

2013-01-01

The crystal structure of the Ruddlesden–Popper compounds (La 1.0 Sr 1.0 ) 0.98 Fe 0.8 Co 0.2 O 4−δ and (La 1.2 Sr 0.8 ) 0.98 (Fe 0.8 Co 0.2 ) 0.8 Mg 0.2 O 4−δ was investigated at 1000 °C in N 2 (a O2 =1×10 −4 ) by in-situ powder neutron diffraction. In-situ powder X-ray diffraction (PXD) was also employed to investigate the temperature dependence of the lattice parameters of the compounds in air and the oxygen activity dependence of the lattice parameters at 800 °C and 1000 °C. The thermal and chemical expansion coefficients, determined along the two crystallographic directions of the tetragonal unit cell, are highly anisotropic. The equivalent pseudo-cubic thermal and chemical expansion coefficients are in agreement with values determined by dilatometry. The chemical stability in CO 2 containing environments of various Ruddlesden–Popper compounds with chemical formula (RE 2−x Sr x ) 0.98 (Fe 0.8 Co 0.2 ) 1−y Mg y O 4−δ (RE=La, Pr), as well as their stability limit in H 2 /H 2 O=4.5 were also determined by in-situ PXD for x=0.9, 1.0 and y=0, 0.2. - Graphical abstract: Influence of electronic configuration on bond length, lattice parameters and anisotropic thermal and chemical expansion. Highlights: ► The thermal and chemical expansion coefficients are largely anisotropic. ► The expansion of the perovskite layers is constrained along the a direction. ► The studied compositions show remarkable thermodynamic stability upon reduction. ► The thermal and chemical expansion coefficients are lower than related perovskites. ► The investigated materials decompose in CO 2 containing atmospheres

Sample environment for in situ synchrotron XRD measurements for CO2 interaction with subsurface materials

Science.gov (United States)

Elbakhshwan, M.; Gill, S.; Weidner, R.; Ecker, L.

2017-12-01

Sequestration of CO2 in geological formations requires a deep understanding of its interaction with the cement-casing components in the depleted oil and gas wells. Portland cement is used to seal the wellbores; however it tends to interact with the CO2. Therefore it is critical to investigate the wellbore integrity over long term exposure to CO2. Studies showed that, CO2 leakage is due to the flow through the casing-cement microannulus, cement-cement fractures, or the cement-caprock interface. The objective of this work is to gain a better understanding of the dissolution process of the cement-casing in the CO2 flow channels alongside with the carbonation reactions at the interfaces using XRF, XANES and X-ray tomography techniques. In this study, a synthetic wellbore system, consisting of cement with an embedded rectangular length of steel casing that had grooves to accommodate fluid flow, was used to investigate the casing-cement microannulus through core-flood experiments. The objective of this work is to gain a better understanding of the dissolution process of the cement-casing in the CO2 flow channels alongside with the carbonation reactions at the interfaces using a sample environment designed and built for in situ X-ray diffraction in the National Synchrotron Light Source II (NSLS II). The formation of carbonate phases at cement -fluid and cement-steel/fluid interfaces will be monitored in real time. Samples may be exposed to super critical CO2 at pressures above 1100 psi and temperatures around 50°C. The reaction cell is built from hastealloy to provide corrosion resistance, while the experimental temperature and pressure are controlled with thermocouples and pressure vessel.

Revealing fate of CO2 leakage pathways in the Little Grand Wash Fault, Green River, Utah

Science.gov (United States)

Han, K.; Han, W. S.; Watson, Z. T.; Guyant, E.; Park, E.

2015-12-01

To assure long-term security of geologic carbon sequestration site, evaluation of natural CO2 leakage should be preceded before actual construction of the CO2 facility by comparing natural and artificial reservoir systems. The Little Grand Wash fault is located at the northwestern margin of the Paradox Basin and roles on a bypass of deep subsurface CO2 and brine water onto the surface, e.g., cold water geyser, CO2 spring, and surface travertine deposits. CO2 degassed out from brine at the Little Grand Wash fault zone may react with formation water and minerals while migrating through the fault conduit. Leakage observed by soil CO2 flux on the fault trace shows this ongoing transition of CO2, from supersaturated condition in deep subsurface to shallow surface equilibria. The present study aims to investigate the reactions induced by changes in hydrological and mineralogical factors inside of the fault zone. The methodology to develop site-specific geochemical model of the Little Grand Wash Fault combines calculated mechanical movements of each fluid end-member, along with chemical reactions among fluid, free CO2 gas and rock formations. Reactive transport modeling was conducted to simulate these property changes inside of the fault zone, using chemistry dataset based on 86 effluent samples of CO2 geysers, springs and in situ formation water from Entrada, Carmel, and Navajo Sandstone. Meanwhile, one- and two-dimensional models were separately developed to delineate features mentioned above. The results from the 3000-year simulation showed an appearance of self-sealing processes near the surface of the fault conduit. By tracking physicochemical changes at the depth of 15 m on the 2-dimensional model, significant changes induced by fluid mixing were indicated. Calculated rates of precipitation for calcite, illite, and pyrite showed increase in 2.6 x 10-4, 2.25 x 10-5, and 3.0 x 10-6 in mineral volume fraction at the depth of 15m, respectively. Concurrently

In situ study of the effects of heavy-ion irradiation on co-evaporated CoSi2 films

International Nuclear Information System (INIS)

Allen, C.W.; Smith, D.A.

1990-11-01

The in situ ion irradiation capability of Argonne's HVEM-Tandem User Facility has been employed to determine the effects of 1.5 MeV Kr + irradiation and 300 kV electron irradiation on the crystallization of as-deposited and of partially crystallized 40 nm thick films of CoSi 2 . Ion fluxes ranged from 8.5 x 10 14 to 6.8 x 10 15 m -2 s -1 for which beam heating effects may be neglected. The maximum electron flux at 300 kV was 0.8 x 10 23 m -2 s -1 . The maximum temperature at which crystalline CoSi 2 is amorphized by the ion irradiation of flux = 6.8 x 10 15 m -2 s -1 is between 250 and 280 K. At higher temperatures amorphous material crystallizes by growth of any preexisting crystals and by classical nucleation and growth, with radial growth rates which are proportional to ion flux. The average degree of transformation per ion is 4 x 10 -26 m 3 per ion. Thermally induced crystallization of as-deposited films occurs above approximately 420 K. For ion doses at least as low as 3.4 x 10 16 m -2 ion irradiation at 300 K promotes thermal crystallization at 450 K, by virtue of enhanced apparant nucleation and at large doses, by enhanced growth rate. 8 refs., 2 figs

Understanding the residence of Co in ore minerals - towards the development of novel Co extraction strategies for laterite deposits

Science.gov (United States)

Dybowska, Agnieszka; Norman, Rachel; Schofield, Paul; Herrington, Richard

2017-04-01

XRD. These low abundance minerals, identified in the samples using Raman spectroscopy, µXRD and EPMA, proved however to be very important Co-hosting phases. Electron microscopy and µ-XRF mapping revealed a strong Mn and Co association in all samples but little correlation between Co and Fe. The important determinant of Co concentration is thus its association with Mn oxides, a variety of which have been found in the samples studied. For example, in Shevchenko laterite asbolane was identified with Co concentrations varying from 0.25 to 12.4 wt% (6.3 wt% on average). Goethite was found to carry only minor Co i.e. below 0.03 wt% or 0.1-0.2 wt%. In samples from the Nkamouna laterite Mn oxide minerals were found to contain Co ranging widely from below 1 wt% in tectomanganate phases such as hollandite and pyrolusite, 5.5% wt% in lithiophorite and up to 21 wt% in lithiophorite-asbolane intermediates. No Co or minor Co (<0.1 wt%) was detected in Fe oxides and oxy-hydroxides. XANES spectroscopy shows that Co is bound in a range of Mn oxide minerals as Co3+. The structural environment of Co in these minerals is very similar with Co in octahedral coordination. Analysis of the EXAFS data for asbolane shows an apparent high degree of structural order around Co which suggest that Co is present as clustered aggregates. Our results indicate that Co should be efficiently and selectively removed from the studied laterites by targeted solubilisation of Mn oxides, which can be achieved via, for example, microbially mediated reductive mineral dissolution.

Carbon Mineralization by Aqueous Precipitation for Beneficial Use of CO2 from Flue Gas

Energy Technology Data Exchange (ETDEWEB)

Devenney, Martin; Gilliam, Ryan; Seeker, Randy

2013-08-01

The objective of this project is to demonstrate an innovative process to mineralize CO2 from flue gas directly to reactive carbonates and maximize the value and versatility of its beneficial use products. The program scope includes the design, construction, and testing of a CO2 Conversion to Material Products (CCMP) Pilot Demonstration Plant utilizing CO2 from the flue gas of a power production facility in Moss Landing, CA. This topical report covers Subphase 2a which is the design phase of pilot demonstration subsystems. Materials of construction have been selected and proven in both lab scale and prototype testing to be acceptable for the reagent conditions of interest. The target application for the reactive carbonate material has been selected based upon small-scale feasibility studies and the design of a continuous fiber board production line has been completed. The electrochemical cell architecture and components have been selected based upon both lab scale and prototype testing. The appropriate quality control and diagnostic techniques have been developed and tested along with the required instrumentation and controls. Finally the demonstrate site infrastructure, NEPA categorical exclusion, and permitting is all ready for the construction and installation of the new units and upgrades.

Field demonstration of CO2 leakage detection in potable aquifers with a pulselike CO2-release test.

Science.gov (United States)

Yang, Changbing; Hovorka, Susan D; Delgado-Alonso, Jesus; Mickler, Patrick J; Treviño, Ramón H; Phillips, Straun

2014-12-02

This study presents two field pulselike CO2-release tests to demonstrate CO2 leakage detection in a shallow aquifer by monitoring groundwater pH, alkalinity, and dissolved inorganic carbon (DIC) using the periodic groundwater sampling method and a fiber-optic CO2 sensor for real-time in situ monitoring of dissolved CO2 in groundwater. Measurements of groundwater pH, alkalinity, DIC, and dissolved CO2 clearly deviated from their background values, showing responses to CO2 leakage. Dissolved CO2 observed in the tests was highly sensitive in comparison to groundwater pH, DIC, and alkalinity. Comparison of the pulselike CO2-release tests to other field tests suggests that pulselike CO2-release tests can provide reliable assessment of geochemical parameters indicative of CO2 leakage. Measurements by the fiber-optic CO2 sensor, showing obvious leakage signals, demonstrated the potential of real-time in situ monitoring of dissolved CO2 for leakage detection at a geologic carbon sequestration (GCS) site. Results of a two-dimensional reactive transport model reproduced the geochemical measurements and confirmed that the decrease in groundwater pH and the increases in DIC and dissolved CO2 observed in the pulselike CO2-release tests were caused by dissolution of CO2 whereas alkalinity was likely affected by carbonate dissolution.

Stochastic Approach to Determine CO2 Hydrate Induction Time in Clay Mineral Suspensions

Science.gov (United States)

Lee, K.; Lee, S.; Lee, W.

2008-12-01

A large number of induction time data for carbon dioxide hydrate formation were obtained from a batch reactor consisting of four independent reaction cells. Using resistance temperature detector(RTD)s and a digital microscope, we successfully monitored the whole process of hydrate formation (i.e., nucleation and crystal growth) and detected the induction time. The experiments were carried out in kaolinite and montmorillonite suspensions at temperatures between 274 and 277 K and pressures ranging from 3.0 to 4.0 MPa. Each set of data was analyzed beforehand whether to be treated by stochastic manner or not. Geochemical factors potentially influencing the hydrate induction time under different experimental conditions were investigated by stochastic analyses. We observed that clay mineral type, pressure, and temperature significantly affect the stochastic behavior of the induction times for CO2 hydrate formation in this study. The hydrate formation kinetics along with stochastic analyses can provide basic understanding for CO2 hydrate storage in deep-sea sediment and geologic formation, securing its stability under the environments.

An Inversion Analysis of Recent Variability in Natural CO2 Fluxes Using GOSAT and In Situ Observations

Science.gov (United States)

Wang, James S.; Kawa, S. Randolph; Collatz, G. James; Baker, David F.; Ott, Lesley

2015-01-01

About one-half of the global CO2 emissions from fossil fuel combustion and deforestation accumulates in the atmosphere, where it contributes to global warming. The rest is taken up by vegetation and the ocean. The precise contribution of the two sinks, and their location and year-to-year variability are, however, not well understood. We use two different approaches, batch Bayesian synthesis inversion and variational data assimilation, to deduce the global spatiotemporal distributions of CO2 fluxes during 2009-2010. One of our objectives is to assess different sources of uncertainties in inferred fluxes, including uncertainties in prior flux estimates and observations, and differences in inversion techniques. For prior constraints, we utilize fluxes and uncertainties from the CASA-GFED model of the terrestrial biosphere and biomass burning driven by satellite observations and interannually varying meteorology. We also use measurement-based ocean flux estimates and two sets of fixed fossil CO2 emissions. Here, our inversions incorporate column CO2 measurements from the GOSAT satellite (ACOS retrieval, filtered and bias-corrected) and in situ observations (individual flask and afternoon-average continuous observations) to estimate fluxes in 108 regions over 8-day intervals for the batch inversion and at 3 x 3.75 weekly for the variational system. Relationships between fluxes and atmospheric concentrations are derived consistently for the two inversion systems using the PCTM atmospheric transport model driven by meteorology from the MERRA reanalysis. We compare the posterior fluxes and uncertainties derived using different data sets and the two inversion approaches, and evaluate the posterior atmospheric concentrations against independent data including aircraft measurements. The optimized fluxes generally resemble those from other studies. For example, the results indicate that the terrestrial biosphere is a net CO2 sink, and a GOSAT-only inversion suggests a shift in

Microbe-driven turnover offsets mineral-mediated storage of soil carbon under elevated CO2

Science.gov (United States)

Sulman, Benjamin N.; Phillips, Richard P.; Oishi, A. Christopher; Shevliakova, Elena; Pacala, Stephen W.

2014-12-01

The sensitivity of soil organic carbon (SOC) to changing environmental conditions represents a critical uncertainty in coupled carbon cycle-climate models. Much of this uncertainty arises from our limited understanding of the extent to which root-microbe interactions induce SOC losses (through accelerated decomposition or `priming') or indirectly promote SOC gains (via `protection' through interactions with mineral particles). We developed a new SOC model to examine priming and protection responses to rising atmospheric CO2. The model captured disparate SOC responses at two temperate free-air CO2 enrichment (FACE) experiments. We show that stabilization of `new' carbon in protected SOC pools may equal or exceed microbial priming of `old' SOC in ecosystems with readily decomposable litter and high clay content (for example, Oak Ridge). In contrast, carbon losses induced through priming dominate the net SOC response in ecosystems with more resistant litters and lower clay content (for example, Duke). The SOC model was fully integrated into a global terrestrial carbon cycle model to run global simulations of elevated CO2 effects. Although protected carbon provides an important constraint on priming effects, priming nonetheless reduced SOC storage in the majority of terrestrial areas, partially counterbalancing SOC gains from enhanced ecosystem productivity.

Geochemical effects of CO2 sequestration in sandstones under simulated in situ conditions of deep saline aquifers

International Nuclear Information System (INIS)

Wigand, M.; Carey, J.W.; Schuett, H.; Spangenberg, E.; Erzinger, J.

2008-01-01

The geochemical effects of brine and supercritical CO 2 (SCCO 2 ) on reservoir rocks from deep (1500-2000 m) saline aquifers were examined via experimental simulation at in situ conditions. Dry sandstone samples were mounted in a triaxial cell and autoclave system, evacuated, and saturated with 1 M NaCl solution. The brine-rock system was allowed to react at 30 MPa confining pressure, 15 MPa pore fluid pressure, and 60 deg. C while SCCO 2 was injected at a pressure gradient of 1-2 MPa. The experiment was conducted for a period of 1496 h, during which fluids were periodically sampled and analyzed. The pH measured in partially degassed fluid samples at 25 deg. C decreased from a starting value of 7.0-4.3 (9 days) and finally 5.1 after saturation with SCCO 2 . Fluid analyses indicate that most of the major (e.g. Ca, Mg, Fe, Mn) and trace elements (e.g. Sr, Ba, Pb) of the sandstone increase in concentration during the reaction with brine and SCCO 2 . These results are supported by scanning electron microscopy which indicates dissolution of dolomite cement, K-feldspar, and albite. In addition to dissolution reactions the formation of montmorillonite was observed. By adjusting surface area and reaction rates of dissolution and precipitation, geochemical modeling of the experiments could reproduce long-term trends in solution chemistry and indicated limited rates of dissolution as the system remained strongly undersaturated with most minerals, including carbonates. The geochemical models could not account for decreases in concentration of some elements, changes in solution composition resulting from changes in imposed pressure gradient, and the observed Ca/Mg and Si/Al ratios in solution

Alteration of bentonite when contacted with supercritical CO2

Science.gov (United States)

Jinseok, K.; Jo, H. Y.; Yun, S. T.

2014-12-01

Deep saline formations overlaid by impermeable caprocks with a high sealing capacity are attractive CO2 storage reservoirs. Shales, which consist of mainly clay minerals, are potential caprocks for the CO2 storage reservoirs. The properties of clay minerals in shales may affect the sealing capacity of shales. In this study, changes in clay minerals' properties when contacted with supercritical (SC) CO2 at various conditions were investigated. Bentonite, whichis composed of primarily montmorillonite, was used as the clay material in this study. Batch reactor tests on wet bentonite samples in the presence of SC CO2 with or without aqueous phases were conducted at high pressure (12 MPa) and moderate temperature (50 oC) conditions for a week. Results show that the bentonite samples obtained from the tests with SC CO2 had less change in porosity than those obtained from the tests without SC CO2 (vacuum-drying) at a given reaction time, indicating that the bentonite samples dried in the presence of SC CO2 maintained their structure. These results suggest that CO2 molecules can diffuse into interlayer of montmorillonite, which is a primary mineral of bentonite, and form a single CO2 molecule layer or double CO2 molecule layers. The CO2 molecules can displace water molecules in the interlayer, resulting in maintaining the interlayer spacing when dehydration occurs. Noticeable changes in reacted bentonite samples obtained from the tests with an aqueous phase (NaCl, CaCl2, or sea water) are decreases in the fraction of plagioclase and pyrite and formation of carbonate minerals (i.e., calcite and dolomite) and halite. In addition, no significant exchanges of Na or Ca on the exchangeable complex of the montmorillonite in the presence of SC CO2 occurred, resulting in no significant changes in the swelling capacity of bentonite samples after reacting with SC CO2 in the presence of aqueous phases. These results might be attributed by the CO2 molecule layer, which prevents

Numerical Simulation and Optimization of Enhanced Oil Recovery by the In Situ Generated CO2 Huff-n-Puff Process with Compound Surfactant

Directory of Open Access Journals (Sweden)

Yong Tang

2016-01-01

Full Text Available This paper presents the numerical investigation and optimization of the operating parameters of the in situ generated CO2 Huff-n-Puff method with compound surfactant on the performance of enhanced oil recovery. First, we conducted experiments of in situ generated CO2 and surfactant flooding. Next, we constructed a single-well radial 3D numerical model using a thermal recovery chemical flooding simulator to simulate the process of CO2 Huff-n-Puff. The activation energy and reaction enthalpy were calculated based on the reaction kinetics and thermodynamic models. The interpolation parameters were determined through history matching a series of surfactant core flooding results with the simulation model. The effect of compound surfactant on the Huff-n-Puff CO2 process was demonstrated via a series of sensitivity studies to quantify the effects of a number of operation parameters including the injection volume and mole concentration of the reagent, the injection rate, the well shut-in time, and the oil withdrawal rate. Based on the daily production rate during the period of Huff-n-Puff, a desirable agreement was shown between the field applications and simulated results.

Micro-CT in situ study of carbonate rock microstructural evolution for geologic CO2 storage

DEFF Research Database (Denmark)

Zheng, Yi; Yang, Yan; Rogowska, M.

2017-01-01

to achieve this is to find a suitable condition to create a stable 3D space in carbonate rock by injecting liquid to prepare space for the later CO2 injection. Micro-CT imaging is a non-destructive 3D method that can be used to study the property changes of carbonate rocks during and after CO2 injection....... The advance in lab source based micro-CT has made it capable of in situ experiments. We used a commercial bench top micro-CT (Zeiss Versa XRM410) to study the microstructure changes of chalk during liquid injection. Flexible temporal CT resolution is essential in this study because that the time scales...... of coupled physical and chemical processes can be very different. The results validated the feasibility of using a bench top CT system with a pressure cell to monitor the mesoscale multiphase interactions in chalk....

Benthic Carbon Mineralization and Nutrient Turnover in a Scottish Sea Loch

DEFF Research Database (Denmark)

Glud, Ronnie N.; Berg, Peter; Stahl, Henrik

2016-01-01

Based on in situ microprofiles, chamber incubations and eddy covariance measurements, we investigated the benthic carbon mineralization and nutrient regeneration in a ~65-m-deep sedimentation basin of Loch Etive, UK. The sediment hosted a considerable amount of infauna that was dominated by the b......Based on in situ microprofiles, chamber incubations and eddy covariance measurements, we investigated the benthic carbon mineralization and nutrient regeneration in a ~65-m-deep sedimentation basin of Loch Etive, UK. The sediment hosted a considerable amount of infauna that was dominated....... The average benthic O2 exchange as derived by chamber incubations and the eddy covariance approach were similar (14.9 ± 2.5 and 13.1 ± 9.0 mmol m−2 day−1) providing confidence in the two measuring approaches. Moreover, the non-invasive eddy approach revealed a flow-dependent benthic O2 flux that was partly...... ascribed to enhanced ventilation of infauna burrows during periods of elevated flow rates. The ratio in exchange rates of ΣCO2 and O2 was close to unity, confirming that the O2 uptake was a good proxy for the benthic carbon mineralization in this setting. The infauna activity resulted in highly dynamic...

Performance evaluation of a green process for microalgal CO2 sequestration in closed photobioreactor using flue gas generated in-situ.

Science.gov (United States)

Yadav, Geetanjali; Karemore, Ankush; Dash, Sukanta Kumar; Sen, Ramkrishna

2015-09-01

In the present study, carbon-dioxide capture from in situ generated flue gas was carried out using Chlorella sp. in bubble column photobioreactors to develop a cost effective process for concomitant carbon sequestration and biomass production. Firstly, a comparative analysis of CO2 sequestration with varying concentrations of CO2 in air-CO2 and air-flue gas mixtures was performed. Chlorella sp. was found to be tolerant to 5% CO2 concentration. Subsequently, inhibitory effect of pure flue gas was minimized using various strategies like use of high initial cell density and photobioreactors in series. The final biofixation efficiency was improved by 54% using the adopted strategies. Further, sequestered microalgal biomass was analyzed for various biochemical constituents for their use in food, feed or biofuel applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Airborne remote sensing and in situ measurements of atmospheric CO2 to quantify point source emissions

Science.gov (United States)

Krings, Thomas; Neininger, Bruno; Gerilowski, Konstantin; Krautwurst, Sven; Buchwitz, Michael; Burrows, John P.; Lindemann, Carsten; Ruhtz, Thomas; Schüttemeyer, Dirk; Bovensmann, Heinrich

2018-02-01

Reliable techniques to infer greenhouse gas emission rates from localised sources require accurate measurement and inversion approaches. In this study airborne remote sensing observations of CO2 by the MAMAP instrument and airborne in situ measurements are used to infer emission estimates of carbon dioxide released from a cluster of coal-fired power plants. The study area is complex due to sources being located in close proximity and overlapping associated carbon dioxide plumes. For the analysis of in situ data, a mass balance approach is described and applied, whereas for the remote sensing observations an inverse Gaussian plume model is used in addition to a mass balance technique. A comparison between methods shows that results for all methods agree within 10 % or better with uncertainties of 10 to 30 % for cases in which in situ measurements were made for the complete vertical plume extent. The computed emissions for individual power plants are in agreement with results derived from emission factors and energy production data for the time of the overflight.

An in situ FTIR step-scan photoacoustic investigation of kerogen and minerals in oil shale.

Science.gov (United States)

Alstadt, Kristin N; Katti, Dinesh R; Katti, Kalpana S

2012-04-01

Step-scan photoacoustic infrared spectroscopy experiments were performed on Green River oil shale samples obtained from the Piceance Basin located in Colorado, USA. We have investigated the molecular nature of light and dark colored areas of the oil shale core using FTIR photoacoustic step-scan spectroscopy. This technique provided us with the means to analyze the oil shale in its original in situ form with the kerogen-mineral interactions intact. All vibrational bands characteristic of kerogen were found in the dark and light colored oil shale samples confirming that kerogen is present throughout the depth of the core. Depth profiling experiments indicated that there are changes between layers in the oil shale molecular structure at a length scale of micron. Comparisons of spectra from the light and dark colored oil shale core samples suggest that the light colored regions have high kerogen content, with spectra similar to that from isolated kerogen, whereas, the dark colored areas contain more mineral components which include clay minerals, dolomite, calcite, and pyrite. The mineral components of the oil shale are important in understanding how the kerogen is "trapped" in the oil shale. Comparing in situ kerogen spectra with spectra from isolated kerogen indicate significant band shifts suggesting important nonbonded molecular interactions between the kerogen and minerals. Copyright © 2011 Elsevier B.V. All rights reserved.

Experimental evidence for carbonate precipitation and CO 2 degassing during sea ice formation

Science.gov (United States)

Papadimitriou, S.; Kennedy, H.; Kattner, G.; Dieckmann, G. S.; Thomas, D. N.

2004-04-01

Chemical and stable carbon isotopic modifications during the freezing of artificial seawater were measured in four 4 m 3 tank incubations. Three of the four incubations were inoculated with a nonaxenic Antarctic diatom culture. The 18 days of freezing resulted in 25 to 27 cm thick ice sheets overlying the residual seawater. The ice phase was characterized by a decrease in temperature from -1.9 to -2.2°C in the under-ice seawater down to -6.7°C in the upper 4 cm of the ice sheet, with a concurrent increase in the salinity of the under-ice seawater and brine inclusions of the ice sheet as a result of physical concentration of major dissolved salts by expulsion from the solid ice matrix. Measurements of pH, total dissolved inorganic carbon (C T) and its stable isotopic composition (δ 13C T) all exhibited changes, which suggest minimal effect by biological activity during the experiment. A systematic drop in pH and salinity-normalized C T by up to 0.37 pH SWS units and 376 μmol C kg -1 respectively at the lowest temperature and highest salinity part of the ice sheet were coupled with an equally systematic 13C enrichment of the C T. Calculations based on the direct pH and C T measurements indicated a steady increase in the in situ concentration of dissolved carbon dioxide (CO 2(aq)) with time and increasing salinity within the ice sheet, partly due to changes in the dissociation constants of carbonic acid in the low temperature-high salinity range within sea ice. The combined effects of temperature and salinity on the solubility of CO 2 over the range of conditions encountered during this study was a slight net decrease in the equilibrium CO 2(aq) concentration as a result of the salting-out overriding the increase in solubility with decreasing temperature. Hence, the increase in the in situ CO 2(aq) concentration lead to saturation or supersaturation of the brine inclusions in the ice sheet with respect to atmospheric pCO 2 (≈3.5 × 10 -4 atm). When all physico

[In situ diffuse reflectance FTIR spectroscopy study of CO adsorption on Ni2P/mesoporous molecule sieve catalysts].

Science.gov (United States)

Liu, Qian-qian; Ji, Sheng-fu; Wu, Ping-yi; Hu, Lin-hua; Huang, Xiao-fan; Zhu, Ji-qin; Li, Cheng-yue

2009-05-01

Abstract The supported nickel phosphate precursors were prepared by incipient wetness impregnation using nickel nitrate as nickel source, diammonium hydrogen phosphate as phosphorus source, and MCM-41, MCM-48, SBA-15 and SBA-16 as supports, respectively. Then, the supported Ni2 P catalysts were prepared by temperature-programmed reduction in flowing Hz from their nickel phosphate precursors. The in situ diffuse reflectance FTIR spectroscopy (DRIFTS) analysis with the probe molecule CO was carried out to characterize the surface properties. The results indicated that there were significant differences in the spectral features of the samples. The upsilon(CO) absorbances observed for adsorbed CO on mesoporous molecule sieve was attributed to weak physical adsorption. There are four different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2 P/MCM-41 catalyst with the following assignments: (1) the formation of Ni(CO)4 at 2055 cm(-1). (2) CO terminally bonded to cus Ni(delta+) (0CO terminally bonded to Ni+ sites at 2127 cm(-1). (4) CO terminally bonded to P and form P==C==O between 2198 and 2202 cm(-1). There are two different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2P/MCM-48, Ni2P/ SBA-15 and Ni2P/SBA-16 catalysts. The absorbance observed at 2051-2055 cm(-1) for CO adsorption on Ni2P/MCM-48, Ni2P/SBA-15 and Ni2P/SBA-16 catalysts is due to the formation of Ni(CO)4 species. The other upsilon absorbances observed at 2093-2096 cm(-1) was attributed to CO terminally bonded to cus Ni(delta+) (0

CO_2 valorization - Part. 2: chemical transformation ways

International Nuclear Information System (INIS)

Dumergues, Laurent

2016-01-01

Carbon dioxide (CO_2) can be used in many ways as a raw material or chemical reagent. The chemical conversion of CO_2 used as a feedstock is achievable by different techniques: mineralization, organic synthesis, hydrogenation, dry reforming, electrolysis, thermolysis, etc. The products obtained have applications as energy products, chemicals, building materials, etc. Choosing an appropriate CO_2 reuse technology will depend on technical and economic requirements (such as the CO_2 purity needed, technological maturity, cost-effectiveness, etc.) and also environmental and social criteria

Seasonal dynamics of permafrost carbon emissions: A passive, quasi-continuous 14CO2 sampler

Science.gov (United States)

Pedron, S.; Xu, X.; Walker, J. C.; Welker, J. M.; Klein, E. S.; Euskirchen, E. S.; Czimczik, C. I.

2017-12-01

Millennia of carbon (C) fixation by tundra vegetation, coupled with low rates of C mineralization by soil microorganisms and preservation in permafrost, have allowed Arctic soils to accumulate vast quantities of organic C (1672 Pg C total). Today, the Arctic is rapidly warming (0.48oC decade-1) and widespread degradation of permafrost may subject permafrost C to microbial mineralization and fluxes to the atmosphere, accelerating climate change. Loss of permafrost C can be quantified in situ by measuring the radiocarbon (14C) content of soil and ecosystem respiration, because permafrost C is older (depleted in 14C) than current plant products and soil C cycling operates on timescales of years to centuries. Here, we use 14C analysis of CO2 respired from graminoid tundra in Arctic Alaska to 1) apportion how plant and microbial respiration contribute to ecosystem respiration in spring, summer, and fall, and 2) elucidate the C sources of microbial respiration throughout the year. We used a novel, passive sampling system, capable of trapping diffusive CO2 throughout the active layer of tussock sedge tundra (n=4, from mineral soil to air) over periods of 2 days to 3 weeks in June 2017. CO2 was collected into various sizes of canisters, ranging from 0.5-32 L, and analyzed for its 14C content at UC Irvine's KCCAMS laboratory. To evaluate the system's efficiency, and quantify the temporal and spatial variability of ecosystem respiration sources, we co-deployed 3 Vaisala Carbocap [CO2] and temperature probes, and traditional chambers (n=6) and gas wells (n=10) for sampling of ecosystem- and soil-respired 14CO2 over 15 min-24 hours. A comparison of traditional methods with our new sampler indicates that the system accurately sampled the expected [CO2] depth gradient. The CO2 sampling rate was positively correlated to soil [CO2] (R2=0.963), equivalent to 1.4*10-3±1.6*10-3 mg C/L/month/ppm (n=8). Gas well and probe concentrations were of the same order of magnitude on the same

Projecting Soil Feedbacks to Atmospheric CO2 Following Erosion and Deposition on Centennial Timescales in Two Contrasting Forests: A Study of Critical Zone-Atmosphere Exchange

Science.gov (United States)

Billings, S. A.; Richter, D., Jr.; Ziegler, S. E.; Prestegaard, K. L.

2016-12-01

For almost 20 y there has been a growing recognition that erosion and associated lateral movement of SOC does not necessarily result in a net CO2 source from terrestrial sources to the atmosphere. Eroded SOC may undergo mineralization to CO2 at a more rapid pace than it would have in situ, but the eroding ecosystem continues to generate SOC at a potentially modified rate, and the eroding profile may also experience changing SOC mineralization rates. No one knows how these process rates may change upon erosion. Years ago, we introduced a model that computes the influence of erosion on biosphere-atmosphere CO2 exchange for any profile of interest. The model permits the user to test how assumptions of changing SOC production and mineralization can influence the degree to which erosion induces a net CO2 sink or source. Here we present an analogous model depicting how deposition of eroded SOC also can result in altered biosphere-atmosphere CO2 exchange. We employ both models to investigate how erosion and deposition in two contrasting forested regions may influence regional C budgets. Runoff-induced erosion in a boreal forest occurs at low rates, but removes C-rich, organic material; anthropogenically-enhanced erosion in a warm temperate forest removed both O- and mineral-rich A-horizons. Model runs (100 y) suggest that even though the great volume of mineral soil eroded from the temperate forest was relatively low-SOC, high erosion rates prompted greater potential for erosion to serve as a net CO2 sink compared to the boreal forest where C-rich material was lost but erosion rates remained low. The models further suggest that changes in SOC production and mineralization at eroding sites in both forest types are a greater influence on CO2 source or sink strength than analogous changes at depositional sites. The fate of eroded material and the influence of erosion and deposition on SOC dynamics remain knowledge gaps critical for projecting atmospheric CO2.

In Situ Spectroscopy and Mechanistic Insights into CO Oxidation on Transition-Metal-Substituted Ceria Nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Elias, Joseph S.; Stoerzinger, Kelsey A.; Hong, Wesley T.; Risch, Marcel; Giordano, Livia [Dipartimento; Mansour, Azzam N. [Naval; Shao-Horn, Yang

2017-09-12

Herein we investigate the reaction intermediates formed during CO oxidation on copper-substituted ceria nanoparticles (Cu0.1Ce0.9O2–x) by means of in situ spectroscopic techniques and identify an activity descriptor that rationalizes a trend with other metal substitutes (M0.1Ce0.9O2–x, M = Mn, Fe, Co, Ni). In situ X-ray absorption spectroscopy (XAS) performed under catalytic conditions demonstrates that O2– transfer occurs at dispersed copper centers, which are redox active during catalysis. In situ XAS reveals a dramatic reduction at the copper centers that is fully reversible under catalytic conditions, which rationalizes the high catalytic activity of Cu0.1Ce0.9O2–x. Ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) show that CO can be oxidized to CO32– in the absence of O2. We find that CO32– desorbs as CO2 only under oxygen-rich conditions when the oxygen vacancy is filled by the dissociative adsorption of O2. These data, along with kinetic analyses, lend support to a mechanism in which the breaking of copper–oxygen bonds is rate-determining under oxygen-rich conditions, while refilling the resulting oxygen vacancy is rate-determining under oxygen-lean conditions. On the basis of these observations and density functional calculations, we introduce the computed oxygen vacancy formation energy (Evac) as an activity descriptor for substituted ceria materials and demonstrate that Evac successfully rationalizes the trend in the activities of M0.1Ce0.9O2–x catalysts that spans three orders of magnitude. The applicability of Evac as a useful design descriptor is demonstrated by the catalytic performance of the ternary oxide Cu0.1La0.1Ce0.8O2–x, which has an apparent activation energy rivaling those of state-of-the-art Au/TiO2 materials. Thus, we suggest that cost-effective catalysts for CO oxidation can be rationally designed by judicious choice of substituting

Evaluation of the Consistency among In Situ and Remote Sensing Measurements of CO2 over North America using the CarbonTracker-Lagrange Regional Inverse Modeling Framework

Science.gov (United States)

Andrews, A. E.; Trudeau, M.; Hu, L.; Thoning, K. W.; Shiga, Y. P.; Michalak, A. M.; Benmergui, J. S.; Mountain, M. E.; Nehrkorn, T.; O'Dell, C.; Jacobson, A. R.; Miller, J.; Sweeney, C.; Chen, H.; Ploeger, F.; Tans, P. P.

2017-12-01

CarbonTracker-Lagrange (CT-L) is a regional inverse modeling system for estimating CO2 fluxes with rigorous uncertainty quantification. CT-L uses footprints from the Stochastic Time-Inverted Lagrangian Transport (STILT) model driven by high-resolution (10 to 30 km) meteorological fields from the Weather Research and Forecasting (WRF) model. We have computed a library of footprints corresponding to in situ and remote sensing measurements of CO2 over North America for 2007-2015. GOSAT and OCO-2 XCO2 retrievals are simulated using a suite of CT-L terrestrial ecosystem flux estimates that have been optimized with respect to in situ atmospheric CO2 measurements along with fossil fuel fluxes from emissions inventories. A vertical profile of STILT-WRF footprints was constructed corresponding to each simulated satellite retrieval, and CO2 profiles are generated by convolving the footprints with fluxes and attaching initial values advected from the domain boundaries. The stratospheric contribution to XCO2 has been estimated using 4-dimensional CO2 fields from the NOAA CarbonTracker model (version CT2016) and from the Chemical Lagrangian Model of the Stratosphere (CLaMS), after scaling the model fields to match data from the NOAA AirCore surface-to-stratosphere air sampling system. Tropospheric lateral boundary conditions are from CT2016 and from an empirical boundary value product derived from aircraft and marine boundary layer data. The averaging kernel and a priori CO2 profile are taken into account for direct comparisons with retrievals. We have focused on North America due to the relatively dense in situ measurements available with the aim of developing strategies for combined assimilation of in situ and remote sensing data. We will consider the extent to which interannual variability in terrestrial fluxes is manifest in the real and simulated satellite retrievals, and we will investigate possible systematic biases in the satellite retrievals and in the model.

The effect of elevated CO2 and temperature on nutrient uptake by plants grown in basaltic soil

Science.gov (United States)

Villasenor Iribe, E.; Dontsova, K.; Juarez, S.; Le Galliard, J. F.; Chollet, S.; Llavata, M.; Massol, F.; Barré, P.; Gelabert, A.; Daval, D.; Troch, P.; Barron-Gafford, G.; Van Haren, J. L. M.; Ferrière, R.

2017-12-01

Mineral weathering is an important process in soil formation. The interactions between the hydrologic, geologic and atmospheric cycles often determine the rate at which weathering occurs. Elements and nutrients weathered from the soil by water can be removed from soils in the runoff and seepage, but they can also remain in situ as newly precipitated secondary minerals or in biomass as a result of plant uptake. Here we present data from an experiment that was conducted at the controlled environment facility, Ecotron Ile-de-France (Saint-Pierre-les-Nemours, France) that studied mineral weathering and plant growth in granular basaltic material with high glass content that is being used to simulate soil in large scale Biosphere 2 Landscape Evolution Observatory (LEO) project. The experiment used 3 plant types: velvet mesquite (Prosopis velutina), green spangletop (Leptochloa dubia), and alfalfa (Medicago sativa), which were grown under varying temperature and CO2 conditions. We hypothesized that plants grown under warmer, higher CO2 conditions would have larger nutrient concentrations as more mineral weathering would occur. Results of plant digestions and analysis showed that plant concentrations of lithogenic elements were significantly influenced by the plant type and were different between above- and below-ground parts of the plant. Temperature and CO2 treatment effects were less pronounced, but we observed significant temperature effect on plant uptake. A number of major and trace elements showed increase in concentration with increase in temperature at elevated atmospheric CO2. Effect was observed both in the shoots and in the roots, but more significant differences were observed in the shoots. Results presented here indicate that climate change would have strong effect on plant uptake and mobility of weathered elements during soil formation and give further evidence of interactions between abiotic and biological processes in terrestrial ecosystems.

Modeling Silicate Weathering for Elevated CO2 and Temperature

Science.gov (United States)

Bolton, E. W.

2016-12-01

A reactive transport model (RTM) is used to assess CO2 drawdown by silicate weathering over a wide range of temperature, pCO2, and infiltration rates for basalts and granites. Although RTM's have been used extensively to model weathering of basalts and granites for present-day conditions, we extend such modeling to higher CO2 that could have existed during the Archean and Proterozoic. We also consider a wide range of surface temperatures and infiltration rates. We consider several model basalt and granite compositions. We normally impose CO2 in equilibrium with the various atmospheric ranges modeled and CO2 is delivered to the weathering zone by aqueous transport. We also consider models with fixed CO2 (aq) throughout the weathering zone as could occur in soils with partial water saturation or with plant respiration, which can strongly influence pH and mineral dissolution rates. For the modeling, we use Kinflow: a model developed at Yale that includes mineral dissolution and precipitation under kinetic control, aqueous speciation, surface erosion, dynamic porosity, permeability, and mineral surface areas via sub-grid-scale grain models, and exchange of volatiles at the surface. Most of the modeling is done in 1D, but some comparisons to 2D domains with heterogeneous permeability are made. We find that when CO2 is fixed only at the surface, the pH tends toward higher values for basalts than granites, in large part due to the presence of more divalent than monovalent cations in the primary minerals, tending to decrease rates of mineral dissolution. Weathering rates increase (as expected) with increasing CO2 and temperature. This modeling is done with the support of the Virtual Planetary Laboratory.

Estimation of the efficiency of hydrocarbon mineralization in soil by measuring CO2-emission and variations in the isotope composition of carbon dioxide

Science.gov (United States)

Dubrovskaya, Ekaterina; Turkovskaya, Olga

2010-05-01

Estimation of the efficiency of hydrocarbon mineralization in soil by measuring CO2-emission and variations in the isotope composition of carbon dioxide E. Dubrovskaya1, O. Turkovskaya1, A. Tiunov2, N. Pozdnyakova1, A. Muratova1 1 - Institute of Biochemistry and Physiology of Plants and Microorganisms, RAS, Saratov, 2 - A.N. Severtsov Institute of Ecology and Evolution, RAS, Moscow, Russian Federation Hydrocarbon mineralization in soil undergoing phytoremediation was investigated in a laboratory experiment by estimating the variation in the 13С/12С ratio in the respired СО2. Hexadecane (HD) was used as a model hydrocarbon pollutant. The polluted soil was planted with winter rye (Secale cereale) inoculated with Azospirillum brasilense strain SR80, which combines the abilities to promote plant growth and to degrade oil hydrocarbon. Each vegetated treatment was accompanied with a corresponding nonvegetated one, and uncontaminated treatments were used as controls. Emission of carbon dioxide, its isotopic composition, and the residual concentration of HD in the soil were examined after two and four weeks. At the beginning of the experiment, the CO2-emission level was higher in the uncontaminated than in the contaminated soil. After two weeks, the quantity of emitted carbon dioxide decreased by about three times and did not change significantly in all uncontaminated treatments. The presence of HD in the soil initially increased CO2 emission, but later the respiration was reduced. During the first two weeks, nonvegetated soil had the highest CO2-emission level. Subsequently, the maximum increase in respiration was recorded in the vegetated contaminated treatments. The isotope composition of plant material determines the isotope composition of soil. The soil used in our experiment had an isotopic signature typical of soils formed by C3 plants (δ13C,-22.4‰). Generally, there was no significant fractionation of the carbon isotopes of the substrates metabolized by the

SERDP ER-1421 Abiotic and Biotic Mechanisms Controlling In Situ Remediation of NDMA: Final Report

Energy Technology Data Exchange (ETDEWEB)

Szecsody, James E.; McKinley, James P.; Crocker, Fiona H.; Breshears, Andrew T.; Devary, Brooks J.; Fredrickson, Herbert L.; Thompson, Karen T.

2009-09-30

This laboratory-scale project was initiated to investigate in situ abiotic/biotic mineralization of NDMA. Under iron-reducing conditions, aquifer sediments showed rapid abiotic NDMA degradation to dimethylamine (DMA), nitrate, formate, and finally, CO2. These are the first reported experiments of abiotic NDMA mineralization. The NDMA reactivity of these different iron phases showed that adsorbed ferrous iron was the dominant reactive phase that promoted NDMA reduction, and other ferrous phases present (siderite, iron sulfide, magnetite, structural ferrous iron in 2:1 clays) did not promote NDMA degradation. In contrast, oxic sediments that were biostimulated with propane promoted biomineralization of NDMA by a cometabolic monooxygenase enzyme process. Other monooxygenase enzyme processes were not stimulated with methane or toluene additions, and acetylene addition did not block mineralization. Although NDMA mineralization extent was the highest in oxic, biostimulated sediments (30 to 82%, compared to 10 to 26% for abiotic mineralization in reduced sediments), large 1-D column studies (high sediment/water ratio of aquifers) showed 5.6 times higher NDMA mineralization rates in reduced sediment (half-life 410 ± 147 h) than oxic biomineralization (half life 2293 ± 1866 h). Sequential reduced/oxic biostimulated sediment mineralization (half-life 3180 ± 1094 h) was also inefficient compared to reduced sediment. These promising laboratory-scale results for NDMA mineralization should be investigated at field scale. Future studies of NDMA remediation should focus on the comparison of this in situ abiotic NDMA mineralization (iron-reducing environments) to ex situ biomineralization, which has been shown successful in other studies.

Reactivity, structure and physical properties of SrCo{sub 2.5+{delta}} and La{sub 2}CoO{sub 4.0+{delta}}. In situ X-ray diffraction and neutrons study; Reactivite, structure et proprietes physiques de SrCoO{sub 2.5+{delta}} et La{sub 2}CoO{sub 4.0+{delta}}. Etude par diffraction des rayons X et des neutrons in situ

Energy Technology Data Exchange (ETDEWEB)

Le Toquin, R.

2003-11-15

This work was devoted to the study of the reactivity and more specifically the influence of the intercalated oxygen amount {delta} on the structure and physical properties of SrCoO{sub 2.5+{delta}} et La{sub 2}CoO{sub 4.0+{delta}} We controlled the oxidation level by means of reversible electrochemical red ox reaction at room temperature. Structural modifications, especially disorder, and electronic properties were studied for the first time on large orientated single crystal. In the SrCoO{sub 2.5+{delta}} system, after structural and electronic characterisation of the end phases, we studied the real structure of the brownmillerite SrCoO{sub 2.5} phase using single crystal. Moreover, we investigated structural and magnetic evolution upon red ox cycle using X-ray diffraction on 6 times twinned single crystal and in situ neutron powder diffraction. Two intermediate SrCoO{sub 2.75} and SrCoO{sub 2.82} phases have been observed. The reaction on single crystal has evidenced the evolution of domain structure. For the La{sub 2}CoO{sub 4+{delta}} system, we synthesised a large variety of single crystal with stoichiometry {delta} 0.0, 0.09, 0.12, 0.16, 0.20 and 0.25. Using single crystal X-ray and neutron diffraction, we showed a disorder-order transition of the apical and interstitial oxygen for the higher {delta} values. (author)

Capture, transport and storage of CO2

International Nuclear Information System (INIS)

De Boer, B.

2008-01-01

The emission of greenhouse gas CO2 in industrial processes and electricity production can be reduced on a large scale. Available techniques include post-combustion, pre-combustion, the oxy-fuel process, CO2 fixation in industrial processes and CO2 mineralization. In the Netherlands, plans for CO2 capture are not developing rapidly (CCS - carbon capture and storage). [mk] [nl

Radiocarbon application in dating 'complex' hot and cold CO{sub 2}-rich mineral water systems: A review of case studies ascribed to the northern Portugal

Energy Technology Data Exchange (ETDEWEB)

Carreira, Paula M. [Instituto Tecnologico e Nuclear, Departamento de Quimica, Estrada Nacional No 10, 2686-953 Sacavem (Portugal)], E-mail: carreira@itn.pt; Marques, Jose M.; Graca, Rui C.; Aires-Barros, Luis [Instituto Superior Tecnico, Laboratorio de Mineralogia e Petrologia, Av. Rovisco Pais, 1049-001 Lisboa (Portugal)

2008-10-15

The use of radioactive isotopes plays a very important role in dating groundwater, providing an apparent age of the systems in the framework of the aquifers conceptual modelling making available important features about the water fluxes, such as recharge, horizontal flow rates and discharge. In this paper, special emphasis has been put on isotopic constraints in the use of {delta}{sup 13}C and {sup 14}C content as a dating tool in some hot (76 deg. C) and cold (17 deg. C) CO{sub 2}-rich mineral waters discharging in the Vilarelho da Raia-Pedras Salgadas region (N-Portugal). The radiocarbon content determined in these CO{sub 2}-rich mineral waters ({sup 14}C activity from 4.3 up to 9.9 pmc) is incompatible with the systematic presence of {sup 3}H (from 1.7 to 7.9 TU). The {delta}{sup 13}C values of the studied CO{sub 2}-rich mineral waters indicate that the total C in the recharge waters is being masked by larger quantities of CO{sub 2} ({sup 14}C-free) introduced from deep-seated (upper mantle) sources. This paper demonstrates that a good knowledge of mineral water systems is essential to allow hydrologists to make sound conclusions on the use of C isotopic data in each particular situation.

Microbial electrolysis desalination and chemical-production cell for CO2 sequestration

KAUST Repository

Zhu, Xiuping

2014-05-01

Mineral carbonation can be used for CO2 sequestration, but the reaction rate is slow. In order to accelerate mineral carbonation, acid generated in a microbial electrolysis desalination and chemical-production cell (MEDCC) was examined to dissolve natural minerals rich in magnesium/calcium silicates (serpentine), and the alkali generated by the same process was used to absorb CO2 and precipitate magnesium/calcium carbonates. The concentrations of Mg2+ and Ca2+ dissolved from serpentine increased 20 and 145 times by using the acid solution. Under optimal conditions, 24mg of CO2 was absorbed into the alkaline solution and 13mg of CO2 was precipitated as magnesium/calcium carbonates over a fed-batch cycle (24h). Additionally, the MEDCC removed 94% of the COD (initially 822mg/L) and achieved 22% desalination (initially 35g/L NaCl). These results demonstrate the viability of this process for effective CO2 sequestration using renewable organic matter and natural minerals. © 2014 Elsevier Ltd.

Dolomite decomposition under CO2

International Nuclear Information System (INIS)

Guerfa, F.; Bensouici, F.; Barama, S.E.; Harabi, A.; Achour, S.

2004-01-01

Full text.Dolomite (MgCa (CO 3 ) 2 is one of the most abundant mineral species on the surface of the planet, it occurs in sedimentary rocks. MgO, CaO and Doloma (Phase mixture of MgO and CaO, obtained from the mineral dolomite) based materials are attractive steel-making refractories because of their potential cost effectiveness and world wide abundance more recently, MgO is also used as protective layers in plasma screen manufacture ceel. The crystal structure of dolomite was determined as rhombohedral carbonates, they are layers of Mg +2 and layers of Ca +2 ions. It dissociates depending on the temperature variations according to the following reactions: MgCa (CO 3 ) 2 → MgO + CaO + 2CO 2 .....MgCa (CO 3 ) 2 → MgO + Ca + CaCO 3 + CO 2 .....This latter reaction may be considered as a first step for MgO production. Differential thermal analysis (DTA) are used to control dolomite decomposition and the X-Ray Diffraction (XRD) was used to elucidate thermal decomposition of dolomite according to the reaction. That required samples were heated to specific temperature and holding times. The average particle size of used dolomite powders is 0.3 mm, as where, the heating temperature was 700 degree celsius, using various holding times (90 and 120 minutes). Under CO 2 dolomite decomposed directly to CaCO 3 accompanied by the formation of MgO, no evidence was offered for the MgO formation of either CaO or MgCO 3 , under air, simultaneous formation of CaCO 3 , CaO and accompanied dolomite decomposition

Comparison of the Wymark CO2 Reservoir with the Midale Beds at the Weyburn CO2 Injection Project

International Nuclear Information System (INIS)

Ryerson, F.; Johnson, J.

2010-01-01

The Devonian carbonates of the Duperow Formation on the western flank of the Williston Basin in southwest Saskatchewan contain natural accumulations of CO 2 , and may have done so for as long as 50 m.y. in the views of some investigations. These carbonate sediments are characterized by a succession of carbonate cycles capped by anhydrite-rich evaporites that are thought to act as seals to fluid migration. The Weyburn CO 2 injection site lies 400 km to the east in a series of Mississippian carbonates that were deposited in a similar depositional environment. That natural CO 2 can be stored long-term within carbonate strata has motivated the investigation of the Duperow rocks as a potential natural analogue to storage of anthropogenic CO 2 that may ultimately provide additional confidence for CO 2 sequestration in carbonate lithologies. For the Duperow strata to represent a legitimate analog for Midale injection and storage, the similarity in lithofacies, whole rock compositions, mineral compositions and porosity with the Midale Beds must be established. Previous workers have demonstrated the similarity of the lithofacies at both sites. Here we compare the whole rock compositions, mineralogy and mineral compositions. The major mineral phases at both locales are calcite, dolomite and anhydrite. In addition, accessory pyrite, fluorite and celestine are also observed. The distribution of porosity in the Midale Vuggy units is virtually identical to that of the Duperow Formation, but the Marly units of the Midale have significantly higher porosity. The Duperow Formation is topped by the Dinesmore evaporite that is particularly rich in anhydrite, and often contains authigenic K-feldspar. The chemistry of dolomite and calcite from the two localities also overlaps. Silicate minerals are in low abundance within the analyzed Duperow samples, < 3 wt% on a normative basis, with quartz the only phase identifiable in x-ray diffraction patterns. The Midale Beds contain

Cu(InGa)Se{sub 2} absorber formation by in-situ, low-temperature annealing of co-evaporated bilayer (InGa){sub 2}Se{sub 3}/CuSe precursors

Energy Technology Data Exchange (ETDEWEB)

Moon, Kyeongchan; Kim, Woo Kyoung, E-mail: wkim@ynu.ac.kr

2015-12-01

Chalcopyrite Cu(InGa)Se{sub 2} (CIGS) absorbers were fabricated by the formation of bilayer stacked glass/Mo/(InGa){sub 2}Se{sub 3}/CuSe precursors followed by in-situ thermal annealing at 450 °C for approximately 10 min in a vacuum evaporator. The material properties (e.g., crystal orientation, compositional depth profile, and overall composition) and device performance of the resulting CIGS absorbers were compared with those of the CIGS absorbers formed by conventional 1-stage and 3-stage CIGS formation processes at a similar temperature. X-ray diffraction confirmed that the 1-stage co-evaporation and in-situ annealing of the bilayer precursor produced a polycrystalline CIGS absorber without a specific texture, whereas the CIGS absorber formed by the 3-stage process showed a highly (220) preferred orientation. Secondary ion mass spectrometry revealed Ga accumulation at the bottom of CIGS formed by in-situ annealing of the bilayer precursors. The cell efficiency of the device with the CIGS absorber formed by the in-situ, low-temperature (450 °C) annealing of bilayer stacked glass/Mo/(InGa){sub 2}Se{sub 3}/CuSe precursors was comparable to that produced by the conventional 3-stage process at a similar temperature. - Highlights: • Annealing of (InGa){sub 2}Se{sub 3}/CuSe precursors was compared with coevaporation process. • In-situ annealing of (InGa){sub 2}Se{sub 3}/CuSe precursors at 450 °C produced about 9% solar cell. • Ga profile within Cu(InGa)Se{sub 2} depended on process profile during co-evaporation.

Mode-I Fracture Toughness Testing and Coupled Cohesive Zone Modeling at In Situ P, T, and Chemical (H2O-CO2-NaCl) Conditions

Science.gov (United States)

Dewers, T. A.; Choens, R. C., II; Regueiro, R. A.; Eichhubl, P.; Bryan, C. R.; Rinehart, A. J.; Su, J. C.; Heath, J. E.

2017-12-01

Propagation of mode I cracks is fundamental to subsurface engineering endeavors, but the majority of fracture toughness measurements are performed at ambient conditions. A novel testing apparatus was used to quantify the relationship between supercritical carbon dioxide (scCO2), water vapor, and fracture toughness in analogs for reservoir rock and caprock lithologies at temperature and pressure conditions relevant to geologic carbon storage. Samples of Boise Sandstone and Marcellus Shale were subject to fracture propagation via a novel short rod fracture toughness tester composed of titanium and Hastelloy® and designed to fit inside a pressure vessel. The tester is controlled by a hydraulically-driven ram and instrumented with a LVDT to monitor displacement. We measure fracture toughness under conditions of dry supercritical CO2 (scCO2), scCO2-saturated brine, and scCO2 with varying water content ( 25%, 90%, and 100% humidity) at 13.8 MPa and 70oC. Water film development as a function of humidity is determined in situ during the experiments with a quartz crystal microbalance. Two orientations of the Marcellus are included in the testing matrix. Dry CO2 has a negligible to slightly strengthening effect compared to a control, however hydrous scCO2 can decrease the fracture toughness, and the effect increases with increasing humidity, which likely is due to capillary condensation of reactive water films at nascent crack tips and associated subcritical weakening. A 2D poromechanical finite element model with cohesive surface elements (CSEs) and a chemo-plasticity phenomenology is being used to describe the chemical weakening/softening effects observed in the testing. The reductions in fracture toughness seen in this study could be important in considerations of borehole stability, in situ stress measurements, changes in fracture gradient, and reservoir caprock integrity during CO2 injection and storage. Sandia National Laboratories is a multimission laboratory managed

History of CO/sub 2/

Energy Technology Data Exchange (ETDEWEB)

Degens, E T

1979-01-01

Upon arrival on earth, the reduced carbon pool split into a series of compartments: core, mantle, crust, hydrosphere, atmosphere, and biosphere. This distribution pattern is caused by the ability of carbon to adjust structurally to a wide range of pressure and temperature, and to form simple and complex molecules with oxygen, hydrogen and nitrogen. Transformation also involved oxidation of carbon to CO/sub 2/ which is mediated at depth by minerals, such as magnetite, and by water vapor above critical temperature. Guided by mineral-organic interactions, simple carbon compounds evolved in near surface environments towards physiologically interesting biochemicals. Life, as an autocatalytic system, is considered an outgrowth of such a development. This article discusses environmental parameters that control the CO/sub 2/ system, past and present. Mantle and crustal evolution is the dynamo recharging the CO/sub 2/ in sea and air; the present rate of CO/sub 2/ release from the magma is 0.05 x 10/sup 15/ g C per year. Due to the enormous buffer capacity of the chemical system ocean, such rates are too small to seriously effect the level of CO/sub 2/ in our atmosphere. In the light of geological field data and stable isotope work, it is concluded that the CO/sub 2/ content in the atmosphere has remained fairly uniform since early Precambrian time; CO/sub 2/ should thus have had little impact on paleoclimate. In contrast, the massive discharge of man-made CO/sub 2/ into our atmosphere may have serious consequences for climate, environment and society in the years to come.

Soil N mineralization profiles of co-existing woody vegetation islands at the alpine tree line

Czech Academy of Sciences Publication Activity Database

Wang, L.; Godbold, Douglas

2017-01-01

Roč. 136, 5-6 (2017), s. 881-892 ISSN 1612-4669 R&D Projects: GA MŠk(CZ) LO1415 Institutional support: RVO:67179843 Keywords : Tree line * Soil N mineralization * in situ field incubation * Soil N availability * Resin capsule * Woody vegetation islands Subject RIV: DF - Soil Science OBOR OECD: Soil science Impact factor: 2.017, year: 2016

Sustained effects of atmospheric [CO2] and nitrogen availability on forest soil CO2 efflux

Science.gov (United States)

A. Christopher Oishi; Sari Palmroth; Kurt H. Johnsen; Heather R. McCarthy; Ram. Oren

2014-01-01

Soil CO2 efflux (Fsoil) is the largest source of carbon from forests and reflects primary productivity as well as how carbon is allocated within forest ecosystems. Through early stages of stand development, both elevated [CO2] and availability of soil nitrogen (N; sum of mineralization, deposition, and fixation) have been shown to increase gross primary productivity,...

Bench top and portable mineral analysers, borehole core analysers and in situ borehole logging

International Nuclear Information System (INIS)

Howarth, W.J.; Watt, J.S.

1982-01-01

Bench top and portable mineral analysers are usually based on balanced filter techniques using scintillation detectors or on low resolution proportional detectors. The application of radioisotope x-ray techniques to in situ borehole logging is increasing, and is particularly suited for logging for tin and higher atomic number elements

The Li–CO2 battery: a novel method for CO2 capture and utilization

KAUST Repository

Xu, Shaomao

2013-01-01

We report a novel primary Li-CO2 battery that consumes pure CO2 gas as its cathode. The battery exhibits a high discharge capacity of around 2500 mA h g-1 at moderate temperatures. At 100 °C the discharge capacity is close to 1000% higher than that at 40 °C, and the temperature dependence is significantly weaker for higher surface area carbon cathodes. Ex-situ FTIR and XRD analyses convincingly show that lithium carbonate (Li2CO3) is the main component of the discharge product. The feasibility of similar primary metal-CO2 batteries based on earth abundant metal anodes, such as Al and Mg, is demonstrated. The metal-CO2 battery platform provides a novel approach for simultaneous capturing of CO2 emissions and producing electrical energy. © 2013 The Royal Society of Chemistry.

Evaluation of a cavity ring-down spectrometer for in situ observations of 13CO2

Directory of Open Access Journals (Sweden)

D. E. J. Worthy

2013-02-01

Full Text Available With the emergence of wide-spread application of new optical techniques to monitor δ13C in atmospheric CO2 there is a growing need to ensure well-calibrated measurements. We characterized one commonly available instrument, a cavity ring-down spectrometer (CRDS system used for continuous in situ monitoring of atmospheric 13CO2. We found no dependency of δ13C on the CO2 concentration in the range of 303–437 ppm. We designed a calibration scheme according to the diagnosed instrumental drifts and established a quality assurance protocol. We find that the repeatability (1-σ of measurements is 0.25‰ for 10 min and 0.15‰ for 20 min integrated averages, respectively. Due to a spectral overlap, our instrument displays a cross-sensitivity to CH4 of 0.42 ± 0.024‰ ppm−1. Our ongoing target measurements yield standard deviations of δ13C from 0.22‰ to 0.28‰ for 10 min averages. We furthermore estimate the reproducibility of our system for ambient air samples from weekly measurements of a long-term target gas to be 0.18‰. We find only a minuscule offset of 0.002 ± 0.025‰ between the CRDS and Environment Canada's isotope ratio mass spectrometer (IRMS results for four target gases used over the course of one year.

In situ Low-temperature Pair Distribution Function (PDF) Analysis of CH4 and CO2 Hydrates

Science.gov (United States)

Cladek, B.; Everett, M.; McDonnell, M.; Tucker, M.; Keffer, D.; Rawn, C.

2017-12-01

Gas hydrates occur in ocean floor and sub-surface permafrost deposits and are stable at moderate to high pressures and low temperatures. They are a clathrate structure composed of hydrogen bonded water cages that accommodate a wide variety of guest molecules. CO2 and CH4 hydrates both crystallize as the cubic sI hydrate and can form a solid solution. Natural gas hydrates are interesting as a potential methane source and for CO2 sequestration. Long-range diffraction studies on gas hydrates give valuable structural information but do not provide a detailed understanding of the disordered gas molecule interactions with the host lattice. In-situ low temperature total scattering experiments combined with pair distribution function (PDF) analysis are used to investigate the gas molecule motions and guest-cage interactions. CO2 and methane hydrates exhibit different decomposition behavior, and CO2 hydrate has a smaller lattice parameter despite it being a relatively larger molecule. Total scattering studies characterizing both the short- and long-range order simultaneously help to elucidate the structural source of these phenomena. Low temperature neutron total scattering data were collected using the Nanoscale Ordered MAterials Diffractometer (NOMAD) beamline at the Spallation Neutron Source (SNS) on CO2 and CH4 hydrates synthesized with D2O. Guest molecule motion within cages and interactions between gases and cages are investigated through the hydrate stability and decomposition regions. Data were collected from 2-80 K at a pressure of 55 mbar on CO2 and CH4 hydrates, and from 80-270 K at 25 bar on CH4 hydrate. The hydrate systems were modeled with classical molecular dynamic (MD) simulations to provide an analysis of the total energy into guest-guest, guest-host and host-host contributions. Combined Reitveld and Reverse Monte Carlo (RMC) structure refinement were used to fit models of the data. This combined modeling and simulation characterizes the effects of CO2 and

Measurements of ²²²Rn, ²²⁰Rn, and CO₂ Emissions in Natural CO₂ Fields in Wyoming: MVA Techniques for Determining Gas Transport and Caprock Integrity

Energy Technology Data Exchange (ETDEWEB)

Kaszuba, John [Univ. of Wyoming, Laramie, WY (United States); Sims, Kenneth [Univ. of Wyoming, Laramie, WY (United States)

2014-09-30

correction factors for measuring radon in CO₂-rich environments. A graduate student earned a Master of Science degree for this part of the field program; she is currently employed with a geologic consulting company. Measurement of radon in springs has improved significantly since the field program first began; however, in situ measurement of ²²²Rn and particularly ²²⁰Rn in springs is problematic. Future refinements include simultaneous salinity measurements and systematic corrections, or adjustments to the partition coefficient as needed for more accurate radon concentration determination. A graduate student earned a Master of Science degree for this part of the field program; he is currently employed with a geologic consulting company. Both graduate students are poised to begin work in a CCS technology area. Laboratory experiments evaluated important process-level fundamentals that effect measurements of radon and CO₂. Laboratory tests established that fine-grained source minerals yield higher radon emissivity compared to coarser-sized source minerals; subtleties in the dataset suggest that grain size alone is not fully representative of all the processes controlling the ability of radon to escape its mineral host. Emissivity for both ²²²Rn and 220Rn increases linearly with temperature due to reaction of rocks with water, consistent with faster diffusion and enhanced mineral dissolution at higher temperatures. The presence of CO₂ changes the relative importance of the factors that control release of radon. Emissivity for both ²²²Rn and ²²⁰Rn in CO₂-bearing experiments is greater at all temperatures compared to the experiments without CO₂, but emissivity does not increase as a simple function of temperature. Governing processes may include a balance between enhanced dissolution versus carbonate mineral formation in CO₂-rich waters.

Multiscale observations of CO2, 13CO2, and pollutants at Four Corners for emission verification and attribution

Science.gov (United States)

Lindenmaier, Rodica; Dubey, Manvendra K.; Henderson, Bradley G.; Butterfield, Zachary T.; Herman, Jay R.; Rahn, Thom; Lee, Sang-Hyun

2014-01-01

There is a pressing need to verify air pollutant and greenhouse gas emissions from anthropogenic fossil energy sources to enforce current and future regulations. We demonstrate the feasibility of using simultaneous remote sensing observations of column abundances of CO2, CO, and NO2 to inform and verify emission inventories. We report, to our knowledge, the first ever simultaneous column enhancements in CO2 (3–10 ppm) and NO2 (1–3 Dobson Units), and evidence of δ13CO2 depletion in an urban region with two large coal-fired power plants with distinct scrubbing technologies that have resulted in ∆NOx/∆CO2 emission ratios that differ by a factor of two. Ground-based total atmospheric column trace gas abundances change synchronously and correlate well with simultaneous in situ point measurements during plume interceptions. Emission ratios of ∆NOx/∆CO2 and ∆SO2/∆CO2 derived from in situ atmospheric observations agree with those reported by in-stack monitors. Forward simulations using in-stack emissions agree with remote column CO2 and NO2 plume observations after fine scale adjustments. Both observed and simulated column ∆NO2/∆CO2 ratios indicate that a large fraction (70–75%) of the region is polluted. We demonstrate that the column emission ratios of ∆NO2/∆CO2 can resolve changes from day-to-day variation in sources with distinct emission factors (clean and dirty power plants, urban, and fires). We apportion these sources by using NO2, SO2, and CO as signatures. Our high-frequency remote sensing observations of CO2 and coemitted pollutants offer promise for the verification of power plant emission factors and abatement technologies from ground and space. PMID:24843169

Experimental investigation of CO2-brine-rock interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers

Science.gov (United States)

Rosenbauer, R.J.; Koksalan, T.; Palandri, J.L.

2005-01-01

Deep-saline aquifers are potential repositories for excess CO2, currently being emitted to the atmosphere from anthropogenic activities, but the reactivity of supercritical CO2 with host aquifer fluids and formation minerals needs to be understood. Experiments reacting supercritical CO2 with natural and synthetic brines in the presence and absence of limestone and plagioclase-rich arkosic sandstone showed that the reaction of CO2-saturated brine with limestone results in compositional, mineralogical, and porosity changes in the aquifer fluid and rock that are dependent on initial brine composition, especially dissolved calcium and sulfate. Experiments reacting CO2-saturated, low-sulfate brine with limestone dissolved 10% of the original calcite and increased rock porosity by 2.6%. Experiments reacting high-sulfate brine with limestone, both in the presence and absence of supercritical CO2, were characterized by the precipitation of anhydrite, dolomitization of the limestone, and a final decrease in porosity of 4.5%. However, based on favorable initial porosity changes of about 15% due to the dissolution of calcite, the combination of CO2 co-injection with other mitigation strategies might help alleviate some of the well-bore scale and formation-plugging problems near the injection zone of a brine disposal well in Paradox Valley, Colorado, as well as provide a repository for CO2. Experiments showed that the solubility of CO2 is enhanced in brine in the presence of limestone by 9% at 25 ??C and 6% at 120 ??C and 200 bar relative to the brine itself. The solubility of CO2 is enhanced also in brine in the presence of arkosic sandstone by 5% at 120 ??C and 300 bar. The storage of CO 2 in limestone aquifers is limited to only ionic and hydraulic trapping. However, brine reacted with supercritical CO2 and arkose yielded fixation and sequestration of CO2 in carbonate mineral phases. Brine desiccation was observed in all experiments containing a discrete CO2 phase

Supercritical CO2 uptake by nonswelling phyllosilicates.

Science.gov (United States)

Wan, Jiamin; Tokunaga, Tetsu K; Ashby, Paul D; Kim, Yongman; Voltolini, Marco; Gilbert, Benjamin; DePaolo, Donald J

2018-01-30

Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2 , can increase CO 2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism. Copyright © 2018 the Author(s). Published by PNAS.

In situ synthesis of 3D CoS nanoflake/Ni(OH)_2 nanosheet nanocomposite structure as a candidate supercapacitor electrode

International Nuclear Information System (INIS)

Li, Songzhan; Wen, Jian; Chen, Tian; Xiong, Liangbin; Wang, Jianbo; Fang, Guojia

2016-01-01

A three-dimensional (3D) CoS/Ni(OH)_2 nanocomposite structure based on CoS nanoflakes and two-dimensional (2D) Ni(OH)_2 nanosheets were in situ synthesized on Ni foam by a whole hydrothermal reaction and electrodeposition process. The 3D CoS/Ni(OH)_2 nanocomposite structures demonstrate the combined advantages of a sustained cycle stability of CoS and high specific capacitance from Ni(OH)_2. The obtained CoS/Ni(OH)_2 nanocomposite structures on Ni foam can directly serve as a binder-free electrode for a supercapacitor. For the 3D CoS/Ni(OH)_2 nanocomposite electrode, the high specific capacitance is 1837 F g"−"1 at a scan rate of 1 mV s"−"1, which is obviously higher than both the bare CoS electrode and Ni(OH)_2 electrode. The galvanostatic charge and discharge measurements illustrate that the 3D CoS/Ni(OH)_2 nanocomposite electrode possesses excellent cycle stability, and it keeps a 95.8% retention of the initial capacity after 5000 cycles. Electrochemical impedance spectroscopy measurements also confirm that the 3D CoS/Ni(OH)_2 nanocomposite electrode has better electrochemical characteristics. These remarkable performances can be attributed to the unique 3D nanoporous structure of CoS/Ni(OH)_2 which leads to a large accessible surface area and a high stability during long-term operation. In addition, 2D Ni(OH)_2 nanosheets in 3D nanocomposite structures can afford rapid mass transport and a strong synergistic effect of CoS and Ni(OH)_2 as individual compositions contribute to the high performance of the nanocomposite structure electrode. These results may promote the design and implementation of nanocomposite structures in advanced supercapacitors. (paper)

Advanced mineral and lithological mapping using high spectral resolution TIR data from the active CO2 remote sensing system; CO2 laser wo mochiita kosupekutoru bunkaino netsusekigai remote sensing data no ganseki kobutsu shikibetsu eno oyo

Energy Technology Data Exchange (ETDEWEB)

Okada, K [Sumitomo Metal Mining Co. Ltd., Osaka (Japan); Hato, M [Earth Remote Sensing Data Analysis Center, Tokyo (Japan); Cudahy, T; Tapley, I

1997-05-27

A study was conducted on rock/mineral mapping technology for the metal ore deposit survey using MIRACO2LAS, an active type thermal infrared ray remote sensing system which was developed by CSIRO of Australia and is now the highest in spectral resolution in the world, and TIMS of NASA which is a passive type system. The area for the survey is the area of Olary/Broken Hill and Mt. Fitton of Australia. A good correlation is seen between the ground reflectance measured by MIRACO2LAS and the value measured by the chamber CO2 laser of rocks sampled at the above-mentioned area. In case that the width of spectral characteristics is below 300nm, the inspection ability by MIRACO2LAS`s high spectral resolution is more determined in mineral mapping as compared with TIMS which is large in band width. Minerals mapped using MIRACO2LAS are quartz, talc, amphibole, hornblende, garnet, supessartine, dolomite, magnesite, etc. 4 refs., 3 figs.

[Data processing and QA/QC of atmosphere CO2 and CH4 concentrations by a method of GC-FID in-situ measurement at Waliguan station].

Science.gov (United States)

Zhang, Fang; Zhou, Ling-Xi; Liu, Li-Xin; Fang, Shuang-Xi; Yao, Bo; Xu, Lin; Zhang, Xiao-Chun; Masarie, Kenneth A; Conway, Thomas J; Worthy, Douglas E J; Ernst, Michele

2010-10-01

To strengthen scientific management and sharing of greenhouse gas data obtained from atmospheric background stations in China, it is important to ensure the standardization of observations and establish the data treatment and quality control procedure so as to maintain consistency in atmospheric carbon dioxide (CO2) and methane (CH4) measurements from different background stations. An automated gas chromatographic system (Hewlett Packard 5890GC employing flame ionization detection) for in situ measurements of atmospheric CO2 and CH4 has been developed since 1994 at the China Global Atmosphere Watch Baseline Observatory at Mt. Waliguan, in Qinhai. In this study, processing and quality control flow of CO2 and CH4 data acquired by HP ChemStation are discussed in detail, including raw data acquisition, data merge, time series inspection, operator flag, principal investigator flag, and the comparison of the GC measurement with the flask method. Atmosphere CO2 and CH4 mixing ratios were separated as background and non-background data using a robust local regression method, approximately 72% and 44% observed values had been filtered as background data for CO2 and CH4, respectively. Comparison of the CO1 and CH, in situ data to the flask sampling data were in good agreement, the relative deviations are within +/- 0.5% for CO2 and for CH4. The data has been assimilated into global database (Globalview-CO2, Globalview-CH4), submitted to the World Data Centre for Greenhouse Gases (WDCGG), and applied to World Meteorological Organization (WMO) Greenhouse Gas Bulletin and assessment reports of the United Nations Intergovernmental Panel on Climate Change (IPCC).

2,4,6-Trinitrotoluene mineralization and bacterial production rates of natural microbial assemblages from coastal sediments

International Nuclear Information System (INIS)

Montgomery, Michael T.; Coffin, Richard B.; Boyd, Thomas J.; Smith, Joseph P.; Walker, Shelby E.; Osburn, Christopher L.

2011-01-01

The nitrogenous energetic constituent, 2,4,6-Trinitrotoluene (TNT), is widely reported to be resistant to bacterial mineralization (conversion to CO 2 ); however, these studies primarily involve bacterial isolates from freshwater where bacterial production is typically limited by phosphorus. This study involved six surveys of coastal waters adjacent to three biome types: temperate broadleaf, northern coniferous, and tropical. Capacity to catabolize and mineralize TNT ring carbon to CO 2 was a common feature of natural sediment assemblages from these coastal environments (ranging to 270+/-38 μg C kg -1 d -1 ). More importantly, these mineralization rates comprised a significant proportion of total heterotrophic production. The finding that most natural assemblages surveyed from these ecosystems can mineralize TNT ring carbon to CO 2 is consistent with recent reports that assemblage components can incorporate TNT ring carbon into bacterial biomass. These data counter the widely held contention that TNT is recalcitrant to bacterial catabolism of the ring carbon in natural environments. - Highlights: → TNT mineralization is a common feature of natural bacterial assemblages in coastal sediments. → TNT mineralization rates comprised a significant proportion of total heterotrophic production. → These data counter the widely held contention that TNT is recalcitrant to bacterial catabolism of the ring carbon in natural environments. - The capacity to mineralize TNT ring carbon to CO 2 is a common feature of natural bacterial assemblages in coastal sediment.

SOIL FLUXES OF CO2, CO, NO AND N2O FROM AN OLD-PASTURE AND FROM NATIVE SAVANNA IN BRAZIL

Science.gov (United States)

We compared fluxes of CO2, CO, NO and N2O, soil microbial biomass, and N-mineralization rates in a 20-year old Brachiaria pasture and a native cerrado area (savanna in Central Brazil). In order to assess the spatial variability of CO2 fluxes, we tested the relation between elect...

Varying response of the concentration and content of soybean seed mineral elements, carbohydrates, organic acids, amino acids, protein, and oil to phosphorus starvation and CO2 enrichment

Science.gov (United States)

A detailed investigation of the concentration (g-1 seed weight) and content (g plant-1) of seed mineral elements and metabolic profile under phosphorus (P) starvation at ambient (aCO2) and elevated carbon dioxide (eCO2) in soybean is limited. Soybean plants were grown in a controlled environment at ...

Comparison of Surface and Column Variations of CO2 Over Urban Areas for Future Active Remote CO2 Sensors

Science.gov (United States)

Choi, Yonghoon; Yang, Melissa; Kooi, Susan; Browell, Edward

2015-01-01

High resolution in-situ CO2 measurements were recorded onboard the NASA P-3B during the DISCOVER-AQ (Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality) Field Campaign, to investigate the ability of space-based observations to accurately assess near surface conditions related to air quality. This campaign includes, Washington DC/Baltimore, MD (July 2011), San Joaquin Valley, CA (January - February 2013), Houston, TX (September 2013), and Denver, CO (July-August 2014). Each of these campaigns consisted of missed approaches and approximately two hundred vertical soundings of CO2 within the lower troposphere (surface to about 5 km). In this study, surface (0 - 1 km) and column-averaged (0 - 3.5 km) CO2 mixing ratio values from the vertical soundings in the four geographically different urban areas are used to investigate the temporal and spatial variability of CO2 within the different urban atmospheric emission environments. Tracers such as CO, CH2O, NOx, and NMHCs are used to identify the source of CO2 variations in the urban sites. Additionally, we apply nominal CO2 column weighting functions for potential future active remote CO2 sensors operating in the 1.57-microns and 2.05-microns measurement regions to convert the in situ CO2 vertical mixing ratio profiles to variations in CO2 column optical depths, which is what the active remote sensors actually measure. Using statistics calculated from the optical depths at each urban site measured during the DISCOVER-AQ field campaign and for each nominal weighting function, we investigate the natural variability of CO2 columns in the lower troposphere; relate the CO2 column variability to the urban surface emissions; and show the measurement requirements for the future ASCENDS (Active Sensing of CO2 Emissions over Nights, Days, and Seasons) in the continental U.S. urban areas.

Sequestering CO2 by mineralization into useful nesquehonite-based products

Directory of Open Access Journals (Sweden)

Fredrik Paul Glasser

2016-02-01

Full Text Available The precipitation of magnesium hydroxy-carbonate hydrates has been suggested as a route to sequester CO2 into solids. We report the development of self-cementing compositions based on nesquehonite, MgCO3·3H2O, that are made from CO2-containing gas streams, the CO2 being separated from other gases by its high solubility in alkaline water, while magnesium is typically provided by waste desalination brines. Precipitation conditions are adjusted to optimize the formation of nesquehonite and the crystalline solid can readily be washed free of chloride. Products can be prepared to achieve self-cementation following two routes: (i thermal activation of the nesquehonite then rehydration of the precursor or (ii direct curing of a slurry of nesquehonite. The products thus obtained contain ~ 30 wt% CO2 and could form the basis for a new generation of lightweight, thermally insulating boards, blocks and panels, with sufficient strength for general construction.

Spectroscopic identification of the active site for CO oxidation on Rh/Al{sub 2}O{sub 3} by concentration modulation in situ DRIFTS

Energy Technology Data Exchange (ETDEWEB)

Cavers, M.; Davidson, J.M.; Harkness, I.R.; Rees, L.V.C.; McDougall, G.S.

1999-12-10

Diffuse reflectance infrared spectroscopy experiments are described in which the concentrations of the reactant gases passing over a solid catalyst are modulated. This simple modification to the normal in situ experiment enables direct correlation of specific surface species with the production of gaseous products. Spectra of solely the active surface intermediates with no contribution from so called spectator species are generated. For CO oxidation over a Rh/alumina catalyst at 576 K, the active CO species is identified as linearly adsorbed CO on oxidized Rh sites ({nu}{sub CO} = 2,100 cm{sup {minus}1}) on a catalyst surface apparently otherwise dominated by CO adsorbed as unreactive geminal dicarbonyl.

Bioelectrochemical removal of carbon dioxide (CO2): an innovative method for biogas upgrading.

Science.gov (United States)

Xu, Heng; Wang, Kaijun; Holmes, Dawn E

2014-12-01

Innovative methods for biogas upgrading based on biological/in-situ concepts have started to arouse considerable interest. Bioelectrochemical removal of CO2 for biogas upgrading was proposed here and demonstrated in both batch and continuous experiments. The in-situ biogas upgrading system seemed to perform better than the ex-situ one, but CO2 content was kept below 10% in both systems. The in-situ system's performance was further enhanced under continuous operation. Hydrogenotrophic methanogenesis and alkali production with CO2 absorption could be major contributors to biogas upgrading. Molecular studies showed that all the biocathodes associated with biogas upgrading were dominated by sequences most similar to the same hydrogenotrophic methanogen species, Methanobacterium petrolearium (97-99% sequence identity). Conclusively, bioelectrochemical removal of CO2 showed great potential for biogas upgrading. Copyright © 2014 Elsevier Ltd. All rights reserved.

An In-Situ Root-Imaging System in the Context of Surface Detection of CO2

Science.gov (United States)

Apple, M. E.; Prince, J. B.; Bradley, A. R.; Zhou, X.; Lakkaraju, V. R.; Male, E. J.; Pickles, W.; Thordsen, J. J.; Dobeck, L.; Cunningham, A.; Spangler, L.

2009-12-01

Carbon sequestration is a valuable method of spatially confining CO2 belowground. The Zero Emissions Research Technology, (ZERT), site is an experimental facility in a former agricultural field on the Montana State University campus in Bozeman, Montana, where CO2 was experimentally released at a rate of 200kg/day in 2009 into a 100 meter underground injection well running parallel to the ground surface. This injection well, or pipe, has deliberate leaks at intervals, and CO2 travels from these leaks upward to the surface of the ground. The ZERT site is a model system designed with the purpose of testing methods of surface detection of CO2. One important aspect of surface detection is the determination of the effects of CO2 on the above and belowground portions of plants growing above sequestration fields. At ZERT, these plants consist of a pre-existing mixture of herbaceous species present at the agricultural field. Species growing at the ZERT site include several grasses, Dactylis glomerata (Orchard Grass), Poa pratensis (Kentucky Bluegrass), and Bromus japonicus (Japanese Brome); the nitrogen-fixing legumes Medicago sativa, (Alfalfa), and Lotus corniculatus, (Birdsfoot trefoil); and an abundance of Taraxacum officinale, (Dandelion). Although the aboveground parts of the plants at high CO2 are stressed, as indicated by changes in hyperspectral plant signatures, leaf fluorescence and leaf chlorophyll content, we are interested in determining whether the roots are also stressed. To do so, we are combining measurements of soil conductivity and soil moisture with root imaging. We are using an in-situ root-imaging system manufactured by CID, Inc. (Camas, WA), along with image analysis software (Image-J) to analyze morphometric parameters in the images and to determine what effects, if any, the presence of leaking and subsequently upwelling CO2 has on the phenology of root growth, growth and turnover of individual fine and coarse roots, branching patterns, and root

Exploratory Research on Simulation of CO2-Brine-Mineral Interactions

Energy Technology Data Exchange (ETDEWEB)

Chen Zhu; Shiao hung Chiang

2005-11-01

Application of many carbon sequestration strategies requires knowledge of thermodynamic properties for the extremely complex chemical system of CO{sub 2}-SO{sub 2}-H{sub 2}O-NaCl-CaCl{sub 2}-MgCl{sub 2}. This University Coal Research Phase I program has been successful and highly productive in exploring an approach to develop an equation of state (EOS) to describe thermodynamic properties in the above chemical system. We have compiled available laboratory experimental data and thermodynamic models, and evaluated their appropriateness for the carbon sequestration process. Based on this literature review, we provided an improved CO{sub 2} solubility model for the CO{sub 2}-H{sub 2}O-NaCl system, which incorporates newly available experimental measurements funded by DOE, and is valid in temperature range from 273 to 533 K, pressure from 0 to 2000 bar, and salinity from 0 to 4.5 molality of NaCl equivalent. The improved model also greatly improves the computational efficiency of CO{sub 2} solubility calculations and thus is better suited to be incorporated into large computer simulation models (e.g., reservoir simulation models). The literature review and model development provided insights of the data needs and directions for future work. Synergetic collaboration with DOE scientists has resulted in simulations of injected CO{sub 2} fate in sandstone aquifer with a one-dimensional numerical coupled reactive transport model. We evaluated over 100 references on CO{sub 2} solubility and submitted two manuscripts to peer-reviewed journals. One paper has been accepted for publication in ''Environmental Geosciences''.

Reactivity of dissolved- vs. supercritical-CO2 phase toward muscovite basal surfaces

Science.gov (United States)

Wan, J.; Tokunaga, T. K.; Kim, Y.; Wang, S.; Altoe, M. V. P.; Ashby, P. D.; DePaolo, D.

2015-12-01

The current understanding of geochemical reactions in reservoirs for geological carbon sequestration (GCS) is largely based on aqueous chemistry (CO2 dissolves in reservoir brine and brine reacts with rocks). However, only a portion of the injected supercritical (sc) CO2 dissolves before the buoyant plume contacts caprock, where it is expected to reside for a long time. Although numerous studies have addressed scCO2-mineral reactions occurring within adsorbed aqueous films, possible reactions resulting from direct CO2-rock contact remain less understood. Does CO2 as a supercritical phase react with reservoir rocks? Do mineral react differently with scCO2 than with dissolved CO2? We selected muscovite, one of the more stable and common rock-forming silicate minerals, to react with scCO2 phase (both water-saturated and water-free) and compared with CO2-saturated-brine. The reacted basal surfaces were analyzed using atomic force microscopy and X-ray photoelectron spectroscopy for examining the changes in surface morphology and chemistry. The results show that scCO2 (regardless of its water content) altered muscovite considerably more than CO2-saturated brine; suggest CO2 diffusion into mica interlayers and localized mica dissolution into scCO2 phase. The mechanisms underlying these observations and their implications for GCS need further exploration.

Geochemical Interaction of Middle Bakken Reservoir Rock and CO2 during CO2-Based Fracturing

Science.gov (United States)

Nicot, J. P.; Lu, J.; Mickler, P. J.; Ribeiro, L. H.; Darvari, R.

2015-12-01

This study was conducted to investigate the effects of geochemical interactions when CO2 is used to create the fractures necessary to produce hydrocarbons from low-permeability Middle Bakken sandstone. The primary objectives are to: (1) identify and understand the geochemical reactions related to CO2-based fracturing, and (2) assess potential changes of reservoir property. Three autoclave experiments were conducted at reservoir conditions exposing middle Bakken core fragments to supercritical CO2 (sc-CO2) only and to CO2-saturated synthetic brine. Ion-milled core samples were examined before and after the reaction experiments using scanning electron microscope, which enabled us to image the reaction surface in extreme details and unambiguously identify mineral dissolution and precipitation. The most significant changes in the reacted rock samples exposed to the CO2-saturated brine is dissolution of the carbonate minerals, particularly calcite which displays severely corrosion. Dolomite grains were corroded to a lesser degree. Quartz and feldspars remained intact and some pyrite framboids underwent slight dissolution. Additionally, small amount of calcite precipitation took place as indicated by numerous small calcite crystals formed at the reaction surface and in the pores. The aqueous solution composition changes confirm these petrographic observations with increase in Ca and Mg and associated minor elements and very slight increase in Fe and sulfate. When exposed to sc-CO2 only, changes observed include etching of calcite grain surface and precipitation of salt crystals (halite and anhydrite) due to evaporation of residual pore water into the sc-CO2 phase. Dolomite and feldspars remained intact and pyrite grains were slightly altered. Mercury intrusion capillary pressure tests on reacted and unreacted samples shows an increase in porosity when an aqueous phase is present but no overall porosity change caused by sc-CO2. It also suggests an increase in permeability

2,4,6-Trinitrotoluene mineralization and bacterial production rates of natural microbial assemblages from coastal sediments

Energy Technology Data Exchange (ETDEWEB)

Montgomery, Michael T., E-mail: michael.montgomery@nrl.navy.mil [Naval Research Laboratory, Marine Biogeochemistry Section, Code 6114, 4555 Overlook Avenue, Washington, DC 20375 (United States); Coffin, Richard B., E-mail: richard.coffin@nrl.navy.mil [Naval Research Laboratory, Marine Biogeochemistry Section, Code 6114, 4555 Overlook Avenue, Washington, DC 20375 (United States); Boyd, Thomas J., E-mail: thomas.boyd@nrl.navy.mil [Naval Research Laboratory, Marine Biogeochemistry Section, Code 6114, 4555 Overlook Avenue, Washington, DC 20375 (United States); Smith, Joseph P., E-mail: joseph.smith@nrl.navy.mil [Naval Research Laboratory, Marine Biogeochemistry Section, Code 6114, 4555 Overlook Avenue, Washington, DC 20375 (United States); Walker, Shelby E., E-mail: Shelby.Walker@noaa.gov [Naval Research Laboratory, Marine Biogeochemistry Section, Code 6114, 4555 Overlook Avenue, Washington, DC 20375 (United States); Osburn, Christopher L., E-mail: chris_osburn@ncsu.edu [Marine, Earth and Atmospheric Sciences, North Carolina State University, Raleigh, NC 27695 (United States)

2011-12-15

The nitrogenous energetic constituent, 2,4,6-Trinitrotoluene (TNT), is widely reported to be resistant to bacterial mineralization (conversion to CO{sub 2}); however, these studies primarily involve bacterial isolates from freshwater where bacterial production is typically limited by phosphorus. This study involved six surveys of coastal waters adjacent to three biome types: temperate broadleaf, northern coniferous, and tropical. Capacity to catabolize and mineralize TNT ring carbon to CO{sub 2} was a common feature of natural sediment assemblages from these coastal environments (ranging to 270+/-38 {mu}g C kg{sup -1} d{sup -1}). More importantly, these mineralization rates comprised a significant proportion of total heterotrophic production. The finding that most natural assemblages surveyed from these ecosystems can mineralize TNT ring carbon to CO{sub 2} is consistent with recent reports that assemblage components can incorporate TNT ring carbon into bacterial biomass. These data counter the widely held contention that TNT is recalcitrant to bacterial catabolism of the ring carbon in natural environments. - Highlights: > TNT mineralization is a common feature of natural bacterial assemblages in coastal sediments. > TNT mineralization rates comprised a significant proportion of total heterotrophic production. > These data counter the widely held contention that TNT is recalcitrant to bacterial catabolism of the ring carbon in natural environments. - The capacity to mineralize TNT ring carbon to CO{sub 2} is a common feature of natural bacterial assemblages in coastal sediment.

Soil warming enhances the hidden shift of elemental stoichiometry by elevated CO2 in wheat.

Science.gov (United States)

Li, Xiangnan; Jiang, Dong; Liu, Fulai

2016-03-22

Increase in atmospheric CO2 concentration ([CO2]) and associated soil warming along with global climate change are expected to have large impacts on grain mineral nutrition in wheat. The effects of CO2 elevation (700 μmol l(-1)) and soil warming (+2.4 °C) on K, Ca and Mg concentrations in the xylem sap and their partitioning in different organs of wheat plant during grain filling were investigated. Results showed that the combination of elevated [CO2] and soil warming improved wheat grain yield, but decreased plant K, Ca and Mg accumulation and their concentrations in the leaves, stems, roots and grains. The reduced grain mineral concentration was attributed to the lowered mineral uptake as exemplified by both the decreased stomatal conductance and mineral concentration in the xylem sap. These findings suggest that future higher atmospheric [CO2] and warmer soil conditions may decrease the dietary availability of minerals from wheat crops. Breeding wheat cultivars possessing higher ability of mineral uptake at reduced xylem flux in exposure to climate change should be a target.

Engineered in situ bioremediation of a petroleum hydrocarbon-contaminated aquifer: assessment of mineralization based on alkalinity, inorganic carbon and stable carbon isotope balances

Science.gov (United States)

Hunkeler, Daniel; Höhener, Patrick; Bernasconi, Stefano; Zeyer, Josef

1999-04-01

A concept is proposed to assess in situ petroleum hydrocarbon mineralization by combining data on oxidant consumption, production of reduced species, CH 4, alkalinity and dissolved inorganic carbon (DIC) with measurements of stable isotope ratios. The concept was applied to a diesel fuel contaminated aquifer in Menziken, Switzerland, which was treated by engineered in situ bioremediation. In the contaminated aquifer, added oxidants (O 2 and NO 3-) were consumed, elevated concentrations of Fe(II), Mn(II), CH 4, alkalinity and DIC were detected and the DIC was generally depleted in 13C compared to the background. The DIC production was larger than expected based on the consumption of dissolved oxidants and the production of reduced species. Stable carbon isotope balances revealed that the DIC production in the aquifer originated mainly from microbial petroleum hydrocarbon mineralization, and that geochemical reactions such as carbonate dissolution produced little DIC. This suggests that petroleum hydrocarbon mineralization can be underestimated if it is determined based on concentrations of dissolved oxidants and reduced species.

Advances in Geological CO{sub 2} Sequestration and Co-Sequestration with O{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Verba, Circe A; O& #x27; Connor, William K.; Ideker, J.H.

2012-10-28

The injection of CO{sub 2} for Enhanced Oil Recovery (EOR) and sequestration in brine-bearing formations for long term storage has been in practice or under investigation in many locations globally. This study focused on the assessment of cement wellbore seal integrity in CO{sub 2}- and CO{sub 2}-O{sub 2}-saturated brine and supercritical CO{sub 2} environments. Brine chemistries (NaCl, MgCl{sub 2}, CaCl{sub 2}) at various saline concentrations were investigated at a pressure of 28.9 MPa (4200 psi) at both 50{degree}C and 85{degree}C. These parameters were selected to simulate downhole conditions at several potential CO{sub 2} injection sites in the United States. Class H portland cement is not thermodynamically stable under these conditions and the formation of carbonic acid degrades the cement. Dissociation occurs and leaches cations, forming a CaCO{sub 3} buffered zone, amorphous silica, and other secondary minerals. Increased temperature affected the structure of C-S-H and the hydration of the cement leading to higher degradation rates.

Co-firing straw and coal in a 150-MWe utility boiler: in situ measurements

DEFF Research Database (Denmark)

Hansen, P. F.B.; Andersen, Karin Hedebo; Wieck-Hansen, K.

1998-01-01

A 2-year demonstration program is carried out by the Danish utility I/S Midtkraft at a 150-MWe PF-boiler unit reconstructed for co-firing straw and coal. As a part of the demonstration program, a comprehensive in situ measurement campaign was conducted during the spring of 1996 in collaboration...... with the Technical University of Denmark. Six sample positions have been established between the upper part of the furnace and the economizer. The campaign included in situ sampling of deposits on water/air-cooled probes, sampling of fly ash, flue gas and gas phase alkali metal compounds, and aerosols as well...... deposition propensities and high temperature corrosion during co-combustion of straw and coal in PF-boilers. Danish full scale results from co-firing straw and coal, the test facility and test program, and the potential theoretical support from the Technical University of Denmark are presented in this paper...

Experimental and simulation studies of iron oxides for geochemical fixation of CO2-SO2 gas mixtures

Science.gov (United States)

Garcia, Susana; Rosenbauer, Robert J.; Palandri, James; Maroto-Valer, M. Mercedes

2011-01-01

Iron-bearing minerals are reactive phases of the subsurface environment and could potentially trap CO2–SO2gas mixtures derived from fossil fuel combustion processes by their conversion to siderite (FeCO3) and dissolved sulfate. Changes in fluid and mineral compositions resulting from reactions, involving the co-injection of SO2 with CO2 were observed both theoretically and experimentally. Experiments were conducted with a natural hematite (α-Fe2O3) sample. A high pressure-high temperature apparatus was used to simulate conditions in geologic formations deeper than 800 m, where CO2 is in the supercritical state. Solid samples were allowed to react with a NaCl–NaOH brine and SO2-bearing CO2-dominated gas mixtures. The predicted equilibrium mineral assemblage at 100 °C and 250 bar became hematite, dawsonite (NaAl(OH)2CO3), siderite (FeCO3) and quartz (SiO2). Experimentally, siderite and dawsonite, derived from the presence of kaolinite (Al2Si2O5(OH)4) in the parent material, were present in residual solids at longer reaction time intervals, which agreed well with results from the modelling work.

In situ synchrotron X-ray diffraction study of scale formation during CO2 corrosion of carbon steel in sodium and magnesium chloride solutions

International Nuclear Information System (INIS)

Ingham, B.; Ko, M.; Laycock, N.; Burnell, J.; Kappen, P.; Kimpton, J.A.; Williams, D.E.

2012-01-01

Highlights: ► We studied the scale formation processes of carbon steel in CO 2 saturated brine at 80 °C. ► Protective scales were formed in all tests. ► Only FeCO 3 formed in saturated brine while Fe(OH) 2 CO 3 detected with presence of MgCl 2 . ► MgCl 2 accelerates the onset of siderite precipitation. - Abstract: In situ synchrotron X-ray diffraction was used to follow the formation of corrosion products on carbon steel in CO 2 saturated NaCl solution and mixed NaCl/magnesium chloride (MgCl 2 ) at 80 °C. Siderite (FeCO 3 ) was the only phase formed in NaCl solution, while Fe(OH) 2 CO 3 was also detected when MgCl 2 was present. The proposed model is that siderite precipitation, occurring once the critical supersaturation was exceeded within a defined boundary layer, caused local acidification which accelerated the anodic dissolution of iron. The current fell once a complete surface scale was formed. It is suggested that MgCl 2 addition decreased the required critical supersaturation for precipitation.

CO2 sequestration: Storage capacity guideline needed

Science.gov (United States)

Frailey, S.M.; Finley, R.J.; Hickman, T.S.

2006-01-01

Petroleum reserves are classified for the assessment of available supplies by governmental agencies, management of business processes for achieving exploration and production efficiency, and documentation of the value of reserves and resources in financial statements. Up to the present however, the storage capacity determinations made by some organizations in the initial CO2 resource assessment are incorrect technically. New publications should thus cover differences in mineral adsorption of CO2 and dissolution of CO2 in various brine waters.

The effects of impure CO2 on reservoir sandstones: results from mineralogical and geomechanical experiments

Science.gov (United States)

Marbler, H.; Erickson, K. P.; Schmidt, M.; Lempp, Ch.; Pöllmann, H.

2012-04-01

An experimental study of the behaviour of reservoir sandstones from deep saline aquifers during the injection and geological storage of CO2 with the inherent impurities SOX and NOX is part of the German national project COORAL*. Sample materials were taken from outcrops of possible reservoir formations of Rotliegend and Bunter Sandstones from the North German Basin. A combination of mineralogical alteration experiments and geomechanical tests was carried out on these rocks to study the potential effects of the impurities within the CO2 pore fluid. Altered rock samples after the treatment with CO2 + SOX/NOX in an autoclave system were loaded in a triaxial cell under in-situ pressure and temperature conditions in order to estimate the modifications of the geomechanical rock properties. Mineralogical alterations were observed within the sandstones after the exposure to impure supercritical (sc)CO2 and brine, mainly of the carbonatic, but also of the silicatic cements, as well as of single minerals. Besides the partial solution effects also secondary carbonate and minor silicate mineral precipitates were observed within the pore space of the treated sandstones. These alterations affect the grain structure of the reservoir rock. Results of geomechanical experiments with unaltered sandstones show that the rock strength is influenced by the degree of rock saturation before the experiment and the chemical composition of the pore fluid (scCO2 + SOX + NOX). After long-term autoclave treatment with impure scCO2, the sandstone samples exhibit modified strength parameters and elastic deformation behaviour as well as changes in porosity compared to untreated samples. Furthermore, the injected fluid volume into the pore space of sandstones from the same lithotype varies during triaxial loading depending on the chemistry of the pore fluid. CO2 with NOX and SOX bearing fluid fills a significantly larger proportion of the sandstone pore space than brine with pure scCO2. * The

Mineralization of soil-aged isoproturon and isoproturon metabolites by Sphingomonas sp. strain SRS2.

Science.gov (United States)

Johannesen, Helle; Sørensen, Sebastian R; Aamand, Jens

2003-01-01

The aim of the study was to determine the effect of aging of the herbicide isoproturon and its metabolites monodesmethyl-isoproturon and 4-isopropyl-aniline in agricultural soil on their availability to the degrading bacterium Sphingomonas sp. strain SRS2. The 14C-ring-labeled isoproturon, monodesmethyl-isoproturon, and 4-isopropyl-aniline were added to sterilized soil and stored for 1, 49, 71, or 131 d before inoculation with strain SRS2. The availability of the compounds was estimated from the initial mineralization and the amount of 14CO2 recovered after 120 d of incubation. Aging in soil for 131 d reduced the initial mineralization of isoproturon and monodesmethyl-isoproturon and, in the case of isoproturon, also reduced the recovery of 14CO2. Initial mineralization and recovery of 14CO2 from aged 4-isopropyl-aniline were slightly reduced, but less 14CO2 was generally produced than with isoproturon or monodesmethyl-isoproturon. Thus, recovery of 14CO2 from 14C-isoproturon and 14C-monodesmethyl-isoproturon was 50.7 to 64.4% of the initially added 14C, while recovery from 14C-4-isopropyl-aniline was only 11.7 to 17.0%. Sorption measurements revealed similar Freundlich constants (K(f)) for isoproturon and monodesmethyl-isoproturon, whereas K(f) for 4-isopropyl-aniline was more than fivefold greater. The findings imply that in soil, partial degradation of isoproturon to 4-isopropyl-aniline may lead to reduced mineralization of the herbicide due to sorption of the aniline moiety.

CO2 Sequestration short course

Energy Technology Data Exchange (ETDEWEB)

DePaolo, Donald J. [Lawrence Berkeley National Laboratory; Cole, David R [The Ohio State University; Navrotsky, Alexandra [University of California-Davis; Bourg, Ian C [Lawrence Berkeley National Laboratory

2014-12-08

Given the public’s interest and concern over the impact of atmospheric greenhouse gases (GHGs) on global warming and related climate change patterns, the course is a timely discussion of the underlying geochemical and mineralogical processes associated with gas-water-mineral-interactions encountered during geological sequestration of CO2. The geochemical and mineralogical processes encountered in the subsurface during storage of CO2 will play an important role in facilitating the isolation of anthropogenic CO2 in the subsurface for thousands of years, thus moderating rapid increases in concentrations of atmospheric CO2 and mitigating global warming. Successful implementation of a variety of geological sequestration scenarios will be dependent on our ability to accurately predict, monitor and verify the behavior of CO2 in the subsurface. The course was proposed to and accepted by the Mineralogical Society of America (MSA) and The Geochemical Society (GS).

The impact of CO2 on shallow groundwater chemistry: observations at a natural analog site and implications for carbon sequestration

Energy Technology Data Exchange (ETDEWEB)

Keating, Elizabeth [Los Alamos National Laboratory; Fessenden, Julianna [Los Alamos National Laboratory; Kanjorski, Nancy [NON LANL; Koning, Dan [NM BUREAU OF GEOLOGY AND MINERAL RESOURCES; Pawar, Rajesh [Los Alamos National Laboratory

2008-01-01

In a natural analog study of risks associated with carbon sequestration, impacts of CO{sub 2} on shallow groundwater quality have been measured in a sandstone aquifer in New Mexico, USA. Despite relatively high levels of dissolved CO{sub 2}, originating from depth and producing geysering at one well, pH depression and consequent trace element mobility are relatively minor effects due to the buffering capacity of the aquifer. However, local contamination due to influx of saline waters in a subset of wells is significant. Geochemical modeling of major ion concentrations suggests that high alkalinity and carbonate mineral dissolution buffers pH changes due to CO{sub 2} influx. Analysis oftrends in dissolved trace elements, chloride, and CO2 reveal no evidence of in-situ trace element mobilization. There is clear evidence, however, that As, U, and Pb are locally co-transported into the aquifer with CO{sub 2}-rich saline water. This study illustrates the role that local geochemical conditions will play in determining the effectiveness of monitoring strategies for CO{sub 2} leakage. For example, if buffering is significant, pH monitoring may not effectively detect CO2 leakage. This study also highlights potential complications that CO{sub 2}carrier fluids, such as saline waters, pose in monitoring impacts ofgeologic sequestration.

NiCo2O4 nanosheets in-situ grown on three dimensional porous Ni film current collectors as integrated electrodes for high-performance supercapacitors

Science.gov (United States)

Wang, Tao; Guo, Ying; Zhao, Bo; Yu, Shuhui; Yang, Hai-Peng; Lu, Daniel; Fu, Xian-Zhu; Sun, Rong; Wong, Ching-Ping

2015-07-01

Three dimensional interconnected hierarchical porous Ni films are easily fabricated as effective current collectors through hydrogen bubble template electrochemical deposition. The binder-free integrated electrodes of spinel NiCo2O4 nanosheets directly coated the three dimensional porous Ni films are facilely obtained through successively electrochemical co-deposition of Ni/Co alloy layer then followed by subsequent annealing at 350 °C in air. Compared with NiCo2O4 nanosheets on smooth Ni foil or porous NiO/Ni film electrodes, the porous NiCo2O4/Ni integrated film electrodes for supercapacitors demonstrate remarkably higher area specific capacitance. The porous NiCo2O4/Ni film electrodes also exhibit excellent rate capability and cycling stability. The super electrochemical capacitive performances are attributed to the unique integrated architecture of NiCo2O4 nanosheets in-situ grown on three dimensional continuous hierarchical porous Ni collector collectors, which could provide large electrode-electrolyte interface area, high active sites, low contact resistance between current collector and active materials, fast electron conduction and ion/electrolyte diffusion.

CO2 and N2O emissions from an Andisol in Chile under a no-till system using non-fixed closed chambers Emisiones de CO2 y N2O desde un Andisol de Chile bajo sistema de cero labranza usando cámaras cerradas no-fijas

Directory of Open Access Journals (Sweden)

Cristina Muñoz

2011-06-01

Full Text Available Chile has different types of soil and climate conditions that favor a wide range of agricultural activities that can generate potential atmospheric contamination like greenhouse gases (GHG. Nevertheless, the contribution of agricultural soils to atmospheric emissions has yet to be measured in Chile. The aim of this study was to assess seasonal variability of CO2 and N2O effluxes in situ from a volcanic ash-derived soil under different agronomic management practices. Gas samples were obtained from headspaces of non-fixed closed chambers in an annual crop rotation under a no-till system in an Andisol in southern Chile (36° S. Two N-sources (NH4+ and NO3- and ammonium fertilization plus two lime doses (0.5 and 1 Mg ha-1 were considered for soil treatments Effluxes of CO2 and N2O were determined periodically for 1 yr, and soil variables, such as temperature, water, and mineral N content, were recorded. Results showed that CO2 effluxes respond to a seasonal pattern. No effect was evidenced when considering crop management practices with a maximum of 53.2 ± 8.5 kg CO2-C ha-1 d-1 in the wet fall period and a minimum of 9.7 ± 2.1 kg CO2-C ha-1 d-1 for summer, fall dry period, and winter. N2O efflux was highly variable throughout the year and showed no influence of treatments or season variability with a mean of 0.95 kg N2O-N ha-1 yr-1. Soil mineral N variations are not related to GHG effluxes as a single variable. Results indicate that an Andisol under a no-till system in southern Chile has a low N2O emission potential, and higher CO2 emissions are mainly produced in wet seasons (wet fall and/or spring.Chile tiene diferentes tipos de suelo y condiciones climáticas que favorecen un amplio rango de actividades agrícolas, las cuales pueden generar contaminación atmosférica potencial como los gases de efecto invernadero (GHG. Sin embargo, mediciones de la contribución de los suelos agrícolas en las emisiones atmosféricas de estos gases no ha sido

Microorganisms implication in the CO2 geologic storage processes

International Nuclear Information System (INIS)

Dupraz, S.

2008-01-01

A first result of this thesis is the building and validation of a circulation reactor named BCC (Bio-mineralization Control Cell). The reactor has the functionality of a biological reactor and allows a monitoring of physico-chemical characteristics such as Eh, pH, electrical conductivity, spectro-photochemical parameters. It also has a capability of percolation through rock cores. It is a first step toward an analogical modeling of interactions between injected CO 2 and deep bio-spheric components. Moreover, a new spectro-photochemical method for monitoring reduced sulfur species has been developed which allows efficient monitoring of sulfate-reducing metabolisms. In the thesis, we have tested four metabolisms relevant to bio-mineralisation or biological assimilation of CO 2 : a reference ureolytic aerobic strain, Bacillus pasteurii, a sulfate-reducing bacterium, Desulfovibrio longus, a sulfate-reducing consortium (DVcons) and an homoacetogenic bacterium, Acetobacterium carbinolicum. In the case of Bacillus pasteurii, which is considered as a model for non photosynthetic prokaryotic carbonate bio-mineralization, we have demonstrated that the biological basification and carbonate bio-mineralization processes can be modelled accurately both analogically and numerically under conditions relevant to deep CO 2 storage, using a synthetic saline groundwater. We have shown that salinity has a positive effect on CO 2 mineral trapping by this bacterium; we have measured the limits of the system in terms of CO 2 pressure and we have shown that the carbonates that nucleate on intracellular calcium phosphates have specific carbon isotope signatures. The studied deep-subsurface strains (Desulfovibrio longus and Acetobacterium carbinolicum) as well as the sulfate-reducing consortium also have capabilities of converting CO 2 into solid carbonates, much less efficient though than in the case of Bacillus pasteurii. However, once inoculated in synthetic saline groundwater and

Structural characterization of framework-gas interactions in the metal-organic framework Co2(dobdc) by in situ single-crystal X-ray diffraction.

Science.gov (United States)

Gonzalez, Miguel I; Mason, Jarad A; Bloch, Eric D; Teat, Simon J; Gagnon, Kevin J; Morrison, Gregory Y; Queen, Wendy L; Long, Jeffrey R

2017-06-01

The crystallographic characterization of framework-guest interactions in metal-organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH 4 , N 2 , O 2 , Ar, and P 4 adsorption in Co 2 (dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate), a metal-organic framework bearing coordinatively unsaturated cobalt(ii) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(ii) sites in the framework that no analogous molecular structures exist, demonstrating the utility of metal-organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co-CH 4 and Co-Ar interactions observed in Co 2 (dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal-CH 4 interaction and the first crystallographically characterized metal-Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(ii) sites in Co 2 (dobdc), with differential enthalpies of adsorption as weak as -17(1) kJ mol -1 (for Ar). Moreover, the structures of Co 2 (dobdc)·3.8N 2 , Co 2 (dobdc)·5.9O 2 , and Co 2 (dobdc)·2.0Ar reveal the location of secondary (N 2 , O 2 , and Ar) and tertiary (O 2 ) binding sites in Co 2 (dobdc), while high-pressure CO 2 , CO, CH 4 , N 2 , and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures.

Contrasting Impact of Future CO2 Emission Scenarios on the Extent of CaCO3 Mineral Undersaturation in the Humboldt Current System

Science.gov (United States)

Franco, A. C.; Gruber, N.; Frölicher, T. L.; Kropuenske Artman, L.

2018-03-01

The eastern boundary upwelling systems are among those regions that are most vulnerable to an ocean acidification-induced transition toward undersaturated conditions with respect to mineral CaCO3, but no assessment exists yet for the Humboldt Current System. Here we use a high-resolution (˜7.5 km) regional ocean model to investigate past and future changes in ocean pH and CaCO3 saturation state in this system. We find that within the next few decades, the nearshore waters off Peru are projected to become corrosive year round with regard to aragonite, the more soluble form of CaCO3. The volume of aragonite undersaturated water off Peru will continue to increase in the future irrespective of the amount of CO2 emitted to the atmosphere. In contrast, the development of the saturation state with regard to calcite, a less soluble form of carbonate, depends strongly on the scenario followed. By 2050, calcite undersaturation appears in the nearshore waters off Peru occasionally, but by 2090 in a high-emission scenario (RCP8.5), ˜60% of the water in the euphotic zone will become permanently calcite undersaturated. Most of this calcite undersaturation off Peru can likely be avoided if a low emission scenario (RCP2.6) consistent with the Paris Agreement is followed. The progression of ocean acidification off Chile follows a similar pattern, except that the saturation states are overall higher. But also here, calcite undersaturated waters will become common in the subsurface waters under the RCP8.5 scenario by the end of this century, while this can be avoided under the RCP2.6 scenario.

Impact of combined CO2 laser irradiation and fluoride on enamel and dentin biofilm-induced mineral loss.

Science.gov (United States)

Esteves-Oliveira, Marcella; El-Sayed, Karim Fawzy; Dörfer, Christof; Schwendicke, Falk

2017-05-01

The caries-protective effects of CO 2 laser irradiation on dental enamel have been demonstrated using chemical demineralization models. We compared the effect of CO 2 laser irradiation, sodium fluoride, or both on biofilm-induced mineral loss (∆Z) and Streptococcus mutans adhesion to enamel and dentin in vitro. Ground, polished bovine enamel, and dentin samples were allocated to four groups (n = 12/group): no treatment (C); single 22,600-ppm fluoride (F) varnish (5 % NaF) application; single CO 2 laser treatment (L) with short pulses (5 μs/λ = 10.6 μm); and laser and subsequent fluoride treatment (LF). Samples were sterilized and submitted to an automated mono-species S. mutans biofilm model. Brain heart infusion plus 5 % sucrose medium was provided eight times daily, followed by rinses with artificial saliva. After 10 days, bacterial numbers in biofilms were enumerated as colony-forming units/ml (CFU/ml) (n = 7/group). ∆Z was assessed using transversal microradiography (n = 12/group). Univariate ANOVA with post hoc Tukey honestly-significant-difference test was used for statistical analysis. Bacterial numbers were significantly higher on dentin than enamel (p  0.05). In dentin, only LF (163/227) significantly reduced ∆Z (p fluoride application was required to protect dentin.

REDUCING UNCERTAINTIES IN MODEL PREDICTIONS VIA HISTORY MATCHING OF CO2 MIGRATION AND REACTIVE TRANSPORT MODELING OF CO2 FATE AT THE SLEIPNER PROJECT

Energy Technology Data Exchange (ETDEWEB)

Zhu, Chen

2015-03-31

An important question for the Carbon Capture, Storage, and Utility program is “can we adequately predict the CO2 plume migration?” For tracking CO2 plume development, the Sleipner project in the Norwegian North Sea provides more time-lapse seismic monitoring data than any other sites, but significant uncertainties still exist for some of the reservoir parameters. In Part I, we assessed model uncertainties by applying two multi-phase compositional simulators to the Sleipner Benchmark model for the uppermost layer (Layer 9) of the Utsira Sand and calibrated our model against the time-lapsed seismic monitoring data for the site from 1999 to 2010. Approximate match with the observed plume was achieved by introducing lateral permeability anisotropy, adding CH4 into the CO2 stream, and adjusting the reservoir temperatures. Model-predicted gas saturation, CO2 accumulation thickness, and CO2 solubility in brine—none were used as calibration metrics—were all comparable with the interpretations of the seismic data in the literature. In Part II & III, we evaluated the uncertainties of predicted long-term CO2 fate up to 10,000 years, due to uncertain reaction kinetics. Under four scenarios of the kinetic rate laws, the temporal and spatial evolution of CO2 partitioning into the four trapping mechanisms (hydrodynamic/structural, solubility, residual/capillary, and mineral) was simulated with ToughReact, taking into account the CO2-brine-rock reactions and the multi-phase reactive flow and mass transport. Modeling results show that different rate laws for mineral dissolution and precipitation reactions resulted in different predicted amounts of trapped CO2 by carbonate minerals, with scenarios of the conventional linear rate law for feldspar dissolution having twice as much mineral trapping (21% of the injected CO2) as scenarios with a Burch-type or Alekseyev et al.–type rate law for feldspar dissolution (11%). So far, most reactive transport modeling (RTM) studies for

Co-digestion of manure and whey for in situ biogas upgrading by the addition of H2: process performance and microbial insights

DEFF Research Database (Denmark)

Luo, Gang; Angelidaki, Irini

2013-01-01

composition. The best biogas composition (75:6.6:18.4) was obtained at stirring speed 150 rpmand using ceramic diffuser, while the biogas in the control reactor consisted of CH4 and CO2 at a ratio of 55:45. The consumed hydrogen was almost completely converted to CH4, and there was no significant accumulation......In situ biogas upgrading was conducted by introducing H2 directly to the anaerobic reactor. As H2 addition is associated with consumption of the CO2 in the biogas reactor, pH increased to higher than 8.0 when manure alone was used as substrate. By co-digestion of manure with acidic whey, the p......H in the anaerobic reactor with the addition of hydrogen could be maintained below 8.0, which did not have inhibition to the anaerobic process. The H2 distribution systems (diffusers with different pore sizes) and liquid mixing intensities were demonstrated to affect the gas-liquid mass transfer of H2 and the biogas...

Soil warming enhances the hidden shift of elemental stoichiometry by elevated CO2 in wheat

DEFF Research Database (Denmark)

Li, Xiangnan; Jiang, Dong; Liu, Fulai

2016-01-01

sap and their partitioning in different organs of wheat plant during grain filling were investigated. Results showed that the combination of elevated [CO2] and soil warming improved wheat grain yield, but decreased plant K, Ca and Mg accumulation and their concentrations in the leaves, stems, roots......Increase in atmospheric CO2 concentration ([CO2]) and associated soil warming along with global climate change are expected to have large impacts on grain mineral nutrition in wheat. The effects of CO2 elevation (700 μmol l(-1)) and soil warming (+2.4 °C) on K, Ca and Mg concentrations in the xylem...... and grains. The reduced grain mineral concentration was attributed to the lowered mineral uptake as exemplified by both the decreased stomatal conductance and mineral concentration in the xylem sap. These findings suggest that future higher atmospheric [CO2] and warmer soil conditions may decrease...

Developments and innovation in carbon dioxide (CO{sub 2}) capture and storage technology. Volume 2: Carbon dioxide (CO{sub 2}) storage and utilisation

Energy Technology Data Exchange (ETDEWEB)

Mercedes Maroto-Valer, M. (ed.)

2010-07-01

This volume initially reviews geological sequestration of CO{sub 2}, from saline aquifer sequestration to oil and gas reservoir and coal bed storage, including coverage of reservoir sealing, and monitoring and modelling techniques used to verify geological sequestration of CO{sub 2}. Terrestrial and ocean sequestration are also reviewed, along with the environmental impact and performance assessments for these routes. The final section reviews advanced concepts for CO{sub 2} storage and utilization, such as industrial utilization, biofixation, mineral carbonation and photocatalytic reduction.

Aluminosilicate Dissolution and Silicate Carbonation during Geologic CO2 Sequestration

Science.gov (United States)

Min, Yujia

Geologic CO2 sequestration (GCS) is considered a promising method to reduce anthropogenic CO2 emission. Assessing the supercritical CO2 (scCO2) gas or liquid phase water (g, l)-mineral interactions is critical to evaluating the viability of GCS processes. This work contributes to our understanding of geochemical reactions at CO 2-water (g, l)-mineral interfaces, by investigating the dissolution of aluminosilicates in CO2-acidified water (l). Plagioclase and biotite were chosen as model minerals in reservoir rock and caprock, respectively. To elucidate the effects of brine chemistry, first, the influences of cations in brine including Na, Ca, and K, have been investigated. In addition to the cations, the effects of abundant anions including sulfate and oxalate were also examined. Besides the reactions in aqueous phase, we also examine the carbonation of silicates in water (g)-bearing supercritical CO2 (scCO2) under conditions relevant to GCS. For the metal carbonation, in particular, the effects of particle sizes, water, temperature, and pressure on the carbonation of wollastonite were systematically examined. For understanding the cations effects in brine, the impacts of Na concentrations up to 4 M on the dissolution of plagioclase and biotite were examined. High concentrations of Na significantly inhibited plagioclase dissolution by competing adsorption with proton and suppressing proton-promoted dissolution. Ca has a similar effect to Na, and their effects did not suppress each other when Na and Ca co-existed. For biotite, the inhibition effects of Na coupled with an enhancing effect due to ion exchange reaction between Na and interlayer K, which cracked the basal surfaces of biotite. The K in aqueous phase significantly inhibited the dissolution. If the biotite is equilibrated with NaCl solutions initially, the biotite dissolved faster than the original biotite and the dissolution was inhibited by Na and K in brine. The outcomes improve our current knowledge of

Element mobilization and immobilization from carbonate rocks between CO 2 storage reservoirs and the overlying aquifers during a potential CO 2 leakage

Energy Technology Data Exchange (ETDEWEB)

Lawter, Amanda R.; Qafoku, Nikolla P.; Asmussen, R. Matthew; Kukkadapu, Ravi K.; Qafoku, Odeta; Bacon, Diana H.; Brown, Christopher F.

2018-04-01

Despite the numerous studies on changes within the reservoir following CO2 injection and the effects of CO2 release into overlying aquifers, little or no literature is available on the effect of CO2 release on rock between the storage reservoirs and subsurface. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in this intermediate zone. After rocks reacted with CO2, liquid analysis showed an increase of major elements (e.g., Ca, and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower concentrations were observed in N2 controls. In experiments with As/Cd and/or organic spikes, representing potential contaminants in the CO2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and Mössbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO2-reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO2-laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation.

Assessment of bioavailability of pesticides in soils and identification of pesticide degradation drivers using the in-situ Mass Distribution Quotient (iMDQ)

Science.gov (United States)

Folberth, Christian

2010-05-01

The in-situ Mass Distribution Quotient (iMDQ) has recently been shown to reliably describe the bioavailability and mineralization of the widely applied pesticide isoproturon in agricultural soils. It is determined by pore water extraction from previously incubated soil samples and subsequent assessment of the mass distribution between solid and liquid phase. The method was verified by comparing the bioavailability with co-metabolic mineralization in soils under optimum microbial soil conditions (water tension -15 kPa and bulk density 1.3 g cm-3). A comparison of the results with the chemical partitioning assessed by the Kd method has shown a higher accuracy of the new method. By combining the iMDQ/pore water extraction method with mineralization of the pesticide under optimum microbial conditions in the soils, further information about mineralization and degradation processes could be obtained or confirmed: a) Metabolically outstanding soils could be identified due to inconsistency between bioavailability and mineralization when compared to the co-metabolic soils. In a metabolically hampered soil, the mineralization was very low compared to the bioavailability and in a soil with metabolically IPU degrading microorganisms the mineralization was extremely high despite low bioavailability. b) Analysis of metabolite patterns in soil water fractions of a degradation experiment allowed for an additional identification of the metabolic status of the soil. In co-metabolic soils, the diversity of metabolites increased proportionally with the degree of mineralization of the parent compound, whereas in a metabolically hampered soil the metabolite pattern was very diverse despite low mineralization. c) A quite stable fractioning between total mineralization of the parent compound to CO2 and build-up of non-extractable bound residues was found. This is a hint that also during co-metabolic degradation that can up to now not be attributed to a certain group of microorganisms

Phase stability and oxygen non-stoichiometry of SrCo0.8Fe0.2O3-d measured by in-situ neutron diffraction

NARCIS (Netherlands)

McIntosh, Steven; McIntosh, S.; Vente, Jaap F.; Haije, Wim G.; Blank, David H.A.; Bouwmeester, Henricus J.M.

2006-01-01

The phase stability, oxygen stoichiometry and expansion properties of SrCo0.8Fe0.2O3−δ (SCF) were determined by in situ neutron diffraction between 873 and 1173 K and oxygen partial pressures of 5×10−4 to 1 atm. At a pO2 of 1 atm, SCF adopts a cubic perovskite structure, space group Pm3¯m, across

Numerical Study on CO2-Brine-Rock Interaction of Enhanced Geothermal Systems with CO2 as Heat Transmission Fluid

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Wan Yuyu

2016-01-01

Full Text Available Enhanced Geothermal Systems (EGS with CO2 instead of water as heat transmission fluid is an attractive concept for both geothermal resources development and CO2 geological sequestration. Previous studies show that CO2 has lots of favorable properties as heat transmission fluid and also can offer geologic storage of CO2 as an ancillary benefit. However, after CO2 injection into geological formations, chemical reaction between brine and rock can change chemical characteristics of saline and properties of rock such as porosity and permeability. Is this advantage or disadvantage for EGS operating? To answer this question, we have performed chemically reactive transport modeling to investigate fluid-rock interactions and CO2 mineral carbonation of Enhanced Geothermal Systems (EGS site at Desert Peak (Nevada operated with CO2. The simulation results show that (1 injection CO2 can create a core zone fulfilled with CO2 as main working domain for EGS, and (2 CO2 storage can induced self-enhancing alteration of EGS.

Sequestering CO{sub 2} by Mineralization into Useful Nesquehonite-Based Products

Energy Technology Data Exchange (ETDEWEB)

Glasser, Fredrik Paul, E-mail: f.p.glasser@abdn.ac.uk; Jauffret, Guillaume; Morrison, Jennie [Department of Chemistry, University of Aberdeen, Aberdeen (United Kingdom); Galvez-Martos, Jose-Luis; Patterson, Naomi; Imbabi, Mohammed Salah-Eldin [School of Engineering, University of Aberdeen, Aberdeen (United Kingdom)

2016-02-11

The precipitation of magnesium hydroxy-carbonate hydrates has been suggested as a route to sequester CO{sub 2} into solids. We report the development of self-cementing compositions based on nesquehonite, MgCO{sub 3}⋅3H{sub 2}O, that are made from CO{sub 2}-containing gas streams, the CO{sub 2} being separated from other gases by its high solubility in alkaline water, while magnesium is typically provided by waste desalination brines. Precipitation conditions are adjusted to optimize the formation of nesquehonite and the crystalline solid can readily be washed free of chloride. Products can be prepared to achieve self-cementation following two routes: (i) thermal activation of the nesquehonite then rehydration of the precursor or (ii) direct curing of a slurry of nesquehonite. The products thus obtained contain ~30 wt% CO{sub 2} and could form the basis for a new generation of lightweight, thermally insulating boards, blocks, and panels, with sufficient strength for general construction.

Abrupt rise in atmospheric CO2 at the onset of the Bølling/Allerød: in-situ ice core data versus true atmospheric signals

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J. Chappellaz

2011-05-01

Full Text Available During the last glacial/interglacial transition the Earth's climate underwent abrupt changes around 14.6 kyr ago. Temperature proxies from ice cores revealed the onset of the Bølling/Allerød (B/A warm period in the north and the start of the Antarctic Cold Reversal in the south. Furthermore, the B/A was accompanied by a rapid sea level rise of about 20 m during meltwater pulse (MWP 1A, whose exact timing is a matter of current debate. In-situ measured CO2 in the EPICA Dome C (EDC ice core also revealed a remarkable jump of 10 ± 1 ppmv in 230 yr at the same time. Allowing for the modelled age distribution of CO2 in firn, we show that atmospheric CO2 could have jumped by 20–35 ppmv in less than 200 yr, which is a factor of 2–3.5 greater than the CO2 signal recorded in-situ in EDC. This rate of change in atmospheric CO2 corresponds to 29–50% of the anthropogenic signal during the last 50 yr and is connected with a radiative forcing of 0.59–0.75 W m−2. Using a model-based airborne fraction of 0.17 of atmospheric CO2, we infer that 125 Pg of carbon need to be released into the atmosphere to produce such a peak. If the abrupt rise in CO2 at the onset of the B/A is unique with respect to other Dansgaard/Oeschger (D/O events of the last 60 kyr (which seems plausible if not unequivocal based on current observations, then the mechanism responsible for it may also have been unique. Available δ13CO2 data are neutral, whether the source of the carbon is of marine or terrestrial origin. We therefore hypothesise that most of the carbon might have been activated as a consequence of continental shelf flooding during MWP-1A. This potential impact of rapid sea level rise on atmospheric CO2 might define the point of no return during the last deglaciation.

Nanoscale Chemical Processes Affecting Storage Capacities and Seals during Geologic CO2 Sequestration.

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Jun, Young-Shin; Zhang, Lijie; Min, Yujia; Li, Qingyun

2017-07-18

Geologic CO 2 sequestration (GCS) is a promising strategy to mitigate anthropogenic CO 2 emission to the atmosphere. Suitable geologic storage sites should have a porous reservoir rock zone where injected CO 2 can displace brine and be stored in pores, and an impermeable zone on top of reservoir rocks to hinder upward movement of buoyant CO 2 . The injection wells (steel casings encased in concrete) pass through these geologic zones and lead CO 2 to the desired zones. In subsurface environments, CO 2 is reactive as both a supercritical (sc) phase and aqueous (aq) species. Its nanoscale chemical reactions with geomedia and wellbores are closely related to the safety and efficiency of CO 2 storage. For example, the injection pressure is determined by the wettability and permeability of geomedia, which can be sensitive to nanoscale mineral-fluid interactions; the sealing safety of the injection sites is affected by the opening and closing of fractures in caprocks and the alteration of wellbore integrity caused by nanoscale chemical reactions; and the time scale for CO 2 mineralization is also largely dependent on the chemical reactivities of the reservoir rocks. Therefore, nanoscale chemical processes can influence the hydrogeological and mechanical properties of geomedia, such as their wettability, permeability, mechanical strength, and fracturing. This Account reviews our group's work on nanoscale chemical reactions and their qualitative impacts on seal integrity and storage capacity at GCS sites from four points of view. First, studies on dissolution of feldspar, an important reservoir rock constituent, and subsequent secondary mineral precipitation are discussed, focusing on the effects of feldspar crystallography, cations, and sulfate anions. Second, interfacial reactions between caprock and brine are introduced using model clay minerals, with focuses on the effects of water chemistries (salinity and organic ligands) and water content on mineral dissolution and

Implications for carbon processing beneath the Greenland Ice Sheet from dissolved CO2 and CH4 concentrations of subglacial discharge

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Pain, A.; Martin, J.; Martin, E. E.

2017-12-01

Subglacial carbon processes are of increasing interest as warming induces ice melting and increases fluxes of glacial meltwater into proglacial rivers and the coastal ocean. Meltwater may serve as an atmospheric source or sink of carbon dioxide (CO2) or methane (CH4), depending on the magnitudes of subglacial organic carbon (OC) remineralization, which produces CO2 and CH4, and mineral weathering reactions, which consume CO2 but not CH4. We report wide variability in dissolved CO2 and CH4 concentrations at the beginning of the melt season (May-June 2017) between three sites draining land-terminating glaciers of the Greenland Ice Sheet. Two sites, located along the Watson River in western Greenland, drain the Isunnguata and Russell Glaciers and contained 1060 and 400 ppm CO2, respectively. In-situ CO2 flux measurements indicated that the Isunnguata was a source of atmospheric CO2, while the Russell was a sink. Both sites had elevated CH4 concentrations, at 325 and 25 ppm CH4, respectively, suggesting active anaerobic OC remineralization beneath the ice sheet. Dissolved CO2 and CH4 reached atmospheric equilibrium within 2.6 and 8.6 km downstream of Isunnguata and Russell discharge sites, respectively. These changes reflect rapid gas exchange with the atmosphere and/or CO2 consumption via instream mineral weathering. The third site, draining the Kiagtut Sermiat in southern Greenland, had about half atmospheric CO2 concentrations (250 ppm), but approximately atmospheric CH4 concentrations (2.1 ppm). Downstream CO2 flux measurements indicated ingassing of CO2 over the entire 10-km length of the proglacial river. CO2 undersaturation may be due to more readily weathered lithologies underlying the Kiagtut Sermiat compared to Watson River sites, but low CH4 concentrations also suggest limited contributions of CO2 and CH4 from OC remineralization. These results suggest that carbon processing beneath the Greenland Ice Sheet may be more variable than previously recognized

Synthesis and Evaluation of CO2 Thickeners Designed with Molecular Modeling

Energy Technology Data Exchange (ETDEWEB)

Robert Enick; Erick Beckman; J. Karl Johnson

2009-08-31

The objective of this research was to use molecular modeling techniques, coupled with our prior experimental results, to design, synthesize and evaluate inexpensive, non-fluorous carbon dioxide thickening agents. The first type of thickener that was considered was associating polymers. Typically, these thickeners are copolymers that contain a highly CO{sub 2}-philic monomer, and a small concentration of a CO{sub 2}-phobic associating monomer. Yale University was solely responsible for the synthesis of a second type of thickener; small, hydrogen bonding compounds. These molecules have a core that contains one or more hydrogen-bonding groups, such as urea or amide groups. Non-fluorous, CO{sub 2}-philic functional groups were attached to the hydrogen bonding core of the compound to impart CO{sub 2} stability and macromolecular stability to the linear 'stack' of these compounds. The third type of compound initially considered for this investigation was CO{sub 2}-soluble surfactants. These surfactants contain conventional ionic head groups and composed of CO{sub 2}-philic oligomers (short polymers) or small compounds (sugar acetates) previously identified by our research team. Mobility reduction could occur as these surfactant solutions contacted reservoir brine and formed mobility control foams in-situ. The vast majority of the work conducted in this study was devoted to the copolymeric thickeners and the small hydrogen-bonding thickeners; these thickeners were intended to dissolve completely in CO{sub 2} and increase the fluid viscosity. A small but important amount of work was done establishing the groundwork for CO{sub 2}-soluble surfactants that reduced mobility by generating foams in-situ as the CO{sub 2}+surfactant solution mixed with in-situ brine.

Bioavailability of mineral-bound iron to a snow algae-bacteria co-culture and implications for albedo-altering snow algae blooms.

Science.gov (United States)

Harrold, Z R; Hausrath, E M; Garcia, A H; Murray, A E; Tschauner, O; Raymond, J; Huang, S

2018-01-26

Snow algae can form large-scale blooms across the snowpack surface and near-surface environments. These pigmented blooms can decrease snow albedo, increase local melt rates, and may impact the global heat budget and water cycle. Yet, underlying causes for the geospatial occurrence of these blooms remain unconstrained. One possible factor contributing to snow algae blooms is the presence of mineral dust as a micronutrient source. We investigated the bioavailability of iron (Fe) -bearing minerals, including forsterite (Fo 90 , Mg 1.8 Fe 0.2 SiO 4 ), goethite, smectite and pyrite as Fe sources for a Chloromonas brevispina - bacteria co-culture through laboratory-based experimentation. Fo 90 was capable of stimulating snow algal growth and increased the algal growth rate in otherwise Fe-depleted co-cultures. Fo 90 -bearing systems also exhibited a decrease in bacteria:algae ratios compared to Fe-depleted conditions, suggesting a shift in microbial community structure. The C. brevispina co-culture also increased the rate of Fo 90 dissolution relative to an abiotic control. Analysis of 16S rRNA genes in the co-culture identified Gammaproteobacteria , Betaprotoeobacteria and Sphingobacteria , all of which are commonly found in snow and ice environments. Archaea were not detected. Collimonas and Pseudomonas , which are known to enhance mineral weathering rates, comprised two of the top eight (> 1 %) OTUs. These data provide unequivocal evidence that mineral dust can support elevated snow algae growth under otherwise Fe-depleted growth conditions, and that snow algae can enhance mineral dissolution under these conditions. IMPORTANCE Fe, a key micronutrient for photosynthetic growth, is necessary to support the formation of high-density snow algae blooms. The laboratory experiments described herein allow for a systematic investigation of snow algae-bacteria-mineral interactions and their ability to mobilize and uptake mineral-bound Fe. Results provide unequivocal and

Re-Examining Embodied SO2 and CO2 Emissions in China

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Rui Huang

2018-05-01

Full Text Available CO2 and SO2, while having different environmental impacts, are both linked to the burning of fossil fuels. Research on joint patterns of CO2 emissions and SO2 emissions may provide useful information for decision-makers to reduce these emissions effectively. This study analyzes both CO2 emissions and SO2 emissions embodied in interprovincial trade in 2007 and 2010 using multi-regional input–output analysis. Backward and forward linkage analysis shows that Production and Supply of Electric Power and Steam, Non-metal Mineral Products, and Metal Smelting and Pressing are key sectors for mitigating SO2 and CO2 emissions along the national supply chain. The total SO2 emissions and CO2 emissions of these sectors accounted for 81% and 76% of the total national SO2 emissions and CO2 emissions, respectively.

Protein-assisted synthesis of double-shelled CaCO3 microcapsules and their mineralization with heavy metal ions.

Science.gov (United States)

Li, Xuan Qi; Feng, Zhiwei; Xia, Yinyan; Zeng, Hua Chun

2012-02-13

Calcium carbonate (CaCO(3)) is one of the most abundant and important biominerals in nature. Due to its biocompatibility, biodegradability and nontoxicity, CaCO(3) has been investigated extensively in recent years for various fundamental properties and technological applications. Inspired by basic wall structures of cells, we report a protein-assisted approach to synthesize CaCO(3) into a double-shelled structural configuration. Due to varying reactivities of outer and inner shells, the CaCO(3) microcapsules exhibit different sorption capacities and various resultant structures toward different kinds of heavy metal ions, analogical to biologically controlled mineralization (BCM) processes. Surprisingly, three mineralization modes resembling those found in BCM were found with these bacterium-like "CaCO(3) cells". Our investigation of the cytotoxicity (MTT assay protocol) also indicates that the CaCO(3) microcapsules have almost no cytotoxicity against HepG2 cells, and they might be useful for future application of detoxifying heavy metal ions after further study. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In Situ Oxygen Generation from CO2 under Benign Conditions, Phase I

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National Aeronautics and Space Administration — Two key technical challenges will be addressed: Construction of binuclear-CO2 complexes with CO2-CO2 spatially close enough to each other and activation of...

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

Science.gov (United States)

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

In situ developmental responses of tropical sea urchin larvae to ocean acidification conditions at naturally elevated pCO2 vent sites.